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SAMSUNG TOTAL PETROCHEMICALS CO., LTD.

SULFUR BLOCK

NO. 2 AROMATICS COMPLEX
DAESAN, KOREA

OPERATING GUIDELINES







Prepared by
Ortloff Engineers, Ltd.
Midland, Texas USA
Project 507000
Fall 2011


Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Table of Contents

Issued 30Aug11 Table of Contents Page i
1. INTRODUCTION .......................................................................................................... 1-1
2. GENERAL SAFETY ..................................................................................................... 2-1
2.1 DEFINITION OF TERMS ....................................................................................... 2-1
2.2 HYDROGEN SULFIDE (H
2
S) ................................................................................ 2-3
2.2.1 Description and Properties ............................................................................. 2-3
2.2.2 First Aid .......................................................................................................... 2-7
2.2.3 Precautions (remember these facts) .............................................................. 2-8
2.2.4 Good Work Practices ...................................................................................... 2-9
2.3 SULFUR DIOXIDE (SO
2
) ..................................................................................... 2-10
2.3.1 Description and Properties ........................................................................... 2-10
2.3.2 First Aid ........................................................................................................ 2-13
2.3.3 Precautions ................................................................................................... 2-14
2.4 SULFUR .............................................................................................................. 2-15
2.4.1 Description and Properties ........................................................................... 2-15
2.4.2 Precautions ................................................................................................... 2-20
2.4.3 Fire Fighting .................................................................................................. 2-21
2.5 AMMONIA (NH
3
) .................................................................................................. 2-22
2.5.1 Description and Properties ........................................................................... 2-22
2.5.2 First Aid ........................................................................................................ 2-26
2.5.3 Precautions ................................................................................................... 2-26
2.6 METHYLDIETHANOLAMINE (MDEA, CH
3
-N-(CH
2
-CH
2
-OH)
2
) ........................... 2-28
2.6.1 Description and Properties ........................................................................... 2-28
2.6.2 First Aid ........................................................................................................ 2-29
2.6.3 Precautions ................................................................................................... 2-30
2.7 SODIUM HYDROXIDE (CAUSTIC SODA, NAOH) ............................................. 2-31
2.7.1 Description and Properties ........................................................................... 2-31
2.7.2 First Aid ........................................................................................................ 2-35
2.7.3 Precautions ................................................................................................... 2-36
2.8 SULFUR PLANT SAFETY ................................................................................... 2-37
2.8.1 Hydrogen Sulfide .......................................................................................... 2-37
2.8.2 Sulfur Dioxide ............................................................................................... 2-37
2.8.3 Sulfur Storage Tank ...................................................................................... 2-38
2.9 HOT WORK ......................................................................................................... 2-39
2.10 VESSEL ENTRY .................................................................................................. 2-39
2.11 PIPES AND LINES .............................................................................................. 2-41
2.11.1 General ......................................................................................................... 2-41
2.11.2 Before Breaking Lines .................................................................................. 2-42
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Table of Contents

Issued 30Aug11 Table of Contents Page ii
2.11.3 When Breaking Lines ................................................................................... 2-42
2.12 ELECTRICAL EQUIPMENT ................................................................................ 2-42
2.12.1 Electrical Repairs .......................................................................................... 2-43
2.12.2 Grounding ..................................................................................................... 2-43
2.12.3 Conduit, Cables, and Wires .......................................................................... 2-43
2.12.4 Fuses ............................................................................................................ 2-43
2.12.5 Switching ...................................................................................................... 2-43
2.12.6 Hand Tools and Portable Equipment ............................................................ 2-44
2.12.7 Miscellaneous ............................................................................................... 2-44
2.13 BOILERS AND OTHER DIRECT-FIRED EQUIPMENT ...................................... 2-45
2.13.1 General ......................................................................................................... 2-45
2.13.2 Boilers ........................................................................................................... 2-45
2.13.3 Direct-Fired Equipment ................................................................................. 2-46
2.14 LABORATORY SAFETY ..................................................................................... 2-47
2.14.1 Good Housekeeping ..................................................................................... 2-47
2.14.2 Equipment .................................................................................................... 2-47
2.14.3 Chemical Sorting and Identification .............................................................. 2-47
2.14.4 Chemical Handling ....................................................................................... 2-48
2.15 MATERIAL SAFETY DATA SHEETS (MSDS) .................................................... 2-49
3. GENERAL .................................................................................................................... 3-1
3.1 ORGANIZATION ................................................................................................... 3-1
3.2 GENERAL PRECOMMISSIONING PROCEDURES ............................................. 3-2
3.2.1 Mechanical ..................................................................................................... 3-2
3.2.2 Electrical ......................................................................................................... 3-3
3.2.3 Instrumentation ............................................................................................... 3-5
3.3 DESIGN BASIS ..................................................................................................... 3-7
3.3.1 Plant Capacity ................................................................................................ 3-7
3.3.2 Sulfur Block Feed Streams ............................................................................. 3-7
3.3.3 Effluent Stream Conditions ........................................................................... 3-12
3.3.4 Other Design Requirements ......................................................................... 3-13
3.3.5 Utility Information .......................................................................................... 3-14
3.3.6 Plant Site Conditions .................................................................................... 3-16
4. POWER DISTRIBUTION .............................................................................................. 4-1
4.1 PURPOSE OF SYSTEM ....................................................................................... 4-1
4.2 SAFETY ................................................................................................................. 4-1
4.2.1 General ........................................................................................................... 4-1
4.2.2 Hazardous (Classified) Areas ......................................................................... 4-1
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Table of Contents

Issued 30Aug11 Table of Contents Page iii
4.3 EQUIPMENT DESCRIPTION ................................................................................ 4-2
4.3.1 Motors and Motor Controls ............................................................................. 4-2
5. PLANT CONTROL SYSTEMS ..................................................................................... 5-1
5.1 DISTRIBUTED CONTROL SYSTEM .................................................................... 5-1
5.2 PROGRAMMABLE LOGIC CONTROL SYSTEM ................................................. 5-2
5.3 EMERGENCY SHUTDOWN SYSTEMS ............................................................... 5-3
5.4 LOCAL CONTROL PANELS ................................................................................. 5-3
6. UTILITY SYSTEMS ...................................................................................................... 6-1
6.1 PURPOSE OF SYSTEM ....................................................................................... 6-1
6.2 SYSTEM DESCRIPTION ...................................................................................... 6-1
6.2.1 Nitrogen Supply .............................................................................................. 6-1
6.2.2 C4 LPG and Treated Fuel Gas Supply .......................................................... 6-2
6.2.3 Hydrogen Supply ............................................................................................ 6-2
6.2.4 Plant Air .......................................................................................................... 6-3
6.2.5 Instrument Air ................................................................................................. 6-3
6.2.6 Sour Water Disposal ....................................................................................... 6-3
6.2.7 Steam, Condensate, Boiler Feed Water, and Blowdown ............................... 6-4
6.3 PRECOMMISSIONING, STARTUP, AND SHUTDOWN PROCEDURES............. 6-8
7. AMINE TREATING & AMINE REGENERATION ......................................................... 7-1
7.1 PURPOSE OF SYSTEM ....................................................................................... 7-1
7.2 SAFETY ................................................................................................................. 7-1
7.3 PROCESS DESCRIPTION .................................................................................... 7-2
7.3.1 General ........................................................................................................... 7-2
7.3.2 Water Washing ............................................................................................... 7-2
7.3.3 Sour Gas Contacting ...................................................................................... 7-3
7.3.4 Solvent Regeneration ..................................................................................... 7-3
7.4 EQUIPMENT DESCRIPTION ................................................................................ 7-6
7.4.1 Wash Water Column, A2-DA1510 .................................................................. 7-6
7.4.2 Amine Absorber, A2-DA1511 ......................................................................... 7-6
7.4.3 Flash Gas Contactor, A2-DA1512 .................................................................. 7-6
7.4.4 Stripper, A2-DA1513 ...................................................................................... 7-6
7.4.5 Wash Water Column Packing, A2-DB1510 .................................................... 7-7
7.4.6 Amine Absorber Trays, A2-DB1511 ............................................................... 7-7
7.4.7 Stripper Trays, A2-DB1513 ............................................................................ 7-7
7.4.8 Amine Absorber Overhead Cooler, A2-EA1510 ............................................. 7-8
7.4.9 Lean/Rich Exchanger, A2-EA1511A/B ........................................................... 7-8
7.4.10 Stripper Reboiler, A2-EA1512A/B .................................................................. 7-8
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Table of Contents

Issued 30Aug11 Table of Contents Page iv
7.4.11 Stripper Reflux Condenser, A2-EC1511 ......................................................... 7-8
7.4.12 Lean Amine Cooler, A2-EC1510 .................................................................... 7-8
7.4.13 Wash Water Feed Knock-Out Drum, A2-FA1510 ........................................... 7-8
7.4.14 Amine Absorber Feed Knock-Out Drum, A2-FA1511 ..................................... 7-9
7.4.15 Amine Absorber Overhead Knock-Out Drum, A2-FA1512 ............................. 7-9
7.4.16 Rich Amine Flash Drum, A2-FA1513 ............................................................. 7-9
7.4.17 Stripper Reflux Accumulator, A2-FA1514 ..................................................... 7-10
7.4.18 Stripper Reboiler Condensate Pot, A2-FA1515A/B ...................................... 7-10
7.4.19 ATU Skim Oil Sump, A2-FA1516 ................................................................. 7-10
7.4.20 ATU Skim Oil Pump Sump, A2-FA1517A/B ................................................. 7-10
7.4.21 ATU Amine Drips Tank, A2-FA1580 ............................................................. 7-11
7.4.22 MDEA Storage Tank, A2-FB1580 ................................................................ 7-11
7.4.23 Wash Water Filter, A2-FD1510A/B ............................................................... 7-11
7.4.24 Rich Amine Filter, A2-FD1511A/B ................................................................ 7-11
7.4.25 Lean Amine Filter, A2-FD1512 ..................................................................... 7-11
7.4.26 Lean Amine Carbon Filter, A2-FD1513 ........................................................ 7-12
7.4.27 Lean Amine After-Filter, A2-FD1514 ............................................................ 7-12
7.4.28 ATU Amine Drips Filter, A2-FD1580 ............................................................ 7-12
7.4.29 Wash Water Pump, A2-GA1510A/B ............................................................. 7-13
7.4.30 Lean Amine Pump, A2-GA1511A/B ............................................................. 7-13
7.4.31 ATU Skim Oil Pump, A2-GA1512A/B ........................................................... 7-13
7.4.32 Rich Amine Pump, A2-GA1513A/B .............................................................. 7-13
7.4.33 Lean Amine Booster Pump, A2-GA1514A/B ................................................ 7-13
7.4.34 Stripper Reflux Pump, A2-GA1515A/B ......................................................... 7-13
7.4.35 MDEA Transfer Pump, A2-GA1580 .............................................................. 7-14
7.5 INSTRUMENTATION AND CONTROL SYSTEMS ............................................. 7-15
7.5.1 Treated Fuel Gas H
2
S Analyzer ................................................................... 7-15
7.5.2 ATU Emergency Shutdown Systems ........................................................... 7-15
7.6 PROCESS PRINCIPLES AND OPERATING TECHNIQUES ............................. 7-19
7.6.1 Amine Absorber Operation ........................................................................... 7-19
7.6.2 Stripper Operation ........................................................................................ 7-22
7.6.3 Amine Water Balance ................................................................................... 7-24
7.6.4 Amine Loss ................................................................................................... 7-27
7.6.5 Operation at Low Flow Rates ....................................................................... 7-29
7.7 PRECOMMISSIONING PROCEDURES ............................................................. 7-30
7.7.1 Preliminary Check-out .................................................................................. 7-30
7.7.2 Shutdown System Check-out ....................................................................... 7-31
7.7.3 Leak Testing the Process Piping and Equipment ......................................... 7-31
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Table of Contents

Issued 30Aug11 Table of Contents Page v
7.7.4 Washing the Wash Water System ................................................................ 7-33
7.7.5 Washing the Amine System ......................................................................... 7-38
7.7.6 Purging the Low Pressure Columns ............................................................. 7-50
7.8 STARTUP PROCEDURES .................................................................................. 7-52
7.8.1 Wash Water and Amine Systems ................................................................. 7-52
7.8.2 Sour Fuel Gas Flow to the Columns ............................................................. 7-53
7.9 SHUTDOWN PROCEDURES ............................................................................. 7-56
7.9.1 Planned Shutdown - ATU ............................................................................ 7-57
7.9.2 Planned Shutdown - ATU and ARU ............................................................. 7-60
7.9.3 Emergency Shutdown .................................................................................. 7-62
7.9.4 Effects of Shutdowns and Outages in Other Systems .................................. 7-63
7.10 ANALYTICAL PROCEDURES ............................................................................ 7-64
7.10.1 General Procedures for Analyzing ATU/ARU Solvent
,
................................. 7-64
7.10.2 Determination of Amine Concentration in ATU/ARU Solvent ....................... 7-68
7.10.3 Determination of Total Acid Gas Loading in ATU/ARU Solvent ................... 7-70
7.10.4 Determination of H
2
S and CO
2
Loading in ATU/ARU Solvent ...................... 7-72
7.10.5 Determination of Foaming Tendency of ATU/ARU Solvent .......................... 7-76
7.10.6 H
2
S Conc. in Amine Absorber Ovhd by the Tutweiler Method ..................... 7-78
7.10.7 H
2
S Conc. in Amine Absorber Ovhd Using Gas Detector Tubes ................. 7-79
8. SOUR WATER STRIPPING ......................................................................................... 8-1
8.1 PURPOSE OF SYSTEM ....................................................................................... 8-1
8.2 SAFETY ................................................................................................................. 8-1
8.3 PROCESS DESCRIPTION .................................................................................... 8-2
8.3.1 General ........................................................................................................... 8-2
8.3.2 Sour Water Collection ..................................................................................... 8-2
8.3.3 Sour Water Stripping ...................................................................................... 8-3
8.4 EQUIPMENT DESCRIPTION ................................................................................ 8-5
8.4.1 Sour Water Stripper, A2-DA1520 ................................................................... 8-5
8.4.2 Sour Water Stripper Packing and Internals, A2-DB1520 ................................ 8-5
8.4.3 Stripper Trays, A2-DB1521 ............................................................................ 8-5
8.4.4 SWS Cross Exchanger, A2-EA1520 .............................................................. 8-5
8.4.5 Sour Water Stripper Reboiler, A2-EA1521 ..................................................... 8-6
8.4.6 SWS Quench Water Cooler, A2-EC1520 ....................................................... 8-6
8.4.7 SWS Bottoms Cooler, A2-EC1521 ................................................................. 8-6
8.4.8 Sour Water Flash Drum, A2-FA1520 .............................................................. 8-6
8.4.9 SWS Skim Oil Sump, A2-FA1522 .................................................................. 8-7
8.4.10 SWS Skim Oil Pump Sump, A2-FA1523A/B .................................................. 8-7
8.4.11 Sour Water Tank, A2-FB1520 ........................................................................ 8-7
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Table of Contents

Issued 30Aug11 Table of Contents Page vi
8.4.12 Sour Water Filter, A2-FD1520A/B .................................................................. 8-7
8.4.13 Sour Water Transfer Pump, A2-GA1520A/B .................................................. 8-7
8.4.14 SWS Feed Pump, A2-GA1521A/B ................................................................. 8-8
8.4.15 SWS Quench Water Pump, A2-GA1522A/B .................................................. 8-8
8.4.16 SWS Bottoms Pump, A2-GA1523A/B ............................................................ 8-8
8.4.17 SWS Skim Oil Pump, A2-GA1524A/B ............................................................ 8-8
8.5 INSTRUMENTATION AND CONTROL SYSTEMS ............................................... 8-9
8.5.1 SWS Shutdowns and Alarms ......................................................................... 8-9
8.6 PROCESS PRINCIPLES AND OPERATING TECHNIQUES ............................. 8-11
8.6.1 SWS Stripper Operation ............................................................................... 8-11
8.6.2 Quench Water Circulation ............................................................................ 8-12
8.6.3 pH Control .................................................................................................... 8-13
8.7 PRECOMMISSIONING PROCEDURES ............................................................. 8-14
8.7.1 Preliminary Check-out .................................................................................. 8-14
8.7.2 Washing the Sour Water System ................................................................. 8-15
8.8 STARTUP PROCEDURES .................................................................................. 8-19
8.8.1 Initial Startup of the SWS ............................................................................. 8-19
8.8.2 Normal Startup of the SWS .......................................................................... 8-23
8.9 SHUTDOWN PROCEDURES ............................................................................. 8-29
8.9.1 Planned Shutdown ....................................................................................... 8-29
8.9.2 Effects of Shutdowns and Outages in Other Systems .................................. 8-31
9. SULFUR RECOVERY .................................................................................................. 9-4
9.1 PURPOSE OF SYSTEM ....................................................................................... 9-4
9.2 SAFETY ................................................................................................................. 9-4
9.3 PROCESS DESCRIPTION .................................................................................... 9-5
9.3.1 Overview ......................................................................................................... 9-5
9.3.2 General ........................................................................................................... 9-6
9.3.3 Feed Gas Processing ..................................................................................... 9-6
9.3.4 Thermal Processing ........................................................................................ 9-7
9.3.5 Catalytic Processing ....................................................................................... 9-8
9.3.6 Air Control System .......................................................................................... 9-9
9.3.7 Molten Sulfur Handling ................................................................................. 9-10
9.3.8 Steam Production ......................................................................................... 9-10
9.4 EQUIPMENT DESCRIPTION .............................................................................. 9-11
9.4.1 Reactor Furnace, A2-BA1530 (A2-BA1540) ................................................. 9-11
9.4.2 Acid Gas Burner Assembly, A2-BA1531 (A2-BA1541) ................................ 9-12
9.4.3 Acid Gas Knock-Out Drum, A2-FA1530 (A2-FA1540) ................................. 9-12
9.4.4 SWS Gas Knock-Out Drum, A2-FA1531 (A2-FA1541) ................................ 9-12
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Table of Contents

Issued 30Aug11 Table of Contents Page vii
9.4.5 Reactor, A2-DC1530 (A2-DC1540) .............................................................. 9-13
9.4.6 Catalyst for Sulfur Plant Reactors, A2-MC1530 (A2-MC1540) ..................... 9-13
9.4.7 Acid Gas Preheater, A2-EA1530 (A2-EA1540) ............................................ 9-13
9.4.8 Sulfur Condenser, A2-EA1531 (A2-EA1541) ............................................... 9-13
9.4.9 Reactor No. 1 Feed Heater, A2-EA1532 (A2-EA1542) ................................ 9-14
9.4.10 Reactor No. 2 Feed Heater, A2-EA1533 (A2-EA1543) ................................ 9-14
9.4.11 Reactor No. 3 Feed Heater, A2-EA1534 (A2-EA1544) ................................ 9-15
9.4.12 Sulfur Surge Tank, A2-FB1530 (A2-FB1540) ............................................... 9-15
9.4.13 Acid Gas Knock-Out Drum Pump, A2-GA1530A/B (A2-GA1540A/B) .......... 9-16
9.4.14 SWS Gas Knock-Out Drum Pump, A2-GA1531A/B (A2-GA1541A/B) ......... 9-17
9.4.15 Sulfur Storage Tank Vent Ejector, A2-EE1530 (A2-EE1540) ....................... 9-17
9.4.16 Process Air Blower, A2-GB1530A/B (A2-GB1540A/B) ................................. 9-18
9.4.17 Air Blower Suction Screen/Silencer, A2-FD1530A/B (A2-FD1540A/B) ........ 9-19
9.4.18 Process Air Vent Silencer, A2-FG1530A/B (A2-FG1540A/B) ....................... 9-19
9.4.19 Sulfur Drain Seal Assembly, A2-ME1530A-D (A2-ME1540A-D) .................. 9-19
9.4.20 Refractory for Reactor Furnace and Waste Heat Boiler, A2-MR1530
(A2-MR1540) .............................................................................................................. 9-20
9.4.21 Ceramic Ferrules for Waste Heat Boiler, A2-MR1532 (A2-MR1542) ........... 9-20
9.4.22 Refractory for Waste Heat Boiler, A2-MR1533 (A2-MR1543) ...................... 9-20
9.4.23 Refractory for Sulfur Condenser, A2-MR1534 (A2-MR1544) ....................... 9-20
9.4.24 Refractory for Reactor, A2-MR1535 (A2-MR1545) ...................................... 9-21
9.4.25 Rainshield for Reactor Furnace, A2-ME1531 (A2-ME1541) ........................ 9-21
9.4.26 Ceramic Ferrule for Reactor Furnace, A2-MR1531 (A2-MR1541) ............... 9-21
9.4.27 Waste Heat Boiler, A2-BF1530 (A2-BF1540) ............................................... 9-22
9.5 INSTRUMENTATION AND CONTROL SYSTEMS ............................................. 9-24
9.5.1 SRU Air:Acid Gas Ratio Control Loop .......................................................... 9-24
9.5.2 Acid Gas Burner Management System ........................................................ 9-30
9.5.3 Process Air Blower Controls ......................................................................... 9-34
9.5.4 Reactor Furnace Temperature Control ......................................................... 9-39
9.5.5 Knock-Out Drum Pump Control .................................................................... 9-41
9.5.6 "Ride-Through" System Considerations ....................................................... 9-41
9.5.7 Boiler Low-Low Level S/D Transmitter Testing ............................................ 9-44
9.5.8 SRU Emergency Shutdown Systems ........................................................... 9-46
9.6 PROCESS PRINCIPLES AND OPERATING TECHNIQUES ............................. 9-56
9.6.1 Equipment Damage ...................................................................................... 9-56
9.6.2 Cold Catalyst Bed Startup ............................................................................ 9-58
9.6.3 Sulfur Solidification ....................................................................................... 9-60
9.6.4 Ammonia Salt Formation .............................................................................. 9-61
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Table of Contents

Issued 30Aug11 Table of Contents Page viii
9.6.5 Catalyst Fouling ............................................................................................ 9-62
9.6.6 Operation of SRUs in Parallel ....................................................................... 9-62
9.6.7 Process air Blower Operation ....................................................................... 9-65
9.6.8 Reactor Furnace Temperature ..................................................................... 9-70
9.6.9 Ammonia Destruction Considerations .......................................................... 9-73
9.6.10 Sulfur Recovery Efficiency ............................................................................ 9-76
9.6.11 Operation at Low Flow Rates ....................................................................... 9-78
9.6.12 Pressure Drop Surveys ................................................................................ 9-82
9.6.13 Boiler Water Treatment ................................................................................ 9-84
9.7 PRECOMMISSIONING PROCEDURES ............................................................. 9-86
9.7.1 Preliminary Check-out .................................................................................. 9-86
9.7.2 Shutdown System Check-out ....................................................................... 9-87
9.7.3 Leak Testing the Process Piping and Equipment ......................................... 9-88
9.7.4 Purging the Inlet Knock-Out Drums .............................................................. 9-93
9.7.5 Commissioning Fuel Gas and Instrument Air to the Process ....................... 9-95
9.7.6 Commissioning Nitrogen to the Process ...................................................... 9-99
9.7.7 Commissioning the Sulfur Surge Tank Heating and Ventilation ................. 9-102
9.7.8 Pre-filling the Sulfur Drain Seal Assemblies ............................................... 9-104
9.8 STARTUP PROCEDURES ................................................................................ 9-105
9.8.1 Initial Firing / Refractory Cure-out ............................................................... 9-105
9.8.2 Amine Acid Gas Flow ................................................................................. 9-117
9.8.3 SWS Gas Flow ........................................................................................... 9-124
9.8.4 Routing SRU Tailgas to the TGCU ............................................................. 9-127
9.8.5 Normal Startup - Cold System .................................................................... 9-129
9.8.6 Normal Startup - Hot System ...................................................................... 9-146
9.8.7 Firing Supplemental Fuel Gas .................................................................... 9-158
9.9 SHUTDOWN PROCEDURES ........................................................................... 9-164
9.9.1 Planned Shutdown - No Reactor Entry ....................................................... 9-165
9.9.2 Planned Shutdown for Reactor Entry ......................................................... 9-170
9.9.3 Shutting Down When Boiler Tubes Are Leaking ........................................ 9-180
9.9.4 Emergency Shutdown ................................................................................ 9-181
9.9.5 Effects of Shutdowns and Outages in Other Systems ................................ 9-183
9.10 ANALYTICAL PROCEDURES .......................................................................... 9-187
9.10.1 Procedure for Sampling and Titrating with a Tutweiler Apparatus ............. 9-187
9.10.2 H
2
S Concentration in Acid Gas by the Tutweiler Method ........................... 9-189
9.10.3 H
2
S and SO
2
Concentration in Tailgas by the Tutweiler Method ................ 9-192
9.10.4 Tailgas Analysis Table ................................................................................ 9-196
9.10.5 Tailgas Analysis Operating Chart ............................................................... 9-197
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Table of Contents

Issued 30Aug11 Table of Contents Page ix
9.10.6 Essential Apparatus for Tutweiler Analysis ................................................ 9-199
9.10.7 Materials for Tutweiler Analysis .................................................................. 9-200
9.10.8 H
2
S and SO
2
Conc. in Tailgas Using Gas Detector Tubes ......................... 9-200
9.11 ADJUSTING STACKMATCH

IGNITOR/PILOTS ............................................. 9-205


10. SULFUR DEGASSING, STORAGE & LOADING .................................................. 10-3
10.1 PURPOSE OF SYSTEM ..................................................................................... 10-3
10.2 SAFETY ............................................................................................................... 10-4
10.3 PROCESS DESCRIPTION .................................................................................. 10-5
10.4 EQUIPMENT DESCRIPTION .............................................................................. 10-7
10.4.1 Sulfur Degassing Reactor, A2-DC1550 ........................................................ 10-7
10.4.2 Sulfur Storage Tank, A2-FB1550 ................................................................. 10-7
10.4.3 Sulfur Feed Pump, A2-GA1532A/B (A2-GA1542A/B) .................................. 10-8
10.4.4 Sulfur Loading Pump, A2-GA1550A/B ......................................................... 10-8
10.4.5 Degassing Air Blower, A2-GB1550A/B ......................................................... 10-9
10.4.6 Bed Support and Limiter for Sulfur Degassing Reactor, A2-DC1551 ........... 10-9
10.4.7 Degassed Sulfur Drain Seal Assembly, A2-ME1550 .................................... 10-9
10.5 INSTRUMENTATION AND CONTROL SYSTEMS ........................................... 10-11
10.5.1 Sulfur Feed Rate Control ............................................................................ 10-11
10.5.2 Degassing Air Flow ..................................................................................... 10-12
10.5.3 Sulfur Degassing Unit Startup Interlock ...................................................... 10-13
10.5.4 Snuffing Steam ........................................................................................... 10-13
10.5.5 Sulfur Loading ............................................................................................ 10-14
10.5.6 Sulfur Loading Pump Local Stop Switches ................................................. 10-17
10.5.7 Sulfur Degassing Shutdown System .......................................................... 10-18
10.5.8 Sulfur Loading ESD System ....................................................................... 10-21
10.6 PROCESS PRINCIPLES AND OPERATING TECHNIQUES ........................... 10-23
10.6.1 Equipment Damage .................................................................................... 10-23
10.6.2 Degassing Air Blower Operation ................................................................ 10-26
10.6.3 Sulfur Solidification ..................................................................................... 10-29
10.6.4 Sulfur Pumping ........................................................................................... 10-29
10.7 PRECOMMISSIONING PROCEDURES ........................................................... 10-31
10.7.1 Preliminary Check-out ................................................................................ 10-31
10.7.2 Commissioning the Heating and Ventilation Systems ................................ 10-32
10.7.3 Purging the Sulfur Degassing Reactor ....................................................... 10-37
10.8 STARTUP PROCEDURES ................................................................................ 10-40
10.8.1 Initial Startup of the Sulfur Degassing Unit ................................................. 10-40
10.8.2 Normal Startup of the Sulfur Degassing System ........................................ 10-46
10.8.3 Initial Sulfur Loading Operation .................................................................. 10-51
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Table of Contents

Issued 30Aug11 Table of Contents Page x
10.8.4 Normal Sulfur Loading Operation ............................................................... 10-53
10.9 SHUTDOWN PROCEDURES ........................................................................... 10-54
10.9.1 Planned Shutdown - No Reactor Entry ....................................................... 10-54
10.9.2 Planned Shutdown for Reactor Entry ......................................................... 10-55
10.9.3 Shutdown for Tank Entry ............................................................................ 10-57
11. TAILGAS CLEANUP .............................................................................................. 11-1
11.1 PURPOSE OF SYSTEM ..................................................................................... 11-1
11.2 SAFETY ............................................................................................................... 11-2
11.3 PROCESS DESCRIPTION .................................................................................. 11-3
11.3.1 General ......................................................................................................... 11-3
11.3.2 Tailgas Hydrogenation/Hydrolysis ................................................................ 11-3
11.3.3 Process Gas Cooling .................................................................................... 11-4
11.3.4 Gas Contacting ............................................................................................. 11-5
11.3.5 Solvent Regeneration Section ...................................................................... 11-6
11.3.6 Steam Production/Consumption ................................................................... 11-7
11.4 EQUIPMENT DESCRIPTION .............................................................................. 11-8
11.4.1 TGCU Quench Column, A2-DA1560 ............................................................ 11-8
11.4.2 TGCU Quench Column Packing, A2-DB1560 .............................................. 11-8
11.4.3 TGCU Contactor, A2-DA1561 ...................................................................... 11-8
11.4.4 TGCU Contactor Packing & Internals, A2-DB1561 ...................................... 11-8
11.4.5 TGCU Stripper, A2-DA1562 ......................................................................... 11-9
11.4.6 TGCU Stripper Trays, A2-DB1562 ............................................................... 11-9
11.4.7 TGCU Reactor, A2-DC1560 ....................................................................... 11-10
11.4.8 TGCU Stripper Reflux Accumulator, A2-FA1560 ....................................... 11-10
11.4.9 Catalyst for TGCU Reactor, A2-MC1560 ................................................... 11-10
11.4.10 TGCU Stripper Reboiler Condensate Pot, A2-FA1562 ........................... 11-10
11.4.11 TGCU Reactor Feed Heater, A2-EA1560 ............................................... 11-11
11.4.12 TGCU Waste Heat Reclaimer, A2-EA1561 ............................................ 11-11
11.4.13 TGCU Quench Water Trim Cooler, A2-EA1562A/B ................................ 11-11
11.4.14 TGCU Lean/Rich Exchanger, A2-EA1564 .............................................. 11-11
11.4.15 TGCU Stripper Reboiler, A2-EA1565 ..................................................... 11-12
11.4.16 TGCU Lean Amine Trim Cooler, A2-EA1563 ......................................... 11-12
11.4.17 TGCU Quench Water Cooler, A2-EC1560 ............................................. 11-12
11.4.18 TGCU Stripper Reflux Condenser, A2-EC1562 ...................................... 11-12
11.4.19 TGCU Lean Amine Cooler, A2-EC1561 ................................................. 11-12
11.4.20 TGCU Quench Water Pump, A2-GA1560A/B ......................................... 11-13
11.4.21 TGCU Rich Amine Pump, A2-GA1561A/B ............................................. 11-14
11.4.22 TGCU Stripper Reflux Pump, A2-GA1563A/B ........................................ 11-14
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Table of Contents

Issued 30Aug11 Table of Contents Page xi
11.4.23 TGCU Lean Amine Pump, A2-GA1562A/B ............................................. 11-14
11.4.24 TGCU Start-Up Blower, A2-GB1560 ....................................................... 11-14
11.4.25 Refractory for TGCU Reactor, A2-MR1560 ............................................ 11-15
11.4.26 TGCU Reactor Feed Mixer, A2-ME1560 ................................................ 11-16
11.4.27 TGCU Quench Water Filter, A2-FD1560A/B .......................................... 11-16
11.4.28 TGCU Rich Amine Filter, A2-FD1562A/B ............................................... 11-16
11.4.29 TGCU Lean Amine Filter, A2-FD1563 .................................................... 11-17
11.4.30 TGCU Amine Carbon Filter, A2-FD1564 ................................................ 11-17
11.4.31 TGCU Amine After-Filter, A2-FD1565 .................................................... 11-17
11.4.32 pH Meter Sample Filter, A2-FD1561A/B ................................................. 11-17
11.5 INSTRUMENTATION AND CONTROL SYSTEMS ........................................... 11-18
11.5.1 TGCU Reactor Feed Control Loops ........................................................... 11-18
11.5.2 Hydrogen and Hydrogen Sulfide Analyzer, A2-AE15858/A2-AE15859 ...... 11-23
11.5.3 Boiler Low-Low Level S/D Transmitter Testing .......................................... 11-24
11.5.4 Tailgas Switching Valve Controls ............................................................... 11-26
11.5.5 TGCU Shutdown System ........................................................................... 11-33
11.6 PROCESS PRINCIPLES AND OPERATING TECHNIQUES ........................... 11-39
11.6.1 Equipment Damage .................................................................................... 11-39
11.6.2 Catalyst Fouling .......................................................................................... 11-40
11.6.3 TGCU Reactor Operation ........................................................................... 11-41
11.6.4 TGCU Catalyst ........................................................................................... 11-43
11.6.5 TGCU Start-Up Blower Operation .............................................................. 11-44
11.6.6 TGCU Quench Column Operation .............................................................. 11-45
11.6.7 TGCU Contactor Operation ........................................................................ 11-48
11.6.8 TGCU Stripper Operation ........................................................................... 11-52
11.6.9 TGCU Amine Water Balance ...................................................................... 11-55
11.6.10 TGCU Amine Loss .................................................................................. 11-59
11.6.11 Operation at Low Flow Rates .................................................................. 11-60
11.6.12 Pressure Drop Surveys ........................................................................... 11-61
11.6.13 Boiler Water Treatment ........................................................................... 11-63
11.7 PRECOMMISSIONING PROCEDURES ........................................................... 11-64
11.7.1 Preliminary Check-out ................................................................................ 11-64
11.7.2 Shutdown System Check-out ..................................................................... 11-65
11.7.3 Commissioning Nitrogen and Utility Air to the Process .............................. 11-66
11.7.4 Commissioning Hydrogen to the Process .................................................. 11-72
11.7.5 Leak Testing the Process Piping and Equipment ....................................... 11-75
11.7.6 Washing the Quench Water System .......................................................... 11-79
11.7.7 Washing the Amine System ....................................................................... 11-85
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Table of Contents

Issued 30Aug11 Table of Contents Page xii
11.7.8 Purging the Low Pressure TGCU Columns ................................................ 11-97
11.8 STARTUP PROCEDURES .............................................................................. 11-102
11.8.1 Initial Startup of the TGCU ....................................................................... 11-102
11.8.2 Pre-Sulfiding the TGCU Catalyst .............................................................. 11-107
11.8.3 Routing SRU Tailgas to the TGCU ........................................................... 11-115
11.8.4 Quench Water and Amine Systems ......................................................... 11-122
11.8.5 Process Gas Flow to the TGCU Columns ................................................ 11-124
11.8.6 Normal Startup of the TGCU .................................................................... 11-128
11.9 SHUTDOWN PROCEDURES ......................................................................... 11-144
11.9.1 Planned Shutdown - No Reactor Entry ..................................................... 11-145
11.9.2 Planned Shutdown for Reactor Entry ....................................................... 11-151
11.9.3 Shutting Down When Boiler Tubes Are Leaking ...................................... 11-158
11.9.4 Special Precaution During Shutdowns ..................................................... 11-159
11.9.5 Emergency Shutdown .............................................................................. 11-163
11.9.6 Effects of Shutdowns and Outages in Other Systems .............................. 11-164
11.10 ANALYTICAL PROCEDURES ..................................................................... 11-167
11.10.1 General Procedures for Analyzing TGCU Solvent
,
............................... 11-167
11.10.2 Determination of Amine Concentration in TGCU Solvent ..................... 11-171
11.10.3 Determination of Total Acid Gas Loading in TGCU Solvent ................. 11-173
11.10.4 Determination of H
2
S and CO
2
Loading in TGCU Solvent .................... 11-175
11.10.5 Determination of Foaming Tendency of TGCU Solvent ........................ 11-179
11.10.6 H
2
S Conc. in TGCU Contactor Ovhd by the Tutweiler Method ............. 11-181
11.10.7 H
2
S Conc. in TGCU Contactor Ovhd Using Gas Detector Tubes ......... 11-182
11.10.8 Monitoring the Performance Level of TGCU Catalyst ........................... 11-185
12. TAILGAS THERMAL OXIDIZER ............................................................................ 12-2
12.1 PURPOSE OF SYSTEM ..................................................................................... 12-2
12.2 SAFETY ............................................................................................................... 12-2
12.3 PROCESS DESCRIPTION .................................................................................. 12-3
12.4 EQUIPMENT DESCRIPTION .............................................................................. 12-4
12.4.1 Thermal Oxidizer, A2-BA1570 ...................................................................... 12-4
12.4.2 Thermal Oxidizer Burner, A2-BA1571 .......................................................... 12-4
12.4.3 Steam Knock-out Drum, A2-FA1570 ............................................................ 12-4
12.4.4 Thermal Oxidizer Air Blower, A2-GB1570A/B .............................................. 12-4
12.4.5 Thermal Oxidizer Vent Stack, A2-ME1570 ................................................... 12-5
12.4.6 Refractory for Thermal Oxidizer, A2-MR1570 .............................................. 12-5
12.4.7 Thermal Oxidizer Waste Heat Boiler, A2-BF1570 ........................................ 12-5
12.5 INSTRUMENTATION AND CONTROL SYSTEMS ............................................. 12-7
12.5.1 Thermal Oxidizer Burner Management System ........................................... 12-7
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Table of Contents

Issued 30Aug11 Table of Contents Page xiii
12.5.2 Thermal Oxidizer Temperature Control ...................................................... 12-10
12.5.3 Thermal Oxidizer Excess Oxygen Control .................................................. 12-10
12.5.4 Boiler Low-Low Level S/D Transmitter Testing .......................................... 12-11
12.5.5 Thermal Oxidizer Shutdown System .......................................................... 12-13
12.6 PROCESS PRINCIPLES AND OPERATING TECHNIQUES ........................... 12-18
12.6.1 Equipment Damage .................................................................................... 12-18
12.6.2 Effect of Upstream Operations on the Thermal Oxidizer ............................ 12-21
12.6.3 "Swapping" Air Blowers During Operation .................................................. 12-23
12.6.4 Boiler Water Treatment .............................................................................. 12-24
12.7 PRECOMMISSIONING PROCEDURES ........................................................... 12-26
12.7.1 Preliminary Check-out ................................................................................ 12-26
12.7.2 Shutdown System Check-out ..................................................................... 12-27
12.7.3 Commissioning Fuel Gas, Pilot Gas, and I/A to the Process ..................... 12-28
12.8 STARTUP PROCEDURES ................................................................................ 12-33
12.8.1 Initial Firing / Refractory Cure-out ............................................................... 12-33
12.8.2 Normal Startup ........................................................................................... 12-48
12.9 SHUTDOWN PROCEDURES ........................................................................... 12-58
12.9.1 Planned Shutdown - No Entry .................................................................... 12-59
12.9.2 Planned Shutdown for Entry ....................................................................... 12-61
12.9.3 Shutting Down When Boiler Tubes Are Leaking ........................................ 12-65
12.9.4 Emergency Shutdown ................................................................................ 12-66
12.9.5 Effects of Shutdowns and Outages in Other Systems ................................ 12-69














Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Introduction Page 1-1
1. INTRODUCTION
THE INFORMATION IN THESE GUIDELINES IS CONFIDENTIAL. SOME OF
THE PROCESSES, DESIGNS, EQUIPMENT, AND/OR PROCEDURES
DESCRIBED HEREIN ARE PROPRIETARY AND/OR LICENSED BY
BP AMOCO CORPORATION, SHELL GLOBAL SOLUTIONS (US) INC., UOP
LLC. AND/OR ORTLOFF ENGINEERS, LTD. DISCLOSURE, REPRODUCTION,
OR USE OF THESE GUIDELINES FOR ANY REASON OTHER THAN
OPERATION OF THIS FACILITY IS IN VIOLATION OF WRITTEN SECRECY
AGREEMENTS.
These Operating Guidelines have been prepared by Ortloff Engineers, Ltd. as a guide
for the initial operation of the new Sulfur Block at Samsung Total Petrochemicals Co.,
Ltd.s Daesan No. 2 Aromatics Complex. The new Sulfur Block consists of an Amine
Treating Unit (ATU), an Amine Regeneration Unit (ARU), a Sour Water Stripper
(SWS), two parallel Sulfur Recovery Units (SRUs), and a common Sulfur Degassing
Unit (SDU), Tailgas Cleanup Unit (TGCU) and Tailgas Thermal Oxidation Unit (TTO).
These units are to process sour gas and sour water streams to remove the contained
sulfur and produce treated fuel gas for consumption in the complex, treated water
safe for reuse or disposal, and commercial grade molten sulfur for sales. These
guidelines contain information concerning the design, startup, operation, and
shutdown of the new facility to assist plant personnel in developing familiarity with
and understanding of the process, equipment, and overall plant operation, and to
supplement equipment manufacturers' operating instructions.
We have tried to present all of the information from an operations viewpoint by
breaking the facility into separate systems for the ease of understanding and startup.
The information for the systems is organized as follows, although some systems will
not require every category:
1. Purpose of System
2. Safety
3. Process Description
4. Instrumentation and Control Systems
5. Operating Principles and Techniques
6. Precommissioning Procedures
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Introduction Page 1-2
7. Startup Procedures
8. Shutdown Procedures
9. Setpoints (Controllers, Alarms, Shutdowns, PCVs, PSVs)
10. Analytical Procedures
The instructions in these guidelines are based on past experience with similar plants
and equipment. They are to be used as guidelines for developing detailed operating
procedures customized for your plant and its actual operating conditions. These
instructions are not intended in any way to supersede or supplant operating
procedures and safety practices established by Samsung Total Petrochemicals Co.,
Ltd., nor are they intended to be used independently of equipment manufacturers
operating instructions. In preparing these instructions, it has been assumed that all
startup and operating personnel have been trained in and are knowledgeable of the
operating instructions provided by the manufacturers of the equipment included in this
facility.
It is expected that Samsung Total Petrochemicals Co., Ltd. will revise and improve
upon the operating instructions in this manual as operating experience is gained, and
as required to incorporate any changes resulting from Samsung Total Petrochemicals
Co., Ltd.'s Process Safety Management program. Update and maintenance of this
manual is Samsung Total Petrochemicals Co., Ltd.'s responsibility and is not within
Ortloff's scope of responsibility.
Operating values and numbers quoted in this manual are design values. They are
presented to enable the operator to have a "ball park" idea of plant operating values.
Actual plant operating conditions may deviate from the design figures, yet yield
satisfactory operations and products. We recommend that operating parameters
such as temperatures, pressures, and flow rates be recorded on a routine basis.
Good data, properly gathered and maintained, form a valuable base for plant studies
and performance evaluations.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Safety Page 2-i
Table of Contents
2. GENERAL SAFETY ..................................................................................................... 2-1
2.1 DEFINITION OF TERMS ....................................................................................... 2-1
2.2 HYDROGEN SULFIDE (H
2
S) ................................................................................ 2-3
2.2.1 Description and Properties ............................................................................. 2-3
2.2.1.1 General .................................................................................................... 2-3
2.2.1.2 Toxicity Information ................................................................................. 2-3
2.2.1.3 Permissible Exposure Limits ................................................................... 2-3
2.2.1.4 Odor ........................................................................................................ 2-3
2.2.1.5 Physical Data .......................................................................................... 2-3
2.2.1.6 Reactivity Data ........................................................................................ 2-4
2.2.1.7 Corrosivity Data ....................................................................................... 2-5
2.2.1.8 Water Solubility ....................................................................................... 2-5
2.2.1.9 Other Characteristics ............................................................................... 2-5
2.2.1.10 Fire and Explosion Hazard ...................................................................... 2-6
2.2.1.11 Life Hazard .............................................................................................. 2-6
2.2.2 First Aid .......................................................................................................... 2-7
2.2.3 Precautions (remember these facts) .............................................................. 2-8
2.2.4 Good Work Practices ...................................................................................... 2-9
2.3 SULFUR DIOXIDE (SO
2
) ..................................................................................... 2-10
2.3.1 Description and Properties ........................................................................... 2-10
2.3.1.1 General .................................................................................................. 2-10
2.3.1.2 Toxicity Information ............................................................................... 2-10
2.3.1.3 Permissible Exposure Limits ................................................................. 2-10
2.3.1.4 Odor ...................................................................................................... 2-11
2.3.1.5 Physical Data ........................................................................................ 2-11
2.3.1.6 Reactivity Data ...................................................................................... 2-11
2.3.1.7 Corrosivity Data ..................................................................................... 2-12
2.3.1.8 Water Solubility ..................................................................................... 2-12
2.3.1.9 Fire and Explosion Hazard .................................................................... 2-12
2.3.1.10 Life Hazard ............................................................................................ 2-12
2.3.2 First Aid ........................................................................................................ 2-13
2.3.3 Precautions ................................................................................................... 2-14
2.4 SULFUR .............................................................................................................. 2-15
2.4.1 Description and Properties ........................................................................... 2-15
2.4.1.1 General .................................................................................................. 2-15
2.4.1.2 Toxicity Information ............................................................................... 2-15
2.4.1.3 Permissible Exposure Limits ................................................................. 2-15
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Safety Page 2-ii
2.4.1.4 Odor ...................................................................................................... 2-15
2.4.1.5 Physical Data ........................................................................................ 2-15
2.4.1.6 Reactivity Data ...................................................................................... 2-16
2.4.1.7 Corrosivity Data ..................................................................................... 2-19
2.4.1.8 Other Characteristics ............................................................................. 2-19
2.4.1.9 Fire and Explosion Hazard .................................................................... 2-19
2.4.1.10 Life Hazard ............................................................................................ 2-20
2.4.2 Precautions ................................................................................................... 2-20
2.4.3 Fire Fighting .................................................................................................. 2-21
2.5 AMMONIA (NH
3
) .................................................................................................. 2-22
2.5.1 Description and Properties ........................................................................... 2-22
2.5.1.1 General .................................................................................................. 2-22
2.5.1.2 Toxicity Information ............................................................................... 2-22
2.5.1.3 Permissible Exposure Limits ................................................................. 2-22
2.5.1.4 Odor ...................................................................................................... 2-22
2.5.1.5 Physical Data ........................................................................................ 2-23
2.5.1.6 Reactivity Data ...................................................................................... 2-23
2.5.1.7 Corrosivity Data ..................................................................................... 2-25
2.5.1.8 Water Solubility ..................................................................................... 2-25
2.5.1.9 Fire and Explosion Hazard .................................................................... 2-25
2.5.1.10 Life Hazard ............................................................................................ 2-25
2.5.2 First Aid ........................................................................................................ 2-26
2.5.3 Precautions ................................................................................................... 2-26
2.6 METHYLDIETHANOLAMINE (MDEA, CH
3
-N-(CH
2
-CH
2
-OH)
2
) ........................... 2-28
2.6.1 Description and Properties ........................................................................... 2-28
2.6.1.1 General .................................................................................................. 2-28
2.6.1.2 Toxicity Information ............................................................................... 2-28
2.6.1.3 Permissible Exposure Limits ................................................................. 2-28
2.6.1.4 Odor ...................................................................................................... 2-28
2.6.1.5 Physical Data ........................................................................................ 2-28
2.6.1.6 Reactivity Data ...................................................................................... 2-28
2.6.1.7 Corrosivity Data ..................................................................................... 2-29
2.6.1.8 Water Solubility ..................................................................................... 2-29
2.6.1.9 Fire and Explosion Hazard .................................................................... 2-29
2.6.1.10 Life Hazard ............................................................................................ 2-29
2.6.2 First Aid ........................................................................................................ 2-29
2.6.3 Precautions ................................................................................................... 2-30
2.7 SODIUM HYDROXIDE (CAUSTIC SODA, NAOH) ............................................. 2-31
2.7.1 Description and Properties ........................................................................... 2-31
2.7.1.1 General .................................................................................................. 2-31
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Safety Page 2-iii
2.7.1.2 Toxicity Information ............................................................................... 2-31
2.7.1.3 Permissible Exposure Limits ................................................................. 2-31
2.7.1.4 Odor ...................................................................................................... 2-31
2.7.1.5 Physical Data ........................................................................................ 2-32
2.7.1.6 Reactivity Data ...................................................................................... 2-32
2.7.1.7 Corrosivity Data ..................................................................................... 2-34
2.7.1.8 Water Solubility ..................................................................................... 2-34
2.7.1.9 Fire and Explosion Hazard .................................................................... 2-34
2.7.1.10 Life Hazard ............................................................................................ 2-35
2.7.2 First Aid ........................................................................................................ 2-35
2.7.3 Precautions ................................................................................................... 2-36
2.8 SULFUR PLANT SAFETY ................................................................................... 2-37
2.8.1 Hydrogen Sulfide .......................................................................................... 2-37
2.8.2 Sulfur Dioxide ............................................................................................... 2-37
2.8.3 Sulfur Storage Tank ...................................................................................... 2-38
2.8.3.1 Poisonous Gases .................................................................................. 2-38
2.8.3.2 Explosion and Fire ................................................................................. 2-38
2.9 HOT WORK ......................................................................................................... 2-39
2.10 VESSEL ENTRY .................................................................................................. 2-39
2.11 PIPES AND LINES .............................................................................................. 2-41
2.11.1 General ......................................................................................................... 2-41
2.11.2 Before Breaking Lines .................................................................................. 2-42
2.11.3 When Breaking Lines ................................................................................... 2-42
2.12 ELECTRICAL EQUIPMENT ................................................................................ 2-42
2.12.1 Electrical Repairs .......................................................................................... 2-43
2.12.2 Grounding ..................................................................................................... 2-43
2.12.3 Conduit, Cables, and Wires .......................................................................... 2-43
2.12.4 Fuses ............................................................................................................ 2-43
2.12.5 Switching ...................................................................................................... 2-43
2.12.6 Hand Tools and Portable Equipment ............................................................ 2-44
2.12.7 Miscellaneous ............................................................................................... 2-44
2.13 BOILERS AND OTHER DIRECT-FIRED EQUIPMENT ...................................... 2-45
2.13.1 General ......................................................................................................... 2-45
2.13.2 Boilers ........................................................................................................... 2-45
2.13.2.1 Repair and Maintenance ....................................................................... 2-45
2.13.2.2 Operations ............................................................................................. 2-46
2.13.3 Direct-Fired Equipment ................................................................................. 2-46
2.14 LABORATORY SAFETY ..................................................................................... 2-47
2.14.1 Good Housekeeping ..................................................................................... 2-47
2.14.2 Equipment .................................................................................................... 2-47
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Safety Page 2-iv
2.14.3 Chemical Sorting and Identification .............................................................. 2-47
2.14.4 Chemical Handling ....................................................................................... 2-48
2.15 MATERIAL SAFETY DATA SHEETS (MSDS) .................................................... 2-49
A. Hydrogen Sulfide
B. Sulfur Dioxide
C. Sulfur
D. Ammonia
E. Methyldiethanolamine
F. Sodium Hydroxide
G. UOP/ESM S-2001 Sulfur Conversion Catalyst
H. Criterion 234 Tailgas Treating Catalyst
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Safety Page 2-1
2. GENERAL SAFETY
General
The safety information published herein is for guidance only and is not intended to
supersede or replace your company's safety procedures program where a conflict of
terminology or procedure may exist.
Safety Considerations
An employee's knowledge of the hazardous chemicals and compounds with which he
will be working is one of the most basic prerequisites for his own safety, the safety of
others, and the protection of equipment. All employees should review the following
information occasionally to refresh their memories. New employees should study this
information until it is thoroughly understood.
2.1 Definition of Terms
A. Auto-Ignition Temperature
The minimum temperature to which a substance (the substance may be
solid, liquid, or gaseous) must be heated to ignite independent of other
ignition sources.
B. Flammability Limits (explosive limits)
When flammable vapors are mixed in air, there is a minimum
concentration below which the propagation of flame does not occur upon
contact with a source of ignition. There is also a maximum concentration
above which propagation of flame does not occur. These boundary line
concentrations of vapor in air are called flammable or explosive limits.
Many people are familiar with lower and upper flammability limits in
connection with engine carburetors which, when adjusted improperly, will
prevent the engines from running if the fuel mixture is either too "lean" or
too "rich".
C. Flash Point
Flash point is the lowest temperature of a liquid at which sufficient vapors
are evolved to form an ignitable mixture with air.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Safety Page 2-2
D. Specific Gravity (solids and liquids)
Specific gravity of solids and liquids is the ratio of the weight of any solid
or liquid to the weight of an equal volume of water. Therefore, if the
specific gravity of a substance is a number less than one, it is lighter than
water, and if the number is greater than one, it is heavier than water.
E. Specific Gravity (gases)
Specific gravity of gases is the ratio of weight of any gas to the weight of
an equal volume of air. Therefore, if the specific gravity of a gas is a
number less than one, it is lighter than air, and if the number is greater
than one, it is heavier than air.
F. Specific Volume
Specific volume of a substance is the volume of a unit mass of the
substance, i.e., the reciprocal of its density. The units used in this manual
are cubic feet per pound, unless otherwise noted.
G. Toxicity
Toxicity is the ability of a chemical or compound to produce injury once it
reaches a susceptible site in or on the body.

Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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2.2 Hydrogen Sulfide (H
2
S)
2.2.1 Description and Properties
2.2.1.1 General
Hydrogen sulfide is a colorless, very flammable, highly toxic gas.
2.2.1.2 Toxicity Information
LCLo: 600 PPM / 30 minutes (death of humans after
inhalation)
LCLo: 800 PPM / 5 minutes (death of humans after
inhalation)
LCLo (Lethal Concentration Low) is the lowest concentration of a
substance in air which has been reported to have caused death in
humans or animals. In other words, exposure to 600 PPM of H
2
S for
30 minutes or to 800 PPM of H
2
S for 5 minutes can cause death.
2.2.1.3 Permissible Exposure Limits
TLV: 10 PPM in air
TLV (Threshold Limit Value) is the highest level of exposure to a
toxic chemical at which no deleterious effect is noted. The American
Conference of Government Industrial Hygienists (ACGIH) has set
such levels for human exposure in industry. OSHA now uses this
10 PPM limit as the maximum allowable concentration for continuous
exposure during an eight hour working day.
2.2.1.4 Odor
In low concentrations, H
2
S smells like rotten eggs. Higher
concentrations quickly damage the ability to smell and cannot be
detected by the characteristic rotten egg odor.
2.2.1.5 Physical Data
a. Melting Point: -122F (-86C)
b. Boiling Point: -77F (-61C)
c. Lower Explosive Limit: 4.3% H
2
S (by volume) vapor in air
d. Upper Explosive Limit: 46% H
2
S (by volume) vapor in air
e. Auto-Ignition Temperature: 500F (260C)
f. Vapor Specific Gravity: 1.2 (heavier than air)
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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2.2.1.6 Reactivity Data
Hydrogen sulfide is dangerously reactive with the following
substances:
Formula Name
C
2
H
4
O acetaldehyde
BaO + Hg
2
O + air barium oxide + mercury oxide in air
BaO + NiO + air barium oxide + nickel monoxide in air
BaO
2
barium peroxide
BrF
5
bromine pentafluoride
C
6
H
4
BrN
2
Cl p-bromobenzene diazonium chloride
ClO chlorine monoxide
ClF
3
chlorine trifluoride
CrO
3
chromium trioxide (chromic anhydride, chromic
acid)
Cu copper
Fe
2
O
3
nH
2
O di-iron trioxide hydrate
F
2
fluorine
hydrated iron oxide
PbO
2
lead dioxide (lead peroxide)
metal oxides
metals
HNO
3
nitric acid
NCl
3
nitrogen trichloride
NF
3
nitrogen trifluoride
NI
3
nitrogen triiodide
oxidizing materials
OF
2
oxygen difluoride
ClO
3
F perchloryl fluoride
C
6
H
5
N
2
Cl phenyl diazonium chloride
rust
Ag
2
C
2
N
2
O
2
silver fulminate
NaOH + CaO soda lime (a mixture of sodium hydroxide and
calcium oxide)
Na sodium
NaOH + CaO + air sodium hydroxide + calcium oxide (lime) in air
Na
2
O
2
sodium peroxide

Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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SULFUR BLOCK
Issued 30 August 2011 General Safety Page 2-5
2.2.1.7 Corrosivity Data
a. H
2
S readily attacks copper and most copper alloys (brass,
bronze, etc.), so such materials should not be exposed to the
process gases in an SRU, or to the atmosphere around an
SRU.
b. H
2
S can cause sulfide stress cracking (SSC) in a variety of
materials as discussed in NACE Standard Material
Requirements MR-01-75, "Sulfide Stress Cracking Resistant
Metallic Materials for Oilfield Equipment". Most sulfur plant
equipment operates at sufficiently low pressure to be outside
the conditions at which SSC would be expected and so is not
constructed in accordance with NACE MR-01-75. The
upstream equipment (including the Knock-Out drums and/or
pumps in the SRU, in some cases) is generally constructed of
carbon steel and stress relieved, or is constructed of austenitic
stainless steel, in accordance with NACE MR-01-75.
c. At elevated temperature (generally, above 650F/343C), H
2
S
will cause rapid corrosion of carbon steel even under low
pressure conditions like those in a sulfur plant. Such steel
surfaces are usually protected by refractory linings, water
cooling, and/or coating the steel surface with a protective
coating (such as Alonizing).
d. H
2
S is considered to be non-corrosive to aluminum, glass, and
Teflon

.
2.2.1.8 Water Solubility
Hydrogen sulfide is soluble in water. At 60F (15C), approximately
3 parts (by volume) H
2
S will dissolve in one part water.
2.2.1.9 Other Characteristics
Hydrogen sulfide is soluble in liquid sulfur and many hydrocarbons.
Many porous materials, such as muds and residues, tend to absorb
hydrogen sulfide. Increased temperature or mechanical disturbance
tends to release the absorbed gas.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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Issued 30 August 2011 General Safety Page 2-6
2.2.1.10 Fire and Explosion Hazard
H
2
S is a dangerous fire hazard when exposed to an ignition source.
2.2.1.11 Life Hazard
Hydrogen sulfide is extremely toxic even in very low concentrations.
The maximum allowable concentration for continuous exposure
during an eight hour working day (per current OSHA regulations) is
10 parts per million by volume, or 0.001%.
Hydrogen sulfide poisoning is not cumulative like mercury, lead, and
some other materials. Repeated exposure to small doses will not
have the same effect as exposure to one long dose.
Hydrogen sulfide is highly irritating to the eyes and mucous
membranes. When inhaled, hydrogen sulfide is both an irritant and
an asphyxiant. Low concentrations of 20-150 PPM cause irritation of
the eyes; slightly higher concentrations may cause irritation of the
upper respiratory tract, and, if exposure is prolonged, pulmonary
edema may result. (Edema is a condition in which irritated tissues
swell, collect fluid, and slowly excrete a watery fluid, in this case into
the lungs or voice box.) The irritation action has been explained on
the basis that H
2
S combines with the alkali present in moist surface
tissues to form sodium sulfide, a caustic compound. (This compound
is used by the leather industry to help remove hair from animal
hides.)
With higher concentrations, the action of H
2
S on the nervous system
becomes more prominent. A 30 minute exposure to 500 PPM results
in headache, dizziness, excitement, staggering gait, diarrhea, and
dysuria, followed sometimes by bronchitis or bronchopneumonia.
The action on the nervous system is, with small amounts, one of
depression; in larger amounts, it stimulates; and, with very high
amounts, the respiratory center is paralyzed. Exposure to
800-1000 PPM may be fatal in 30 minutes, and higher
concentrations are instantly fatal. Fatal hydrogen sulfide poisoning
may occur even more rapidly than that following exposure to a
similar concentration of hydrogen cyanide. H
2
S does not combine
with the hemoglobin of the blood; its asphyxiant action is due to
paralysis of the respiratory center (which is usually the cause of
death).
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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With repeated exposures to low concentrations, conjunctivitis,
photophobia, corneal bullae, tearing, pain, and blurred vision are the
most common findings. Higher concentrations may cause rhinitis,
bronchitis, and occasionally pulmonary edema. Exposure to very
high concentrations results in immediate death. Chronic poisoning
results in headache, inflammation of the conjunctivae and eyelids,
digestive disturbances, loss of weight, and general debility. H
2
S is a
common air contaminant. It is an insidious poison since sense of
smell may be fatigued and fail to give warning of high concentrations.
The following table from the U.S. Bureau of Mines represents the
degree of inhalation hazard with varying concentrations of hydrogen
sulfide:
HYDROGEN SULFIDE INHALATION HAZARDS
PERIOD OF EXPOSURE EXPOSURE
PPM PERCENT
Maximum allowable concentration for
prolonged exposure
10 0.001
Slight symptoms after exposure of several
hours
70-150 0.007-0.015
Maximum concentration that can be inhaled
for one hour without serious consequences
170-300 0.017-0.03
Dangerous after exposure of thirty minutes
to one hour
400-500 0.04-0.05
Fatal in exposures of thirty minutes or less 600 & above 0.06 & above
Concentrations exceeding 0.1% are considered rapidly fatal.
2.2.2 First Aid
Anyone overcome by H
2
S should be removed immediately to fresh air,
preferably a warm, well ventilated room. If breathing has stopped, begin
artificial respiration immediately. The arm lift-back pressure method of
artificial respiration is recommended. Since H
2
S paralyzes the respiratory
system, time is very important. Administer oxygen (or carbogen,
97% oxygen and 3% carbon dioxide) if available and if someone trained
with oxygen inhalation apparatus is present. Attempts to give oxygen by
someone unfamiliar with the use of the apparatus may result in the loss of
valuable time or may be harmful to the patient.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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For severe irritation of the eyes, hold the lids open and pour clean water
over the eyeball and lids (or use an eye irrigation fountain). Wash
thoroughly in this fashion for 15 minutes. A physician, preferably an eye
specialist, should be summoned immediately.
2.2.3 Precautions (remember these facts)
1. Odor is not a reliable test for the presence of hydrogen sulfide.
2. Since hydrogen sulfide is heavier than air, it settles when released
into the atmosphere and becomes more concentrated near the
ground and in low places.
3. Water at room temperature will dissolve approximately three times its
volume of hydrogen sulfide. Heating or agitation of the water will
cause the hydrogen sulfide to be released.
4. Hydrogen sulfide dissolves in liquid sulfur and is a hazard in storage
tanks and pits.
5. H
2
S is a serious fire and explosion hazard.
6. Low concentrations of hydrogen sulfide hinder the ability of an
individual to think clearly and function properly.
7. H
2
S concentrations higher than 0.06% can be fatal within 30 minutes
and concentrations higher than 0.1% are rapidly fatal.
8. In the Sulfur Block, H
2
S will always be present in the following
locations:
a. In most of the process gas streams.
b. In the rich and lean amine streams in the Amine Treating Unit.
c. In the rich and lean amine streams in the Amine Regeneration
Unit.
d. In the Sour Water Stripper liquid streams.
e. In the Acid Gas Knock-Out Drum and the SWS Knock-Out
Drum liquids, TGCU quench water, TGCU solvent, and the
TGCU Stripper reflux.
f. In the amine acid gas, the TGCU recycle gas, and the SWS gas
(the feed gases for the Sulfur Recovery Unit).
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g. In all of the Sulfur Recovery, Tailgas Cleanup, Tailgas Thermal
Oxidation, and Sulfur Degassing system process gases, with
the exception of the incinerated vent gas.
h. In the vapors from the molten sulfur storage tank.
2.2.4 Good Work Practices
Know the above facts and use caution when working around any
equipment that may contain H
2
S. If H
2
S will be a hazard in any operation:
1. Make adequate plans to cope with any situation that may develop.
2. Adequate respiratory protective equipment is essential; have it
available and use it. Persons who must work in an atmosphere
contaminated with H
2
S should use either a self-contained breathing
unit or a hose mask with a hand-operated blower.
3. Observe the wind direction. Stay upwind if possible and warn others
who may be downwind.
4. Keep ignition sources away from the area.
5. Two men should always be present when opening a flange or
performing any other work where the release of H
2
S is possible.
6. When one man is working in an area of potential H
2
S exposure, the
other man should concentrate on the wind direction and on the action
of the man performing the work. At the first sign of loss of
coordination or illogical action, the worker should be removed
immediately to fresh air. If a man is being overcome by H
2
S, he will
be outwardly sluggish and poorly coordinated (although inwardly he
will be peacefully unconcerned) and he will then begin illogical
actions as his mind begins to imagine things. Any sign of actions
that are out of the ordinary is a last minute warning.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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SULFUR BLOCK
Issued 30 August 2011 General Safety Page 2-10
2.3 Sulfur Dioxide (SO
2
)
2.3.1 Description and Properties
2.3.1.1 General
Sulfur dioxide is a colorless, nonflammable, highly toxic gas.
2.3.1.2 Toxicity Information
LCLo: 400 PPM / 1 minute (death of humans after
inhalation)
LCLo (Lethal Concentration Low) is the lowest concentration of a
substance in air which has been reported to have caused death in
humans or animals. In other words, exposure to 400 PPM of SO
2
for
1 minute can cause death.
TCLo: 3 PPM / 5 days (pulmonary system effects on
humans after inhalation)
TCLo: 4 PPM / 1 minute (pulmonary system effects on
man after inhalation)
TCLo (Toxic Concentration Low) is the lowest concentration of a
substance in air to which humans or animals have been exposed for
any given period of time that has produced any toxic effect in
humans or produced a carcinogenic, neoplastigenic, or teratogenic
effect in animals or humans. In other words, exposure to 3 PPM SO
2

for 5 days or to 4 PPM SO
2
for 1 minute have both been reported to
have toxic effects on the human pulmonary system.
2.3.1.3 Permissible Exposure Limits
TLV: 2 PPM in air
TLV (Threshold Limit Value) is the highest level of exposure to a
toxic chemical at which no deleterious effect is noted. The American
Conference of Government Industrial Hygienists (ACGIH) has set
such levels for human exposure in industry. OSHA regulations set a
limit of 5 PPM TWA (Time Weighted Average) concentration for
continuous exposure during an eight hour working day.
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2.3.1.4 Odor
Sulfur dioxide has a pungent, suffocating odor that can be detected
at very low concentrations, 0.3 to 1.0 PPM, possibly by taste rather
than odor.
2.3.1.5 Physical Data
a. Melting Point: -104F (-76C)
b. Boiling Point: 14F (-10C)
c. Lower Explosive Limit: N/A (SO
2
will not burn)
d. Upper Explosive Limit: N/A
e. Auto-Ignition Temperature: N/A
f. Vapor Specific Gravity: 2.2 (heavier than air)
2.3.1.6 Reactivity Data
Sulfur dioxide is dangerously reactive with the following substances:
Formula Name
C
3
H
4
O acrolein
Al aluminum
CsHC
2
cesium hydrogencarbide
Cs
2
O cesium oxide
x-ClO
3
chlorates
ClF
3
chlorine trifluoride
Cr chromium
FeO ferrous oxide
F
2
fluorine
lithium acetylene carbide diammino
Mn manganese
KHC
2
potassium carbide
KClO
3
potassium chlorate
Rb
2
C
2
rubidium carbide
Na sodium
Na
2
C
2
sodium carbide
SnO tin monoxide

Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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Sulfur dioxide is incompatible with the following substances:
Formula Name
halogens or interhalogens
LiNO
3
lithium nitrate
x-C
2
H metal acetylides
metal oxides
metals
polymeric tubing
NaH sodium hydride

2.3.1.7 Corrosivity Data
a. Dry SO
2
causes only mild corrosion of carbon steel and
stainless steel.
b. Wet SO
2
(sulfurous acid) is very corrosive to carbon steel and
most stainless steels. Certain alloy materials (Carpenter
20Cb-3

, for instance) are relatively impervious to attack by wet


SO
2
.
c. SO
2
is considered to be non-corrosive to graphite, glass, and
Teflon

.
2.3.1.8 Water Solubility
Sulfur dioxide will dissolve readily in water to form a weak solution of
sulfurous acid (H
2
SO
3
). At 60F (15C), about 50 parts (by volume)
SO
2
will dissolve in one part water.
2.3.1.9 Fire and Explosion Hazard
None
2.3.1.10 Life Hazard
Like hydrogen sulfide, sulfur dioxide is extremely toxic in very low
concentrations. The serious life threat is through paralysis of the
respiratory system. The maximum allowable concentration for
continuous exposure during an eight hour working day (per current
OSHA regulations) is 5 parts per million by volume, or 0.0005%.
Sulfur dioxide is highly irritating to skin, eyes, and mucous
membranes. When inhaled, sulfur dioxide is very irritating and can
cause pulmonary distress. This gas is dangerous to the eyes, as it
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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causes irritation at 20 PPM and inflammation of the conjunctiva. It
has a suffocating odor and is a corrosive and poisonous material. In
moist air or fogs, it combines with water to form sulfurous acid, but is
only slowly oxidized to sulfuric acid. Concentrations of 6-12 PPM
cause immediate irritation of the nose and throat, while 0.3-1 PPM
can be detected by the average individual, possibly by taste rather
than by sense of smell. 3 PPM has an easily noticeable odor and
20 PPM is the least amount which is irritating to the eyes.
10,000 PPM is an irritant to moist areas of the skin within a few
minutes of exposure.
SO
2
chiefly affects the upper respiratory tract and the bronchi. It may
cause edema of the lungs or glottis, and can produce respiratory
paralysis. (Edema is a condition in which irritated tissues swell,
collect fluid, and slowly excrete a watery fluid, in this case into the
lungs or voice box.)
This material is so irritating that it provides its own warning of toxic
concentrations. 400-500 PPM is immediately dangerous to life, and
50-100 PPM is considered to be the maximum permissible
concentration for exposures of 30-60 minutes. Excessive exposures
to high enough concentrations of this material can be fatal. Its
toxicity is comparable to that of hydrogen chloride. However, less
than fatal concentrations can be borne for fair periods of time with no
apparent permanent damage. It is used as a fumigant, insecticide
and fungicide, and a chemical preservative food additive. It is a
common air contaminant.
2.3.2 First Aid
In cases of inhalation, remove the victim to fresh air and begin artificial
respiration immediately if breathing has ceased. The arm lift-back
pressure method of artificial respiration is recommended. If an oxygen
apparatus is available, oxygen (100%) should be administered only by
someone trained in the use of the apparatus. Preferably, oxygen should
be administered against a positive exhalation pressure of 1.25 inches of
water.
Oxygen inhalation must be continued as long as necessary to maintain
the normal color of the skin and mucous membranes. In cases of severe
exposure, the patient should breathe 100% oxygen under positive
exhalation pressure for 30 minute periods every hour for at least 3 hours.
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If there are no signs of lung congestion at the end of this period, and if the
breathing is easy and the color is good, oxygen inhalation may be
discontinued. Throughout this time, the patient should be kept
comfortably warm, but not hot.
For irritation of the eyes, flush them with large amounts of warm water for
at least 15 minutes. It is advisable to irrigate the eyes gently with water at
room temperature in order to minimize additional pain and discomfort.
Take the patient to a physician, preferably an eye specialist, at once.
2.3.3 Precautions
Special precautions should be observed when fighting sulfur fires. Sulfur
fires should be approached from an upwind direction if possible, and
respiratory equipment should be used in the case of larger fires or when
fires are in enclosed areas. SO
2
is always present in the following
locations:
1. In all of the Sulfur Recovery Unit process gases downstream of the
Reactor Furnace, up through and including the TGCU Reactor in the
TGCU Unit.
2. In the stack or flare gases in any process where sulfur or hydrogen
sulfide is being burned, including the Thermal Oxidizer.
3. In the vapors from the molten sulfur storage tank.
4. In the fumes from sulfur fires.
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SULFUR BLOCK
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2.4 Sulfur
2.4.1 Description and Properties
2.4.1.1 General
Sulfur is a yellow solid at normal ambient temperatures. However, it
is normally handled in bulk quantities in plant operations as a liquid.
2.4.1.2 Toxicity Information
Sulfur is nontoxic. Sulfur dust in air can produce irritation of the
human eye at concentrations of 6 PPM or above, resulting in its
classification as a nuisance dust. Repeated inhalation can cause
irritation to the mucous membranes.
2.4.1.3 Permissible Exposure Limits
There are no standards or regulations concerning sulfur.
2.4.1.4 Odor
Pure sulfur is odorless.
2.4.1.5 Physical Data
a. Melting Point: 246F (119C)
b. Boiling Point: 832F (444C)
c. Auto-Ignition Temperature: 450F (232C) for liquid sulfur
374F (190C) for sulfur dust
suspended in air
d. Flash Point: 405F (207C)
e. Liquid Specific Gravity: 1.8 (almost twice as heavy as
water)
f. Color Pure sulfur is bright yellow when
solid. Sulfur produced by Claus
sulfur plants may be contaminated
with hydrocarbons, causing the
color to be orange, green, tan,
brown, gray, or black. The color of
liquid sulfur ranges from bright
yellow to dark orange (almost red),
depending on its temperature.
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2.4.1.6 Reactivity Data
Sulfur can react violently with the following substances:
Formula Name
alkali metal nitrides
Al aluminum
Al + Cu aluminum + copper
Al + Nb
2
O
5
aluminum + niobium pentoxide
NH
3
ammonia
NH
4
NO
3
ammonium nitrate
NH
4
ClO
4
ammonium perchlorate
Ba(BrO
3
)
2
H
2
O barium bromate
BaC
2
barium carbide
Ba(ClO
3
)
2
H
2
O barium chlorate
Ba(IO
3
)
2
barium iodate
B boron
BrF
5
bromine pentafluoride
BrF
3
bromine trifluoride
Cd cadmium
Ca calcium
Ca(BrO
3
)
2
H
2
O calcium bromate
CaC
2
calcium carbide
Ca(ClO
3
)
2
calcium chlorate
Ca(ClO)
2
calcium hypochlorite
Ca(IO
3
)
2
calcium iodate
Ca
3
P
2
calcium phosphide
Ca + VO + H
2
O calcium + vanadium oxide + water carbides
Cs
3
N cesium nitride
C + impurities charcoal
ClO
2
chlorine dioxide
ClO chlorine monoxide
ClF
3
chlorine trifluoride
ClO
3
chlorine trioxide
Cr(ClO)
2
chromium oxychloride (chromyl chloride)
CrO
3
chromium trioxide (chromic acid) anhydride,
chromic
Cu + x-ClO
3
copper + chlorates
As
2
S
3
diarsenic trisulfide
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Formula Name
Cl
2
O dichlorine monoxide
(C
2
H
5
)
2
O diethyl ether
fiberglass + iron filings
F
2
fluorine
halogenates
halogenites
halogens
Ag
7
NO
11
heptasilver nitrate octaoxide
C
x
H
y
hydrocarbons
In indium
interhalogens
IF
5
iodine pentafluoride
IO
5
iodine pentoxide
C lampblack (carbon black)
Pb(ClO
3
)
2
lead chlorate
PbCl
2
lead chloride
Pb(ClO
2
)
2
lead chlorite
PbCrO
4
lead chromate
PbO
2
lead dioxide (lead peroxide)
Li lithium
Li + NH
3
lithium dissolved in ammonia
Li
2
C
2
lithium carbide
Mg magnesium
Mg(BrO
3
)
2
6H
2
O magnesium bromate
Mg(ClO
3
)
2
magnesium chlorate
Mg(IO
3
)
2
4H
2
O magnesium iodate
Hg(NO
3
)
2
H
2
O mercuric nitrate
HgO mercury(II) oxide (mercuric oxide)
Hg
2
O mercury(I) oxide (mercurous oxide)
x-C
2
H metal acetylides of carbides
x-(ClO
3
)
n
metal chlorates
x-(zO
3
)
n
metal halogenates
x-O
n
metal oxides
metals
RbC
2
H monorubidium acetylide (rubidium acetylene
carbide)
Ni nickel
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Formula Name
NO
2
nitrogen dioxide
Os osmium
oxidants
Pd palladium
x-(ClO
4
)
n
inorganic perchlorates
x-(MnO
4
)
n
permanganates
P phosphorus (phosphorus, red)
P
4
phosphorus, white (phosphorus, yellow)
P
2
O
3
phosphorus trioxide
K potassium
KBrO
3
potassium bromate (bromic acid)
KClO
3
potassium chlorate
KClO potassium chlorite (potassium hypochlorite)
KIO
3
potassium iodate
KNO
3
+ As
2
S
3
potassium nitrate (saltpeter) + arsenic sulfide
K
3
N potassium nitride
KClO
4
potassium perchlorate
KMnO
4
potassium permanganate
K + SnI
4
potassium + tin(IV) iodide (stannic iodide)
Rh rhodium
Rb rubidium
Se selenium
SeC
2
selenium carbide
AgBrO
3
silver bromate
AgClO
3
silver chlorate
AgClO
2
silver chlorite
AgNO
3
silver nitrate
Ag
2
O silver oxide
Na sodium
NaBrO
3
sodium bromate
NaClO
3
sodium chlorate
NaClO
2
sodium chlorite
NaH sodium hydride
NaIO
3
sodium iodate
NaNO
3
+ charcoal sodium nitrate + charcoal
Na
2
O
2
sodium peroxide
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Formula Name
Na + SnI
4
sodium + tin(IV) iodide (stannic iodide)
SrC
2
strontium carbide
SrC
2
+ Se strontium carbide + selenium
SCl
2
sulfur dichloride
(C
6
H
5
)
4
Pb tetraphenyl lead
Tl
2
O
3
thallic oxide (thallium peroxide)
Th thorium
ThC
2
thorium carbide
Sn tin
U uranium
UC
2
uranium carbide (uranium dicarbide)
Zn zinc
Zn(BrO
3
)
2
6H
2
O zinc bromate
Zn(ClO
3
)
2
zinc chlorate
Zn(IO
3
)
2
zinc iodate
2.4.1.7 Corrosivity Data
Dry sulfur is not corrosive but in the presence of moisture it will
attack steel rapidly.
2.4.1.8 Other Characteristics
a. Both hydrogen sulfide and sulfur dioxide will dissolve in liquid
sulfur.
b. At temperatures up to about 317F (158C), the viscosity of
pure liquid sulfur decreases as the temperature increases. As
the temperature increases from 317F to 370F (158C to
188C), the viscosity of pure liquid sulfur rises rapidly to a
tremendously high maximum, causing the liquid to become a
dark, sticky, plastic material impossible to pump. However,
sulfur produced by Claus sulfur plants contains dissolved H
2
S
that lowers the viscosity of the molten sulfur so that fluidity is
not normally a concern, regardless of the temperature.
2.4.1.9 Fire and Explosion Hazard
a. Solid Sulfur
The primary hazard in handling solid sulfur results from the fact
that sulfur dust suspended in the air ignites easily. Even though
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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the explosion hazard is considered moderate, an explosion
occurring in a confined area could cause considerable damage.
Sulfur, being a very poor conductor of electricity, tends to
develop static electric charges when it is in motion. Ignition of
sulfur dust by static-caused sparks is not uncommon. Frictional
heat in equipment has also been responsible for starting sulfur
fires.
b. Liquid Sulfur
The fire hazards of liquid sulfur result primarily from the low
ignition point of sulfur and from the presence of hydrogen
sulfide.
2.4.1.10 Life Hazard
a. Solid Sulfur
Solid elemental sulfur is considered to be more of a nuisance
dust with a very low toxicity. Occasionally, sulfur dust will
irritate the inner surfaces of the eyelids.
b. Molten Sulfur
Molten sulfur is capable of inflicting severe burns.
2.4.2 Precautions
1. Employees operating equipment containing molten sulfur should
wear clothing capable of protecting the chest and arms, trousers
without cuffs, high top shoes, safety glasses with side shields, and
heat resistant gloves. When making connections or other changes in
molten sulfur piping, full-face shields (in addition to safety glasses)
and leather protective clothing may be needed.
2. Every reasonable step should be taken to minimize formation of dust
during the handling of solid sulfur.
3. Eliminate ignition sources where sulfur dust may be produced.
Enclosed areas are considered Class II hazardous locations
according to the United States National Electrical Code. Where
static electricity is a hazard, equipment should be grounded.
4. Eliminate ignition sources near liquid sulfur where H
2
S may be
liberated.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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Issued 30 August 2011 General Safety Page 2-21
5. Sulfur spills and drips should be cleaned up to avoid accumulations
of sulfur. Sulfur dust should never be allowed to accumulate in
buildings.
2.4.3 Fire Fighting
1. Small sulfur fires may be extinguished by smothering them with dirt
or sand or by using a fire extinguisher. Water is the most satisfactory
extinguishing agent but should be used as a fine spray or fog.
Steam smothering can be used in storage pits and in other relatively
small enclosures. Carbon dioxide is also a satisfactory fire
extinguishing agent.
2. Sulfur fires should be approached very carefully, from the upwind
side if possible, because burning sulfur emits highly toxic fumes of
sulfur dioxide.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
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Issued 30 August 2011 General Safety Page 2-22
2.5 Ammonia (NH
3
)
2.5.1 Description and Properties
2.5.1.1 General
Ammonia is a colorless, flammable, toxic gas.
2.5.1.2 Toxicity Information
LCLo: 5,000 PPM / 1 minute (death of mammals after
inhalation)
LCLo (Lethal Concentration Low) is the lowest concentration of a
substance in air which has been reported to have caused death in
humans or animals. In other words, exposure to 5,000 PPM of NH
3

for 1 minute can cause death.
TCLo: 20 PPM (toxic and irritant effects on
humans after inhalation)
TCLo (Toxic Concentration Low) is the lowest concentration of a
substance in air to which humans or animals have been exposed for
any given period of time that has produced any toxic effect in
humans or produced a carcinogenic, neoplastigenic, or teratogenic
effect in animals or humans. In other words, exposure to 20 PPM
NH
3
has been reported to have toxic and irritant effects on humans.
2.5.1.3 Permissible Exposure Limits
TLV: 25 PPM in air
TLV (Threshold Limit Value) is the highest level of exposure to a
toxic chemical at which no deleterious effect is noted. The American
Conference of Government Industrial Hygienists (ACGIH) has set
such levels for human exposure in industry. OSHA regulations set a
limit of 50 PPM TWA (Time Weighted Average) concentration for
continuous exposure during an eight hour working day.
2.5.1.4 Odor
Ammonia has a pungent odor that can be detected at low
concentrations, 20 to 50 PPM.
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2.5.1.5 Physical Data
a. Melting Point: -108F (-78C)
b. Boiling Point: -28F (-33C)
c. Lower Explosive Limit: 15% NH
3
(by volume) in air
d. Upper Explosive Limit: 28% NH
3
(by volume) in air
e. Auto-Ignition Temperature: 1204F (651C)
f. Vapor Specific Gravity: 0.6 (lighter than air)
2.5.1.6 Reactivity Data
Ammonia is incompatible with the following substances:
Formula Name
C
2
H
4
O acetaldehyde
C
3
H
4
O acrolein
H
8
N
2
O
8
S
2
ammonium peroxo disulfate
Sb antimony
SbH
3
antimony hydride
B boron
boron halides
BI
3
boron triiodide
BrF
5
bromine pentafluoride
HClO
3
chloric acid
ClN
3
chlorine azide
ClO chlorine monoxide
ClF
3
chlorine trifluoride
x-ClO
2
chlorites
SiH
x
Cl
4-x
chlorosilane
CrO
3
chromium trioxide (chromic anhydride, chromic
acid)
CrCl
2
chromyl chloride
Cl
2
O dichlorine oxide
C
2
H
4
Cl
2
+ NH
3
(liq) ethylene dichloride + liquid ammonia
C
2
H
4
O ethylene oxide
Au gold
AuCl
3
gold (III) chloride
halogens
C
3
N
6
Cl
6
hexachloromelamine
H
4
N
2
+ Li, Na, etc. hydrazine + alkali metals
HBr hydrogen bromide (hydrobromic acid)
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Formula Name
HOCl hypochlorous acid
H
2
O
2
hydrogen peroxide
Mg(ClO
4
)
2
magnesium perchlorate
Hg mercury
HNO
3
nitric acid
NO
2
nitrogen dioxide (nitrogen peroxide)
N
2
O
4
nitrogen tetraoxide
NCl
3
nitrogen trichloride
NF
3
nitrogen trifluoride
NO
2
Cl nitryl chloride
OF
2
oxygen difluoride
O
2
+ Pt oxygen + platinum
P
2
O
5
phosphorus pentoxide
P
2
O
3
phosphorus trioxide
C
6
H
3
N
3
O
7
picric acid
K + AsH
3
potassium + arsine
KClO
3
potassium chlorate
K
3
Fe(CN)
6
potassium ferricyanide
K
2
Hg(CN)
4
potassium mercuric cyanide
K + PH
3
potassium + phosphine
K + NaNO
2
potassium + sodium nitrite
Ag silver
AgCl silver chloride
AgNO
3
silver nitrate
Ag
2
O silver oxide
Na + CO sodium + carbon monoxide
S sulfur
SCl
2
sulfur dichloride
TeCl
4
tellurium chloride
tellurium hydropentachloride
(CH
3
)
4
N
2
COH
2
tetramethyl ammonium amide
SOCl
2
thionyl chloride
N
3
S
4
Cl thiotrithiazyl chloride
C
3
H
3
N
6
Cl
3
trichloromelamine
O
3
F
2
trioxygen difluoride
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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2.5.1.7 Corrosivity Data
a. Iron and carbon steel are recommended for ammonia service.
b. Moist ammonia will rapidly attack copper, tin, zinc, and their
alloys.
c. Mixtures of ammonia and hydrogen sulfide are often very
corrosive to carbon and stainless steels when wet. The
corrosivity appears to increase when hydrogen cyanide (HCN)
is present. (Hydrogen cyanide is a common contaminant in the
sour water processed in many refineries.)
d. Ammonia is considered to be non-corrosive to glass and
Teflon

.
2.5.1.8 Water Solubility
Ammonia will dissolve very readily in water. At 60F (15C), about
800 parts (by volume) NH
3
will dissolve in one part water.
2.5.1.9 Fire and Explosion Hazard
Ammonia is a low fire hazard when exposed to heat or flame
because it is difficult to ignite. It is a moderate explosion hazard
when exposed to flame or fire. Air-ammonia mixtures can detonate
in a fire.
2.5.1.10 Life Hazard
Ammonia is toxic in moderate concentrations. However, its pungent
odor will provide ample warning of its presence, so it is unlikely that
an individual would unknowingly become overexposed. The
maximum allowable concentration for continuous exposure during an
eight hour working day (per current OSHA regulations) is 50 parts
per million by volume, or 0.005%.
Ammonia is highly irritating to the eyes and mucous membranes.
When inhaled, ammonia is both an irritant and an asphyxiant, and
can cause respiratory distress. This gas is dangerous to the eyes,
as it causes irritation at 40-100 PPM. Prolonged exposure to
700 PPM or more can cause extensive injuries to the eyes - irritation,
hemorrhages, swollen lids, corneal ulcers, even partial or total loss of
sight. Ammonia will also irritate the skin, particularly if the skin is
moist, to the point of causing chemical burns from prolonged
exposure.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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The life hazard from ammonia is due to its damage to the lungs when
inhaled. This material is so irritating that it provides its own warning
well below toxic concentrations. Ammonia can usually be detected
at levels of 20-50 PPM. There will be noticeable irritation of the eyes
and nasal passages when exposed to 100 PPM, severe irritation of
the throat, nasal passages, and upper respiratory tract at 400 PPM,
and severe eye irritation at 700 PPM. At 1700 PPM, there will be
severe coughing and bronchial spasms, and an exposure of
30 minutes or less may be fatal. Concentrations of 5000 PPM and
above are fatal almost immediately, causing serious edema of the
lungs, strangulation, and asphyxiation. (Edema is a condition in
which irritated tissues swell, collect fluid, and slowly excrete a watery
fluid, in this case into the lungs.)
2.5.2 First Aid
Anyone overcome by ammonia should be removed immediately to fresh
air, preferably a warm, well-ventilated room. If breathing has stopped,
begin artificial respiration immediately (by trained personnel only). The
arm lift-back pressure method of artificial respiration is recommended. Be
aware that excessive force during artificial respiration will further injure the
lungs. Administer oxygen if available and if someone trained with oxygen
inhalation apparatus is present.
For severe irritation of the eyes, hold the lids open and pour clean water
over the eyeball and lids (or use an eye irrigation fountain). Wash
thoroughly in this fashion for 15 minutes. A physician, preferably an eye
specialist, should be summoned immediately.
2.5.3 Precautions
In this part of the complex, ammonia will usually be found mixed with
hydrogen sulfide. Ammonia will always be present in the following
locations:
1. In the process gas and liquid streams in the Sour Water Stripping
Unit.
2. In the Sour Water Stripper off-gas feeding the sulfur plant.
3. In the SWS Gas Knock-Out Drum liquids, the TGCU quench water,
and the TGCU Stripper reflux.
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4. In the overhead gas from the TGCU Stripper, and possibly in the
TGCU recycle gas.
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2.6 Methyldiethanolamine (MDEA, CH
3
-N-(CH
2
-CH
2
-OH)
2
)
2.6.1 Description and Properties
2.6.1.1 General
MDEA is a colorless, viscous liquid.
2.6.1.2 Toxicity Information
Ingestion of MDEA is moderately toxic, and may cause nausea,
vomiting, and abdominal discomfort. Single dose oral toxicity is low.
MDEA can cause moderate irritation of the eyes, with possible
corneal damage. Prolonged or repeated exposure can cause skin
irritation or burns. Inhalation of vapors is unlikely at room
temperature due to its low vapor pressure. MDEA at elevated
temperature may produce sufficient vapor to cause moderately
severe eye and upper respiratory irritation.
2.6.1.3 Permissible Exposure Limits
There are no standards or regulations concerning MDEA.
2.6.1.4 Odor
MDEA has a slight odor of amine.
2.6.1.5 Physical Data
a. Melting Point: -6F (-21C)
b. Boiling Point: 477F (247C)
c. Vapor Pressure: <0.01 mm Hg @ 68F (20C)
d. Flash Point: 260F (127C)
e. Lower Explosive Limit: not determined
f. Upper Explosive Limit: not determined
g. Specific Gravity: 1.042 (about the same as water)
h. Color: Clear to light straw color
2.6.1.6 Reactivity Data
MDEA is incompatible with strong oxidizers and strong acids. MDEA
should not be allowed to contact sodium nitrite (NaNO
2
) or other
nitrosating agents, as nitrosamines (suspected cancer-causing
agents) could be formed.
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2.6.1.7 Corrosivity Data
a. MDEA and MDEA-water solutions are generally non-corrosive
to carbon and stainless steels.
b. Acid gas (H
2
S and/or CO
2
) dissolved in MDEA-water solutions
can cause appreciable corrosion of carbon steel, particularly in
areas subjected to erosion.
c. Copper, copper alloys, and galvanized steel should not be
exposed to MDEA. Aluminum should not be exposed to MDEA
at elevated temperatures.
d. Oxygen will degrade MDEA by forming corrosive organic acids.
e. MDEA is considered to be non-corrosive to glass, asbestos,
Teflon

, and EPDM.
2.6.1.8 Water Solubility
MDEA is completely soluble in water.
2.6.1.9 Fire and Explosion Hazard
MDEA is considered a slight fire hazard when exposed to heat or
flame.
2.6.1.10 Life Hazard
The toxicity of MDEA is low. Ingestion of MDEA can cause nausea
and vomiting. MDEA will irritate the skin and eyes, and can cause
damage to the eyes. If heated, sufficient MDEA vapor may be
evolved to irritate the nose and/or eyes.
2.6.2 First Aid
If large amounts of MDEA are ingested, induce vomiting, then take the
patient to a physician.
If MDEA vapors are inhaled, remove the patient to fresh air. A physician
should be consulted.
In case of eye contact, flush the eyes with large amounts of water for at
least 15 minutes. Take the patient to a physician, preferably an eye
specialist, at once.
In case of skin contact, flush the affected area with plenty of water. If
exposure has produced a burn, it should be treated like a thermal burn,
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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with treatment based on the physician's judgment. Contaminated clothing
should be removed and washed before reuse.
2.6.3 Precautions
1. When handling MDEA, employees should wear protective clothing
resistant to MDEA. The choice of gloves, boots, apron, or full-body
suit will depend on the tasks to be performed. Chemical-resistant
goggles should always be worn.
2. Good general ventilation should be sufficient for most operations. If
vapor concentrations are high, use local exhaust ventilators.
3. If irritation of the nose and/or respiratory system is experienced, use
an approved air-purifying respirator.
4. Minimize the exposure of MDEA to oxygen to avoid forming organic
acids.
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2.7 Sodium Hydroxide (Caustic Soda, NaOH)
2.7.1 Description and Properties
2.7.1.1 General
Pure sodium hydroxide is a white solid. When dissolved in water,
NaOH forms a clear, colorless or water-white, strongly alkaline liquid.
2.7.1.2 Toxicity Information
Sodium hydroxide has acute oral toxicity if ingested. It will cause
severe burns, including perforation and scarring, on the mouth,
throat, esophagus, and stomach, and death may result. Cases of
squamous cell carcinoma of the esophagus have occurred years
after ingestion.
Sodium hydroxide, both solid and in solution, has a markedly
corrosive action on all body tissues. Inhalation of dust or mist can
cause injury to the entire respiratory tract. The effects of inhalation
depend on the severity of the exposure, ranging from mild irritation of
the mucous membranes to severe pneumonitis. Contact with the
eyes may cause irritation and, with greater exposure, severe burns
and possible blindness. Skin contact may cause burns, frequently
with deep ulceration and scarring. Prolonged contact, even with
dilute solutions, can cause tissue damage.
2.7.1.3 Permissible Exposure Limits
TLV: 2 mg/m
3
in air (approximately 2 PPM by weight)
TLV (Threshold Limit Value) is the highest level of exposure to a
toxic chemical at which no deleterious effect is noted. The American
Conference of Government Industrial Hygienists (ACGIH) has set
such levels for human exposure in industry. OSHA regulations set a
limit of 2 mg/m
3
TWA (Time Weighted Average) concentration for
continuous exposure during an eight hour working day.
2.7.1.4 Odor
Sodium hydroxide has no odor, in pure form or when dissolved in
water.
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2.7.1.5 Physical Data
Solid Form
a. Melting Point: 608F (320C)
b. Boiling Point: 2534F (1390C)
c. Auto-Ignition Temperature: Not combustible
d. Flash Point: N/A
e. Specific Gravity: 2.1 (more than twice as heavy as
water)
f. Color: White
Water Solutions
25 wt% 50 wt%
a. Melting Point: -2F (-19C) 50F (10C)
b. Boiling Point: 232F (111C) 288F (142C)
c. Auto-Ignition Temp.: Not combustible Not combustible
d. Flash Point: N/A N/A
e. Specific Gravity: 1.27 1.53
f. Color: Colorless or
water-white
Colorless or
water-white

2.7.1.6 Reactivity Data
Adding water to sodium hydroxide or sodium hydroxide solutions
may cause localized overheating and spattering.
Under the proper conditions, sodium hydroxide can react violently
with the following substances:
Formula Name
C
2
H
2
O acetaldehyde
C
2
H
2
O
2
acetic acid
C
2
H
6
O
3
acetic anhydride
C
3
H
4
O acrolein
C
3
H
3
N acrylonitrile
C
3
H
6
O allyl alcohol
C
3
H
5
Cl allyl chloride
Al aluminum
ClF
3
chlorine trifluoride
CHCl
3
+ CH
3
OH chloroform + methanol
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Formula Name
C
3
H
7
ClO
2
chlorohydrin (chlorhydrin)
C
7
H
7
ClO 4-chloro-2-methylphenol
C
7
H
6
ClNO
2
chloronitrotoluene
ClHSO
3
chlorosulfonic acid (chlorosulfuric acid)
C
9
H
8
O cinnamaldehyde
Cu copper
CN
4
cyanogen azide
B
2
H
6
diborane (boron hydride)
C
2
H
2
Cl
2
1,2-dichloroethylene
C
2
H
4
F
2
difluoroethane
C
3
H
5
NO ethylene cyanohydrin (hydracrylonitrile)
C
2
H
2
O
2
glyoxal
HCl hydrochloric acid (hydrogen chloride)
HF hydrofluoric acid (hydrogen fluoride)
C
6
H
6
O
2
hydroquinone
Mg magnesium
C
4
H
2
O
3
maleic anhydride
CH
3
OH + C
6
H
2
Cl
4
methanol + tetrachlorobenzene
C
7
H
7
NO
3
4-methyl-2-nitrophenol
3-methyl-2-penten-4-yn-1-ol
HNO
3
nitric acid
C
2
H
5
NO
2
nitroethane (forms shock-sensitive salts)
CH
3
NO
2
nitromethane (forms shock-sensitive salts)
CxH
2x+1
NO
2
nitroparaffins (forms shock-sensitive salts)
C
3
H
7
NO
2
nitropropane (forms shock-sensitive salts)
H
2
SO
4
SO
3
oleum (fuming sulfuric acid)
C
5
H
12
O pentol
P phosphorus
P
2
O
5
phosphorus pentoxide
C
3
H
4
O
2
-propiolactone (2-oxetanone)
strong mineral or organic acids
H
2
SO
4
sulfuric acid
C
6
H
2
Cl
4
1,2,4,5-tetrachlorobenzene
C
4
H
8
O tetrahydrofuran
Sn tin
C
2
H
3
Cl
3
O 1,1,1-trichloroethanol
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Formula Name
C
2
HCl
3
trichloroethylene
CCl
3
NO
2
trichloronitromethane
H
2
O water
Zn zinc
Zr zirconium
2.7.1.7 Corrosivity Data
a. At ambient temperature, sodium hydroxide solutions will cause
only slight corrosion of carbon steel.
b. Carbon steel can experience caustic embrittlement and
intergranular corrosion when exposed to sodium hydroxide
solutions at elevated temperature. Stress relieving the carbon
steel after fabrication may reduce the susceptibility to this.
c. If sodium hydroxide solutions must be handled at elevated
temperatures, special resistant alloys should be used. Nickel
and copper are common components in such alloys.
d. Aluminum, tin, zinc, and their alloys are rapidly attacked by
sodium hydroxide solutions, and should not be allowed to come
in contact with NaOH.
e. Sodium hydroxide is considered to be non-corrosive to glass,
natural rubber, EPDM, and Teflon

.
2.7.1.8 Water Solubility
Sodium hydroxide will dissolve readily in water, with the amount
depending on the solution temperature. If a solution of sodium
hydroxide is cooled below its saturation temperature, it will
precipitate solid hydrates. At 60F (15C), sodium hydroxide will
dissolve in water to produce solutions exceeding 50 wt% NaOH.
2.7.1.9 Fire and Explosion Hazard
Sodium hydroxide and its water solutions are not flammable.
However, adding water to NaOH or solutions of NaOH can cause
localized overheating due to its heat of dilution.
Sodium hydroxide will generate gaseous hydrogen (which is
flammable and/or explosive) when in contact with aluminum, copper,
tin, zinc, and their alloys.
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2.7.1.10 Life Hazard
Sodium hydroxide will cause damage to any tissue it contacts. It is
acutely toxic if swallowed, causing severe burns and scarring to the
mouth, throat, esophagus, and stomach, and may lead to death.
Squamous cell carcinoma of the esophagus can occur years after
the exposure.
Contact with the skin, eyes, nose, or respiratory passages can result
in severe burns and scarring. In the case of eye contact, blindness
can occur rapidly.
2.7.2 First Aid
If swallowed, do not induce vomiting - this will cause further damage to the
throat and esophagus. Dilute by giving water to the patient immediately.
Vinegar, 1% acetic acid solution, citrus fruit juices, or 5% citric acid
solution may also be administered to help neutralize the alkaline solution.
Follow this with milk, egg white in water, or milk of magnesia. Keep the
patient warm and still, and summon a physician immediately.
If dust or mist is inhaled, remove the patient to fresh air at once. If
breathing has stopped, begin artificial respiration immediately. The air
lift-back pressure method of artificial respiration is recommended. Keep
the patient warm and still, and summon a physician immediately.
In case of eye contact, immediately begin flushing the eyes with large
amounts of water, preferably with an eye wash fountain. Continue
flushing for at least 15 minutes, forcibly holding the eyelids apart and
rotating the eyeball, to ensure complete irrigation of all eye and lid tissue.
A physician, preferably an eye specialist, should be summoned
immediately.
In case of skin contact, immediately flush the affected areas with large
amounts of water. If large areas of the body are contaminated, or if
clothing has been penetrated to the skin, immediately use a safety
shower, preferably removing clothing while under the shower. Continue
flushing the areas for at least 15 minutes. If available, follow the water
flush with a generous application of vinegar or 1% acetic acid solution to
neutralize the residual NaOH. After the acid treatment, apply a good
protective dressing as with any other burn and take the patient to a
physician. Contaminated clothing should be washed before reuse.
Contaminated leather articles (shoes, belts, etc.) should be discarded.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Safety Page 2-36
2.7.3 Precautions
1. Employees should wear impervious rubber, neoprene, or vinyl
gloves, boots, and overalls or full-body suits, plus tightly fitting
goggles and face shields.
2. If dust or mist is present, use an appropriate respirator.
3. When diluting sodium hydroxide, use agitation (mixing) and add the
concentrated sodium hydroxide to water at a controlled rate to
control the heat of dilution and avoid spattering. Never add water to
sodium hydroxide.

Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Safety Page 2-37
2.8 Sulfur Plant Safety
2.8.1 Hydrogen Sulfide
Hydrogen sulfide will be present in all of the process gas streams flowing
in the ATU, the SWS, the SRU, the SDU, the TGCU, and the Thermal
Oxidizer. The hydrogen sulfide content will decrease as the sulfur is
extracted from the gas stream and will reach its lowest concentration in
the incinerated vent gas. Some hydrogen sulfide will be dissolved in the
liquid sulfur produced. Review the characteristics of this poisonous gas
often, and be fully familiar with them.
Avoid all possibility of exposure to hydrogen sulfide. Plan and think
ahead, so that when there is a possibility of hydrogen sulfide release, you
will know what to do. Plant safety procedures should be established that
require the presence of at least two men before a flange is loosened, or
any other opening is created, to allow a possible H
2
S release. The man
doing the work should either wear a gas mask with canister, manufactured
specifically for hydrogen sulfide protection, or a fresh air pack. The
second man should stand on the side a few yards away, upwind, with the
oxygen supply in his hands.
If the job requires entering a vessel or enclosure which might contain
some hydrogen sulfide, a safety harness with lifeline shall be attached to
the man entering the vessel. Two men should remain outside the vessel
to pull the man who entered the vessel to safety if he should be overcome.
If a man who is working in a hydrogen sulfide exposure should begin
moving sluggishly or lose coordination, the man who is standing by should
remove him immediately to fresh air. Any sign of actions that are out of
the ordinary is a last minute warning. After an extended exposure, a man
will be unusually sensitive to even small concentrations of H
2
S gas.
2.8.2 Sulfur Dioxide
Sulfur dioxide will not be present within the SRU, the SDU, the TGCU unit,
and the Thermal Oxidizer as a pure gas but will be present in the
following:
1. Most process gas streams (reactor gases, tailgas, and stack gas).
2. Sulfur tank gases.
3. Smoke from any sulfur fire.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Safety Page 2-38
The maximum allowable concentration in which it is safe to work is
5 PPM. Reactor gases, tailgas, and stack gas may have concentrations
up to 10,000 PPM and vapors from sulfur fires may have concentrations
up to 100,000 PPM.
The most likely source of sulfur dioxide in sufficient concentration to cause
problems is a fire in the sulfur storage tank. The simplest way to stop
such a fire is to smother it by covering all openings to the air, then putting
water into the storage tank. This water will vaporize to steam and help
smother the fire. Smothering a sulfur fire with plant steam is also
effective.
2.8.3 Sulfur Storage Tank
Molten sulfur produced in each SRU flows through the drain seals and is
stored in the sulfur surge tanks. These drain seals and tanks present a
combination of principle hazards.
2.8.3.1 Poisonous Gases
Hydrogen sulfide and sulfur dioxide are present in the vapor space
above the molten sulfur. They should not be inhaled as they are
extremely toxic.
2.8.3.2 Explosion and Fire
The surge tanks are equipped with steam-powered eductors to
provide ventilation of the vapor space. Each tank also has a
steam-jacketed stack that can provide natural-draft ventilation if its
eductor system is not functioning. These ventilation systems are
designed to sweep sufficient fresh air through the vapor space to
prevent hydrogen sulfide liberated from the sulfur from reaching
explosive concentrations. However, common sense dictates that no
ignition sources should be allowed near the tanks in case some
obstruction of the ventilation system should occur and allow an
explosive concentration of H
2
S to build up. Therefore, tools which
might cause a spark or open flame, should not be brought into the
area around the sulfur surge tanks without special review and
precautions, and smoking must be prohibited in the area.
Operators should be aware of the possible existence of an explosive
mixture in the sulfur surge tanks, as there is some history of
explosions in European sulfur pits and at least one U.S. pit. The
breather vents, where the air is sucked into the tanks, should be
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Safety Page 2-39
checked regularly for adequate air flow. The motive steam supply to
the eductors, as well as the steam supply to and condensate from
the ventilation system jacketing, should also be monitored.
Sulfur fires may occur in the tanks. Molten sulfur has an auto-ignition
temperature of approximately 450F (232C). This is a spontaneous
reaction; no spark or flame is required. Steam system temperatures
are normally well below the auto-ignition point of sulfur. However,
some iron-sulfur corrosion compounds are unstable and can ignite,
or decompose, at lower temperatures to create localized hot spots
and sulfur burning.
SECTIONS 2.9 THROUGH 2.14 LIST SOME IMPORTANT SAFETY
CONSIDERATIONS THAT PERSONNEL SHOULD KEEP IN MIND WHEN
WORKING IN THE PLANT. THESE SECTIONS ARE NOT A COMPLETE LIST OF
SAFETY CONSIDERATIONS AND DO NOT OUTLINE COMPLETE OPERATING
OR MAINTENANCE PROCEDURES. ALL PERSONNEL SHOULD FOLLOW
THEIR EMPLOYER'S DETAILED SAFETY PROCEDURES FOR ANY WORK
DONE IN THE PLANT.
2.9 Hot Work
Any work which requires the use of equipment that is capable of being an
ignition source in an area where flammable vapors or materials may be present
is defined as "Hot Work". Examples of equipment considered as ignition
sources are: welding equipment, open lights, gasoline engines, grinders, etc.
"Hot Work" normally requires specific approval by plant management and
should be implemented by following detailed instructions for obtaining "Hot
Work" permits.
2.10 Vessel Entry
The procedures used for vessel entry shall be in conformance with ANSI Z117.1
(latest edition), the "American National Standard Safety Requirements for
Confined Spaces". The discussion in this section is a general information
supplement to ANSI Z117.1. In all cases, consult ANSI Z117.1 and any
applicable Samsung Total Petrochemicals policies for specific precautions and
procedures regarding each instance of vessel entry.
Vessel entry refers to any tank, vessel, equipment, or other enclosed place
where there is a hazard of: 1) a toxic, corrosive, or flammable substance;
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Safety Page 2-40
2) insufficient oxygen; or 3) severe restrictions that would hinder escape or
rescue. Vessel entry normally requires specific approval by plant management.
Almost all of the vessels in this facility fit at least one of the three categories
mentioned above, due to the potential presence of hydrocarbon gas, caustic or
corrosive chemicals, or toxic H
2
S and SO
2
. All vessels should be assumed
unsafe for normal entry until prescribed vessel entry procedures have been
followed.
Consider the precautions advised for vessel entry when gauging tanks,
sampling, and blowing down lines or instruments.
Some or all of the following items should be considered for most vessel entry
jobs:
A. Disconnect and blank off all lines to the vessel.
B. Remove all sources of ignition before removing manway covers.
C. Check all internal lines and liquid traps to verify they are free of hazardous
liquid.
D. Clean the vessel as thoroughly as possible by draining, purging with inert
gas, steaming, ventilating, or other suitable means.
If steam is used, guard against static electricity by grounding the steam
nozzle. After steaming, allow the vessel to cool slowly. Sudden cooling
with water spray may cause a static electric charge. Also, it is not good
practice to allow the inside surfaces of the sulfur plant process piping and
vessels to become water wetted. Excessive corrosion occurs when
oxygen and water are present.
E. Test the Atmosphere for:
(1) Oxygen - The atmosphere must contain 19.5-23.5% oxygen and the
vessel should have adequate ventilation, either forced or natural.
(2) Explosive mixture - A vessel may not be entered if the testing
instrument indicates an air-vapor mixture that exceeds 10% of the
lower explosive limit, or the value specified in your organization's
safety procedures.
(3) Toxic fumes - The presence of any toxic fumes requires the use of
respiratory protective equipment, normally an air supplied mask with
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Safety Page 2-41
hand blower, or a self-contained breathing unit; otherwise, additional
cleaning or purging of the vessel is indicated.
F. A safety harness and a lifeline shall be worn by the person entering the
vessel if respiratory equipment is required.
G. Personal protective clothing suitable for the job inside the vessel should
be worn.
H. An observer should be stationed outside the vessel. His duty should be to
watch the person inside the vessel. When respiratory equipment is
required for the person entering the vessel, the observer should also have
the suitable respiratory equipment available.
I. Fire extinguisher and other emergency equipment should be available as
required.
2.11 Pipes and Lines
In the discussion that follows, line breaking is defined as the opening of any line,
the contents of which are flammable, corrosive, toxic, or under high pressure.
All other line opening jobs or work are excluded from this definition. Line
breaking usually requires specific approval by plant management.
The following items should be considered in all work involving lines and valves:
2.11.1 General
1. Know the contents of each line being worked on.
2. Know the pressure ratings of the pipes and fittings. Never install low
pressure connections on high pressure lines.
3. Never hammer on high-pressure lines.
4. Use extreme caution when thawing frozen lines.
5. Never use fire to locate leaks of flammable materials.
6. Be very cautious when attempting to tighten steam pipe fittings while
pressure is on a line.
7. When opening valves, do so slowly to allow pressure to equalize
before opening the valve fully.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Safety Page 2-42
8. When removing blinds, loosen bolts and allow any pressure to bleed
down. Gas sometimes leaks into the space between the blind and
the valve.
2.11.2 Before Breaking Lines
1. Drain the contents into a tank or to the lowest point.
2. Lock out, tag out, and try the pump. All gauges and sight glasses
should be checked for zero readings.
3. Close and tag the nearest upstream and downstream valves.
2.11.3 When Breaking Lines
1. Wear suitable personal protective equipment, such as full clothing.
At times, rubber suits should be worn to guard against chemical
splash. Goggles should be worn to protect eyes against chemical
splash and flying particles.
2. Always assume a line is full and under maximum possible pressure.
3. The placement of a deflector over the flange joint is usually desirable
for the initial "cracking" of flanges in lines containing corrosive or
toxic material.
4. The worker should slowly open the bolts on the far side, so that if
there is a spray it will be away from him.
5. Sections that have been removed should be handled carefully until
they are inspected for trapped material or residues and flushed if
required.
2.12 Electrical Equipment
Everyone recognizes that high voltages can be very dangerous. However,
some people fail to realize that so-called "low-voltage" can be hazardous and
under certain conditions can produce fatal injuries. Deaths have occurred
because of contact with circuits of less than 50 volts. It is not voltage but
amperage that kills. Under certain conditions, as little as 1/10 ampere is
sufficient to cause death. The following may be used as a guide when working
with electrical equipment.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Safety Page 2-43
2.12.1 Electrical Repairs
When electrical equipment is to be repaired, switches must be locked
open, tagged, and the circuit "tried" to confirm the power is off. Working
on "hot circuits" normally requires the permission of plant management.
Refer to detailed plant tag-out procedures before proceeding.
2.12.2 Grounding
1. All electrical equipment is to be grounded.
2. If it is necessary to move any equipment, the ground should be
replaced before the equipment is used.
2.12.3 Conduit, Cables, and Wires
1. Electrical conduits should not be used to support other equipment.
2. Exposed ends of electrical wires must be taped.
3. Unused and abandoned electric wires must be removed or
disconnected at each end.
2.12.4 Fuses
1. Fuses should be replaced only by authorized personnel.
2. Fuse tongs and/or rubber electrical gloves should be used and the
disconnect should be opened. Rubber gloves must always be used
for voltages in excess of 150 volts.
3. Never use coins or tin foil in lieu of fuses.
4. Never use fuses of greater capacity than is specified by the
equipment manufacturer.
2.12.5 Switching
1. When starting electric motors, handle all switches according to
instructions. Make contact so as to prevent arcs. Stand in a safe
position.
2. Never pull a disconnect switch under load except in an emergency.
3. Always be certain that hands are dry and that the footing is dry when
operating switches or plugging in electrical appliances.
4. Keep rubber mats in front of switchboards where possible.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Safety Page 2-44
5. Switch-panel fronts should be kept closed.
6. Maintain clear access to disconnects/switches.
2.12.6 Hand Tools and Portable Equipment
1. Extension lights without bulb protectors must not be used. Use only
low voltage lights with isolating transformers in boilers and similar
places.
2. All extension cords should be the grounded type. Before each period
of use, examine extension cords carefully for any failure of the outer
insulation, particularly at terminal points where the cord enters a plug
or a fixture.
3. Lights and tools should not be disconnected from an extension cord
while the other end of the cord is in a socket or receptacle.
4. The ground cable with which each tool is equipped should be
secured to a suitable ground before the tool is plugged into a source
of electricity.
2.12.7 Miscellaneous
1. Contact with electrical conductors should be avoided whether they
are energized or not.
2. Fenced sub-station areas should be entered only by authorized
personnel.
3. Faulty electrical equipment must not be used. Report it immediately.
4. Before changing broken light bulbs, be certain the current is turned
off.
5. No employee may work within 15 feet of a high voltage power line
except by special authorization of plant management.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Safety Page 2-45
2.13 Boilers and Other Direct-Fired Equipment
2.13.1 General
1. In this facility, the Waste Heat Boiler, Sulfur Condenser, TGCU
Waste Heat Reclaimer, and Thermal Oxidizer Waste Heat Boiler are
classified as boilers, but they are not direct-fired. The Reactor
Furnace and Thermal Oxidizer are the direct-fired pieces of
equipment.
2. Work on the Waste Heat Boiler, Sulfur Condenser, TGCU Waste
Heat Reclaimer, Thermal Oxidizer Waste Heat Boiler, Reactor
Furnace, and Thermal Oxidizer should be approved as required by
local procedures.
3. Control valves should be operated only when necessary by the
operator in charge.
4. Refer to detailed vendor instructions for specific descriptions of
actual safety procedures and equipment on the direct-fired
equipment in this plant.
2.13.2 Boilers
2.13.2.1 Repair and Maintenance
a. Only boiler inspectors or the State boiler agency should
determine a new setting for safety relief valves. Seals on safety
relief valves should never be removed. If a valve leaks, remove
it to a Code-authorized shop for repairs.
b. Before entering a boiler fire box:
(1) Ventilate the fire box.
(2) Lock, tag, and try the blower valve.
(3) Blank or disconnect fuel gas lines.
c. Before entering the drum or shell:
(1) Feed water lines and blow-off lines should be blinded or
suitably locked.
(2) Blank the steam line between the stop valve and the
boiler.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Safety Page 2-46
(3) If blinding is prevented by piping connections, non-return
and main stop valves should be locked and vents between
valves should be opened.
d. If valves are to be locked, the man entering the boiler shall
supervise the operations and retain the keys to the locks.
e. After repairs, examine the boiler carefully for tools and other
matter before replacing the manhole cover.
f. Before filling begins, all locks should be removed by the man, or
men, who have retained keys to the locks.
2.13.2.2 Operations
a. Open steam valves very slowly to allow cold lines to heat up
and water to drain out before pressure builds.
b. Open blow-off valves or cocks slowly. Before a boiler is blown
out, it is advisable to attain a high water level so that scale and
sediment can be blown out without lowering the water to a
dangerous level.
2.13.3 Direct-Fired Equipment
1. Before attempting to light burners, be certain that combustible gases
are purged from the system.
2. Stand to one side of openings when lighting burners.
3. Ignite each burner or pilot as described in operating instructions.
4. Observation ports should be used with care when lighting burners
because of the chance of high positive pressures and explosion.
5. Before entering a fire box:
a. Ventilate the fire box.
b. Lock, tag, and try the blower valve.
c. Blank or disconnect fuel gas and tailgas lines.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Safety Page 2-47
2.14 Laboratory Safety
2.14.1 Good Housekeeping
1. Cleanliness and orderliness are essential to the operations of
laboratories.
2. A continuous program should be in effect to prevent the
accumulation of rubbish, rags, partly used samples, dismantled
equipment, etc.
2.14.2 Equipment
1. Inspect all gas hoses for leaks each day that they are used.
2. Extinguish all gas burners when they are not in use.
3. Glassware
a. Discard all cracked, broken, or scrap glassware.
b. Fire-polish all chipped edges on burettes, beakers, graduates,
etc.
c. Avoid thermal shock with all glassware.
d. Use only glass tubing with fire-polished ends.
e. Before attempting to insert glass tubing into stopper holes, be
certain that the holes are the proper size. Always moisten the
stopper hole and the glass tubing with water, and rotate the
glass tube as it is inserted, pushing it away from the body.
When rubber tubing or stoppers stick on glassware, cut them
away.
f. Do not drink or eat out of laboratory glassware.
2.14.3 Chemical Sorting and Identification
1. Adequately label or mark bottles and containers to identify the
chemical within.
2. Keep chemicals stored in their proper place. Solvents should not be
brought into laboratory in quantities greater than five gallons.
3. Keep volatile combustible liquids in safety containers and away from
direct flames or sources of heat.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Safety Page 2-48
2.14.4 Chemical Handling
1. When handling acids or caustics in quantities, always wear protective
clothing and eye protection.
2. Always pour acids and caustics into water, never the reverse.
3. If acids or caustics enter the eye, flush with plenty of water and
report for first aid treatment.
4. Wash hands immediately after handling chemicals bearing poison
labels. Wash hands after handling mercury and clean up mercury
spills at once.
5. Use large quantities of water when disposing of acids or caustic
materials through the drains.
6. Refer to vendor information for specifics on the safe handling of
individual types of chemicals and first aid steps for accidents
involving them.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Safety Page 2-49
2.15 Material Safety Data Sheets (MSDS)
This section contains Material Safety Data Sheets (MSDS) for the hazardous
chemicals listed below that operating personnel in this part of the complex may
encounter while operating the unit and systems described in this manual. Of
necessity, these MSDS are generic in nature. As they become available,
Samsung Total Petrochemicals Co. should replace and/or supplement the
MSDS provided in this manual with those prepared by the manufacturers and/or
suppliers of the specific chemicals used in the complex.
A. Hydrogen Sulfide
B. Sulfur Dioxide
C. Sulfur
D. Ammonia
E. Methyldiethanolamine
F. Sodium Hydroxide
G. UOP/ESM S-2001 Sulfur Conversion Catalyst
H. Criterion 234 Tailgas Treating Catalyst


MATERIAL SAFETY DATA SHEET

HYDROGEN SULFIDE

SECTION I - PRODUCT IDENTIFICATION

Substance: HYDROGEN SULFIDE CAS Number: 7783-06-4

Trade Names / Synonyms: Hepatic Gas; Hydrosulfuric Acid; Stink Damp; Sulfureted Hydrogen; Sulfur
Hydride


Molecular Formula: H
2
S Molecular Weight: 34.08

General or Generic ID: Inorganic Gas

SECTION II - COMPONENTS

Component: Hydrogen Sulfide Percent: > 99.0

Other Contaminants: Methyl Mercaptan; Carbon Disulfide; Oxides of Carbon and Sulfur

Exposure Limits: Hydrogen Sulfide
20 PPM OSHA acceptable ceiling concentration
50 PPM / 10 minutes OSHA peak
10 PPM ACGIH TWA
10 PPM ACGIH STEL
15 mg/m
3
(10 PPM) NIOSH recommended 10 minute ceiling

SECTION III - PHYSICAL DATA

Description: Colorless gas at atmospheric temperature and pressure, with the odor of
rotten eggs.


Melting Point: -122F (-86C) Boiling Point: -77F (-60C)

Liquid Specific Gravity: 1.54 Vapor Specific Gravity: 1.18
(water = 1.0) (air = 1.0)

Vapor Pressure: 294 PSI (20 atm) @ 78F (25C)

Odor Threshold: 0.05 PPM

Solubility in Water: 4.2 g/l @ 60F (15C), 3.2 g/l @ 78F (25C)

Other Solvents Carbon Disulfide, Weak Acids, Ethanol, Gasoline, Kerosene, Crude Oil, Liquid
Sulfur


Other Physical Data: Solubility decreases with increasing temperature or with mechanical
disturbance (agitation), causing evolution of dissolved gas.






ISSUE DATE: 06/12/95 SUPERSEDES: 02/19/93 PAGE 1 OF 6

MATERIAL SAFETY DATA SHEET

HYDROGEN SULFIDE

SECTION IV- FIRE AND EXPLOSION INFORMATION

Fire and Explosion Hazard: Highly flammable gas when exposed to heat, flame, or oxidizers.
Moderate explosion hazard. Gas-air mixtures are explosive. Vapors
are heavier than air, and may travel a considerable distance to a
source of ignition and flash back.


Auto-Ignition Temperature: 500F (260C) Flash Point Temperature: N/A

Explosive Limits in Air: Lower: 4.3% Upper: 46%

Extinguishing Media: Let burn unless leak can be stopped immediately.
(1984 Emergency Response Guidebook, DOT P 5800.3).

For larger fires, use water spray, fog, or foam.
(1984 Emergency Response Guidebook, DOT P 5800.3).

Fire-Fighting Procedures: Extinguish only if flow can be stopped; use water in flooding amounts
as fog. Apply from as far a distance as possible. Avoid breathing
poisonous vapors, keep upwind. Evacuate to a radius of 2500 feet for
uncontrollable fires. Evacuate downwind areas as required for leaks.


Fire-Fighting Phases: Stop flow of gas. Use water to keep fire-exposed containers cool and
to protect personnel effecting the shut off. (NFPA 49, Hazardous
Chemicals Data, 1975).


SECTION V - HEALTH HAZARD DATA

Permissible Exposure Level: 10 PPM

Threshold Limit Value: 10 PPM

Health Effects from Exposure

Swallowing: Ingestion of a gas is unlikely.

Inhalation: Corrosive/Neurotoxin/Toxic. 300 PPM immediately dangerous to life or health.

Acute Exposure - Low concentrations may produce nasal and respiratory tract irritation.
At 50 PPM, anosmia, anoxia, headache, nausea, dizziness, vomiting, confusion,
weakness, ataxia, irritability, and insomnia may occur. Rhinitis, pharyngitis, coughing,
bronchitis, and pneumonitis are also possible. At 500-1000 PPM, coma, convulsions,
and death may occur within 30 minutes. At extremely high concentrations, respiratory
paralysis and death from asphyxia may be immediate. Non-fatal exposures may result
in sequelae including residual cough, cardiac dilation, slow pulse, peripheral neuritis,
albuminuria, amnesia, psychic disturbances, and permanent brain damage.



ISSUE DATE: 06/12/95 SUPERSEDES: 02/19/93 PAGE 2 OF 6

MATERIAL SAFETY DATA SHEET

HYDROGEN SULFIDE

SECTION V- HEALTH HAZARD DATA (continued)

Inhalation:
(continued)
Chronic Exposure - Prolonged or repeated exposure to low concentrations may cause
hypotension, nausea, anorexia, weight loss, incoordination, and chronic cough.
Prolonged exposure to 250 PPM has led to pulmonary edema.


Eye Contact: Corrosive.

Acute exposure - 50 PPM for one hour has caused conjunctivitis, pain, lacrimation,
photophobia, and appearance of haloes around lights. Within a few hours or days,
symptoms may progress to keratoconjunctivitis and vesiculation of the corneal
epithelium. Higher concentrations may cause severe irritation, lacrimation, and intense
pain.


Chronic Exposure - Prolonged or repeated exposure may cause conjunctivitis.

Skin Contact: Corrosive.

Acute Exposure - High vapor concentrations may cause severe irritation of the skin.

Chronic Exposure - A high incidence of furunculosis has been reported in industrial
hydrogen sulfide workers.


First Aid Measures

Swallowing: Treat symptomatically and supportively. Get medical attention immediately. If vomiting
occurs, keep head lower than hips to prevent aspiration.


Inhalation: Remove from exposure area to fresh air immediately. If breathing has stopped, give
artificial respiration. Maintain airway and blood pressure and administer oxygen if
available. Keep affected person warm and at rest. Administration of oxygen should be
performed by qualified personnel. Get medical attention immediately.


Eye Contact: Wash eyes immediately with large amounts of water, occasionally lifting upper and
lower lids, until no evidence of chemical remains (at least 15-20 minutes). In case of
burns, apply sterile bandages loosely without medication. Get medical attention
immediately.


Skin Contact: Flush affected areas with large amounts of water. Consult a physician for further
treatment.


Antidote: Amyl nitrite or sodium nitrite can be used to aid in the formation of sulfmethemoglobin,
thus removing sulfide from combination in tissues. Pyridoxine 25 mg/kg intravenously,
or 10% urea, 1 g/kg intravenously, has been suggested as a sulfide acceptor.
Administration of antidotes should be performed by qualified medical personnel. The
nitrite antidote is toxic; therapy is dangerous. (Dreisbach, Handbook of Poisoning, 11th
ed.)


ISSUE DATE: 06/12/95 SUPERSEDES: 02/19/93 PAGE 3 OF 6

MATERIAL SAFETY DATA SHEET

HYDROGEN SULFIDE

SECTION VI- REACTIVITY DATA

Reactivity: Stable under normal temperatures and pressures.

Incompatibilities: Acetaldehyde: Violent reaction.
Barium Oxide, Mercurous Oxide, and Air: Incandescent reaction or explosion.
Barium Oxide, Nickel Oxide, and Air: Incandescent reaction or explosion.
Barium Peroxide: Ignition reaction.
Bromine Pentafluoride: Fire and explosion hazard.
Chlorine Monoxide: Ignition reaction on contact.
Chlorine Trifluoride: Explosive reaction.
Chromic Anhydride: Incandescent reaction on heating.
Copper: Intense exothermic reaction.
Copper Powder: Intense reaction.
Diiron Trioxide Hydrate: Formation of combustible substance.
Fluorine: Ignition reaction.
Metals: Attacks most metals, especially in the
presence of water.

Metal oxides: Combustion, incandescent reaction, or
explosion.

Lead Dioxide: Combustion reaction.
Nitric Acid: Incandescent reaction.
Nitric Acid (Fuming or Concentrated): Violent reaction.
Nitrogen Trichloride: Explosive reaction.
Nitrogen Trifluoride: Formation of explosive mixture.
Nitrogen Triiodide and Ammonia: Explosive reaction.
Oxidants: Violent reaction.
Oxygen Difluoride: Explosive reaction on mixing.
Perchloryl Fluoride: Ignition or explosion at 100-300C.
Phenyl Diazonium Chloride: Formation of explosive substance.
Rust: Hydrogen sulfide may ignite if passed
through rusty iron pipes.

Silver Fulminate: Violent reaction at ambient
temperatures.

Soda Lime and Air: Incandescent reaction.
Sodium: Rapid reaction on contact with moist gas.
Sodium Peroxide: Violent reaction or ignition, even in the
absence of air.


Decomposition: Thermal decomposition products may include toxic and hazardous hydrogen, sulfur,
and oxides of sulfur.


Polymerization: Hazardous polymerization has not been reported to occur under normal temperatures
and pressures.






ISSUE DATE: 06/12/95 SUPERSEDES: 02/19/93 PAGE 4 OF 6

MATERIAL SAFETY DATA SHEET

HYDROGEN SULFIDE

SECTION VII- SPILL OR LEAK PROCEDURES

Steps to Be Taken in Case Material is Released or Spilled

Shut off ignition sources. Stop leak if you can do it without risk. Use water spray to reduce vapors.
Isolate area until gas has dispersed. No smoking, flames, or flares in hazard area! Keep unnecessary
people away; isolate hazard area and deny entry. Ventilate closed spaces before entering. Evacuate
area endangered by gas.


Waste Disposal Method

Water used to knock-down vapors is corrosive and toxic, and should be diked for containment. Add
suitable agent to neutralize to 7 pH prior to disposal.






SECTION VIII - PROTECTIVE EQUIPMENT TO BE USED

Ventilation: Provide local exhaust or process enclosure ventilation to meet the published exposure
limits. Ventilation equipment must be explosion-proof.


Respirator: The following respirators and maximum use concentrations are recommendations by the
U.S. Department of Health and Human Services; NIOSH Pocket Guide to Chemical
Hazards or NIOSH Criteria Documents; or, Department of Labor, 29CFR1910,
Subpart Z.


The specific respirator selected must be based on contamination levels found in the work
place and be jointly approved by the National Institute of Occupational Safety and Health
and the Mine Safety and Health Administration.


Hydrogen Sulfide:
100 PPM - Supplied-air respirator.
Self contained breathing apparatus.

250 PPM - Supplied-air respirator operated in continuous flow mode.
Self-contained breathing apparatus.

300 PPM - Self-contained breathing apparatus.
Supplied-air respirator with full facepiece.

Escape - Air-purifying full facepiece respirator (gas mask) with chin-style or front-
or back-mounted canister.

Escape-type self-contained breathing apparatus.





ISSUE DATE: 06/12/95 SUPERSEDES: 02/19/93 PAGE 5 OF 6

MATERIAL SAFETY DATA SHEET

HYDROGEN SULFIDE

SECTION VIII - PROTECTIVE EQUIPMENT TO BE USED (continued)

Respirator For firefighting and other immediately dangerous to life or health conditions:
(continued):
Self-contained breathing apparatus with full facepiece operated in pressure-demand
or other positive pressure mode.


Supplied-air respirator with full facepiece and operated in pressure-demand or other
positive pressure mode in combination with an auxiliary self-contained breathing
apparatus operated in pressure-demand or other positive pressure mode.


Clothing: Wear protective clothing. Prevent any possibility of repeated or prolonged vapor contact
with skin.


Gloves: Wear full protective gloves.

Eye Protection: Employee must wear splash-proof or dust-resistant safety goggles and a faceshield to
prevent contact with this substance.


Where there is any possibility that an employee's eyes may be exposed to this substance,
the employer shall provide an eye-wash fountain within the immediate work area for
emergency use.





SECTION IX - SPECIAL PRECAUTIONS OR OTHER COMMENTS

1. Odor is not a reliable test for the presence of hydrogen sulfide.

2. Since hydrogen sulfide is heavier than air, it settles when released into the atmosphere and becomes
more concentrated near the ground and in low places.


3. Hydrogen sulfide dissolves in liquid sulfur and is a hazard in storage tanks and pits.












Disclaimer
The information contained herein is believed to be accurate, but is not warranted to be, whether originating within the company or not. Health and safety precautions in this data sheet
may not be adequate for all individuals and/or situations. Recipients are advised to confirm in advance of need that the information is current, applicable, and suitable to their
circumstances. It is the end users responsibility to evaluate and use this product safely, and to comply with all applicable laws and regulations. No statement made in this data sheet
shall be construed as a permission or recommendation for use of any product in a manner that might infringe existing patents. No warranty is made, either expressed or implied.
ISSUE DATE: 06/12/95 SUPERSEDES: 02/19/93 PAGE 6 OF 6


MATERIAL SAFETY DATA SHEET

SULFUR DIOXIDE

SECTION I - PRODUCT IDENTIFICATION

Substance SULFUR DIOXIDE CAS Number: 7446-09-5

Trade Names / Synonyms: Sulfurous Acid Anhydride; Sulfurous Anhydride; Sulfurous Oxide;
Sulfur Oxide


Molecular Formula: SO
2
Molecular Weight: 64.06

General or Generic ID: Inorganic Gas

SECTION II - COMPONENTS

Component: Sulfur Dioxide Percent: > 99.0

Other Contaminants: Hydrogen Sulfide

Exposure Limits: Sulfur Dioxide
5 PPM OSHA TWA per 8-hour working day
2 PPM ACGIH TWA
0.5 PPM NIOSH recommended TWA

SECTION III - PHYSICAL DATA

Description: Colorless gas at atmospheric temperature and pressure, with an irritating,
suffocating odor.


Melting Point: -104F (-76C) Boiling Point: 14F (-10C)

Liquid Specific Gravity: 1.43 Vapor Specific Gravity: 2.21
(water = 1.0) (air = 1.0)

Vapor Pressure: 49 PSIA (3.3 atm) @ 70F (21C)

Odor Threshold: 0.47 PPM

Solubility in Water: 129 g/l @ 60F (15C), 102 g/l @ 68F (20C)

Other Solvents: Sulfur

Other Physical Data:









ISSUE DATE: 02/19/93 SUPERSEDES: PAGE 1 OF 5

MATERIAL SAFETY DATA SHEET

SULFUR DIOXIDE

SECTION IV- FIRE AND EXPLOSION INFORMATION

Fire and Explosion Hazard: None

Auto-Ignition Temperature: N/A Flash Point Temperature: N/A

Explosive Limits in Air: Lower: N/A Upper: N/A

Extinguishing Media: Material is nonflammable. Use what is appropriate to the surrounding fire.
SO
2
will form a corrosive acidic mist with water fog or steam.


Fire-Fighting Procedures: Fire fighters must use full protective clothing, eye protection, and self-
contained breathing equipment when this material is involved in a fire
situation.


Fire-Fighting Phases: N/A



SECTION V - HEALTH HAZARD DATA

Permissible Exposure Level: 5 PPM

Threshold Limit Value: 2 PPM

Health Effects from Exposure

Swallowing: Ingestion of a gas is unlikely.

Inhalation: Chiefly affects the upper respiratory tract and the bronchi, causing irritation, difficulty
with breathing, pulmonary edema, and, at high levels, respiratory paralysis. Short
exposures above 50-100 PPM can be dangerous, and, above 400-500 PPM,
immediately life threatening.


Systemic effects of acute or chronic exposure are not fully known. Statistical evidence
has been reported to show increased pulmonary function impairment at chronic SO
2

levels of 1-4 PPM. Mixture with smoke particulate or aerosols may increase the
hazards of SO
2
inhalation.


Eye Contact: At 20 PPM and above, irritation and inflammation of the conjunctiva.

Skin Contact: At 10,000 PPM, irritating to moist areas within a few minutes.









ISSUE DATE: 02/19/93 SUPERSEDES: PAGE 2 OF 5

MATERIAL SAFETY DATA SHEET

SULFUR DIOXIDE

SECTION V- HEALTH HAZARD DATA (continued)

First Aid Measures

Swallowing: Treat symptomatically and supportively. Get medical attention immediately. If vomiting
occurs, keep head lower than hips to prevent aspiration.


Inhalation: The victim must be carried at once to an uncontaminated atmosphere and effective
artificial respiration started immediately if breathing has ceased. Oxygen (100%)
should be administered (by trained personnel only) as soon as possible after a severe
exposure, preferably against a positive exhalation pressure of 1.25 inches of water.


Oxygen inhalation must be continued as long as necessary to maintain the normal
color of the skin and mucous membranes. In cases of severe exposure, the patient
should breathe 100% oxygen under positive exhalation pressures for 30 minute
periods every hour for at least 3 hours. If there are no signs of lung congestion at the
end of this period, and if the breathing is easy and the color is good, oxygen inhalation
may be discontinued. Throughout this time, the patient should be kept comfortably
warm, but not hot.


Eye Contact: If sulfur dioxide has contacted the eyes, they should be washed promptly with large
quantities of water for at least 15 minutes. Chemical neutralizers are not advisable. It
is advisable to irrigate the eyes gently with water at room temperature in order to
minimize additional pain and discomfort. Refer the victim at once to a physician,
preferably an eye specialist.


Skin Contact: On skin contact with sulfur dioxide, use an emergency safety shower at once. Clothing
and shoes contaminated with sulfur dioxide should be removed under the shower.
Sulfur dioxide should be washed off with very large quantities of water. Wash skin
areas with large quantities of soap and water. Do not apply salves or ointments to
chemical burns for 24 hours.




















ISSUE DATE: 02/19/93 SUPERSEDES: PAGE 3 OF 5

MATERIAL SAFETY DATA SHEET

SULFUR DIOXIDE

SECTION VI- REACTIVITY DATA

Reactivity: Stable under normal temperatures and pressures.

Incompatibilities: Acrolein Manganese
Aluminum Metal Acetylides
Cesium Hydrogencarbide Metal Oxides
Cesium Oxide Metals
Chlorates Polymeric Tubing
Chlorine Trifluoride Potassium Carbide
Chromium Potassium Chlorate
Ferrous Oxide Rubidium Carbide
Fluorine Sodium
Halogens or Interhalogens Sodium Carbide
Lithium Acetylene Carbide Diammino Sodium Hydride
Lithium Nitrate Tin Monoxide

Polymerization: Hazardous polymerization has not been reported to occur under normal temperatures
and pressures.







SECTION VII- SPILL OR LEAK PROCEDURES

Steps to Be Taken in Case Material is Released or Spilled

Notify safety personnel of significant leaks. Exclude all from area except those assigned to leak and
spill control who are using full protective gear (see Section VIII). Provide ventilation. Locate and control
leakage.


Waste Disposal Method

If water is used to knock-down vapors, it will be corrosive and toxic, and should be diked for
containment. Add suitable agent to neutralize to 7 pH prior to disposal.















ISSUE DATE: 02/19/93 SUPERSEDES: PAGE 4 OF 5


MATERIAL SAFETY DATA SHEET

SULFUR DIOXIDE

SECTION VIII - PROTECTIVE EQUIPMENT TO BE USED

Ventilation: Provide local exhaust or process enclosure ventilation to meet the published exposure
limits. (Treatment of exhausted air to remove SO
2
may be necessary before discharge
to the outside environment.)


Respirator: For fire fighting and other immediately dangerous to life or health conditions:

Self-contained breathing apparatus with full facepiece operated in
pressure-demand or other positive pressure mode.


Supplied-air respirator with full facepiece and operated in pressure-demand or
other positive pressure mode in combination with an auxiliary self-contained
breathing apparatus operated in pressure-demand or other positive pressure
mode.


(An approved cartridge respirator can be used when contamination is known to
be below 20 PPM.)


Clothing: Wear protective clothing. Prevent any possibility of repeated or prolonged vapor
contact with skin.


Gloves: Wear full protective gloves.

Eye Protection: Employee must wear splash-proof or dust-resistant safety goggles and a faceshield to
prevent contact with this substance.


Where there is any possibility that an employee's eyes may be exposed to this
substance, the employer shall provide an eye-wash fountain within the immediate work
area for emergency use.





SECTION IX - SPECIAL PRECAUTIONS OR OTHER COMMENTS












Disclaimer
The information contained herein is believed to be accurate, but is not warranted to be, whether originating within the company or not. Health and safety precautions in this data sheet
may not be adequate for all individuals and/or situations. Recipients are advised to confirm in advance of need that the information is current, applicable, and suitable to their
circumstances. It is the end users responsibility to evaluate and use this product safely, and to comply with all applicable laws and regulations. No statement made in this data sheet
shall be construed as a permission or recommendation for use of any product in a manner that might infringe existing patents. No warranty is made, either expressed or implied.
ISSUE DATE: 02/19/93 SUPERSEDES: PAGE 5 OF 5



MATERIAL SAFETY DATA SHEET

SULFUR

SECTION I - PRODUCT IDENTIFICATION

Substance: SULFUR CAS Number: 7704-34-9

Trade Names / Synonyms: Asulfa-Supra; Bensulfoid; Brimstone; Colloidal Sulfur; Cosan; Devisulphur;
Flowers of Sulfur; Ground Vocle Sulphur; Hexasul; Kumulus; Microwetsulf;
Precipitated Sulfur; Precipitated Sulphur; S-590; S-594; S-595;
Solid Sulfur; Solid Sulphur; Sublimed Sulfur; Sublimed Sulphur; Sulfex;
Sulfran; Sulphur; Uni350


Molecular Formula: S Molecular Weight: 32.06

General or Generic ID: Non-metallic Element

SECTION II - COMPONENTS

Component: Sulfur Percent: > 99.0

Other Contaminants: Hydrogen Sulfide, Sulfur Dioxide, Hydrocarbons, Carbon

Exposure Limits: The Nuisance Dust TLV should govern exposure to solid sulfur in the absence of
other standards:


10 mg/m
3
(8 PPMW) ACGIH TWA for total dust
5 mg/m
3
(4 PPMW) ACGIH TWA for respirable dust

Liquid sulfur may release hydrogen sulfide and/or sulfur dioxide as gases. Refer
to the specific Material Safety Data Sheets for these substances giving the
applicable exposure limits.


SECTION III - PHYSICAL DATA

Description: Solid sulfur is odorless, tasteless, yellow rhombic or monoclinic crystals, lumps,
granules, or powder. Sulfur contaminated with hydrocarbon or carbon may be
orange, green, tan, brown, or black in color. Liquid sulfur is viscous and odorless,
with a color ranging from bright yellow to dark orange (almost red) depending on
temperature. Contaminants (particularly hydrogen sulfide) sometimes give sulfur
the odor of rotten eggs.


Melting Point: 246F (119C) Boiling Point: 832F (444C)

Liquid Specific Gravity: 1.80 Solid Specific Gravity: 2.07
(water = 1.0) (water = 1.0)

Vapor Pressure: 0.05 PSIA (2.50 mm Hg) @ 400F (204C)

Odor Threshold: N/A

Solubility in Water: Negligible

ISSUE DATE: 06/13/95 SUPERSEDES: 02/19/93 PAGE 1 OF 10

MATERIAL SAFETY DATA SHEET

SULFUR

SECTION III- PHYSICAL DATA (continued)

Other Solvents: Other Solvents:
Slightly soluble in Ethyl Alcohol; Ethyl Ether; Benzene; Toluene; Olive Oil.

Other Physical Data: At temperatures up to about 317F (158C), the viscosity of pure liquid sulfur
decreases as the temperature increases. As the temperature increases from
317F to 370F (158C to 188C), the viscosity of pure liquid sulfur rises rapidly to
a tremendously high maximum, causing the liquid to become a dark, sticky,
plastic material impossible to pump.


SECTION IV - FIRE AND EXPLOSION INFORMATION

Fire and Explosion Hazard: Solid - The primary hazard in handling solid sulfur results from the fact that
sulfur dust suspended in the air ignites easily. Even though the explosion
hazard is considered moderate, an explosion occurring in a confined area
could cause considerable damage.


Sulfur, being a very poor conductor of electricity, tends to develop static
electric charges when it is in motion. Ignition of sulfur dust by static-caused
sparks is not uncommon. Frictional heat in equipment has also been
responsible for starting sulfur fires.


Liquid - The fire hazards of liquid sulfur result primarily from the low ignition
point of sulfur and from the presence of hydrogen sulfide.


Auto-Ignition Temperature: 450F (232C) for liquid sulfur
374F (190C) for sulfur dust suspended in air

Flash Point Temperature: 405F (207C)

Explosive Limits in Air: Lower: 35 g/m
3
(2.9% by wt) Upper: 1400 g/m
3
(53% by wt)

Extinguishing Media: Small Fires: Water, dry chemical, soda ash, or sand.
(1987 Emergency Response Guidebook, DOT P 5800.4)

Larger fires: Use water spray, fog, or standard foam.
(1987 Emergency Response Guidebook, DOT P 5800.4)

Steam smothering can be used in storage pits and other relatively small
enclosures. Carbon dioxide is also a satisfactory fire extinguishing agent.


Fire-Fighting Procedures: Straight streams of water from a nozzle can scatter molten sulfur and
disperse sulfur dust into the air. Sulfur dust is a moderate explosion hazard
when dispersed in air. As sulfur burns, it generates sulfur dioxide, a toxic
gas. Wear self-contained breathing apparatus.


Unusual Hazards: Small dust explosions may disperse larger quantities of dust into the air,
resulting in a serious explosion, particularly in confined areas.


ISSUE DATE: 06/13/95 SUPERSEDES: 02/19/93 PAGE 2 OF 10

MATERIAL SAFETY DATA SHEET

SULFUR

SECTION V- HEALTH HAZARD DATA

Permissible Exposure Level: None indicated.

Threshold Limit Value: None indicated.

Health Effects from Exposure

Swallowing: Acute Exposure - A man has survived ingestion of 60 grams of sulfur over a period of
24 hours. Large doses (15 grams) by mouth may lead to hydrogen sulfide production
in vivo, chiefly due to bacterial action within the colon. Small particles are generally
more toxic than large ones. If high levels of impurities are present, sore throat, nausea,
headache, dullness, and possible unconsciousness may occur.


Chronic Exposure - In medicine, it is used as a laxative. No adverse effects have been
reported.


Inhalation: Irritant.

Acute Exposure - Inhalation of large amounts of dust may cause catarrhal inflammation
of the nasal mucosa which may lead to hyperplasia with abundant nasal secretions.
Tracheobronchitis is a frequent occurrence, with dyspnea, persistent cough, and
expectoration, which may sometimes be streaked with blood.


Chronic Exposure - Prolonged inhalation of dust may cause bronchopulmonary
disease which, after several years, may be complicated by emphysema and
bronchiectasis. Early symptoms in sulfur miners often include upper respiratory tract
catarrh, with cough and expectoration which is mucoid and may even contain granules
of sulfur. Asthma is a frequent complication. The maxillary and frontal sinuses may be
affected; involvement is usually bilateral and pansinusitis may occur. Pulmonary
function may be reduced. Radiological examinations have revealed irregular opacities
in the lungs and occasionally nodulation has been reported.


Eye Contact: Irritant.

Acute Exposure - 8 PPM has caused irritation of human eyes. Dust may cause
irritation, redness and pain with lacrimation, photophobia, conjunctivitis, and
blepharoconjunctivitis; cases of damage to the crystalline lens have been reported
with the formation of opacities and even cataract and focal chorioretinitis.


Chronic Exposure - Low levels may cause conjunctivitis. Higher levels may cause
symptoms similar to acute exposure.






ISSUE DATE: 06/13/95 SUPERSEDES: 02/19/93 PAGE 3 OF 10

MATERIAL SAFETY DATA SHEET

SULFUR

SECTION V - HEALTH HAZARD DATA (continued)

Skin Contact: Irritant.

Acute Exposure - In highly purified form, the dust is low in irritation effects, but
frequently impurities of hydrogen sulfide are present and may produce irritation or
possibly burns.


Chronic Exposure - Soaps, ointments, gels, and drugs containing sulfur are used as
fungicides and parasiticides in the treatment of cutaneous disorders such as psoriasis,
seborrhea, eczema-dermatitis, and scalp disorders. Sulfur possesses a keratolytic
property which may be the basis of its therapeutic reaction. Prolonged local use of
sulfur may result in characteristic dermatitis venenata, possibly with erythematous and
eczematous lesions and signs of ulceration.


Molten sulfur - Capable of inflicting severe burns.

First Aid Measures

Swallowing: Give water or fluids. Emesis is not necessary. Treat supportively and symptomatically.
If irritation or digestive upset occurs, get medical attention.


Inhalation: Remove from exposure area to fresh air immediately. If breathing has stopped,
perform artificial respiration. Keep person warm and at rest. Get medical attention
immediately.


Eye Contact: Wash eyes immediately with large amounts of water, occasionally lifting upper and
lower lids, until no evidence of chemical remains (approximately 15-20 minutes). Get
medical attention immediately.


Skin Contact: Remove contaminated clothing and shoes immediately. Wash affected area with soap
or mild detergent and large amounts of water until no evidence of chemical remains
(approximately 15-20 minutes). Get medical attention immediately.



















ISSUE DATE: 06/13/95 SUPERSEDES: 02/19/93 PAGE 4 OF 10

MATERIAL SAFETY DATA SHEET

SULFUR

SECTION VI- REACTIVITY DATA

Reactivity: Stable under normal temperatures and pressures.

Incompatibilities: Alkali Metal Nitrides: Highly flammable mixture which evolves
ammonia and hydrogen sulfide in contact with
water.

Aluminum Powder: Possible explosion if ignited with a magnesium
fuse.

Aluminum Powder: Violent reaction.
Aluminum and Copper: Possible explosion when heated in a closed
container.

Aluminum and Niobium Oxide: Ignition.
Ammonia: Possible formation of an explosive product.
Ammonia Nitrate: Possible explosion on impact.
Ammonia Perchlorate: Possible explosion on impact.
Barium Bromate: When both are finely divided, explosion with heat,
percussion, or friction.

Barium Carbide: Ignites in sulfur vapor at 150C and incandesces.
Barium Chlorate: Possible spontaneous ignition at 108C. When
both are finely divided, explosion with heat,
percussion, or friction.

Barium Iodate: When both are finely divided, explosion with heat,
percussion, or friction.

Boron: Incandesces at 600C.
Bromine Pentafluoride: Violent reaction with possible ignition.
Bromine Trifluoride: Incandescence on contact.
Cadmium: Vigorous reaction.
Calcium: Burns in the vapor at 400C. Explodes on
ignition.

Calcium Bromate: When both are finely divided, explosion with heat,
percussion, or friction.

Calcium Carbide: Ignites in the vapor at 400C.
Calcium Chlorate: When both are finely divided, explosion with heat,
percussion, or friction.

Calcium Hypochlorite Powder: Explosion if heated in closed vessel.
Calcium Hypochlorite: With damp sulfur, produces a crimson flash with
scattering of molten sulfur.

Calcium Iodate: When both are finely divided, explosion with heat,
percussion, or friction.

Calcium Phosphide: Incandesces at 300C.
Calcium, Vanadium Oxide, and
Water:
Ignition.
Cesium Nitride: Intense reaction.
Charcoal, Freshly Calcined: Ignites spontaneously.
Chlorate and Copper: Probable explosion.
Chlorine Dioxide: Ignition and possible explosion.
Chlorine Monoxide: Violent explosion.

ISSUE DATE: 06/13/95 SUPERSEDES: 02/19/93 PAGE 5 OF 10

MATERIAL SAFETY DATA SHEET

SULFUR

SECTION VI - REACTIVITY DATA (continued)

Incompatibilities: Chlorine Trifluoride: Violent reaction with possible ignition.
(continued) Chlorine Trioxide: Possible violent reaction.
Chromic Anhydride: Ignition on heating, possible explosion.
Chromium Trioxide: Ignition on warming.
Chromyl Chloride: Ignition.
Copper: Attacked corrosively.
Copper Alloy: Attacked corrosively.
Diarsenic Trisulfide: Formation of explosion mixture.
Dichlorine Monoxide: Probable explosion.
Diethyl Ether: Possible explosion on evaporation.
Fiberglass and Iron Filings: Exothermic reaction above 125C.
Fluorine: Ignition at ambient temperatures.
Halogen Oxides: Possible explosion.
Heptasilver Nitrate Octaoxide: Explosion on impact.
Hydrocarbons: Explosive products produced on contact with
molten sulfur.

Indium: Ignition and incandescence on heating.
Interhalogens: Possible ignition or incandescent reaction.
Iodine Pentafluoride: Incandescence on contact.
Iodine Pentoxide: Explosive reaction on warming.
Lampblack: Spontaneous ignition.
Lead Chlorate: Possible spontaneous ignition at 63C.
Lead Chloride: Explosion.
Lead Chlorite: Explosion.
Lead Chromate: Pyrophoric mixture.
Lead Dioxide: Explosion.
Lead (IV) Oxide: Ignition on grinding or addition of sulfuric acid.
Lithium: When either is molten, explosively violent
reaction.

Lithium dissolved in Ammonia: Vigorous reaction, even at -33C.
Lithium Carbide: Burns in sulfur vapor.
Magnesium: Vigorous reaction with molten sulfur or its vapor.
Magnesium Bromate: When both are finely divided, explosion with heat,
percussion, or friction.

Magnesium Chlorate: When both are finely divided, explosion with heat,
percussion, or friction.

Magnesium Iodate: When both are finely divided, explosion with heat,
percussion, or friction.

Mercuric Nitrate: Possible explosion.
Mercuric Oxide: Explosion when heated.
Mercurous Oxide: Ignition on light impact.
Mercury (I) Oxide: Ignition on frictional initiation.
Mercury (II) Oxide: Explosion on heating.
Metal Acetylides of Carbides: Possible ignition.
Metal Chlorates: Powerfully explosive, sensitive to friction or
shock.


ISSUE DATE: 06/13/95 SUPERSEDES: 02/19/93 PAGE 6 OF 10

MATERIAL SAFETY DATA SHEET

SULFUR

SECTION VI - REACTIVITY DATA (continued)

Incompatibilities: Metal Halogenates: Possible violent or explosive reaction.
(continued) Metal Oxides: Possible ignition or explosion on initiation.
Metals: Possible ignition or explosion.
Monorubidium Acetylide: Ignites in molten sulfur.
Nickel Powder: Ignition and incandescence in boiling sulfur or its
vapor at 600C.

Nitrogen Dioxide: Sulfur burns vigorously.
Osmium: Ignition and incandescence in boiling sulfur or its
vapor at 600C.

Oxidants: Possible ignition or explosion.
Palladium: Ignition and incandescence on heating.
Perchlorates (Inorganic): Explosive on impact.
Permanganates: Formation of an explosive mixture.
Phosphorus: Ignition or explosion.
Phosphorus, Red: Violent exothermic reaction or explosion.
Phosphorus, Yellow: Ignition or explosion on heating.
Phosphorus Trioxide: Violent reaction or explosion.
Potassium: Violent reaction on warming.
Potassium: Vapors of both react with chemiluminescence at
300C and low pressure.

Potassium Bromate: Unstable mixture which may ignite after several
hours. When both are finely divided, explosion
may occur with heat, percussion, or friction.

Potassium Chlorate: Ignition at 160-162C. When both are finely
divided, explosion with heat, percussion, or
friction.

Potassium Chlorite: Violent reaction.
Potassium Iodate: When both are finely divided, explosion with heat,
percussion, or friction.

Potassium Nitrate and Arsenic
Trisulfide:
Pyrotechnic formulation.
Potassium Nitride: Highly flammable mixture which evolves
ammonia and hydrogen sulfide.

Potassium Perchlorate: Explosion on moderately strong impact.
Potassium Permanganate: Possible explosion on heating.
Rhodium: Ignition and incandescence on heating.
Rubidium (Molten): Ignition in the vapor at 200-300C.
Rubidium Acetylene Carbide: Ignition.
Selenium: Ignition.
Selenium Carbide: When heated, incandesces with the vapor.
Silver Bromate: Ignition at 73-75C. Explosive reaction in
presence of water.

Silver Chlorate: Possible spontaneous ignition. Ignition at 74C.
Silver Chlorite: Explosion on rubbing.
Silver Nitrate: Explosion on percussion.

ISSUE DATE: 06/13/95 SUPERSEDES: 02/19/93 PAGE 7 OF 10

MATERIAL SAFETY DATA SHEET

SULFUR

SECTION VI - REACTIVITY DATA (continued)

Incompatibilities: Silver Oxide: Ignition on grinding.
(Continued) Sodium: Violent or explosive reaction with heat or friction.
Sodium Bromate: When both are finely divided, explosion with heat,
percussion, or friction.

Sodium Chlorate: When both are finely divided, explosion with heat,
percussion, or friction.

Sodium Chlorite: Ignition in presence of water.
Sodium Hydride: Vigorous reaction with vapors.
Sodium Iodate: When both are finely divided, explosion with heat,
percussion, or friction.

Sodium Nitrate and Charcoal: Explosion.
Sodium Peroxide: Explosive mixture.
Stannic Iodide and Potassium: Explosion on impact.
Stannic Iodide and Sodium: Explosion on impact.
Static Discharges: Easily ignited due to very low minimum ignition
energy.

Steel: Attacked corrosively in presence of moisture.
Strontium Carbide: Incandescence or ignition in vapors about 500C.
Strontium Carbide and Selenium: Incandescence at 500C.
Sulfur Dichloride: Very violent explosion on impact.
Tetraphenyllead: Possible explosion.
Thallic Oxide: Explosion on grinding.
Thorium: Ignition and incandescence with heating.
Thorium Carbide: Incandesces when heated. Ignites in the vapors
about 500C.

Tin: Vigorous reaction with incandescence. Ignition
on heating.

Uranium: Incandescence and ignition with boiling sulfur or
its vapor.

Uranium Carbide: Ignition in the vapors about 500C.
Zinc Bromate: When both are finely divided, explosion with heat,
percussion, or friction.

Zinc Chlorate: When both are finely divided, explosion with heat,
percussion, or friction.

Zinc Iodate: When both are finely divided, explosion with heat,
percussion, or friction.

Zinc Powder: Explosive reaction on warming.

Decomposition: Combustion may release toxic oxides of sulfur, some of which may react with air and
moisture to produce corrosive sulfurous and sulfuric acids. Toxic and corrosive
hydrogen sulfide may be generated by molten sulfur.


Polymerization: Hazardous polymerization has not been reported to occur under normal temperatures
and pressures.



ISSUE DATE: 06/13/95 SUPERSEDES: 02/19/93 PAGE 8 OF 10

MATERIAL SAFETY DATA SHEET

SULFUR

SECTION VII- SPILL OR LEAK PROCEDURES

Steps to Be Taken in Case Material is Released or Spilled

Small Spill: Shut off ignition sources. Do not touch spilled material. With clean shovel, place material
into clean, dry container and cover; move containers from spill area.


Large Spill: Shut off ignition sources. Do not touch spilled material. Wet down with water and dike
for later disposal. No smoking, flames, or flares in hazard area! Keep unnecessary
people away. Isolate hazard area and deny entry.


Waste Disposal Method

Waste should be mixed with four times its weight of crushed limestone, marble, or shell, and then buried
at a permitted disposal site.


SECTION VIII- PROTECTIVE EQUIPMENT TO BE USED

Ventilation: Provide local exhaust or process enclosure ventilation to meet the published exposure
limits. Ventilation equipment must be explosion-proof.


Respirator: In routine handling of molten sulfur in adequately ventilated premises, respiratory
protective equipment is not required, but should be available nearby.


For areas containing sulfur dust, the specific respirator selected must be based on the
contamination levels found in the work place, must not exceed the working limits of
the respirator, and be jointly approved by the National Institute for Occupational Safety
and Health and the Mine Safety and Health Administration.


The following respirators are recommended based on the data found in the Physical
Data and Health Hazard Data sections. They are ranked in order from minimum to
maximum respiratory protection:


Chemical cartridge respirator with an organic vapor cartridge(s) with a high-
efficiency particulate filter and full facepiece.


High-efficiency particulate respirator with a full facepiece.

Powered air-purifying respirator with a high-efficiency filter with a full facepiece.

Type "C" supplied-air respirator with a full facepiece operated in
pressure-demand or other positive pressure mode, or with a full facepiece,
helmet, or hood operated in continuous-flow mode.


Self-contained breathing apparatus with a full facepiece operated in
pressure-demand or other positive pressure mode.



ISSUE DATE: 06/13/95 SUPERSEDES: 02/19/93 PAGE 9 OF 10





MATERIAL SAFETY DATA SHEET

SULFUR

SECTION VIII- PROTECTIVE EQUIPMENT TO BE USED

Respirator: For firefighting and other immediately dangerous to life or health conditions:
(continued)
Self-contained breathing apparatus with a full facepiece operated in
pressure-demand or other positive pressure mode.


Supplied-air respirator with a full facepiece operated in pressure-demand or other
positive pressure mode in combination with an auxiliary self-contained breathing
apparatus operated in pressure-demand or other positive pressure mode.


Clothing: Employees operating equipment containing molten sulfur should wear clothing capable
of protecting the chest and arms, trousers without cuffs, and high-top shoes. When
making connections or other changes in molten sulfur piping, leather protective clothing
may be needed.


Gloves: Employee must wear heat-resistant gloves when working with molten sulfur.

Eye Protection: Employee must wear splash-proof or dust-resistant safety goggles to prevent eye
contact with this substance. When making connections or other changes in molten
sulfur piping, full face shields (in addition to safety glasses or goggles) should be worn.




SECTION IX - SPECIAL PRECAUTIONS OR OTHER COMMENTS




















Disclaimer
The information contained herein is believed to be accurate, but is not warranted to be, whether originating within the company or not. Health and safety precautions in this data sheet
may not be adequate for all individuals and/or situations. Recipients are advised to confirm in advance of need that the information is current, applicable, and suitable to their
circumstances. It is the end users responsibility to evaluate and use this product safely, and to comply with all applicable laws and regulations. No statement made in this data sheet
shall be construed as a permission or recommendation for use of any product in a manner that might infringe existing patents. No warranty is made, either expressed or implied.
ISSUE DATE: 06/13/95 SUPERSEDES: 02/19/93 PAGE 10 OF 10


MATERIAL SAFETY DATA SHEET

AMMONIA

SECTION I - PRODUCT IDENTIFICATION

Substance: AMMONIA CAS Number: 7664-41-7

Trade Names / Synonyms: Ammonia Anhydrous; Ammonia Gas; Spirit of Hartshorn

Molecular Formula: NH
3
Molecular Weight: 17.03

General or Generic ID: Inorganic Gas

SECTION II - COMPONENTS

Component: Ammonia Percent: > 99.0

Other Contaminants:

Exposure Limits: Ammonia
50 PPM OSHA TWA per 8-hour working day
35 PPM ACGIH STEL
50 PPM NIOSH recommended 5 minute ceiling

SECTION III - PHYSICAL DATA

Description Colorless gas at atmospheric temperature and pressure, with a pungent odor.

Melting Point: -108F (-78C) Boiling Point: -28F (-33C)

Liquid Specific Gravity: 0.77 Vapor Specific Gravity: 0.59
(water = 1.0) (air = 1.0)

Vapor Pressure: 147 PSIA (10 atm) @ 78F (25C)

Odor Threshold: 20 PPM

Solubility in Water: 579 g/l @ 60F (15C), 444 g/l @ 68F (20C)

Other Solvents:

Other Physical Data:











ISSUE DATE: 06/29/06 SUPERSEDES: 02/19/93 PAGE 1 OF 5

MATERIAL SAFETY DATA SHEET

AMMONIA

SECTION IV - FIRE AND EXPLOSION INFORMATION

Fire and Explosion Hazard: Ammonia is a low fire hazard when exposed to heat or flame
because it is difficult to ignite. It is a moderate explosion hazard
when exposed to flame or fire. Air-ammonia mixtures can detonate
in a fire.


Auto-Ignition Temperature: 1204F (651C) Flash Point Temperature: N/A


Explosive Limits in Air: Lower: 15% Upper: 28%

Extinguishing Media: Water Fog.

Hazardous Decomposition Products: Toxic fumes of NH
3
and NO
X
.

Fire-Fighting Procedures: Stop flow of gas. Wear self-contained breathing apparatus with a
full facepiece operated in pressure-demand mode and full body
protection when fighting fires.



SECTION V- HEALTH HAZARD DATA

Permissible Exposure Level: 50 PPM

Threshold Limit Value: 25 PPM

Health Effects from Exposure


Swallowing: Ingestion of a gas is unlikely.

Inhalation: The life hazard from ammonia is due to its damage to the lungs when inhaled. When
inhaled, ammonia is both an irritant and an asphyxiant, and can cause respiratory
distress. Ammonia can usually be detected at levels of 20-50 PPM. There will be
noticeable irritation of the eyes and nasal passages when exposed to 100 PPM, and
severe irritation of the throat, nasal passages, and upper respiratory tract at 400 PPM.
At 1700 PPM, there will be severe coughing and bronchial spasms, and an exposure of
30 minutes or less may be fatal. Concentrations of 5000 PPM and above are fatal
almost immediately, causing serious edema of the lungs, strangulation, and
asphyxiation.


Eye Contact: This gas is dangerous to the eyes, as it causes irritation at 40-100 PPM. Prolonged
exposure to 700 PPM or more can cause extensive injuries to the eyes - irritation,
hemorrhages, swollen lids, corneal ulcers, even partial or total loss of sight.


Skin Contact: Ammonia will irritate the skin, particularly if the skin is moist, to the point of causing
chemical burns from prolonged exposure.



ISSUE DATE: 06/29/06 SUPERSEDES: 02/19/93 PAGE 2 OF 5


MATERIAL SAFETY DATA SHEET

AMMONIA

SECTION V - HEALTH HAZARD DATA (continued)

First Aid Measures

Swallowing: Treat symptomatically and supportively. Get medical attention immediately. If vomiting
occurs, keep head lower than hips to prevent aspiration.


Inhalation: Where breathing is weak, administer oxygen or mixtures of carbon dioxide and oxygen,
containing not more than 5% carbon dioxide. It should be administered intermittently
for periods of two minutes over a total time not to exceed fifteen minutes. If breathing
has ceased, start artificial respiration immediately, by trained personnel only. Artificial
respiration, when administered by an inexperienced person, is definitely hazardous
following exposure to ammonia, and should be avoided where possible. The use of a
pulmotor is definitely not recommended as its more violent action will irritate and may
severely injure the lungs. A resuscitator used with oxygen and operated by a trained
person is recommended. Keep the patient warm and still, and get medical attention
immediately.


Eye Contact: Hold the lids open and pour clean water over the eyeball and lids (or use an eye
irrigation fountain). Wash thoroughly in this way for 15 minutes. A doctor, preferably
an eye specialist, should be summoned immediately


Skin Contact: Speed is essential. Strip the ammonia-saturated clothing from the body immediately.
Flood affected areas continuously with clean water for at least 15 minutes. Do not
cover burns with clothing or dressings. Allow them to remain open to the air.


























ISSUE DATE: 06/29/06 SUPERSEDES: 02/19/93 PAGE 3 OF 5

MATERIAL SAFETY DATA SHEET

AMMONIA

SECTION VI- REACTIVITY DATA

Reactivity: Stable under normal temperatures and pressures.

Incompatibilities: Acetaldehyde Nitrogen Dioxide
Acrolein Nitrogen Tetraoxide
Ammonium Peroxo Disulfate Nitrogen Trichloride
Antimony Nitrogen Trifluoride
Antimony Hydride Nitryl Chloride
Boron Oxygen + Platinum
Boron Halides Oxygen Difluoride
Boron Triiodide Phosphorus Pentoxide
Bromine Pentafluoride Phosphorus Trioxide
Chloric Acid Picric Acid
Chlorine Azide Potassium + Arsine
Chlorine Monoxide Potassium + Phosphine
Chlorine Trifluoride Potassium + Sodium Nitrite
Chlorites Potassium Chlorate
Chlorosilane Potassium Ferricyanide
Chromium Trioxide Potassium Mercuric Cyanide
Chromyl Chloride Silver
Dichlorine Oxide Silver Chloride
Ethylene Dichloride + Liquid Ammonia Silver Nitrate
Ethylene Oxide Silver Oxide
Gold Sodium + Carbon Monoxide
Gold (III) Chloride Sulfur
Halogens Sulfur Dichloride
Hexachloromelamine Tellurium
Hydrazine + Alkali Metals Tellurium Chloride
Hydrogen Bromide Tellurium Hydropentachloride
Hydrogen Peroxide Tetramethyl Ammonium Amide
Hypochlorous Acid Thionyl Chloride
Magnesium Perchlorate Thiotrithiazyl Chloride
Mercury Trichloromelamine
Nitric Acid Trioxygen Difluoride

Polymerization: Cannot occur.

SECTION VII - SPILL OR LEAK PROCEDURES

Steps to Be Taken in Case Material is Released or Spilled

Notify safety personnel of significant leaks. Exclude all from area except those assigned to leak and spill
control who are using full protective gear (see Section VIII). Provide ventilation. Locate and control
leakage.


Waste Disposal Method

If water is used to knock-down vapors, it will be corrosive and toxic, and should be diked for containment.
Add suitable agent to neutralize to 7 pH prior to disposal.


ISSUE DATE: 06/29/06 SUPERSEDES: 02/19/93 PAGE 4 OF 5

MATERIAL SAFETY DATA SHEET

AMMONIA

SECTION VIII - PROTECTIVE EQUIPMENT TO BE USED

Ventilation: Provide local exhaust or process enclosure ventilation to meet the published exposure
limits. Ventilation equipment must be explosion-proof.


Respirator: If work place exposure limit(s) of product or any component is exceeded (see Section
II), a NIOSH/MSHA approved air supplied respirator is advised in absence of proper
environmental control. OSHA regulations also permit other NIOSH/MSHA respirators
(negative pressure type) under specified conditions (see your safety equipment
supplier). Engineering or administrative controls should be implemented to reduce
exposure.


Clothing: To prevent repeated or prolonged skin contact, wear impervious clothing and boots.

Gloves: Wear resistant gloves such as neoprene, nitrile rubber, butyl rubber.

Eye Protection: Employee must wear splash-proof or dust resistant safety goggles and a faceshield to
prevent contact with this substance.


Where there is any possibility that an employee's eyes may be exposed to this
substance, the employer shall provide an eye-wash fountain within the immediate work
area for emergency use.





SECTION IX - SPECIAL PRECAUTIONS OR OTHER COMMENTS




















DISCLAIMER
The information contained herein is believed to be accurate, but is not warranted to be, whether originating within the company or not. Health and safety precautions in this data
sheet may not be adequate for all individuals and/or situations. Recipients are advised to confirm in advance of need that the information is current, applicable, and suitable to their
circumstances. It is the end user's responsibility to evaluate and use this product safely, and to comply with all applicable laws and regulations. No statement made in this data
sheet shall be construed as a permission or recommendation for use of any product in a manner that might infringe existing patents. No warranty is made, either expressed or
implied.

ISSUE DATE: 06/29/06 SUPERSEDES: 02/19/93 PAGE 5 OF 5








MATERIAL SAFETY DATA SHEET

METHYLDIETHANOLAMINE

SECTION I - PRODUCT IDENTIFICATION

Substance: METHYLDIETHANOLAMINE CAS Number: 105-59-9


Trade Names / Synonyms: MDEA; n-Methyldiethanolamine; n-Methyliminodiethanol;
n-Methyl-2,2'-iminodiethanol; N,N-di(2-hydroxyethyl)-N-methylamine; 2,2'-
(Methylimino) bis-ethanol


Molecular Formula: CH
3
-N-(CH
2
CH
2
OH)
2
Molecular Weight: 119.17

General or Generic ID: Organic Base

SECTION II - COMPONENTS

Component: Methyldiethanolamine Percent: > 99.0

Other Contaminants: Often stored and transported as an aqueous solution containing about 10% water
by weight.


Exposure Limits: Methyldiethanolamine

There are no standards or regulations concerning MDEA.

SECTION III - PHYSICAL DATA

Description: Clear, colorless, viscous liquid.

Melting Point: -6F (-21C) Boiling Point: 477F (247C)

Liquid Specific Gravity: 1.042 Vapor Specific Gravity 4.11
(water = 1.0) (air = 1.0)

Vapor Pressure: < 0.0002 PSIA (0.01 mm Hg) @ 68F (20C)

Odor Threshold: MDEA has a slight ammoniacal odor.

Solubility in Water: MDEA is completely soluble in water.

Other Solvents:

Other Physical Data:








ISSUE DATE: 01/25/95 SUPERSEDES: PAGE 1 OF 3

MATERIAL SAFETY DATA SHEET

METHYLDIETHANOLAMINE

SECTION IV- FIRE AND EXPLOSION INFORMATION
Fire and Explosion Hazard: MDEA is considered a slight fire hazard when exposed to heat or flame.

Auto-Ignition Temperature: N/A Flash Point Temperature: 260F (127C)

Explosive Limits in Air: not determined

Extinguishing Media: Small Fire - dry chemical or CO
2
.
Large Fire - water fog, alcohol foam, polymer foam, ordinary foam.

Fire-Fighting Procedures: Wear positive pressure, self-contained breathing apparatus.
SECTION V - HEALTH HAZARD DATA
Permissible Exposure Level: None established.

Threshold Limit Value: None established.

Health Effects from Exposure

Swallowing: Single dose oral toxicity is low. The oral LD50 for rats is 4780 mg/kg for MDEA.
Amounts ingested incidental to industrial handling are not likely to cause injury;
however, ingestion of larger amounts may cause injury. Ingestion of MDEA can
cause nausea, vomiting, and abdominal discomfort.


Inhalation:: At room temperature, exposure to vapors is unlikely due to physical properties.
Higher temperatures may generate vapor levels sufficient to cause irritation.


Eye Contact: May cause moderately severe irritation with corneal injury.

Skin Contact: Prolonged or repeated exposure may cause skin irritation, even a burn. A single
prolonged exposure is not likely to result in the material being absorbed through
skin in harmful amounts. The dermal LD50 has not been determined.


Systemic Effects: Repeated excessive exposures may cause kidney effects.

First Aid Measures

Swallowing: Induce vomiting if large amounts are ingested. Consult medical personnel.

Inhalation: Remove to fresh air if effects occur. Consult a physician.

Eye Contact: Flush eyes with large amounts of water for at least 15 minutes. Take the patient to a
physician, preferably an eye specialist, at once.


Skin Contact: Flush the affected area with plenty of water. If exposure has produced a burn, it
should be treated like a thermal burn, with treatment based on the physician's
judgement. Contaminated clothing should be removed and washed before reuse.
Contaminated leather articles (shoes, belts, etc.) should be removed and destroyed.

ISSUE DATE: 01/25/95 SUPERSEDES: PAGE 2 OF 3




MATERIAL SAFETY DATA SHEET

METHYLDIETHANOLAMINE

SECTION VI- REACTIVITY DATA

Reactivity: Stable under normal storage conditions.

Incompatibilities: Incompatible with strong oxidizers and strong acids. Do not allow
MDEA to contact sodium nitrite (NaNO
2
) or other nitrosating
agents, as nitrosamines (suspected cancer-causing agents) could
be formed.


Hazardous Decomposition Products: Nitrous oxides, carbon monoxide, and/or carbon dioxide.

Polymerization Hazardous polymerization will not occur.

SECTION VII - SPILL OR LEAK PROCEDURES

Steps to Be Taken in Case Material is Released or Spilled

Wear suitable protective equipment, especially eye protection. Collect for disposal. Toxic to fish; avoid
discharge to natural waters.


Waste Disposal Method

Burn in approved incinerator. Follow all local, state, and federal requirements for disposal.

SECTION VIII - PROTECTIVE EQUIPMENT TO BE USED

Ventilation: General (mechanical) room ventilation is expected to be satisfactory.

Respirator: None required in normal use. If irritation of the nose and/or respiratory system is
experienced, use an approved air-purifying respirator.


Clothing: Use protective clothing impervious to this material. Selection of specific items such as
boots, apron, or full-body suit will depend on operation.


Gloves: Use gloves impervious to this material, such as rubber.

Eye Protection: Use chemical goggles.

SECTION IX - SPECIAL PRECAUTIONS OR OTHER COMMENTS

Avoid contact with eyes, skin, and clothing when handling and storing MDEA. Wash thoroughly after
handling.





Disclaimer
The information contained herein is believed to be accurate, but is not warranted to be, whether originating within the company or not. Health and safety precautions in this data sheet
may not be adequate for all individuals and/or situations. Recipients are advised to confirm in advance of need that the information is current, applicable, and suitable to their
circumstances. It is the end users responsibility to evaluate and use this product safely, and to comply with all applicable laws and regulations. No statement made in this data sheet
shall be construed as a permission or recommendation for use of any product in a manner that might infringe existing patents. No warranty is made, either expressed or implied.
ISSUE DATE: 01/25/95 SUPERSEDES: PAGE 3 OF 3


MATERIAL SAFETY DATA SHEET

SODIUM HYDROXIDE

SECTION I - PRODUCT IDENTIFICATION
Substance: SODIUM HYDROXIDE CAS Number: 1310-73-2

Trade Names / Synonyms: Caustic; Caustic Soda; Caustic Soda Liquid; Liquid Caustic; Lye;
Lye Solution; Soda Lye; Sodium Hydrate; Quaker Caustic Blend;
White Caustic


Molecular Formula: NaOH Molecular Weight: 40.00

General or Generic ID: Alkali

SECTION II - COMPONENTS
Component: Sodium Hydroxide Percent: > 99.0

Other Contaminants: Often stored and transported as an aqueous solution. Common strengths are
25, 50, and 73 weight percent NaOH.


Exposure Limits: Sodium Hydroxide
2 mg/m
3
(2 PPM) OSHA TWA for an 8-hour working day
2 mg/m
3
(2 PPM) ACGIH ceiling
2 mg/m
3
(2 PPM) NIOSH recommended ceiling

SECTION III - PHYSICAL DATA
Description: Pure sodium hydroxide is a white solid. When dissolved in water, NaOH forms
a clear, colorless or water-white, strongly alkaline liquid. Neither form has an
odor.


Melting Point: Solid: 608F (320C)
25 wt% solution: -2F (-19C)
50 wt% solution: 50F (10C)

Boiling Point: Solid: 2534F (1390C)
25 wt% solution: 232F (111C)
50 wt% solution: 288F (142C)

Specific Gravity: Solid: 2.13
(water = 1.0) 25 wt% solution: 1.27
50 wt% solution: 1.53

Vapor Pressure: Solid: 0.02 PSIA (1 mm Hg) @ 1362F (739C)

Odor Threshold: N/A

Solubility in Water: At 60F (15C), more than 50 wt% will dissolve in water.

Other Solvents:

Other Physical Data:


ISSUE DATE: 02/19/93 SUPERSEDES: PAGE 1 OF 5

MATERIAL SAFETY DATA SHEET

SODIUM HYDROXIDE

SECTION IV- FIRE AND EXPLOSION INFORMATION

Fire and Explosion Hazard: Sodium hydroxide and its water solutions are not flammable. However,
adding water to NaOH or solutions of NaOH can cause localized
overheating due to its heat of dilution.

Sodium hydroxide will generate gaseous hydrogen (which is flammable
and/or explosive) when in contact with aluminum, copper, tin, zinc, and
their alloys.


Auto-Ignition Temperature: N/A Flash Point Temperature: N/A

Explosive Limits in Air: Lower: N/A Upper: N/A

Extinguishing Media: Not combustible. Use extinguishing agents as may be suitable for
material in surrounding fire.


Fire-Fighting Procedures: Not combustible. Use clothing and safety equipment as may be suitable
for sodium hydroxide and materials in the surrounding fire.






SECTION V - HEALTH HAZARD DATA

Permissible Exposure Level: 2 mg/m
3
(approximately 2 PPMW)

Threshold Limit Value: 2 mg/m
3
(approximately 2 PPMW) ceiling

Health Effects from Exposure

Swallowing: Acutely toxic if swallowed, causing severe burns and scarring to the mouth,
throat, esophagus, and stomach, and may lead to death. Squamous cell
carcinoma of the esophagus can occur years after the exposure.


Inhalation: Inhalation of dust or mist can cause injury to the entire respiratory tract. The
effects of inhalation depend on the severity of the exposure, ranging from mild
irritation of the mucous membranes to severe pneumonitis.


Eye Contact: Contact with the eyes may cause irritation and, with greater exposure, severe
burns and possible blindness.


Skin Contact: Skin contact may cause burns, frequently with deep ulceration and scarring.
Prolonged contact, even with dilute solutions, can cause tissue damage.







ISSUE DATE: 02/19/93 SUPERSEDES: PAGE 2 OF 5

MATERIAL SAFETY DATA SHEET

SODIUM HYDROXIDE

SECTION V - HEALTH HAZARD DATA (continued)

First Aid Measures

Swallowing: Do not induce vomiting - this will cause further damage to the throat and
esophagus. Dilute by giving water to the patient immediately. Vinegar, 1% acetic
acid solution, citrus fruit juices, or 5% citric acid solution may also be administered
to help neutralize the alkaline solution. Follow this with milk, egg white in water, or
milk of magnesia. Keep the patient warm and still, and summon a physician
immediately.


Inhalation: Remove the patient to fresh air at once. If breathing has stopped, begin artificial
respiration immediately. Keep the patient warm and still, and summon a physician
immediately.


Eye Contact: Immediately begin flushing the eyes with large amounts of water, preferably with
an eye wash fountain. Continue flushing for at least 15 minutes, forcibly holding
the eyelids apart and rotating the eyeball, to ensure complete irrigation of all eye
and lid tissue. A physician, preferably an eye specialist, should be summoned
immediately.


Skin Contact: Immediately flush the affected areas with large amounts of water. If large areas of
the body are contaminated, or if clothing has been penetrated to the skin,
immediately use a safety shower, preferably removing clothing while under the
shower. Continue flushing the areas for at least 15 minutes. If available, follow
the water flush with a generous application of vinegar or 1% acetic acid solution to
neutralize the residual NaOH. After the acid treatment, apply a good protective
dressing as with any other burn and take the patient to a physician. Contaminated
clothing should be washed before reuse. Contaminated leather articles (shoes,
belts, etc.) should be discarded.























ISSUE DATE: 02/19/93 SUPERSEDES: PAGE 3 OF 5




MATERIAL SAFETY DATA SHEET

SODIUM HYDROXIDE

SECTION VI- REACTIVITY DATA

Reactivity: Stable.

Incompatibilities: Acetaldehyde Hydroquinone
Acetic Acid Magnesium
Acetic Anhydride Maleic Anhydride
Acrolein Methanol + Tetrachlorobenzene
Acrylonitrile 4-Methyl-2-nitrophenol
Allyl Alcohol 3-Methyl-2-penten-4-yn-1-ol
Allyl Chloride Nitric Acid
Aluminum Nitroethane (forms shock-sensitive salts)
Chlorine Trifluoride Nitromethane (forms shock-sensitive salts)
Chloroform + Methanol Nitroparaffins (forms shock-sensitive salts)
Chlorohydrin (Chlorhydrin) Nitropropane (forms shock-sensitive salts)
4-Chloro-2-methylphenol Oleum (fuming Sulfuric Acid)
Chloronitrotoluene Pentol
Chlorosulfonic Acid Phosphorus
(Chlorosulfuric Acid) Phosphorus Pentoxide
Cinnamaldehyde -Propiolactone (2-Oxetanone)
Copper Strong Mineral or Organic Acids
Cyanogen Azide Sulfuric Acid
Diborane (Boron Hydride) 1,2,4,5-Tetrachlorobenzene
1,2-Dichloroethylene Tetrahydrofuran
Difluoroethane Tin
Ethylene Cyanohydrin 1,1,1-Trichloroethanol
(Hydracrylonitrile) Trichloroethylene
Glyoxal Trichloronitromethane
Hydrochloric Acid Trifluoride
(Hydrogen Chloride) Water
Hydrofluoric Acid Zinc
(Hydrogen Fluoride) Zirconium

Polymerization: Hazardous polymerization cannot occur.

Other Hazards: Adding water to sodium hydroxide or sodium hydroxide solutions may cause
localized overheating and spattering.















ISSUE DATE: 02/19/93 SUPERSEDES: PAGE 4 OF 5


MATERIAL SAFETY DATA SHEET

SODIUM HYDROXIDE

SECTION VII - SPILL OR LEAK PROCEDURES

Steps to Be Taken in Case Material is Released or Spilled

Cleanup personnel must wear proper protective equipment (refer to Section VIII). Completely contain
spilled material with dikes, sandbags, etc., and prevent run-off into ground or surface waters or
sewers. Recover as much material as possible into containers for disposal. Remaining material may
be diluted with water and neutralized with dilute hydrochloric acid. Neutralization products, both liquid
and solid, must be recovered for disposal.


Waste Disposal Method

Recovered solids or liquids may be sent to a licensed reclaimer or disposed of in a permitted waste
management facility. Consult federal, state, or local disposal authorities for approved procedures.




SECTION VIII - PROTECTIVE EQUIPMENT TO BE USED

Ventilation: Ventilation is not usually required for caustic solutions. Avoid creation of mist or
spray. If present, wear appropriate safety clothing and provide local exhaust
systems.


Respirator: Provide mist protection where applicable. Use NIOSH or MSHA approved
respirators.


Clothing: Employees should wear impervious rubber, neoprene, or vinyl boots, overalls, and/or
full-body suits.


Gloves: Use impervious rubber, neoprene, or vinyl gloves.

Eye Protection: Use chemical goggles and face shield.



SECTION IX - SPECIAL PRECAUTIONS OR OTHER COMMENTS

When diluting sodium hydroxide, use agitation (mixing) and add the concentrated sodium hydroxide to
water at a controlled rate to control the heat of dilution and avoid spattering. Never add water to sodium
hydroxide.









Disclaimer
The information contained herein is believed to be accurate, but is not warranted to be, whether originating within the company or not. Health and safety precautions in this data sheet
may not be adequate for all individuals and/or situations. Recipients are advised to confirm in advance of need that the information is current, applicable, and suitable to their
circumstances. It is the end users responsibility to evaluate and use this product safely, and to comply with all applicable laws and regulations. No statement made in this data sheet
shall be construed as a permission or recommendation for use of any product in a manner that might infringe existing patents. No warranty is made, either expressed or implied.
ISSUE DATE: 02/19/93 SUPERSEDES: PAGE 5 OF 5


Activated Alumina S-2001/ESM-221 Revision Number: 1
Page 1 of 9 June 2008
MATERI AL SAFETY DATA SHEET
1. CHEMICAL PRODUCT AND COMPANY INFORMATION

Product Name: Activated Alumina S-2001/ESM-221

Product Use: Alumina

ASM Catalysts, LLC Euro Support B.V.
8550 United Plaza Blvd., Suite 702 Kortegracht 26
Baton Rouge, LA 70809-0200 3811 KH Amersfoort
USA The Netherlands
Tel.: +1-225-752-4276 Tel: +31-33-4650465
Fax: +1-225-922-4550 Fax: +31-33-4650721


2. HAZARDS IDENTIFICATION
Emergency Overview:
Repeated or prolonged exposure may irritate eyes, skin and respiratory system. The product gets hot as it first adsorbs
water.

Form: Spheres
Color: White

Potential Health Effects:

Primary Routes of Exposure: Contact with skin and eyes. Exposure may also occur via inhalation or
ingestion if product dust is generated.

Eye Contact: Dust and/or product may cause eye discomfort and/or irritation seen as tearing and reddening.

Skin Contact: Repeated or prolonged exposure may cause skin irritation.

Ingestion: The product is considered to have a low order of oral toxicity.

Inhalation: Exposure to dust particles generated from this material may cause irritation of the respiratory tract.
Irritation may be accompanied by coughing and chest discomfort.

Chronic Effects: Prolonged or repeated inhalation of dust generated from this material may cause lung injury.


Activated Alumina S-2001/ESM-221 Revision Number: 1
Page 2 of 9 June 2008


Carcinogenicity Classification:

International Agency for Research on Cancer (IARC):
Neither the product nor the components are classified.

U.S. National Toxicology Program (NTP):
Neither the product nor the components are classified.

U.S. Occupational Safety and Health Administration (OSHA):
Neither the product nor the components are classified or regulated.

American Conference of Governmental Industrial Hygienists (ACGIH):
Aluminum oxide Not Classifiable as a Human Carcinogen (A4).

3. COMPOSITION/INFORMATION ON INGREDIENTS
INGREDIENT
& CAS NO.
% WEIGHT ACGIH TLV-TWA OSHA PEL-TWA UNITS
Aluminum oxide (non-fibrous)
1344-28-1
<95

1(R)

15 (TD)
5(R)
mg/m
3

Water
7732-18-5
<10

N.E.

N.E. N.A.

Abbreviations:
N.A. - Not Applicable RD - Respirable Dust Fu - Fume IS - Insoluble
N.E. - None Established R - Respirable Fraction I - Inhalable FuD - Fume and Dust
STEL - Short Term Exposure Limit F - Respirable Fibers TD - Total Dust SC - Soluble Compounds

4. FIRST AID MEASURES
Eye contact: Flush immediately with plenty of water for at least 15 minutes. If eye irritation persists, consult a physician.

Skin contact: Wash off with soap and plenty of water. If skin irritation persists, call a physician.

After inhalation: Remove the victim into fresh air. If symptoms persist, call a physician.

After ingestion: Drink at least 2 glasses of water. Obtain medical attention. Never give anything by mouth to an
unconscious person.

Notes to physician: This product is a desiccant and generates heat as it adsorbs water. Symptomatic treatment is
advised. The used product can retain material of a hazardous nature. Identify that material and treat symptomatically.


Activated Alumina S-2001/ESM-221 Revision Number: 1
Page 3 of 9 June 2008


5. FIRE FIGHTING MEASURES
Suitable extinguishing media: Non-combustible. Use extinguishing media for surrounding fire.

Unsuitable extinguishing media: N.A.

Fire and explosion hazards: The product itself does not burn. The used product can retain material of a hazardous
nature. Identify that material and inform the fire fighters.

Special protective equipment: In the case of respirable dust and/or fumes, use self-contained breathing apparatus and
dust impervious protective suit.

Flash point: N.A.

6. ACCIDENTAL RELEASE MEASURES
Personal protection: See Section 8.

Environmental precautions: No special environmental precautions required.

Clean-up: Sweep, shovel or vacuum spilled product into appropriate containers (do not use a vacuum if material has
contacted a hydrocarbon material). Pick-up and arrange disposal without creating dust. Never use spilled product. Spilled
product should be disposed of in accordance with all applicable government regulations.

7. HANDLING AND STORAGE
Handling: Handle and open container with care. Avoid formation of dust particles. Avoid contact with skin and eyes.
Provide an electrical ground connection during loading and transfer operations to avoid static discharge in an explosive
atmosphere and to prevent persons handling the product from receiving static shocks.

Storage: Store in original container. Keep in a dry place.

8. EXPOSURE CONTROLS/PERSONAL PROTECTION
Engineering measures: Where natural ventilation is inadequate, especially in confined areas, use mechanical
ventilation, other engineering controls or respiratory protection to prevent inhalation of product dust.

Personal protection equipment: Handle in accordance with good industrial hygiene and safety practice.

Eye protection: Safety glasses or goggles.

Hand protection: Protective gloves.

Skin and body protection: Work uniform and gloves to prevent prolonged contact.

Respiratory protection: In case of insufficient ventilation, wear suitable respiratory equipment. Air-purifying
respirator with NIOSH classification N-95 filter or P-95 (or equivalent) if oil/liquid aerosols are present (42 CFR 84).


Activated Alumina S-2001/ESM-221 Revision Number: 1
Page 4 of 9 June 2008


9. PHYSICAL AND CHEMICAL PROPERTIES
These data do not represent technical or sales specifications.

Form: Spheres Color: White

Odor: None pH: 9 11 (AS)

Boiling point/range: None Melting point/range: N.A.

Flash point: N.A. Autoignition temperature: N.A.

Bulk density: 38-60 lbs/ft
3
Explosion limits: N.A.

Vapor pressure: N.A. Relative density/Specific gravity: 3.0

Vapor density: N.A. Viscosity: N.A.

Water solubility: Insoluble Solubility: N.D.

10. STABILITY
St abil i t y: Stable

Hazardous Decomposi t i on Product s: No decomposition if used as directed. Hydrocarbons and other materials that
contact the product during normal use can be retained on the product. It is reasonable to expect that decomposition
products will come from these retained materials of use. I f the product is subject to extreme temperatures or chemical
conditions, decomposition may occur and he product will include the oxides shown in Section 3.

Condi t i ons/ Mat eri al s t o avoi d: Reacts violently with chlorine trifluoride, producing flames. May cause ethylene oxide
to polymerize violently, releasing heat.


Activated Alumina S-2001/ESM-221 Revision Number: 1
Page 5 of 9 June 2008


11. TOXICOLOGICAL INFORMATION
Acute toxicity:

LD50/oral/rat: No data available.

LD50/dermal/rabbit: No data available.

LD50/inhalation/rat: No data available.

Chronic toxicity: Classification of Ingredients

EC Carcinogenic: Carcinogenicity (ACGIH):
Not listed. A4 (Aluminum oxide)

EC Mutagenic: IARC classification:
Not listed. Not listed.

EC Toxic for Reproduction:
Not listed.

Routes of exposure: Exposure may occur via inhalation, contact with skin and eyes.

Irritation:

Skin (rabbit): No data available.

Eye (rabbit): No data available.

Additional product information:
Avoid repeated exposure.

Additional component information:
No data available.

12. ECOLOGICAL INFORMATION
Mobility: Biodegradation:
No data available. No data available.

Bioaccumulation: Aquatic toxicity:
No data available. No data available.

Further Information:
No information available.


Activated Alumina S-2001/ESM-221 Revision Number: 1
Page 6 of 9 June 2008


13. DISPOSAL CONSIDERATIONS
Provisions relating to waste: EPA Resource Conservation and Recovery Act (RCRA) Hazardous and Solid Waste
Management Regulations.

Disposal information: This product (in its fresh unused state) is not listed by generic name or trademark name in the
U.S. EPAs RCRA regulations and does not possess ay of the four identifying characteristics of hazardous waste
(ignitability, corrosivity, reactivity or toxicity). Materials of a hazardous nature that contact the product during normal use
may be retained on this product. The user of the product must identify the hazards associated with the retained material
in order to assess the waste disposal options.

14. TRANSPORT INFORMATION

UN-No.: Proper shipping name: Packing group:
N.A. Not applicable. N.A.

Transport mode Class Additional Information Remarks

U.S. DOT: Not regulated. Reportable N.A. N.A.
Quantity:
Marine Pollutant DOT: No

ADR/RID: Not regulated. Danger Code: N.A. N.A.

IMDG: Not regulated. Marine pollutant: No N.A.
EmS: N.A.

IATA: Not regulated. Instr. Passenger: N.A. N.A.
Instr. Cargo: N.A.


Activated Alumina S-2001/ESM-221 Revision Number: 1
Page 7 of 9 June 2008


15. REGULATORY INFORMATION
United States

Toxic Substances Control Act (TSCA): All the ingredients of this mixture are registered on the TSCA Chemical
Substance Inventory.

CERCLA (Comprehensive Environmental Response, Compensation, and Liability Act) Reportable Quantity:
The following component(s) of this product is/are subject to release reporting under 40 CFR 302 when release exceeds
the Reportable Quantity (RQ):
--None

SARA Title III (Superfund Amendments and Reauthorization Act of 1986):
Section 302 (Extremely Hazardous Substances):
The following component(s) of this product is/are subject to the emergency planning provisions of 40 CFR 355 when
there are amounts equal to or greater than the Threshold Planning Quantity (TPQ):
--None

Section 313 (toxic Chemicals):
The following component(s) have been specified as Toxic Chemicals under SARA Section 313 and may be subject to the
Toxic Release Inventory (TRI) reporting requirements under 40 CFR 372:
--None

The following components are listed in U.S. State Regulations:
State Reg Reference: State Reg Reference:

California Proposition 65: None.

Massachusetts Right-to-Know: Aluminum oxide

New Jersey Right-To-Know: Aluminum oxide

Pennsylvania Right-to-Know: Aluminum oxide

Note: Other U.S. State Regulations may exist, check your local sources if available.



Activated Alumina S-2001/ESM-221 Revision Number: 1
Page 8 of 9 June 2008

Canada

Canadian Hazardous Products Act:
This product is not classified as a controlled product under regulations pursuant to the Federal Hazardous Product Act
(e.g. WHMIS).

Canadian Environmental Protection Act: All the ingredients of this mixture are notified to CEPA and on the DSL
(Domestic Substances List).


European Union (EU)

European Inventory of Existing Commercial Chemical Substances: All components of this product are included in
EINECS/ELINCS.

Council of European Communities Directive on Classification, Packaging and Labeling of Dangerous
Substances/Preparation (67/548/EEC & 1999/45/EC, as amended):
No Dangerous Goods Label Required.

Additional Governmental Inventories

Australia Inventory of Chemical Substances (AICS): All the ingredients of this mixture appear on the AICS.

China All the ingredients of this mixture appear on the China Inventory.

Japan Existing and New Chemical Substances (ENCS): All the ingredients of this mixture appear on the
ENCS.

Korea Existing and Evaluated Chemical Substances (ECL): All the ingredients of this mixture appear on the
ECL.

Philippines Inventory of Chemicals and Chemical Substances (PICCS): All the ingredients of this mixture
appear on the PICCS.


Activated Alumina S-2001/ESM-221 Revision Number: 1
Page 9 of 9 June 2008


16. OTHER INFORMATION


HMIS - Hazardous Material Identification System:
HMIS Ratings: 0-minimal hazard, 1-slight hazard, 2-moderate hazard, 3-serious hazard, 4-severe hazard

HEALTH: 1
FLAMMABILITY: 0
REACTIVITY: 1

For additional information concerning this product, contact the following:

ASM Catalysts, LLC Euro Support B.V.
8550 United Plaza Blvd., Suite 702 Kortegracht 26
Baton Rouge, LA 70809-0200 3811 KH Amersfoort
USA The Netherlands
Tel: +1-225-752-4276, Fax: +1-225-922-4550 Tel: +31-33-465-0465, Fax: +31-33-465-0721

The data and recommendations presented in this data sheet concerning the use of our product and the materials contained therein are believed to be
accurate and are based on information which is considered reliable as of the date hereof. However, the customer should determine the suitability of
such materials for his purpose before adopting them on a commercial scale. Since the use of our products by others is beyond our control, no
guarantee, express or implied, is made and no responsibility assumed for the use of this material or the results to be obtained therefrom. Information on
this form is furnished for the purpose of compliance with Government Health and Safety Regulations and shall not be used for any other purposes.
Moreover, the recommendations contained in this data sheet are not to be construed as a license to operate under or a recommendation to infringe, any
existing patents, nor should they be confused with state, municipal or insurance requirements, or with national safety codes.

Page 1 of 8



Material Safety Data Sheet (MSDS)

MSDS Number: 6179-12 01/26/2010

EMERGENCY ASSISTANCE

CANUTEC (Canada): 613-996-6666
CHEMTREC (US): 1-800-424-9300

CHEMTREC (International): +1-703-527-3887
(Call Collect)

SECTION I. MATERIAL IDENTIFICATION
PRODUCT:
CRITERION 234 CATALYST

COMMON NAME: Metal Oxide

PRODUCT USE: Hydrotreating Catalyst

SECTION 2. COMPOSITION/INFORMATION ON INGREDIENTS
COMPONENTS OF THE MATERIAL
Component Chemical
Formula
CAS Concentration
Aluminum oxide
Al2O3
1344-28-1 74 - 98 %
Cobalt oxide
CoO
1307-96-6 1 - 5 %
Molybdenum oxide
MoO3
1313-27-5 10 - 19 %


SECTION 3. HAZARDS IDENTIFICATION

EMERGENCY OVERVIEW
Physical Appearance: Blue Extrudates or Spheres. Odorless
Human Health Hazards:
Irritating to eyes and respiratory system.
May cause allergic reaction (rash) with skin contact and asthma-like allergic reaction by inhalation in
sensitive individuals.

Physical Hazards:
No specific hazards.

Environmental Hazards:
Toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment.



CRITERION 234 CATALYST MSDS Number: 6179
Page 2 of 8

Potential Health Effects
Eye:
Mildly irritating to eyes.

Skin:
Mildly irritating to the skin. May cause contact dermatitis (allergic skin rash) in cobalt sensitive
individuals.


Inhalation:
Dusts may be irritating to the nose, throat and respiratory tract. May cause sensitization by inhalation
due to presence of a cobalt compound. Existing respiratory diseases may be aggravated by exposure to
this material.

Ingestion:
Low-level cobalt ingestion is known to cause effects on the heart after a short-term exposure. The
symptoms of heart damage may be a swelling of the feet (edema) and shortness of breath on exertion
or when lying flat on the back (supine).

Other Health Effects:
Molybdenum compounds have a low order of toxicity, may be irritating and may cause anemia.

SECTION 4. FIRST AID MEASURES
Eye Contact:
Flush eyes with water. If persistent irritation occurs, get medical attention.

Skin Contact:
Wash skin with water and, if available, soap. If persistent irritation occurs, get medical attention.

Inhalation:
Move to fresh air. If rapid recovery does not occur, get medical attention.

Ingestion:
Do not induce vomiting. Give nothing by mouth. Get medical attention immediately.

Note to Physicians:
Treat symptomatically. If skin sensitization has developed and a causal relationship has been
confirmed, further exposure should not be allowed.

SECTION 5. FIRE FIGHTING MEASURES
Extinguishing Media:
Material will not burn; use an extinguishing medium appropriate for the surrounding fire.


SECTION 6. ACCIDENTAL RELEASE MEASURES
Precautionary Measures:
Do not breathe dust. Avoid contact with skin and eyes. Avoid dust generation. Wear suitable
protective clothing and gloves. Wear a NIOSH approved respirator if there is a possibility of exposures
above the established occupational exposure limits. (See Section 8 for exposure limits.)

Spill Management:
Prevent contamination of soil and water. Do not wash spills into sewers or other public water systems.
Prevent further leakage or spillage and prevent from entering drains.

CRITERION 234 CATALYST MSDS Number: 6179
Page 3 of 8

Spill Disposal:
Shovel up and place in a labeled, sealable container for subsequent safe disposal.

Environmental Compliance:
Refer to latest state or local regulations to determine if there are disposal or reporting requirements.


SECTION 7. HANDLING AND STORAGE
Handling Recommendations:
Avoid contact with skin and eyes.
Avoid dust generation.
Do not breathe dust.
Do not eat, smoke or drink in areas where catalyst is present.
Use only in well ventilated areas. Use local exhaust extraction.
Take precautionary measures against static discharge.
Ground all equipment.

Storage Recommendations:
Keep container tightly closed and dry.
Reseal plastic liner.


SECTION 8. EXPOSURE CONTROLS/PERSONAL PROTECTION
Engineering Controls:
Use only in well ventilated areas. Use local exhaust extraction.

Hygiene Measures:
Avoid contact with material. Wash hands thoroughly after handling. Do not reuse clothing if
contaminated until thoroughly decontaminated.

Respiratory Protection:
Use either an atmosphere-supplying respirator or an air-purifying respirator for particulates.

Eye Protection:
Wear safety goggles or glasses to prevent eye contact.

Hand Protection:
Wear neoprene, nitrile, PVC or latex gloves to prevent contact.

Body Protection:
When there is a possibility of exposure wear a one piece coated overall with integral hood, safety
boots, chemical-resistant without lace holes.

Chemical Name

Authority

Limits

Special Notations

Aluminum oxide OSHA PEL 15 mg/m total dust
Aluminum oxide OSHA PEL 5 mg/m respirable dust
Aluminum oxide ACGIH TWA 10 mg/m total dust
Cobalt oxide OSHA PEL 0.1 mg/m metal dust & fumes; as Co;
Cancer: 3
Cobalt oxide ACGIH TWA 0.02 mg/m as Co
Cobalt oxide ACGIH BEI 15 g/m as creatinine
Cobalt oxide ACGIH BEI 20 g/m BEI
Molybdenum oxide OSHA PEL 15 mg/m as Mo; total dust
CRITERION 234 CATALYST MSDS Number: 6179
Page 4 of 8

Molybdenum oxide OSHA PEL 5 mg/m as Mo; respirable dust
Molybdenum oxide ACGIH TWA 10 mg/m as Mo; total dust


SECTION 9. PHYSICAL AND CHEMICAL PROPERTIES

Product
Physical & Chemical Properties Characteristics
Appearance and Odor: Blue Extrudates or Spheres. Odorless
Solubility in water: <5%
Bulk density (solids): 0.48 g/cc
Melting point: ~3700

SECTION 10. STABILITY AND REACTIVITY
Stability:
Stable. Hygroscopic.

Materials To Avoid:
Strong acids, strong bases, strong oxidizing agents.



SECTION 11. TOXICOLOGICAL INFORMATION
The hazard determination and the information presented below is based on available data derived from
testing for the material, hazardous components of this material and/or a testing on a substantially
similar material(s). The material tested is indicated in the data.

Acute Lethality
Route Material Tested LD/LC50 Species
Dermal Molybdenum oxide >2000 mg/kg Rat


Sensitization
Route Material Tested Description Species
Dermal Cobalt oxide Sensitizer Human
Inhalation Cobalt oxide Sensitizer Human

Other Health Effects:

Cobalt was used as a defoaming agent in beer at 1 ppm. After a few weeks of exposure beer drinkers were found
to have myocardial effects. Deaths were reported. Medical evaluations found myocardial infarction.

In a lifetime feeding study with cobalt in hamsters, no statistically significant increases in tumors were seen.
Carcinogenicity:
Cobalt oxide is classified by:
IARC as a possible human carcinogen (Group 2B)

CRITERION 234 CATALYST MSDS Number: 6179
Page 5 of 8


SECTION 12. ECOLOGICAL INFORMATION
Ecotoxicological data have not been determined specifically for this material. The information given
below is based on knowledge of the components and the ecotoxicology of similar products.

Toxicity to Aquatic Organisms:
Toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment.

Persistence & Bioaccumulation:
Not inherently biodegradable.

Mobility:
Sinks in water. If product enters soil, one or more constituents will be mobile and may contaminate
groundwater.

Sewage Treatment:
Not toxic at the limit of water solubility.


SECTION 13. DISPOSAL CONSIDERATIONS
Product disposal:
Recover or recycle, if possible. Otherwise: Send to an approved contractor for regeneration or metal
recovery or dispose with a licensed disposal contractor.

Waste Disposal:
If product is unused, see above. If used, evaluate the toxicity and physical properties of the material
you have generated and dispose of the material in accordance with local, state and federal regulations.

Container Disposal:
Empty containers may contain residues. Ensure container is properly cleaned. Remove all packaging
for recovery or waste disposal. DO NOT USE CONTAINER FOR OTHER PURPOSES.

Regulatory Controls:
Comply with all federal, state and local laws regulating the handling and disposal of wastes.

SECTION 14. TRANSPORTATION INFORMATION
Transport Statement:
Not dangerous for conveyance under USA DOT, Canadian TDG, and IATA/ICAO codes. Consult
local laws to determine transportation regulations.

U. S. A. - DEPARTMENT OF TRANSPORTATION (DOT)
Not regulated by DOT (USA).

CANADA - TRANSPORTATION OF DANGEROUS GOODS (TDG)
Not dangerous for conveyance under Canadian TDG.

Maritime transport (IMO)
UN No. UN 3077
Proper Shipping Name ENVIRONMENTALLY HAZARDOUS SUBSTANCE, SOLID,
N.O.S. ( Cobalt compounds )
Class 9
Packing Group III , MARINE POLLUTANT
Hazard symbol MISCELLANEOUS DANGEROUS SUBSTANCES AND ARTICLES
ENVIRONMENT
CRITERION 234 CATALYST MSDS Number: 6179
Page 6 of 8


Air transport ICAO/IATA
Not dangerous for conveyance under IATA/ICAO codes.

SECTION 15. REGULATORY INFORMATION

National Inventories
National Authority Country Status
EINECS/ELINCS EC All ingredients listed.
TSCA USA All ingredients listed.
MITI Japan All ingredients listed.
DSL/NDSL Canada All ingredients listed.
TCCL Korea All ingredients listed.
AICS Australia All ingredients listed.
PICCS Philippines All ingredients listed.
IECS China All ingredients listed.



PRODUCT SAFETY CLASSIFICATIONS
Canada WHMIS
Canadian - Workplace Hazardous Materials Information System (WHMIS)
Class D - Toxic and Infectious Materials Division 2 - Materials Causing other Toxic Effects
Subdivision A - Very Toxic Materials



California Proposition 65
Name on List Classification
Cobalt oxide Carcinogen


Massachusetts
Aluminum oxide Right-To-Know Substances List


Pennsylvania
Aluminum oxide Right-To-Know Hazardous Substance
Molybdenum oxide PA Environmental Hazard E (1 % threshold)
CRITERION 234 CATALYST MSDS Number: 6179
Page 7 of 8


European Community
Label Name CONTAINS COBALT OXIDE / MOLYBDENUM OXIDE
Hazard Symbols Xn: Harmful
N: Dangerous to the Environment
Classification Harmful Dangerous to the Environment
Risk Phrases R48/20/22: Harmful: danger of serious damage to health by prolonged
exposure through inhalation and if swallowed.
R42/43: May cause sensitization by inhalation and skin contact.
R36/37: Irritating to eyes and respiratory system.
R51/53: Toxic to aquatic organisms, may cause long-term adverse
effects in the aquatic environment.
Safety Phrases S22: Do not breathe dust.
S24: Avoid contact with skin.
S37/39: Wear suitable gloves and eye/face protection.
S61: Avoid release to the environment. Refer to special
instructions/Safety data sheets.


NATIONAL ENVIRONMENTAL AND SAFETY REGULATIONS



Superfund Amendments and Reauthorization Act (SARA)

SARA 311/312 Classification: Immediate (acute) health hazard
Delayed health hazard

SARA 313 Chemicals: Cobalt compounds Molybdenum oxide

SECTION 16. OTHER INFORMATION

COMPANY NAME: Criterion Catalysts & Technologies L.P.
16825 Northchase Drive,
2 Greenspoint Plaza
Houston, Tx. 77060 (USA)
+1 281 874 2600
+1 281 874 2641 (FAX)


MSDS Prepared By: CRI/Criterion, Inc.
16825 Northchase Drive, Suite #1110
Houston, TX 77060 (USA)
+1 281-874-2600 (USA CST)
Product.Steward@CRI-Criterion.com

Uses and restrictions:
Use as a raw material/intermediate for catalyst manufacture, as a catalyst for refinery processing or for
petrochemicals manufacture.

MSDS Distribution:
The information in this document should be made available to all who may handle the product.

CRITERION 234 CATALYST MSDS Number: 6179
Page 8 of 8

Amendment Notation:
Amendments from the previous version of the MSDS are indicated by two vertical bars in the left
margin and the section is highlighted.

Disclaimer:
This information is based on our current knowledge and is intended to describe the product for the
purposes of health, safety and environmental requirements only. It should not, therefore, be construed
as guaranteeing any specific property of the product.

Issue Date:
01/25/2010
US/Canada - (English)

Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Page 3-i
Table of Contents
3. GENERAL .................................................................................................................... 3-1
3.1 ORGANIZATION ................................................................................................... 3-1
3.2 GENERAL PRECOMMISSIONING PROCEDURES ............................................. 3-2
3.2.1 Mechanical ..................................................................................................... 3-2
3.2.2 Electrical ......................................................................................................... 3-3
3.2.3 Instrumentation ............................................................................................... 3-5
3.3 DESIGN BASIS ..................................................................................................... 3-7
3.3.1 Plant Capacity ................................................................................................ 3-7
3.3.2 Sulfur Block Feed Streams ............................................................................. 3-7
3.3.3 Effluent Stream Conditions ........................................................................... 3-12
3.3.4 Other Design Requirements ......................................................................... 3-13
3.3.5 Utility Information .......................................................................................... 3-14
3.3.6 Plant Site Conditions .................................................................................... 3-16


Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Page 3-1
3. GENERAL
3.1 Organization
This manual discusses the startup and operation of the new Sulfur Block,
consisting of an Amine Treating Unit, an Amine Regeneration Unit, a Sour
Water Stripping Unit, two Sulfur Recovery Units, a common Tailgas Thermal
Oxidation Unit, Tailgas Cleanup Unit, and Sulfur Degassing Unit, on a systems
basis. The systems are discussed individually, but are also grouped together
into two main categories. The categories and systems, in order of presentation,
are:
A. UTILITY SYSTEMS
1. Power Distribution
2. Plant Control Systems
3. Utility Systems
B. PROCESS SYSTEMS
1. Amine Treating / Amine Regeneration
2. Sour Water Stripping
3. Sulfur Recovery
4. Tailgas Thermal Oxidation
5. Tailgas Cleanup
6. Sulfur Degassing and Transfer
7. Solvent Storage and Drain
The systems are presented in the sequence required for a normal startup. That
is, electric power is usually the first system commissioned and the Sulfur
Degassing system is usually the last.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Page 3-2
3.2 General Precommissioning Procedures
Prior to placing each of the Amine Treating, Sour Water Stripping, Sulfur
Recovery, Tailgas Thermal Oxidation, Tailgas Cleanup, Sulfur Degassing, and
associated systems in operation, check-out of the various systems should be
made in as much detail as practical. This will help eliminate problems during
startup and familiarize personnel with the plant equipment.
3.2.1 Mechanical
A complete check of all plant construction should be made to assure it is
in accordance with the Piping & Instrument Diagrams and equipment
manufacturer's recommendations. Any discrepancies or defects should
be corrected before attempting to put the plant in operation. Each piece of
equipment should be checked against the vendor's recommendations and
guidelines. Some of the steps that should be taken to ensure the plant is
mechanically ready for startup include:
A. Make an internal check of vessels for correct installation of mist
pads, support grids, trays, vortex breakers, etc.
B. Check to ensure suction strainers are installed in all pump suction
lines before the pumps are operated for any reason.
C. Perform all necessary pressure tests. After tests, remove the test
blinds, giving special attention to those below relief valves.
D. Check the nameplate on each relief valve to ensure it has been
installed in the proper location.
E. Clear the plant area involved in startup of construction equipment
and debris that could cause fire or injuries.
F. Check for proper rotation of all motors.
G. Check all motors and rotating equipment to ensure proper lubrication
and that belts are free and properly aligned.
H. Check pumps for packing where required (follow manufacturer's
instructions).
I. Check filters to ensure they contain properly installed filter elements
or charcoal media and that adequate spare elements are on hand.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Page 3-3
J. Prior to commencement of startup, the following items should be on
hand:
(1) Spare parts
(2) Lubricants, greases, etc.
(3) Chemicals, or provisions to provide chemicals
(4) Spare filter elements
(5) Any special tools required
(6) Fire extinguishers
(7) Safety equipment
(8) Oxygen analyzer
(9) Laboratory test equipment
(10) Pertinent test procedures
3.2.2 Electrical
The purpose of commissioning electrical components and control systems
prior to the startup of a plant is to ensure correct performance per
specifications under simulated operating conditions.


POWER SHOULD NOT BE APPLIED TO ANY ELECTRICAL
DEVICE, CONTROL PANEL, CONTROL SYSTEM, OR MOTOR IN
THE FACILITY UNTIL SUCH TIME THAT ALL POWER AND
CONTROL WIRING FOR THE FACILITY HAS BEEN TERMINATED
AND PROPERLY MADE-UP ON EACH CONDUCTOR END.
Electrical power circuits must be energized in order to make an electrical
check-out prior to startup. Some of the following procedures may be
accomplished during construction; however, before the plant is put in
operation the following should be completed:
WARNING
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Page 3-4
A. Test each circuit with a megger, phase-to-phase and
phase-to-ground.
B. Test the motor feeder with the motor out of the circuit. After motors
are connected, make phase-to-ground tests on the motor circuit.
C. Test the control circuit with the push-buttons and over-current
devices connected.
D. Test the feeders to the panel-boards with the branch circuits open.
E. Test the power feeder with switches and circuit breakers in place.
F. Megger the power and control circuits of the switchgear and motor
control centers.
G. Check the control switches, alarm and shutdown devices, indicating
lights, and meters for proper operation.
H. Install thermal overload heaters where required after checking them
against the manufacturer's heat tables and motor nameplate data to
ensure the heaters are of the proper size and rating. Check
operation of time-delay under-voltage devices for proper timing,
proper restart, and dropout action.
I. Megger motor windings and transformer windings for ground.
Examine them for moisture accumulation. If evidence of moisture
accumulation is found, the equipment must be dried before being
placed in operation.
J. Check circuit breakers, motor starters, switches, relays, and other
equipment for loose connections (both mechanical and electrical)
and to see that contacts and working parts are correctly aligned and
free from dust and foreign material.
K. Check motors for proper rotation, lubrication, and alignment.
L. For circuit breakers with adjustable trips, check the thermal rating
against the value shown on the drawings and adjust the magnetic
setting to the "LO" position. On magnetic-only (instantaneous trip)
breakers in combination starters, the instantaneous setting should be
adjusted so that the setting is just above the motor in-rush current.
Lower the setting to the point where the contacts open when the
motor is started, then raise the setting in small increments to the
point where the breaker allows the motor to start.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Page 3-5
M. Ensure that all individual motor starter and feeder breakers are in the
"OFF" position.
N. Provide power to the MCC by engaging the main feeder breaker.
O. Turn the MCC feeder breakers to the "ON" positions, applying power
to all individual circuit breakers, contactors, and motor switches.
P. In order to initially energize any motor, pump, or fan, the shutdown
control system should first be energized and the emergency
shutdown system reset.
3.2.3 Instrumentation
The purpose of commissioning instruments prior to the startup of the
facility is to ensure correct performance per specifications under simulated
operating conditions. Handling of instruments after calibration should be
kept to a minimum.
The instruments have been ordered pre-calibrated and set. It should be
necessary only to verify the factory calibration and zero of the instruments.
In the event that an instrument requires re-calibration or major mechanical
adjustments, the manufacturer's recommendations and guidelines should
be adhered to, and will be considered the applicable standard.
All instruments, components, and accessory devices (including charts,
scales, dials, gauges, switches, etc.) should be checked against their
specification sheets for agreement.
Specific steps that should be taken to ensure the plant pneumatic
instrumentation system is ready for startup include:
A. The instrument air system must be put into operation in order to
check-out the instrument loops. The individual block valves for each
air user should be closed as the air system is pressurized. Once
operating pressure is reached, dirt and pipe scale should be blown
from the headers. The individual instrument lines should then be
disconnected at the instruments and any debris blown from the entire
tubing run.
B. All air supply regulators should be adjusted to the recommended
settings.
C. Once the instrument air system is pressurized, the piping and tubing
should be checked for leaks.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Page 3-6
D. All instrument loops should be checked to ensure the instruments
and control devices are properly interconnected. The controllers
should be set to the proper control action with the proper control
modes and tuning characteristics.
E. "Stroke" the control valves to ensure the valves move in the proper
direction.
F. Check orifice plates for proper bore and direction of installation.
G. Level switches and transmitters should be put in service and
checked for proper actuation. Calibration of level devices may be
completed after liquid levels are established.
H. Check the tag numbers on the steam traps to confirm that each trap
has been installed in the proper location.
I. In plants controlled by a distributed control system (DCS), confirm
that the range stored in the DCS for each field instrument matches
the actual range of the instrument. This is particularly important for
flow meters used in ratio control loops, as an incorrect range may
prevent the control loop from functioning properly. It is also
important on flow loops to confirm that either the transmitter or the
DCS (and not both) is extracting the square root of the signal.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Page 3-7
3.3 Design Basis
The information used to design the Sulfur Block is given in this section.
Unless stated otherwise, the design conditions presented below are assumed to
be available at the battery limits for the new units.
3.3.1 Plant Capacity
The feedstock basis for the Sulfur Block is a nominal sulfur production of
35 MT/D. In order to provide a design margin for the Sulfur Recovery
Units, each unit is designed for 75% of the normal feed rates, which
results in a nominal sulfur production of 52 MT/D.
3.3.2 Sulfur Block Feed Streams
3.3.2.1 Amine Treating Unit Feed Gas (Max Contaminate Case)
Composition, mol fraction
Combined Sour
Offgas
H
2
0.583538
H
2
S 0.133806
NH
3
0.000146
Methane 0.023661
Ethane 0.018913
Propane 0.016896
i-Butane 0.008563
n-Butane 0.115412
i-Pentane 0.057487
n-Pentane 0.030181
nC6 0.00264
H
2
O 0.008757
Naphtha + -
Total, kgmol/hr 463.85
Total, kg/hr 9902

Temp, C 38
Press, kg/cm
2
(g) 6

Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Page 3-8
3.3.2.2 Rich Amine to Amine Regeneration Unit
Composition,
kmol/hr
Rich MDEA
from DHT RGS
Rich MDEA
from LPG
Absorber
H
2
O 752.79 1027.14
MDEA 61.32 83.56
H
2
S 14.31 11.49
NH
3
0.00088 -
CO
2
- 8.24
H
2
0.51 -
Methane
0.01 -
Ethane
0.004 0.04
Propane
0.002 0.09
i-Butane
0.0004 0.04
n-Butane
0.0004 0.12
Heptane 0.0006
C1/C2 RSH - 0.04
Total 828.95 1130.75
Total, kg/hr 21358 29231
Temp, C 63 41
Press, kg/cm
2
(g) 4.5 4.5

Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Page 3-9
3.3.2.1 Sour Water to SWS (Max Contaminant Case)
Composition
kgmol/hr
Sour
Water
from
NHT
(1)

Sour
Water
from
KHT
Sour
Water
from
DHT
Sour
Water
from
CFU
Sour
Water
from UOP
Guard
Bed
H
2

--- 0.23 0.16 --- ---
NH
3

0.03 0.06 0.22 0.02 0.0005
H
2
S
0.53 0.58 0.50 0.02 0.0010
H
2
O
834.34 425.94 320.09 447.70 0.7986
Total
834.90 426.81 320.97 447.75 0.8000
Total - kg/hr
15050 7695 5788 8067 14
Temp, C
52 55 54 60 38
Press,
kg/cm
2
(g) 3.0 3.0 3.0 3.0 3.0
Note (1) The maximum NHT sour water rate is 19585 kg/h containing 35 wt
ppm H2S and 18 wt ppm NH3 when running 100% NWS Narrow
feed.

Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Page 3-10
3.3.2.2 Fuel Gas Streams
Fuel gas for the Sulfur Block is supplied from the treated fuel gas
header. The treated fuel gas is used only for the fuel to the Thermal
Oxidizer Burner. Vaporized C4 LPG is supplied to the Acid Gas
Burner, Acid Gas Burner Pilot, and the Thermal Oxidizer Burner
Pilot.
Composition, mole %
Treated Fuel
Gas
Hydrogen 67.353
H2S 0.010
Water Vapor 1.067
Methane 2.729
Ethane 2.180
Propane 1.948
i-Butane 0.988
n-Butane 13.306
i-Pentane 6.633
n-Pentane 3.481
C
6
+ 0.305
Totals 100.000


Temperature, C
38
Pressure, kg/cm
2
(g) (min)
3.5
LHV, kcal/kg
10,425

Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Page 3-11
3.3.2.3 Hydrogen Stream (Reducing Gas)
Composition, mole % PSA Hydrogen
Hydrogen 99.9
Nitrogen ---
CO & CO
2
20 ppm
Methane 0.1
Ethane ---
Propane ---
i-Butane ---
n-Butane ---
Totals 100.0
Temperature, C 40
Pressure, kg/cm
2
(g) (min) 25

Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Page 3-12
3.3.3 Effluent Stream Conditions
3.3.3.1 Treated Fuel Gas from ATU
Stream: Treated Gas
Temperature C normal / max 38 / 40
Pressure kg/cm
2
(g) min / max 3.5 / 4.2
H
2
S ppmv max (dry) 100

3.3.3.1 Treated Water from SWS
Stream: Treated water
Temperature C max 60
Pressure kg/cm
2
(g) min 5.0
H
2
S ppmw max 20
NH
3
ppmw max 20

3.3.3.1 Incinerated Effluent from TTO

Min. Norm. Max.
Temperature
C
232 288 400
Pressure
kg/cm
2
(g)
atm.
SO
2

ppmv (dry, 0% oxygen)
200
H
2
S ppmv
10
CO
(1)

ppmv
50
NO
X

ppmw
65

Note (1) For oxidation of H
2
S to SO
2,
the normal operating
temperature for the Tailgas Thermal Oxidizer (TTO) is
about 650C. If CO emissions must be limited and,
therefore, the CO must be oxidized to CO
2
, then the
normal operating temperature for the TTO is about
816C.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Page 3-13
3.3.3.1 Molten Sulfur
Min. Norm. Max.
Temperature C 119 138
Pressure kg/cm
2
(g) atm.
Purity % (dry basis) 99.9
H
2
S ppmw
10
Carbon % 0.2
Color Texas Bright

3.3.4 Other Design Requirements
3.3.4.1
The Lean Amine from the Amine Regeneration Unit is a 35 wt%
MDEA solution with a residual loading of 0.01 mole acid gas / mole
MDEA.
3.3.4.2
The Rich Amine from the DHT, LPG Absorber and Amine Treating
Unit will go to the Amine Regeneration Unit for regeneration. The
maximum Rich Amine loading will be 0.40 mole acid gas / mole
MDEA.
3.3.4.3
Liquid sulfur from the SRU is to be degassed to convert H
2
S
X

species to H
2
S and reduce the concentration of H
2
S to less than
10 PPMW for safe handling.
3.3.4.4
In general, the Sulfur Block is to be designed for a 3-4 year run
length between turnarounds. Mechanical turnaround duration is
usually 3-7 days for each unit.
3.3.4.5
All units are to be designed individually for a 98% or better
on-stream factor.
3.3.4.6
Critical equipment is to be spared, to permit on-line maintenance.


Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Page 3-14
3.3.5 Utility Information
3.3.5.1 Electricity
Service Voltage Phase Cycles
Motors above 132 kW 6,600 V 3 60
Motors 0.2 kW up to and including 132 kW 440 V 3 60
Fractional kW motors up to 0.2 kW 440 V 3 60

3.3.5.2 Steam

Operating Pressure:
kg/cm(g)
Operating Temp.
C
Mechanical
Design


Press: Temp:

Min Norm Max Min Norm Max kg/cm(g) C
HP Steam 44 45 46 380 400 420 50 427
MP Steam 16 17 17.5 275 280 300 20 350
IP Steam 13.7 14.4 15.1 202 204 206 16.7 227
LP Steam 3 3.5 4 190 195 210 5.5 300

3.3.5.3 Condensate

Condensate Destination
or Designation

Grade Level Battery Limit
Pressure: kg/cm(g)
HP Steam HP Condensate 19
MP Steam MP Condensate 6
IP Steam LP Condensate 1.5
LP Steam LP Condensate 1.5

3.3.5.4 Boiler Feed Water
Min.

Normal Max.

Design
BFW Temperature, C 132 132 132 160
BFW Pressure, kg/cm
2
(g) 57 57 58 63

Dissolved Solids, PPMW (avg) < 5
Conductivity, S/cm (avg) <20

Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Page 3-15
3.3.5.5 Cooling Water

Normal Min. Design
kg/cm
2
(g) C kg/cm
2
(g) C kg/cm
2
(g)

C
Supply 5
(1)
-- -- 32 8 60
Return 2
(1)
-- -- 42 8 60

TSS ppmw 20 max
Chlorides ppmw 1200
Ammonia ppmw nil

Note (1) These conditions are not necessarily the conditions
at the inlet or outlet connections of the equipment.

3.3.5.6 Instrument Air and Plant Air
Min.

Normal Max.

Design
Plant Air, kg/cm
2
(g) 5.5 5.5 6 10
Instrument Air, kg/cm
2
(g) 4 7 8 10

Plant Air Dewpoint C ---
Instrument Air Dewpoint C -40

Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 General Page 3-16
3.3.5.7 Gaseous Nitrogen
Min.

Normal Max.

Design
Pressure, kg/cm
2
(g) 4 6 8 10
Composition, mole %
Nitrogen 99.5
Oxygen 20 ppmv (max)
CO 20 ppmv (max)
CO
2
20 ppmv (max)
Other C Compounds 5 ppmv (max)
Chlorine 1 ppmv (max)
H
2
O 5 ppmv (max)
Hydrogen 20 ppmv (max)
Noble Gases Remainder
Total 100.0


3.3.6 Plant Site Conditions
3.3.6.1 Barometric Pressure:
760 mm Hg (average)
3.3.6.2 Air Temperature: 37C (dry bulb) maximum summer design
30C (dry bulb) for air blower design
-10C (dry bulb) minimum winter design
-14.3C (dry bulb) winterizing
3.3.6.3 Site Elevation:
5.6 m above mean sea level

Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Power Distribution Page 4-i
Table of Contents
4. POWER DISTRIBUTION .............................................................................................. 4-1
4.1 PURPOSE OF SYSTEM ....................................................................................... 4-1
4.2 SAFETY ................................................................................................................. 4-1
4.2.1 General ........................................................................................................... 4-1
4.2.2 Hazardous (Classified) Areas ......................................................................... 4-1
4.3 EQUIPMENT DESCRIPTION ................................................................................ 4-2
4.3.1 Motors and Motor Controls ............................................................................. 4-2



Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Power Distribution Page 4-1
4. POWER DISTRIBUTION
4.1 Purpose of System
This utility system supplies electrical power to all users in the Amine Treating,
Amine Regeneration, Sour Water Stripping, Sulfur Recovery, Tailgas Cleanup,
Tailgas Thermal Oxidation, and Sulfur Degassing units including motors,
instruments, controls, lights, receptacles, and heat tracing.
4.2 Safety
4.2.1 General
Only authorized and qualified personnel should maintain and repair
electrical equipment. All operator controls and adjustments are accessible
without opening electrical equipment enclosures.
Maintain extreme care when operating electrical equipment and
machinery driven by electrical motors. Equipment may start without
warning.
Observe company safety rules and permit-to-work system.
If you suspect a person has been electrocuted, DO NOT approach the
victim until the source of power has been turned off or it is obvious the
victim is no longer in contact with the source. If possible, drag victim clear
of any metal or potential electrical sources using victim's clothing or by
wearing insulating gloves. If the victim is still in contact with the electrical
source and skin contact is made, you may also be electrocuted.
4.2.2 Hazardous (Classified) Areas
Most of the process areas in the Amine Treating, Amine Regeneration,
Sour Water Stripping, Sulfur Recovery, Tailgas Cleanup, Tailgas Thermal
Oxidation, and Sulfur Degassing units have been classified as Zone 2,
Gas Group IIA/IIB for electrical installation. The only exceptions to this are
any below-grade vaults which have been classified as Zone 1, Gas Group
IIA/IIB.
Locations are classified depending on the properties of the flammable
vapors, liquids, or gases which may be present and the likelihood that a
flammable or combustible concentration or quantity is present. The
electrical equipment and installation in classified areas conforms to the
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Power Distribution Page 4-2
International Electrotechnical Commission (IEC) Standards. Special
precautions are required when operating electrical equipment in classified
areas. The equipment should be approved for the area classification or a
"hot-work" permit system should be followed during the period a
non-approved piece of equipment is used in the classified area.
4.3 Equipment Description
4.3.1 Motors and Motor Controls
A. In general, the electric motors are TEFC, 444 VAC, 3 , 60 Hz with
the exception of:
(1) The motors on the Process Air Blower, A2-GB1530A/B, are
TEFC, 6600 VAC, 3 , 60 Hz.
B. The motor control circuits for the Process Air Blower
(A2-GB1530A/B), Thermal Oxidizer Air Blower (A2-GB1570A/B), and
TGCU Start-Up Blower (A2-GB1560) include provisions that allow
the blowers to "ride-through" brief power interruptions.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Plant Control Systems Page 5-i
Table of Contents
5. PLANT CONTROL SYSTEMS ..................................................................................... 5-1
5.1 DISTRIBUTED CONTROL SYSTEM .................................................................... 5-1
5.2 PROGRAMMABLE LOGIC CONTROL SYSTEM ................................................. 5-2
5.3 EMERGENCY SHUTDOWN SYSTEMS ............................................................... 5-3
5.4 LOCAL CONTROL PANELS ................................................................................. 5-3


Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Plant Control Systems Page 5-1
5. PLANT CONTROL SYSTEMS
This section of the manual describes the various control systems associated with the
new Amine Treating, Amine Regeneration, Sour Water Stripping, Sulfur Recovery,
Tailgas Cleanup, Tailgas Thermal Oxidation, and Sulfur Degassing units. Most of the
process control functions are performed by a Distributed Control System (DCS). The
DCS, with its operator interface screens and keyboards, allows the control room
operator to monitor and control nearly all of the systems within the new units.
The safety system interlocks and sequential control functions are performed by a
programmable logic controller (PLC). A PLC is a solid-state microprocessor that
performs the functions of a traditional relay logic system. The PLC for the new units
will communicate with the DCS to allow the operator to monitor the PLC using the
operator interface screens of the DCS.
5.1 Distributed Control System
The Distributed Control System (DCS) provides control, monitoring, recording,
alarming, and all other functions required for dependable and effective process
control of the facility. It is a microprocessor based, fully engineered system of
hardware and software products integrated into an industrially-proven DCS
design capable of both functional and geographic distribution. A communication
system links these locations to a centralized operating center with video displays
configured as operator workstations.
The system has been designed so that control and monitoring functions are
distributed on a modular basis to minimize control and data information loss in
the event of a failure anywhere within the system. Control functionality does not
depend on a single centrally-based device or communication system to assure
that on a single failure the system will remain operative to allow continued
control and monitoring of the remainder of the process. To achieve this,
redundancy has been included for controllers, power supplies, communication
modules and cables, and operator workstations.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Plant Control Systems Page 5-2
5.2 Programmable Logic Control System
A Programmable Logic Control (PLC) system is used for the new Amine
Treating, Amine Regeneration, Sour Water Stripping, Sulfur Recovery, Tailgas
Cleanup, Tailgas Thermal Oxidation, and Sulfur Degassing units to perform the
functions of traditional relay logic systems. The logic control systems for each
unit are all contained in one or more PLCs. Each logic control system will be
discussed in more detail in later sections of the manual:
a. Amine Treating Unit Emergency Shutdown System (see Section 7.4.2).
b. Sour Water Stripper Unit Interlocks (see Section 8.4).
c. Sulfur Recovery Unit Emergency Shutdown System (SRU ESD) and
Burner Management System (see Sections 9.5.2 and 9.5.8).
d. Sulfur Degassing Unit Startup Interlock and Emergency Shutdown System
(SDU ESD) (see Sections 10.5.3 and 10.5.7).
e. Sulfur Loading Emergency Shutdown System (see Section 10.5.8).
f. Tailgas Cleanup Unit Emergency Shutdown System (TGCU ESD) (see
Section 11.5.5).
g. Tailgas Thermal Oxidation Emergency Shutdown System (TTO ESD) and
Burner Management System (see Sections 12.5.1 and 12.5.5).
The PLC hardware and programs are fail-safe by design. Loss of power to the
PLC will de-energize all its outputs and send devices (control valves, etc.) to
their "fail" position. The restoration of power to the PLC will restart the PLC, but
program interlocks will "lock-out" control actions until the respective ESD
systems are reset. Similarly, the PLC logic has been designed such that open
circuits in field wiring or open field contacts will de-energize their respective
outputs and render equipment and process to a "safe" status.
The PLC system is connected by both "hard-wired" cables and software "links"
that allow it to communicate with the DCS. This enables the DCS operator
interface to be used by the operators to monitor the status of the PLC and its
safety and sequential control systems.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Plant Control Systems Page 5-3
5.3 Emergency Shutdown Systems
The purpose of the Amine Treating Unit Emergency Shutdown (ATU ESD), Sulfur
Recovery Unit Emergency Shutdown (SRU ESD), Tailgas Cleanup Unit
Emergency Shutdown (TGCU ESD), Tailgas Thermal Oxidation Unit Emergency
Shutdown (TTO ESD), and Sulfur Degassing Unit Emergency Shutdown (SDU
ESD) systems is to shut down the appropriate equipment and divert the
appropriate streams to the flare when serious problems occur. Each of these
ESD systems can be initiated either by a system response or by an operator.
Refer to the Instrumentation and Control Systems sections of these guidelines for
complete discussions of these emergency shutdown systems.
These ESD systems are mostly independent of each other, with the exception of
the TGCU ESD system, which is activated when both of the SRU ESD systems
are activated. Except for this situation, activation of the ESD system in a
particular unit will not cause any other ESD systems to be directly activated. Of
course, depending on the particular circumstances, the effects that result when
a particular ESD system is activated may indirectly cause another ESD system
to be activated due to the process upset that occurs.
5.4 Local Control Panels
There are three local control panels that are used for startup of each Sulfur
Recovery Unit and the Tailgas Thermal Oxidation Unit. The functions of these
local panels are described in the Instrumentation and Control Systems sections
of these guidelines for the Sulfur Recovery system and the Tailgas Thermal
Oxidation system.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Utility Systems Page 6-i
Table of Contents
6. UTILITY SYSTEMS ...................................................................................................... 6-1
6.1 PURPOSE OF SYSTEM ....................................................................................... 6-1
6.2 SYSTEM DESCRIPTION ...................................................................................... 6-1
6.2.1 Nitrogen Supply .............................................................................................. 6-1
6.2.2 C4 LPG and Treated Fuel Gas Supply .......................................................... 6-2
6.2.3 Hydrogen Supply ............................................................................................ 6-2
6.2.4 Plant Air .......................................................................................................... 6-3
6.2.5 Instrument Air ................................................................................................. 6-3
6.2.6 Sour Water Disposal ....................................................................................... 6-3
6.2.7 Steam, Condensate, Boiler Feed Water, and Blowdown ............................... 6-4
6.2.7.1 Purpose of Systems ................................................................................ 6-4
6.2.7.2 Safety ...................................................................................................... 6-4
6.2.7.3 Process Description ................................................................................ 6-5
6.2.7.4 Boiler Feed Water ................................................................................... 6-5
6.2.7.5 HP Steam ................................................................................................ 6-6
6.2.7.6 LP Steam ................................................................................................. 6-7
6.2.7.7 Condensate Return ................................................................................. 6-7
6.3 PRECOMMISSIONING, STARTUP, AND SHUTDOWN PROCEDURES............. 6-8

Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Utility Systems Page 6-1
6. UTILITY SYSTEMS
6.1 Purpose of System
The utility headers supply the fluids necessary for plant operation and
maintenance.
6.2 System Description
The Piping and Instrument Diagrams show the utility system tie-ins for this
project. Some of the more important or complex systems are discussed in more
detail in the sections below.
6.2.1 Nitrogen Supply
The SRUs and TGCU have two sections of equipment or piping that are
stagnant during certain modes of operation. One of these, the SRU
warmup bypass line(s), would cause undesirable effects on sulfur
recovery and/or severe corrosion if leakage occurred in the line. The
other one, the TGCU Start-Up Blower, could suffer corrosion if exposed to
wet process gases when it is not running.
The most positive means of preventing these problems is to isolate the
section in question and purge it with inert gas (such as nitrogen). If the
pressure of the purge gas is higher than the process operating pressure,
then any leakage through the isolation valves will be the inert purge gas
leaking out rather than process gas leaking in. Nitrogen is used in this
manner at each of these locations within the new unit.
Nitrogen is also used for several other purposes within the new units: 1) to
purge instruments (flame scanners, pyrometers, flow meters, etc.)
exposed to process gas containing sulfur vapor or ammonia; 2) to empty
out and purge vessels before opening them for maintenance; 3) to prevent
a vacuum from forming in several overhead lines; 4) as the motive fluid for
the aspirator in the air demand analyzer; and 5) as a cool-down medium
for the SRUs and the front-end of the TGCU. A dedicated low pressure
header is used for purges permanently connected to low pressure sulfur
plant equipment; a high pressure header operating at about 7.0 kg/cm
2
(g)
provides nitrogen for the other users.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Utility Systems Page 6-2
6.2.2 C4 LPG and Treated Fuel Gas Supply
When the refractory in the Reactor Furnace, A2-BA1530 (A2-BA1540),
must be heated in a controlled fashion according to its cure-out schedule,
fuel is fired in the Acid Gas Burner, A2-BA1531 (A2-BA1541), on manual
control. Variable fuel gas quality could lead to temperature "run-aways" if
there is not close operator attention throughout the heating cycle. For this
reason, vaporized C4 LPG is used as the fuel gas for the Acid Gas
Burner. The heating value of vaporized LPG normally varies much less
than the heating value of a typical treated fuel gas stream, so vaporized
LPG should be much less likely to cause temperature control problems
during this manual operation.
The fuel gas to the Thermal Oxidizer Burner, A2-BA1571, is automatically
adjusted to maintain the desired temperature in the Thermal Oxidizer,
A2-BA1570. In addition, this burner normally operates with considerable
excess air, since the oxygen to oxidize the sulfur compounds entering the
Thermal Oxidizer comes from the burner combustion products. As a
result, the variable nature of treated fuel gas can be tolerated by this
burner much more easily than the Acid Gas Burner, so this burner is
designed to burn treated fuel gas.
The pilot burners for the Acid Gas Burner and the Thermal Oxidizer
Burner are not as reliable if variable quality fuel gas is used. For this
reason, vaporized LPG is used for both pilots to ensure reliable light-off
and good service life.
During normal operation, loss of the treated fuel gas supply will cause the
Thermal Oxidizer to shut down. However, the SRU should continue to
operate. The Thermal Oxidizer shutdown will be due to "flame failure" of
the Thermal Oxidizer Burner. Loss of LPG will normally not affect either
unit, but it will not be possible to restart either unit should a shutdown
occur until the LPG supply is restored.
6.2.3 Hydrogen Supply
The TGCU Unit is designed to use an external supply of reducing gas to
hydrogenate the sulfur compounds in the SRU tailgas back into H
2
S,
rather than generate its own reducing gas. High-purity hydrogen is
imported into the Sulfur Block, let-down to low pressure, and combined
with the SRU tailgas upstream of the TGCU Reactor Feed Mixer,
A2-ME1560. If the hydrogen supply is interrupted, it is likely that the
TGCU Unit will have to be bypassed until the hydrogen supply is restored.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Utility Systems Page 6-3
6.2.4 Plant Air
The Plant Air system provides compressed air for the utility air stations
throughout the plant. It can be used for operating pneumatic tools and
other pneumatic equipment such as air movers, spray guns, and sand
blasting apparatus. Plant air is also used in the Tailgas Cleanup Unit for
catalyst passivation.
6.2.5 Instrument Air
Dry instrument air is used to provide the motive force to operate the
control valves and shutdown valves in the Sulfur Block. Loss of the air
supply for brief periods will probably not cause any operational problems.
However, if the instrument air pressure falls below about 4.2 kg/cm
2
(g),
some of the large process gas valves may begin to move. If one of the
process gas valves that is in the open flowpath through the SRUs, the
TGCU, and the TTO should begin to close, the ESD system for that SRU
and/or the TGCU will be activated, resulting in an SRU and/or TGCU
shutdown.
6.2.6 Sour Water Disposal
Sour water is produced at several points in the SRU and TGCU, such as
in the Acid Gas Knock-Out Drums, A2-FA1530 (A2-FA1540), the SWS
Gas Knock-Out Drum, A2-FA1531 (A2-FA1541), and the excess water
condensed in the TGCU Quench Column, A2-DA1560. Some of this sour
water is intermittent in nature, like the knock-out drum liquids, whereas the
excess quench water will be a continuous flow. The sour water from the
Acid Gas Knock-Out Drum is pumped to the Rich Amine Flash Drum,
A2-FA1513, while the remaining sources are sent to the Sour Water Flash
Drum, A2-FA1520.
Sour water must also be drained from equipment items periodically (pump
cases, level instruments, etc.). The Closed Drain Tank, A2-FA1582, has
an underground header system to collect these liquids and hold them. As
the tank fills, the Closed Drain Pump, A2-GA1581A/B, can be used to
send the collected sour water to Sour Water Stripping Unit.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Utility Systems Page 6-4


THE LIQUID DRAINED INTO THE CLOSED DRAIN TANK AND ITS
UNDERGROUND HEADER SYSTEM CONTAINS DISSOLVED H
2
S.
ALWAYS OBSERVE PROPER PROCEDURES AND PRECAUTIONS
WHEN DRAINING LIQUID FROM THESE ITEMS OR PERFORMING
MAINTENANCE ON THEM. THE "GENERAL SAFETY" SECTION
OF THIS MANUAL SHOULD BE CONSULTED IF THERE IS ANY
DOUBT ABOUT HOW TO WORK SAFELY WHEN H
2
S MAY BE
PRESENT.
6.2.7 Steam, Condensate, Boiler Feed Water, and Blowdown
6.2.7.1 Purpose of Systems
The Steam system provides heating media for plant systems and
equipment and motive driving power for each vent ejector. The
Condensate system is designed to collect and return the steam
which has been condensed by the users to the Steam system. The
Boiler Feed Water system provides suitably conditioned water to the
steam generators located within the Sulfur Block. The Blowdown
system collects the blowdown water from the boilers in the Sulfur
Block for safe disposal.
6.2.7.2 Safety
Use appropriate safety precautions when handling the boiler feed
water chemicals (sulfite, amine, phosphate, etc.).
The normal operating temperatures in the Steam, Condensate, and
Boiler Feed Water systems are high enough to cause burns:
Steam Pressure Steam Temperature
48.5 kg/cm
2
(g) 262C
45.0 kg/cm
2
(g) 400C superheated
4.2 kg/cm
2
(g) 153C

Personnel should take the appropriate precautions to avoid burns
when working around open vents, open drains, steam traps, or any
WARNING
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Utility Systems Page 6-5
un-insulated piping in the Steam, Condensate, and Boiler Feed
Water systems. It is common for hot water to drip from steam tracing
connections, steam traps, etc. Steam leaks and steam vent streams
can cause severe burns and lacerations. Also, refer to the
discussion concerning boilers in the General Safety section of this
manual, Section 2.13.
6.2.7.3 Process Description
There are three Steam headers (saturated 48.5 kg/cm
2
(g),
superheated 45 kg/cm
2
(g) and saturated 3.5 kg/cm
2
(g)), a low
pressure Condensate Return header, a high pressure Condensate
Return Header, a Cold Condensate Header, a Boiler Feed Water
header, and an atmospheric pressure Blowdown header.
There are six steam generators in the Sulfur Block:
A2-BF1530

Waste Heat Boiler
(sat. 48.5 kg/cm
2
(g) steam)
A2-BF1540

Waste Heat Boiler
(sat. 48.5 kg/cm
2
(g) steam)
A2-EA1531

Sulfur Condenser
(sat. 4.2 kg/cm
2
(g) steam)
A2-EA1541

Sulfur Condenser
(sat. 4.2 kg/cm
2
(g) steam)
A2-EA1561

TGCU Waste Heat Reclaimer
(sat. 4.2 kg/cm
2
(g) steam)
A2-BF1570 Thermal Oxidizer Waste Heat Boiler
(superheated 45.0 kg/cm
2
(g) steam)
The different subsystems are described below.
6.2.7.4 Boiler Feed Water
In accordance with the ASME Section I Code for Power Boilers,
boiler feed water must be provided to the Waste Heat Boiler,
A2-BF1530 (A2-BF1540), and the Thermal Oxidizer Waste Heat
Boiler, A2-BF1570, at 58.3 kg/cm
2
(g) or higher (i.e., 6% above the
relief valve settings). The BFW supply header must be maintained at
or above this pressure to safely satisfy this requirement.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Utility Systems Page 6-6
In accordance with the ASME Section VIII Code for Unfired Steam
Boilers, boiler feed water must be provided to the Sulfur Condenser,
A2-EA1531 (A2-EA1541), and the TGCU Waste Heat Reclaimer,
A2-EA1561, at 5.8 kg/cm
2
(g)or higher (i.e., 6% above the relief valve
settings).
6.2.7.5 HP Steam
The Waste Heat Boiler, A2-BF1530 (A2-BF1540), generates
HP steam at a normal operating pressure of about 48.5 kg/cm
2
(g). A
small portion of this steam is consumed in the reactor feed heaters to
reheat the feed streams to the catalytic reactors in the SRUs. The
rest of the HP steam is combined with the steam from the Thermal
Oxidizer Waste Heat Boiler, A2-BF1570, enters the Steam
Knock-Out Drum, A2-FA1570, to remove any entrained water
droplets, and is then routed to the superheat passes in the Thermal
Oxidizer Waste Heat Boiler.
The Thermal Oxidizer Waste Heat Boiler includes a water-tube boiler
that uses part of the waste heat from the Thermal Oxidizer to
generate 48.5 kg/cm
2
(g) saturated steam. The remainder of the
waste heat is used to superheat the steam from this boiler after it
combines with the HP steam produced by the Waste Heat Boiler.
The Thermal Oxidizer Waste Heat Boiler allows a major portion of
the heat required to incinerate the sulfur compounds to SO
2
to be
recovered as useful steam. The superheated steam is exported to
the refinery HP steam header at about 400C and 45.0 kg/cm
2
(g).
Note that the Thermal Oxidizer Waste Heat Boiler is the only source
of superheat for the HP steam produced in the Sulfur Block. If the
Thermal Oxidizer shuts down and begins to cool, the steam will no
longer be sufficiently superheated to satisfy the requirements of the
users located outside of battery limits. Under this circumstance, the
steam from the superheat passes of the TTO Waste Heat Boiler will
instead be vented to atmosphere automatically until the Thermal
Oxidizer is restarted and the steam is once again superheated to the
proper temperature.
HP steam is used as motive fluid for the Sulfur Surge Tank Vent
Ejector, A2-EE1530 (A2-EE1540). The steam for this service is
normally supplied from the steam produced within the process train.
When the HP steam is being vented to atmosphere as described
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Utility Systems Page 6-7
above, however, steam must be imported into the Sulfur Block for
this equipment item.
6.2.7.6 LP Steam
The Sulfur Condenser, A2-EA1531 (A2-EA1541), in the sulfur plant
and the TGCU Waste Heat Reclaimer, A2-EA1561, in the tailgas
cleanup unit generate LP steam at a normal operating pressure of
about 4.2 kg/cm
2
(g). This LP Steam is used for heating amine acid
gas in the Acid Gas Preheater, A2-EA1530 (A2-EA1540), reboiling
the solvent in the ARU Stripper Reboiler, A2-EA1512A/B, the water
in the Sour Water Stripper Reboiler, A2-EA1521, and the TGCU
solvent in the TGCU Stripper Reboiler, A2-EA1565, miscellaneous
steam tracing and steam jacketing of process gas lines, sulfur
rundown lines, sulfur vapor valves, etc., and for the heating coils in
the Sulfur Surge Tank, A2-EA1531 (A2-EA1531), and Sulfur Storage
Tank, A2-FB1550. The remaining LP Steam is exported to the
refinery.
6.2.7.7 Condensate Return
The HP condensate produced from the HP Steam used in the Sulfur
Block is collected and routed to the HP Condensate return system.
The LP condensate produced from the LP Steam used in the Sulfur
Block is collected and routed to the LP Condensate return system.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Utility Systems Page 6-8
6.3 Precommissioning, Startup, and Shutdown Procedures
The utility equipment and piping may be put into service as required by the
process systems they serve. Normal procedures should be followed after
completion of construction to ensure that the lines have been adequately blown
or flushed clean before being commissioned. Other than checking for
cleanliness and possible leaks, and following good practice in venting lines
while they are being filled, no other special procedures should be required to
commission the utility systems.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Tailgas Cleanup Page 7-i
Table of Contents
7. AMINE TREATING & AMINE REGENERATION ......................................................... 7-1
7.1 PURPOSE OF SYSTEM ....................................................................................... 7-1
7.2 SAFETY ................................................................................................................. 7-1
7.3 PROCESS DESCRIPTION .................................................................................... 7-2
7.3.1 General ........................................................................................................... 7-2
7.3.2 Water Washing ............................................................................................... 7-2
7.3.3 Sour Gas Contacting ...................................................................................... 7-3
7.3.4 Solvent Regeneration ..................................................................................... 7-3
7.4 EQUIPMENT DESCRIPTION ................................................................................ 7-6
7.4.1 Wash Water Column, A2-DA1510 .................................................................. 7-6
7.4.2 Amine Absorber, A2-DA1511 ......................................................................... 7-6
7.4.3 Flash Gas Contactor, A2-DA1512 .................................................................. 7-6
7.4.4 Stripper, A2-DA1513 ...................................................................................... 7-6
7.4.5 Wash Water Column Packing, A2-DB1510 .................................................... 7-7
7.4.6 Amine Absorber Trays, A2-DB1511 ............................................................... 7-7
7.4.7 Stripper Trays, A2-DB1513 ............................................................................ 7-7
7.4.8 Amine Absorber Overhead Cooler, A2-EA1510 ............................................. 7-8
7.4.9 Lean/Rich Exchanger, A2-EA1511A/B ........................................................... 7-8
7.4.10 Stripper Reboiler, A2-EA1512A/B .................................................................. 7-8
7.4.11 Stripper Reflux Condenser, A2-EC1511 ......................................................... 7-8
7.4.12 Lean Amine Cooler, A2-EC1510 .................................................................... 7-8
7.4.13 Wash Water Feed Knock-Out Drum, A2-FA1510 ........................................... 7-8
7.4.14 Amine Absorber Feed Knock-Out Drum, A2-FA1511 ..................................... 7-9
7.4.15 Amine Absorber Overhead Knock-Out Drum, A2-FA1512 ............................. 7-9
7.4.16 Rich Amine Flash Drum, A2-FA1513 ............................................................. 7-9
7.4.17 Stripper Reflux Accumulator, A2-FA1514 ..................................................... 7-10
7.4.18 Stripper Reboiler Condensate Pot, A2-FA1515A/B ...................................... 7-10
7.4.19 ATU Skim Oil Sump, A2-FA1516 ................................................................. 7-10
7.4.20 ATU Skim Oil Pump Sump, A2-FA1517A/B ................................................. 7-10
7.4.21 ATU Amine Drips Tank, A2-FA1580 ............................................................. 7-11
7.4.22 MDEA Storage Tank, A2-FB1580 ................................................................ 7-11
7.4.23 Wash Water Filter, A2-FD1510A/B ............................................................... 7-11
7.4.24 Rich Amine Filter, A2-FD1511A/B ................................................................ 7-11
7.4.25 Lean Amine Filter, A2-FD1512 ..................................................................... 7-11
7.4.26 Lean Amine Carbon Filter, A2-FD1513 ........................................................ 7-12
7.4.27 Lean Amine After-Filter, A2-FD1514 ............................................................ 7-12
7.4.28 ATU Amine Drips Filter, A2-FD1580 ............................................................ 7-12
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Tailgas Cleanup Page 7-ii
7.4.29 Wash Water Pump, A2-GA1510A/B ............................................................. 7-13
7.4.30 Lean Amine Pump, A2-GA1511A/B ............................................................. 7-13
7.4.31 ATU Skim Oil Pump, A2-GA1512A/B ........................................................... 7-13
7.4.32 Rich Amine Pump, A2-GA1513A/B .............................................................. 7-13
7.4.33 Lean Amine Booster Pump, A2-GA1514A/B ................................................ 7-13
7.4.34 Stripper Reflux Pump, A2-GA1515A/B ......................................................... 7-13
7.4.35 MDEA Transfer Pump, A2-GA1580 .............................................................. 7-14
7.5 INSTRUMENTATION AND CONTROL SYSTEMS ............................................. 7-15
7.5.1 Treated Fuel Gas H
2
S Analyzer ................................................................... 7-15
7.5.2 ATU Emergency Shutdown Systems ........................................................... 7-15
7.5.2.1 Causes of ATU ESD .............................................................................. 7-15
7.5.2.2 Effects of ATU ESD ............................................................................... 7-17
7.5.2.3 Non-ESD Shutdowns and Alarms ......................................................... 7-17
7.6 PROCESS PRINCIPLES AND OPERATING TECHNIQUES ............................. 7-19
7.6.1 Amine Absorber Operation ........................................................................... 7-19
7.6.1.1 Low Temperature .................................................................................. 7-19
7.6.1.2 Acid Gas Loading .................................................................................. 7-20
7.6.1.3 High Amine Concentration .................................................................... 7-20
7.6.2 Stripper Operation ........................................................................................ 7-22
7.6.3 Amine Water Balance ................................................................................... 7-24
7.6.4 Amine Loss ................................................................................................... 7-27
7.6.5 Operation at Low Flow Rates ....................................................................... 7-29
7.7 PRECOMMISSIONING PROCEDURES ............................................................. 7-30
7.7.1 Preliminary Check-out .................................................................................. 7-30
7.7.2 Shutdown System Check-out ....................................................................... 7-31
7.7.3 Leak Testing the Process Piping and Equipment ......................................... 7-31
7.7.4 Washing the Wash Water System ................................................................ 7-33
7.7.4.1 Water Flush ........................................................................................... 7-33
7.7.4.2 Acid Wash ............................................................................................. 7-35
7.7.4.3 Alkaline Wash ........................................................................................ 7-36
7.7.4.4 Initial Water Fill ...................................................................................... 7-37
7.7.5 Washing the Amine System ......................................................................... 7-38
7.7.5.1 Water Flush ........................................................................................... 7-38
7.7.5.2 Acid Wash ............................................................................................. 7-43
7.7.5.3 Weak Amine Wash ................................................................................ 7-45
7.7.5.4 Initial Solvent Fill ................................................................................... 7-46
7.7.6 Purging the Low Pressure Columns ............................................................. 7-50
7.7.6.1 Purging the Columns ............................................................................. 7-50
7.8 STARTUP PROCEDURES .................................................................................. 7-52
7.8.1 Wash Water and Amine Systems ................................................................. 7-52
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Tailgas Cleanup Page 7-iii
7.8.2 Sour Fuel Gas Flow to the Columns ............................................................. 7-53
7.9 SHUTDOWN PROCEDURES ............................................................................. 7-56
7.9.1 Planned Shutdown - ATU ............................................................................ 7-57
7.9.2 Planned Shutdown - ATU and ARU ............................................................. 7-60
7.9.3 Emergency Shutdown .................................................................................. 7-62
7.9.4 Effects of Shutdowns and Outages in Other Systems .................................. 7-63
7.9.4.1 Steam System Outage .......................................................................... 7-63
7.10 ANALYTICAL PROCEDURES ............................................................................ 7-64
7.10.1 General Procedures for Analyzing ATU/ARU Solvent
,
................................. 7-64
7.10.2 Determination of Amine Concentration in ATU/ARU Solvent ....................... 7-68
7.10.3 Determination of Total Acid Gas Loading in ATU/ARU Solvent ................... 7-70
7.10.4 Determination of H
2
S and CO
2
Loading in ATU/ARU Solvent ...................... 7-72
7.10.5 Determination of Foaming Tendency of ATU/ARU Solvent .......................... 7-76
7.10.6 H
2
S Conc. in Amine Absorber Ovhd by the Tutweiler Method ..................... 7-78
7.10.7 H
2
S Conc. in Amine Absorber Ovhd Using Gas Detector Tubes ................. 7-79
7.10.7.1 Operating Principles .............................................................................. 7-79
7.10.7.2 Sampling the Amine Absorber Overhead Gas ...................................... 7-80
7.10.7.3 Calculations ........................................................................................... 7-81
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-1
7. AMINE TREATING & AMINE REGENERATION
7.1 Purpose of System
The purpose of the Amine Treating system is to remove essentially all the
H
2
S from the sour fuel gas stream using an aqueous amine solvent, MDEA
(methyldiethanolamine). The H
2
S is absorbed in the amine solvent and the
treated fuel gas stream, containing with less than 100 ppmv of H
2
S, is
returned to the complex for consumption as fuel.
The purpose of the Amine Regeneration system is to strip the H
2
S from the
rich amine solvent produced in the Amine Treating, LPG Treating and DHT
units. The H
2
S-laden acid gas is sent to the Sulfur Recovery Unit (SRU) for
disposal and the lean amine is recycled back to the upstream process units.
7.2 Safety


ALL PIPING AND VESSELS INCLUDED IN THIS UNIT EITHER CONTAIN
OR HAVE THE POTENTIAL FOR CONTAINING HAZARDOUS GAS THAT
MAY CAUSE SERIOUS INJURY OR DEATH. THE GAS THAT IS MOST
COMMON AND HAZARDOUS IN A TOXIC WAY IS HYDROGEN SULFIDE.
CLOSE ATTENTION SHOULD BE PAID TO THE "GENERAL SAFETY"
SECTION OF THESE GUIDELINES AS TO THE NATURE AND ABILITY
OF THIS GAS TO CONTAMINATE OTHER ELEMENTS IN THIS UNIT.
AN EMPLOYEE'S KNOWLEDGE OF THE HAZARDOUS CHEMICALS AND
COMPOUNDS WITH WHICH HE WILL BE WORKING IS ONE OF THE
MOST BASIC PREREQUISITES FOR HIS OWN SAFETY, THE SAFETY
OF OTHERS, AND THE PROTECTION OF EQUIPMENT. ALL
EMPLOYEES SHOULD REVIEW THE "GENERAL SAFETY" SECTION OF
THESE GUIDELINES OCCASIONALLY TO REFRESH THEIR MEMORIES.
NEW EMPLOYEES SHOULD STUDY IT UNTIL THE INFORMATION IS
THOROUGHLY UNDERSTOOD. PEOPLE WHO HAVE NOT BEEN
PROPERLY TRAINED SHOULD NOT BE ALLOWED TO OPERATE OR
WORK IN AND AROUND THIS PLANT.
WARNING
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-2
7.3 Process Description
7.3.1 General
The Systems Diagram, Material Balance and Process Flow Diagrams,
Dwg. Nos. 507000-7000-01, through -04, are contained in the "Process
Flow Diagrams" Section of the Basic Engineering Package. Please refer
to these drawings to follow this description of the process.
The Amine Treating Unit (ATU) uses an aqueous amine solvent, MDEA
(methyldiethanolamine), to remove essentially all the H
2
S from the sour
fuel gas stream. The normal solvent concentration is 45 wt % MDEA in
water. The ATU is designed to treat 10,397 Nm
3
/hr of sour fuel gas. The
treated gas stream is returned to the refinery for consumption as fuel, and
the acid gas (H
2
S, plus CO
2
) is routed to the Sulfur Recovery Units
(SRUs). Less than 100 PPMV of H
2
S remains in the treated fuel gas.
7.3.2 Water Washing
Sour fuel gas streams in chemical complexes are often contaminated with
various gaseous, liquid, and even solid substances. In order to prevent
these contaminants from causing operating problems (foaming, poor
treating, corrosion, etc.) in the amine solvent system, the sour fuel gas
streams are washed with water to remove the contaminants upstream of
the amine contactors. Some of the more common contaminants are
ammonia (NH
3
), hydrogen cyanide (HCN), and hydrocarbon liquids.
The sour fuel gas enters Wash Water Feed Knock-out Drum, A2-FA1510,
at 38C [100F] and 6.0 kg/cm
2
(g) [85 PSIG]. Any entrained liquids are
removed automatically on level control and routed to the sour liquids
system. The scrubbed gas enters the bottom of the Wash Water Column,
A2-DA1510, and passes upward through a packed bed where it is
countercurrently contacted with a stream of circulating water. The washed
sour gas stream leaves the top of the column and flows to Amine
Absorber Feed Knock-out Drum, A2-FA1511, to remove any wash water
that may be carried over with the gas. The scrubbed gas proceeds to the
Amine Absorber, A2-DA1511, while any wash water carry-over is routed
to the Closed Drain system on level control.
The wash water leaving the bottom of the column is pumped by the Wash
Water Pump, A2-GA1510A/B, to the Wash Water Filter, A2-FD1510A/B,
for removal of any particulates or other solid material removed from the
sour gas feed. Most of the filtered water is returned to the top of Wash
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-3
Water Column on flow control, after being mixed with fresh makeup water.
The remainder of the filtered water is directed to the Sour Water Stripping
Unit (SWS) to purge the gaseous and liquid contaminants removed by the
wash water from the system. The makeup water rate can be adjusted as
necessary to control the contaminants (primarily ammonia in most cases)
at an acceptable concentration, and the level control on the column
bottoms will automatically adjust the purge rate to balance the water
added to the system with the makeup water flow control.
7.3.3 Sour Gas Contacting
The washed sour refinery fuel gas enters the bottom of the Amine
Absorber at 37C [98F] and 5.8 kg/cm
2
(g) [82 PSIG] and passes upward
through 30 trays to be contacted countercurrently with lean MDEA solvent.
As the sour gas is contacted by the amine, the acidic H
2
S (and CO
2
, if
present) in the gas reacts with the basic amine solution:
(1) H
2
S + CH
3
(CH
2
OHCH
2
)
2
N CH
3
(CH
2
OHCH
2
)
2
NH
+
+ HS


(2) CO
2
+ CH
3
(CH
2
OHCH
2
)
2
N + H
2
O CH
3
(CH
2
OHCH
2
)
2
NH
+
+ HCO
3


This is an acid-base reaction, forming an amine "salt" that remains
dissolved in the aqueous solution. The rich amine leaves the bottom of
the column at 58C [136F] on level control and is routed to the Rich
Amine Flash Drum, A2-FA1513. The treated gas leaves the top of the
column and flows to the Amine Absorber Overhead Cooler, A2-EA1510,
where it is cooled to 37C [98F] before flowing to the Amine Absorber
Overhead Knock-out Drum, A2-FA1512, where any solvent carry-over is
recovered and returned to the rich solvent stream on level control. The
scrubbed treated gas at 37C [98F] and 4.5 kg/cm
2
(g) [64 PSIG] is then
routed to the treated fuel gas header for consumption elsewhere in the
complex.
7.3.4 Solvent Regeneration
The combined rich solvent stream from the Amine Treating Unit, the LPG
Treating Unit, and the DHT Unit enters the Rich Amine Flash Drum at
54C [130F]. This vessel is operated at low pressure (0.64 kg/cm
2
(g)
[9 PSIG]) to maximize the vaporization and removal of any light
hydrocarbons that may be entrained or dissolved in the amine solvent. A
small amount of H
2
S will be liberated from the rich amine by the pressure
reduction, so the resulting flash gases enter the bottom of the Flash Gas
Contactor, A2-DA1512, and flow upward through its packed bed to be
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countercurrently contacted with a small stream of lean amine. The amine
will remove most of the H
2
S from the flash gas, so that the treated gas
flowing to the flare will contain 200 PPMV or less of H
2
S. The rich amine
from the bottom of the packed bed falls into the flash drum to join the
other rich solvent.
The flash drum is large enough to provide 30-40 minutes or more of
residence time for the rich solvent. This allows time for any heavy
hydrocarbons entrained in the solvent to separate as a second liquid
phase that spills over the internal weir at the inlet end of the drum,
collecting in the ATU Skim Oil Sump, A2-FA1516. The ATU Skim Oil
Pump, A2-GA1512A/B, sends the collected hydrocarbon to the
Condensate Feed Tank on start/stop level control.
After removal of any liquid hydrocarbon, the heavier amine phase passes
under the internal weir at the outlet end of the drum to be pumped through
the Rich Amine Filter, A2-FD1511A/B, by the Rich Amine Pump,
A2-GA1513A/B, on level/flow cascade control. The filter removes
particulates from the solvent before it enters the tube side of the
Lean/Rich Amine Exchanger, A2-EA1511A/B. The Rich Amine is
preheated to 105C [221F] by cooling the lean solvent before flowing to
the Stripper, A2-DA1513, entering between trays #4 and #5.
The Stripper contains 30 valve trays (4 wash water trays, 26 stripping
trays) and one chimney draw tray. As the solvent flows down the column,
the absorbed H
2
S and CO
2
are stripped from the MDEA by countercurrent
contact with stripping steam rising upward. This stripping steam is
generated in the Stripper Reboiler, A2-EA1512A/B, using LP
(3.5 kg/cm
2
(g) [50 PSIG]) steam as the heat input. The heat input to the
reboilers is adjusted by flow control of the steam. The steam flow
controllers can be reset by the Stripper overhead temperature, which will
maintain the desired overhead temperature of 114C [238F] by varying
the heat input in proportion to the amount of acid gas contained in the
Rich Amine.
The stripping steam supplies the heat of reaction required to reverse
reactions (1) and (2), and carries the H
2
S and CO
2
stripped from the
solvent overhead to the Stripper Reflux Condenser, A2-EC1511, where
the steam is condensed as the stream is cooled to 49C [120F]. The
condensed water is removed by the Stripper Reflux Accumulator,
A2-FA1514, and returned as reflux to the wash water trays in the tower by
the Stripper Reflux Pump, A2-GA1515A/B. The acid gas (H
2
S and CO
2
,
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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along with the uncondensed water) stripped from the solvent exits the
reflux drum at 0.85 kg/cm
2
(g) [12 PSIG] and flows to the SRUs.
The Lean Amine Booster Pump, A2-GA1514A/B, pumps the regenerated
lean MDEA solvent from the bottom of the Stripper through the shell side
of the Lean/Rich Amine Exchanger, cooling the lean solvent from 259F to
78C [172F] by countercurrent heat exchange with the cool rich amine. A
slipstream of the lean amine then flows through the Lean Amine Filter,
A2-FD1512, to remove accumulated solids from the solvent and through
the Lean Amine Carbon Filter, A2-FD1513, where the activated carbon
adsorbs contaminants such as hydrocarbons and degradation products
from solvent. The Lean Amine After-Filter, A2-FD1514, catches any
carbon "fines" before the filtered slipstream rejoins the main solvent
stream. A portion of the lean amine flows to the DHT unit on temperature
control while the remainder flows to the Lean Amine Cooler, A2-EC1510,
where it is cooled to 50C [122F].
A small stream of cool lean amine is directed on flow control to the top of
the Flash Gas Contactor as described previously. A portion of the cool
lean amine flows to the LPG Treating Unit and a portion flows to the DHT
unit on temperature control. The remaining lean amine is pumped to
higher pressure by the Lean Amine Pump, A2-GA1511A/B before being
directed on flow control to the top of the Amine Absorber.
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7.4 Equipment Description
7.4.1 Wash Water Column, A2-DA1510
The Wash Water Column contains a single bed of random packing to
provide good contact between the sour fuel gas and the circulating wash
water. The tower has a 304 S.S. woven wire mist eliminator above the
packed bed to remove entrained water droplets from the gas before it
leaves the tower.
7.4.2 Amine Absorber, A2-DA1511
The Amine Absorber contains a 30 valve trays to provide good contact
between the sour fuel gas and the amine solvent to remove H
2
S from the
fuel gas. The tower has a 304 S.S. woven wire mist eliminator above the
top bed to remove entrained solvent droplets from the gas before it leaves
the tower.
7.4.3 Flash Gas Contactor, A2-DA1512
As lighter hydrocarbons are allowed to disengage from the amine in the
Rich Amine Flash Tank, a small amine flow scrubs these lighter
hydrocarbons of acid gas as the amine and hydrocarbon flow counter
currently. The Flash Gas Contactor contains a single bed of random
packing which provides good contact between the light hydrocarbon gas
entering below it and the amine fed above it.
7.4.4 Stripper, A2-DA1513
The Stripper contains 28 valve trays to provide good contact between the
rich amine solvent and the reboiler vapors to strip H
2
S and CO
2
from the
solvent. The rich amine enters on the fifth tray from the top; the four trays
above that are "water wash" trays that allow the reflux water (entering on
the top tray) to remove traces of MDEA from the overhead vapor and
minimize solvent losses.
A chimney tray is located below the bottom valve tray to gather all of the
column liquids to feed the Stripper Reboiler. The column section located
below this chimney tray serves to separate the outlet steam and lean
amine from the reboiler and to provide surge for the solvent circulating
system.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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7.4.5 Wash Water Column Packing, A2-DB1510
This bed of random packing provides good contact between the sour fuel
gas entering below it and the wash water fed above it inside the Wash
Water Column. The packing has a bed limiter above it and rests on a bed
support. The quench water is distributed over the packing by a distributor
tray. The packing is 304 S.S.; the other internals are 304 S.S.
Gaskets are installed where the bed support and distributor tray bolt to the
support ring and clips inside the Wash Water Column to prevent direct
contact between the stainless steel internals and the carbon steel vessel.
This electrically isolates the dissimilar metals from each other to prevent
direct contact that could lead to galvanic corrosion.
7.4.6 Amine Absorber Trays, A2-DB1511
These 1-pass valve trays provide good contact between the fuel gas
entering below it and lean amine fed above it inside the Amine Absorber.
The tray decks and tray downcomers are 304L S.S., and the valves are
fabricated from 304 S.S. to resist corrosion and to prevent "sticking" to the
tray decks.
7.4.7 Stripper Trays, A2-DB1513
These 1-pass valve trays provide good contact between the rich amine
solvent fed above them and the reboiler vapors fed below them inside the
Stripper. The tray decks are 304L S.S., and the valves are fabricated
from 304 S.S. to resist corrosion and to prevent "sticking" to the tray
decks. The chimney tray deck is 304L S.S. The bottom valve tray has a
seal pan for its downcomer to maintain a liquid seal and prevent gas from
blowing up the downcomer.
The chimney tray gathers the tower liquids to feed the reboiler. The outlet
from the reboiler reenters the column below the chimney tray, with the
vapor produced by the reboiler flowing upward through the chimneys in
order to reach the valve trays above.
The top four trays in the column are located above the rich amine feed
point and serve as water-wash trays to minimize the amount of amine
carried-over in the tower overhead. Since these trays have only the reflux
water flowing over them, the liquid rates for these trays are much lower
than for the trays lower in the column. For this reason, these four trays
are designed for minimum leakage (i.e., picket fence weirs, minimum
downcomer clearance, etc.).
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Issued 30 August 2011 Amine Treating & Regeneration Page 7-8
7.4.8 Amine Absorber Overhead Cooler, A2-EA1510
This shell and tube exchanger is used to provide the final cooling of the
treated fuel gas, with cooling water from the complex as the cooling
medium.
7.4.9 Lean/Rich Exchanger, A2-EA1511A/B
These shell and tube exchangers conserve energy by providing heat
exchange between the rich amine and the lean amine, so that the hot lean
amine leaving the Stripper can preheat the rich amine before it feeds the
Stripper. This cross exchange saves reboiler duty by preheating the rich
amine, and reduces the load on the Lean Amine Cooler by partially
cooling the hot lean amine.
7.4.10 Stripper Reboiler, A2-EA1512A/B
The Stripper Reboilers are a fixed tubesheet shell and tube heat
exchangers. The exchangers are arranged as once-through vertical
thermosiphon reboilers, mounted on the side of the Stripper. The static
head of the solvent above the inlet nozzle on the lower channel provides
the driving force to circulate the solvent through the tubes. LP steam on
the shell of the exchangers heats the solvent inside the tubes, partially
vaporizing it to create stripping steam to remove the H
2
S and the CO
2

from the solvent flowing down the Stripper.
7.4.11 Stripper Reflux Condenser, A2-EC1511
This forced-draft aerial exchanger provides cooling to condense the
majority of the water from the acid gas stream leaving the overhead of the
Stripper. Fans are used to circulate air across the finned tubes to remove
heat from the overhead stream and condense the water to be used as
reflux for the tower.
7.4.12 Lean Amine Cooler, A2-EC1510
This forced-draft aerial exchanger provides the final cooling of the lean
amine stream returning from the regeneration section of the process.
Fans are used to circulate air across the finned tubes to remove heat from
the solvent.
7.4.13 Wash Water Feed Knock-Out Drum, A2-FA1510
This vertical vessel is installed in the inlet sour fuel gas line to remove
liquids from the gas stream before it is routed to the Wash Water Column.
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The liquid produced in this vessel is routed to the closed drain on
automatic start/stop control. The vessel is equipped with high level alarms
to warn of a rising level in the drum, and a high-high level shutdown to
activate the ATU ESD system before liquids can reach the column. The
shutdown requires that 2 out of 3 transmitters have a high-high level
indicated.
7.4.14 Amine Absorber Feed Knock-Out Drum, A2-FA1511
This vertical vessel is installed in the overhead line from the Wash Water
Column to remove liquids from the gas stream before it is routed to the
Amine Absorber. The liquid produced in this vessel is routed to the closed
drain on automatic start/stop control. The vessel is equipped with high
level alarms to warn of a rising level in the drum, and a high-high level
shutdown to activate the ATU ESD system before liquids can reach the
absorber. The shutdown requires that 2 out of 3 transmitters have a
high-high level indicated.
7.4.15 Amine Absorber Overhead Knock-Out Drum, A2-FA1512
This vertical vessel is installed in the overhead line from the Amine
Absorber to remove liquids from the treated fuel gas stream before it is
routed to the complex fuel gas system. The liquid produced in this vessel
is combined with the rich amine stream leaving the Amine Absorber on
automatic start/stop control.
7.4.16 Rich Amine Flash Drum, A2-FA1513
This horizontal vessel allows for the removal of hydrocarbons that may be
carried out of the various upstream processes with the amine. The rich
amine enters the vessel through a slotted, vertical distributor. Any
hydrocarbon that may be carried with the amine from the upstream
processes will accumulate in the center section of this vessel. When a
sufficient amount of hydrocarbon has accumulated, the hydrocarbon will
overflow the partition and flow into the hydrocarbon section. Lighter
hydrocarbons are disengaged from the amine and exit through the Flash
Gas Contactor where they are washed free of any acid gases.
Hydrocarbon-free amine then passes under another partition, at the
opposite end of the vessel, and into the amine outlet section, where the
amine is pumped to the Stripper.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
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Issued 30 August 2011 Amine Treating & Regeneration Page 7-10
7.4.17 Stripper Reflux Accumulator, A2-FA1514
This vertical pressure vessel removes condensed water from the stream
leaving the Stripper Reflux Condenser so that the water can be used as
reflux for the Stripper. The vessel has a 304 S.S. woven wire mist
eliminator in the top to remove entrained liquid droplets from the gas
before it leaves the vessel.
7.4.18 Stripper Reboiler Condensate Pot, A2-FA1515A/B
These two vertical pressure vessels collect the condensate from the
Stripper Reboiler and return it to the condensate system on level control.
This method of removing condensate from the exchanger provides much
smoother control of the heat input to the reboiler than a conventional
steam trap could.
As stated above, this vessel is simply a very good steam trap. During
normal operation, the steam pressure required to provide the necessary
reboil heat to the Stripper may be much less than the 3.5-4.2 kg/cm
2
(g)
steam pressure available in the LP steam system. The normal steam
pressure in the shell of the reboiler may be such that the water level in the
condensate pot will rise upwards from the pot, perhaps even within the
shell of the reboiler. During these periods, the level valve will remain fully
open and the sight glass will indicate a full water level. This is a normal
operating condition for this vessel. The vessel will usually operate with a
visible level only when the Stripper Reboiler is operating near its
maximum capacity with full steam pressure on the shell of the exchanger.
Under these conditions, the level control and level valve will function
normally and maintain a water level in the vessel.
7.4.19 ATU Skim Oil Sump, A2-FA1516
This horizontal vessel is located in a below-ground concrete vault. It
collects the heavy hydrocarbons from the Rich Amine Flash Tank. The
collected hydrocarbon liquid is pumped back to the Condensate Feed
Tank on stop/start level control.
7.4.20 ATU Skim Oil Pump Sump, A2-FA1517A/B
These vertical vessels house the ATU Skim Oil pumps. Hydrocarbon
liquids from the ATU Skim Oil Sump flow into this vessel and are pumped
out by the ATU Skim Oil Pump.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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Issued 30 August 2011 Amine Treating & Regeneration Page 7-11
7.4.21 ATU Amine Drips Tank, A2-FA1580
This horizontal pressure vessel is located in a below-ground concrete
vault. It collects solvent from the ATU via headers when equipment is
drained for maintenance, etc. The vessel will normally operate with little
or no pressure so that gravity-flow is sufficient to cause solvent to drain
into the vessel. The collected solvent is pumped back to the solvent
system in the ATU for reuse when the vessel gets full.
7.4.22 MDEA Storage Tank, A2-FB1580
This vertical, cylindrical, cone roof storage tank holds fresh MDEA solvent
unloaded from transport trucks until it is needed for make-up to the ATU
solvent system.
7.4.23 Wash Water Filter, A2-FD1510A/B
These filters are designed to remove solid particles 5 microns and larger
from the circulating wash water.
7.4.24 Rich Amine Filter, A2-FD1511A/B
These full-flow filters are designed to remove solid particles 5 microns and
larger from the circulating rich solvent, which will help prevent fouling of
the downstream heat exchangers.


THESE FILTERS HANDLE LIQUID CONTAINING H
2
S AND OTHER
HARMFUL SUBSTANCES. ALWAYS OBSERVE PROPER
PROCEDURES AND PRECAUTIONS WHEN PERFORMING
MAINTENANCE ON THIS FILTER. THE "GENERAL SAFETY"
SECTION OF THESE GUIDELINES SHOULD BE CONSULTED IF
THERE IS ANY DOUBT ABOUT HOW TO WORK SAFELY WHEN
H
2
S MAY BE PRESENT.
7.4.25 Lean Amine Filter, A2-FD1512
This full-flow filter is designed to remove solid particles 5 microns and
larger from the circulating lean solvent.
WARNING
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
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Issued 30 August 2011 Amine Treating & Regeneration Page 7-12
7.4.26 Lean Amine Carbon Filter, A2-FD1513
This full-flow filter is designed to remove organic contaminants (trace
hydrocarbons, degradation products, etc.) from a slipstream of the
circulating lean solvent using a bed of activated carbon.
7.4.27 Lean Amine After-Filter, A2-FD1514
This filter is designed to remove solid particles, particularly carbon fines,
5 microns and larger from the lean solvent leaving the Lean Amine
Carbon Filter.
7.4.28 ATU Amine Drips Filter, A2-FD1580
This filter is designed to remove solid particles 5 microns and larger from
the recovered solvent drained from equipment, etc. in the ATU. The
recovered solvent is filtered as it is routed back to the ATU.


SINCE THE PUMPS DESCRIBED IN THE FOLLOWING SECTIONS ARE
CONSTRUCTED OF STAINLESS STEEL, DO NOT HYDROTEST THE
ASSOCIATED VESSELS OR PIPING WITH WATER CONTAINING HIGH
LEVELS OF CHLORIDES. AVOID ALLOWING WATER CONTAINING MORE
THAN 50 PPM CHLORIDES TO COME IN CONTACT WITH THESE PUMPS TO
PREVENT STRESS CORROSION CRACKING OF THE STAINLESS STEEL.


THE LIQUID IN THESE PUMPS CONTAINS DISSOLVED H
2
S. THIS H
2
S CAN
BE RELEASED TO THE SURROUNDINGS WHEN LIQUID IS DRAINED FROM
THESE PUMPS OR FROM THE PIPING CONNECTED TO THE PUMPS.
ALWAYS OBSERVE PROPER PROCEDURES AND PRECAUTIONS WHEN
DRAINING LIQUID FROM THESE PUMPS OR PERFORMING MAINTENANCE
ON THEM. THE "GENERAL SAFETY" SECTION OF THESE GUIDELINES
SHOULD BE CONSULTED IF THERE IS ANY DOUBT ABOUT HOW TO WORK
SAFELY WHEN H
2
S MAY BE PRESENT.
CAUTION
WARNING
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
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Issued 30 August 2011 Amine Treating & Regeneration Page 7-13
7.4.29 Wash Water Pump, A2-GA1510A/B
These centrifugal pumps are used to circulate wash water to which is
used to remove contaminates from the sour gas feed stream. Each pump
is designed for the total duty; the other pump is a 100% spare. These
pumps are equipped with tandem seals to reduce the likelihood of
releasing H
2
S to the surroundings.
7.4.30 Lean Amine Pump, A2-GA1511A/B
These centrifugal pumps are used to send the lean amine from the Amine
Regeneration Unit to the Amine Absorber. Each pump is designed for the
total duty; the other pump is a 100% spare. These pumps are equipped
with tandem seals to reduce the likelihood of releasing H
2
S to the
surroundings.
7.4.31 ATU Skim Oil Pump, A2-GA1512A/B
These vertical sump-type pump is mounted in the ATU Skim Oil Pump
Sump to transfer the recovered hydrocarbons back to the Condensate
Feed Tank.
7.4.32 Rich Amine Pump, A2-GA1513A/B
These centrifugal pumps are used to send the rich amine from the Rich
Amine Flash Drum to the Stripper. Each pump is designed for the total
duty; the other pump is a 100% spare. These pumps are equipped with
tandem seals to reduce the likelihood of releasing H
2
S to the
surroundings.
7.4.33 Lean Amine Booster Pump, A2-GA1514A/B
These centrifugal pumps are used to send the lean amine from the Amine
Regeneration Unit to the DHT Unit, the LPG Treating Unit, and to the
suction of the Lean Amine Pumps in the Amine Treating Unit. Each pump
is designed for the total duty; the other pump is a 100% spare. These
pumps are equipped with tandem seals to reduce the likelihood of
releasing H
2
S to the surroundings.
7.4.34 Stripper Reflux Pump, A2-GA1515A/B
These centrifugal pumps are used to send the reflux from the Stripper
Reflux Accumulator to the Stripper. Each pump is designed for the total
duty; the other pump is a 100% spare. These pumps are equipped with
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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Issued 30 August 2011 Amine Treating & Regeneration Page 7-14
tandem seals to reduce the likelihood of releasing H
2
S to the
surroundings.
7.4.35 MDEA Transfer Pump, A2-GA1580
This single-stage centrifugal pump is used to transfer amine from the
MDEA Storage Tank to the ATU solvent system. This pump does not run
continuously so no spare is provided.


Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-15
7.5 Instrumentation and Control Systems
7.5.1 Treated Fuel Gas H
2
S Analyzer
Analyzer A2-AE15057 measures the H
2
S concentration in the treated fuel
gas leaving Amine Absorber Overhead Knock-out Drum, A2-FA1512. If
the H
2
S concentration exceeds the specification for fuel gas (200 PPMV),
DCS relay A2-AY15057 should start ramping down the signal that
pressure controller A2-PC15057 is supplying to control valve
A2-PV15057. As this valve closes, the pressure will start to rise, until it
reaches the setpoint (6.0 kg/cm
2
(g)) of the over-ride pressure controller,
A2-PC15059, which will then open control valve A2-PV15059 to divert the
fuel gas to the flare header. The duration of the ramping should be about
60 seconds or so, so that the pressure in the system does not change too
rapidly.
Once the H
2
S concentration is back on-specification, A2-AY15057 should
start ramping up the signal from A2-PC15057 to A2-PV15057. As this
control valve opens and the pressure starts to drop back to its normal
value (5.0 kg/cm
2
(g)), the over-ride pressure controller will then close
A2-PV15059, so that the fuel gas is flowing to the fuel gas header once
again. The duration of this ramping should again be about 60 seconds or
so, so that the pressure in the system does not change too rapidly.
A2-HS15057 in the DCS is a bypass to disable relay A2-AY15057 and
prevent it from changing the control signal to A2-PV15057. This switch
can be used to prevent upset of process operations when calibrating or
performing maintenance on the analyzer.
7.5.2 ATU Emergency Shutdown Systems
The purpose of the ATU ESD system is to shut off the flow of sour fuel
gas to the treating system when serious problems occur. The Cause and
Effect Diagrams are contained in the Instrumentation and Controls
Drawings section of the Basic Engineering Package. These diagrams
describe the ATU ESD system in block format. For reference, the causes
and effects of the ESD system shown on these diagrams is explained
below.
7.5.2.1 Causes of ATU ESD
Any one of the devices listed below will activate the ATU ESD
system:
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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a. Manual Shutdown Switch, A2-HS15022
An operator can activate the ATU ESD system using these
guidelines shutdown switch in the DCS, a "timed pulse" switch.
b. Wash Water Feed Knock-out Drum High-High Liquid Level,
A2-LT15008A/B/C.
This device prevents liquids in this vessel from entering the
wash water system for the sour refinery fuel gas and
contaminating it, since this could then lead to contamination of
the solvent system. It is set to actuate if the liquid level reaches
1,050 mm above the bottom seam of the vessel. Note that
there are three independent transmitters and 2oo3 voting logic
is used for the ESD (i.e., at least two transmitters must show
high-high level) to avoid spurious "trips" due to the malfunction
of a single transmitter.
c. Amine Absorber Feed Knock-out Drum High-High Liquid Level,
A2-LT15030A/B/C.
This device prevents liquids in this vessel from entering the
Amine Absorber and contaminating the solvent system. It is set
to actuate if the liquid level reaches 1,200 mm above the
bottom seam of the vessel. Note that there are three
independent transmitters and 2oo3 voting logic is used for the
ESD.
d. Amine Absorber Low-Low Liquid Level, A2-LT15040A/B/C.
If the solvent level drops too low in the Amine Absorber, large
amounts of high pressure gas could blow through control valve
A2-LV15040 into the Rich Solvent Flash Drum, A2-FA1513, and
other equipment and piping in the ATU/ARU with a lower design
pressure than this column. Loss of solvent in this column could
also result in the treated fuel gas going sour.
This device is set to actuate if the liquid level drops to 450 mm
above the bottom seam of the vessel. To reduce the chances
of blow-through, this device will also de-energize solenoid valve
A2-NY15040 to close the control valve. Note that there are
three independent transmitters and 2oo3 voting logic is used for
the ESD.
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7.5.2.2 Effects of ATU ESD
A shutdown of the Amine Absorber, activated either manually or
automatically, has the following effects on the ATU/ARU:
a. Closes A2-NV15002, blocking the flow of high pressure sour
fuel gas into the ATU.
b. If the ESD system is activated by low-low level in the Amine
Absorber, closes A2-LV15040 to prevent possible blow-through
of high pressure gas into the low pressure sections of the
ATU/ARU.
When S/D valve A2-NV15002 closes to stop the gas flow into the
ATU, the pressure of the incoming sour fuel gas will begin to rise.
When it reaches the setpoint (6.3 kg/cm
2
(g)) of over-ride pressure
controller A2-PC15001, the controller will open control valve
A2-PV15001 to divert the sour gas to the flare header.
7.5.2.3 Non-ESD Shutdowns and Alarms
In addition to the devices listed in Section 7.5.2.1 that activate the
ATU ESD system, there are several interlocks of significance that
either generate an alarm or shut down an individual piece of
equipment. These devices/interlocks and their effects are described
in this section.
a. Wash Water Column Low-Low Level, A2-LT15014A/B/C
The Wash Water Pump (A2-GA1510A/B) could be damaged if
the pump loses suction because the level in the Wash Water
Column drops too low. This device will protect the pump by
stopping it before this can occur. The setpoint is 450 mm
above the bottom seam of the column. Note that there are
three independent transmitters and 2oo3 voting logic is used for
the shutdown.
b. Treated Fuel Gas High-High H
2
S, A2-AE15057
This device closes pressure control valve A2-PV15057 to the
treated fuel gas header and opens pressure control valve
A2-PV15059 to the flare header when the H
2
S concentration for
the treated fuel gas exceeds 200 ppmv.
a. Rich Amine Flash Drum Low-Low Level, A2-LT15068A/B/C
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
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Issued 30 August 2011 Amine Treating & Regeneration Page 7-18
The Rich Amine Pump (A2-GA1513A/B) could be damaged if
the pump loses suction because the level in the Rich Amine
Flash Drum drops too low. This device will protect the pump by
stopping it and closing the downstream flow control valve
before this can occur. The setpoint is 685 mm above the
bottom of the vessel. Note that there are three independent
transmitters and 2oo3 voting logic is used for the shutdown.
c. Lean Amine Cooler Fan High Vibration, A2-WSH15080
Each fan on the Lean Amine Cooler (A2-EC1510) is provided
with its own vibration switch. If the vibration sensed by the
switch exceeds the preset level, the switch will trip to stop the
associated fan and activate an alarm in the DCS.
d. Stripper Low-Low Level, A2-LT15108A/B/C
The Lean Amine Booster Pump (A2-GA1514A/B) could be
damaged if the pump loses suction because the level in the
Stripper drops too low. Likewise, the Lean Amine Pump
(A2-GA1511A/B) could be damaged if the pump loses suction
because the Lean Amine Booster Pump has stopped. This
device will protect these pumps by stopping both pumps before
this scenario can occur. The setpoint is 450 mm above the
bottom seam line of the column. Note that there are three
independent transmitters and 2oo3 voting logic is used for the
shutdown.
e. Stripper Reflux Condenser Fan High Vibration, A2-WSH15118
Each fan on the Stripper Reflux Condenser (A2-EC1511) is
provided with its own vibration switch. If the vibration sensed
by the switch exceeds the preset level, the switch will trip to
stop the associated fan and activate an alarm in the DCS.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-19
7.6 Process Principles and Operating Techniques
The more important considerations involved in startup, operation, shutdown,
maintenance, and emergency procedures for the ATU and ARU are
discussed in the remaining sections of this portion of the operating guidelines.
The operator should also be thoroughly acquainted with the equipment and
the "Process Description" section of these guidelines before attempting to
operate the plant in accordance with the operating techniques that follow. If
the function of each portion of the plant equipment is understood, the
sequence of steps outlined in the "procedures" sections will be more easily
understood. In addition, the following general discussion of principles and
techniques will clarify the reasons for some of the procedures.
7.6.1 Amine Absorber Operation
The main requirement for the Amine Absorber is to consistently produce
treated fuel gas which contains a low level of residual H
2
S.
The absorption of H2S in the amine solution is favored by:
1. Low temperature
2. Acid gas loading
3. High amine concentration
4. High H2S partial pressure in the feed stream
5. Intimate contacting
In general practice, items 4 and 5 are not operating variables, having been
fixed by the design criteria for the unit and choice of equipment in the
absorber design.
7.6.1.1 Low Temperature
The lower the temperature of the lean amine solution, the better the
H2S removal. When treating a hydrocarbon gas, however, the lean
amine temperature is limited by the temperature of the gas being
treated. The lean amine temperature must be maintained 3-6C
higher than that of the gas feed stream to avoid any possible
condensation of these vapors. The circulating lean amine
temperature before it enters the absorber is commonly between
27C and 49C.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-20
7.6.1.2 Acid Gas Loading
Good acid gas removal efficiency depends on good amine solution
regeneration, as will be discussed in the following sections. However,
it also depends on restricting the H2S loading in the rich amine to
favor the forward direction of reaction (1) given in section 7.3.3. The
loading of the amine solution is controlled by adjustment of the amine
circulation rate. In most cases, unless special design considerations
have been employed, the rich amine acid gas loading (H2S plus
CO2) should not exceed 0.3 to 0.4 mols total acid gas per mol of
amine present.
7.6.1.3 High Amine Concentration
The concentration of uncombined amine ion is favored by high amine
concentration in the amine solution, good regeneration, and freedom
from strong acids. Practical and economic considerations confirmed
by field experience have generally shown that the optimum amine
concentration is between 15 and 50 wt-% amine depending upon the
type of amine used. This is based on the lowest heat requirement for
the desired H2S removal, the lowest chemical losses, and the fewest
operational problems. The free amine ion concentration in the lean
amine is mainly affected by the efficiency and control of amine
regeneration. The fewer the sulfide ions in the lean amine, the
greater the free amine ion concentration available for removal of
H2S. In most cases, lean amine should not contain more than 0.03
mol H2S per mol amine nor more than 0.1 mol CO2 per mol amine.
The amine strength should be monitored and the amine content of
the circulating amine should be maintained close to the 45% (by
weight) design value. Should the amine concentration decrease
(normally due to blowdown and other amine losses), it will be
necessary to add fresh amine to compensate. Laboratory
procedures for analyzing amine are given in a later section of these
guidelines.
The amine should also be checked periodically for heat-stable salt
content. Heat-stable salts form when the amine in the amine solution
(a base) reacts with strong acids to form salts that do not decompose
at the normal amine regeneration temperature. The most common
heat-stable salts encountered in amine systems are SO
2
salts,
although oxygen contamination of the amine is another common
culprit for heat-stable salts in these systems. Heat-stable salts
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-21
increase the corrosivity of the amine (particularly at higher
temperatures, like in the Stripper Reboiler) and increase the foaming
tendencies of the amine. (Interestingly, heat-stable salts sometimes
improve the H
2
S-removal capability of the amine, but the higher
corrosion rate caused by the salt far outweighs this advantage.)
A heat-stable salt content of 2 wt % or lower is desirable. Salt
contents in the 5-20 wt % range can be corrosive and should be
avoided if possible. The only way to reduce the heat-stable salt
content of the amine is by dilution, blowing down some of the
circulating amine and making up with fresh amine. There is no
means for regenerating heat-stable salt from the amine while it is in
the ATU/ARU, as vacuum distillation is required. (In recent years,
however, several companies have successfully reclaimed amine
on-line using ion exchange on a slipstream of the amine.) There are
firms that specialize in reclaiming amine (usually off-site), and it may
be economical to use such a firm if a large amount of amine has
been contaminated with heat-stable salts. The best practice,
however, is to avoid forming heat-stable salt in the first place by
proper operation of the ATU, and gas-blanketing the fresh amine to
avoid oxygen contamination.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-22
7.6.2 Stripper Operation
The lean amine must remain comparatively free of H
2
S and CO
2
to assure
attainment of the fuel gas specification. These acid gases are removed
from the rich amine in the Stripper by stripping them out with steam. The
stripping steam supplies heat to reverse the acid-base reaction between
the H
2
S/CO
2
and the amine, and also reduces the H
2
S/CO
2
partial
pressure in the vapor phase inside the column to promote mass transfer
from the liquid.
The stripping steam is produced by vaporizing some of the water in the
amine in the Stripper Reboiler, using LP (3.5-4.2 kg/cm
2
(g)) steam for the
heat input. The steam rate to the reboiler (and, hence, the amine stripping
rate) is controlled by A2-FC15112A. Adjust this steam rate as needed to
keep the H
2
S and CO
2
loading in the lean amine low. See Section 7.10 in
these guidelines for appropriate laboratory procedures. For a given
column operating pressure, the overhead temperature is a direct
indication of the stripping rate: the higher the temperature, the more
stripping. Column bottoms temperature should not be used as a guideline
for degree of stripping, as it is a function only of amine concentration and
column pressure.


THE DESIGN STRIPPING STEAM RATE SHOWN ON THE
PROCESS FLOW DIAGRAM SHOULD BE CLOSE TO OPTIMUM.
ALTHOUGH IT MAY BE POSSIBLE TO REDUCE THIS SOMEWHAT
WITHOUT GOING OUT OF COMPLIANCE (I.E., WITH LITTLE
CHANGE IN THE H
2
S LOADING OF THE LEAN SOLVENT),
REDUCING THE STRIPPING STEAM RATE SIGNIFICANTLY CAN
CAUSE ACCELERATED CORROSION DUE TO HIGH CO
2

LOADINGS IN THE LEAN SOLVENT. SEVERAL PLANTS HAVE
REPORTED UNEXPECTEDLY HIGH CORROSION RATES IN THE
HOT, HIGH VELOCITY AREAS OF THE LEAN SOLVENT SYSTEM,
SUCH AS THE OUTLET ENDS OF THE REBOILER TUBES AND
THE LEAN SOLVENT PUMPS, AFTER REDUCING THE REBOILER
STEAM.
CAUTION
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-23
IF IT IS NECESSARY TO OPTIMIZE THE STEAM TO THE
STRIPPER REBOILER, REDUCE THE STEAM BY SMALL
INCREMENTS AND CHECK THE LEAN SOLVENT LOADINGS
(BOTH H
2
S AND CO
2
) AFTER EACH CHANGE. DO NOT REDUCE
THE STEAM FURTHER IF EITHER LOADING BEGINS TO RISE
SIGNIFICANTLY, AND BE PREPARED TO PERFORM MORE
EXTENSIVE CORROSION MONITORING WHEN OPERATING THE
STRIPPER IN THIS MANNER. REFER TO SECTION 7.10 OF
THESE GUIDELINES FOR THE PROCEDURES TO BE USED TO
DETERMINE THE LEAN SOLVENT LOADINGS.
The withdrawal of lean amine from the bottom of the Stripper is on flow
control to the Amine Absorber. As a result, the level in the bottom of the
Stripper, which serves as the "surge" for the system, will usually indicate if
adjustments of water makeup to the amine system (or water "bleed" from
the system) are required to maintain the proper water balance, as
discussed later in Section 7.6.3 Even if water must be bled from the
system by diverting some of the column reflux to Sour Water Stripping, the
amine content of that waste stream should be low and only infrequent
makeup of fresh amine should be required.
It may also be necessary to "purge" ammonia from the reflux water
periodically by routing some of the reflux water to the Sour Water
Stripping Unit. Although ammonia is usually removed by the circulating
water in the Wash Water Column, over a period of time, however, some of
the ammonia may carry over into the Amine Absorber and dissolve in the
amine.
When this ammonia-containing amine reaches the Stripper, the ammonia
becomes "trapped" because it is too light (volatile) to leave in the column
bottoms and too heavy to leave in the overhead (the acid gas). As a
result, the ammonia will become concentrated in the reflux water, to the
point where it exceeds its solubility limits and begins to cause plugging
problems. If this problem is suspected, simply "bleed" a small amount of
the reflux water to the disposal header to purge the ammonia from the
system, using the bleed water flow controller in the DCS to control the
bleed water rate while monitoring the reflux flow rate to ensure that
adequate reflux is maintained to the Stripper. Operating experience will
show how often (and how much) the reflux must be purged in this manner
to prevent excessive ammonia concentrations for a particular plant.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-24
There is full-flow of rich amine through the Rich Amine Filter, and full-flow
of lean amine flow through the Lean Amine Filter, the Lean Amine Carbon
Filter, and the Lean Amine After-Filter. These four filters will remove
solids and organic contaminants from the circulating amine, such as
degradation or corrosion products. The filter elements should be changed
as soon as the "change" pressure drop is reached, to remove as many
solids from the amine as possible. Finely divided solids can cause
foaming and thereby limit column capacity. While it is possible to reduce
foaming to some extent with anti-foam agents, the presence of such
agents may also reduce H
2
S/CO
2
selectivity in the Amine Absorber, so it
is preferable that they not be used as an alternative to regular
conscientious filter maintenance
7.6.3 Amine Water Balance
The water content of the circulating amine is determined by the following
factors:
1. The water content of the feed gas to the Amine Absorber (the
overhead from the Wash Water Column).
2. The water content of the treated gas leaving the Amine
Absorber.
3. The water content of the acid gas leaving the Stripper Reflux
Accumulator.
4. The amount of water makeup to (or water "bleed" from) the
amine system.
For given operating pressures, the water content of each gas stream will
be determined by the temperature at the top of the respective vessel
(Water Wash Column, Amine Absorber, and Stripper Reflux Accumulator,
respectively), and will increase as the temperature increases. Since the
Amine Absorber inlet gas is at a slightly higher pressure than the outlet
treated gas, the inlet gas will normally contain less water than is contained
in the outlet gas (if both gas streams are at the same temperature), thus
requiring water makeup to maintain the proper water content of the amine.
This situation will be reversed if the Amine Absorber overhead
temperature is lower than the Wash Water Column overhead temperature,
requiring a "bleed" of water to maintain water balance.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-25
Since the lean amine to the Amine Absorber is on flow control and
withdrawal of the rich amine from the bottom of the Amine Absorber is on
level control, a net gain or loss in the amine water balance will be reflected
by an increase or decrease, respectively, of the liquid level in the bottom
of the Stripper. Observation of this liquid level can thus guide adjustment
of water makeup/bleed rate or operating conditions to maintain the desired
water concentration of the circulating amine. Since the degree of H
2
S
removal can depend on the amine concentration of the amine, the
concentration should be maintained close to the design value (45 wt %)
by appropriate maintenance of water concentration. It is usually possible
to control the water balance without adding fresh water or "bleeding" water
to the Sour Water Stripping Unit by adjusting the operating temperatures
in the unit, as discussed in the following paragraphs. Following the steps
outlined below will allow controlling the water balance with minimum
usage of treated makeup water and minimum impact on the sour water
system.
A persistently increasing liquid level in the bottom of the Stripper at
constant flow rates and conditions for Amine Absorber feed gas and
amine indicates a gain in the amine water content. To reduce the water
content of the amine, the preferred sequence of gradual adjustments is:
A. Reduce or terminate water makeup to the amine. Makeup water is
cold condensate.
(1) Begin "bleeding" water (or increase the "bleed" water rate) from
the amine system with the flow controller on the discharge line
of the Stripper Reflux Pump.
Be careful, however, not to starve the Stripper for reflux by
withdrawing too much water. Use the DCS flow indicator for the
reflux water to monitor the operation so that adequate reflux is
maintained to the Stripper when bleeding water from the amine
system.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-26


UNDER NORMAL CONDITIONS, THE REFLUX WATER
CONTAINS LITTLE OR NO AMINE BECAUSE OF THE "WASH
WATER" TRAYS ABOVE THE SOLVENT FEED TRAY IN THE
STRIPPER. HOWEVER, IF THE STRIPPER IS FLOODING OR
FOAMING (AS INDICATED BY HIGH OR ERRATIC COLUMN
DIFFERENTIAL PRESSURE), THE REFLUX CAN CONTAIN
LARGE AMOUNTS OF AMINE.
IF THE "BLEED" WATER LINE IS IN USE AT SUCH TIMES, A
SIGNIFICANT QUANTITY OF SOLVENT CAN BE LOST TO
THE SOUR WATER SYSTEM, AND WILL HAVE TO BE
REPLACED WITH FRESH AMINE FROM THE STORAGE
TANK. FOR THIS REASON, THE "BLEED" WATER SYSTEM
SHOULD BE BLOCKED-IN DURING UPSETS IN THE
STRIPPER.
(2) Increase the Amine Absorber overhead temperature by raising
the setpoint of the lean solvent temperature controller to
increase the lean solvent temperature.
This will increase the amount of water leaving in the fuel gas,
and it will also reduce the H
2
S-removal capability of the solvent.
An increase in solvent flow rate will probably be needed to
maintain the same H
2
S content in the vent gas, increasing the
load on the Stripper and the other process equipment
associated with the circulating solvent.
(3) Increase the acid gas temperature by increasing the
temperature setpoint of the reflux temperature controller to raise
the outlet temperature from the Stripper Reflux Condenser.
Although this will increase the water content of this stream and
reduce the water in the solvent, the effect will be small because
the quantity of acid gas is small relative to the fuel gas. This
adjustment is the least effective and would not normally be
considered during routine operations.
CAUTION
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-27
(4) Should the solvent inventory be difficult to control due to
continuing problems with an excessive amount of water in the
solvent, the steam-heated Stripper Reboiler should be checked
for tube leaks.
B. Conversely, a persistently decreasing liquid level in the bottom of the
Stripper indicates a loss in the solvent water content. To increase
the water content of the solvent, the preferred sequence of gradual
adjustments is:
1. Reduce or terminate the "bleed" water from the Stripper Reflux
Accumulator.
2. Decrease the Amine Absorber overhead temperature by
lowering the lean solvent temperature with the lean solvent
temperature controller to reduce the amount of water leaving in
the fuel gas.
3. Decrease the acid gas temperature with the aerial cooling from
the Stripper Reflux Condenser to reduce the water loss in the
stream as much as possible.
4. Begin water makeup (or increase the makeup water rate) to the
solvent system using the make-up flow controller to add
condensate to the system..
7.6.4 Amine Loss
The loss of MDEA by chemical degradation in the ATU/ARU is expected
to be negligible because the upstream Wash Water Column should wash
out any acids or other contaminates that enter with the sour fuel gas.
Amine degradation can occur, however, under abnormal operating
conditions.
Amine degradation occurs via reactions with acids which can enter the
Amine Absorber when the Wash Water Column is experiencing an upset.
Any traces of acid entering the Amine Absorber will react with the MDEA
to form a thermally non-regenerable complex (i.e., heat-stable salt). If
present in sufficient quantity, this salt can alter the H
2
S-amine equilibrium
and prevent removal of H
2
S to the desired level in the Amine Absorber
overhead. Heat-stable salts also increase the corrosivity of the amine.
Amine quality can be restored by treatment with an amount of caustic
equivalent to the non-regenerable salt present but, if repeated caustic
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-28
treatments are necessary due to repeated mal-operation, the potential for
salt deposition in the system may rise.
The equipment in the ATU/ARU, including the seals of pumps and
blowers, should be operated at positive pressure to minimize the potential
for oxygen (air) ingress into the amine. Oxygen will react with the amine
to produce carboxylic acids that cause the solution to be corrosive. For
this same reason, it is important to maintain an inert gas "blanket" on the
MDEA storage tank to prevent oxygen contamination of the fresh amine.
Amine losses due to entrainment in the treated fuel gas or the acid gas
can be minimized by proper process operation (avoidance of column
overloading, foaming, etc.) and routine inspection of the vessel internals.
Amine losses in the water "bleed" from the Stripper reflux should be
negligible if the rectifying trays (the "wash water" trays above the amine
feed point) in the Stripper are operating properly (no flooding or foaming,
no mechanical damage).
The primary source of amine loss will likely be the mechanical losses from
pump drips, cleaning of filters, etc. Good housekeeping practices,
including prompt replacement or repair of leaking pumps, together with
proper collection of amine drips for reuse (via the ATU Drips Tank,
A2-FA1580), will minimize the mechanical loss of amine.

Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-29
7.6.5 Operation at Low Flow Rates
The ATU/ARU contains four columns: the Wash Water Column and the
Flash Gas Contactor, which contain structured packing; and the Amine
Absorber and Stripper, which contain valve trays. In general, the liquid
feed rate to packed towers can decrease in proportion with the gas flow
rate down to about 50% of design gas flow rate. Below this point, the
liquid rate cannot be allowed to drop any further without risking poor
column performance due to uneven liquid distribution and wetting of the
packing. Trayed towers typically offer somewhat better turndown,
allowing the liquid rate to drop to 30-40% of design before "weeping" of
the trays begins to significantly affect performance.
In the case of the Wash Water Column, decrease the wash water rate in
proportion with the gas flow rate down to about 50% of design should
maintain adequate performance. (It should be noted, however, that there
is really no detrimental effect if the wash water circulation is simply left at
the design value at all times. The only drawback is slightly higher power
consumption by the pump and aerial cooler.)
In the packed Amine Absorber, circulating more amine relative to the gas
flow rate should maintain performance. The liquid flow rate should be
maintained at a minimum of about 50%.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-30
7.7 Precommissioning Procedures
Prior to the initial startup, there are a number of precommissioning activities that
are necessary to ensure that the newly constructed plant is ready to be placed
in service. The activities outlined below should serve as a guide, but there may
be others required as a part of your normal plant procedures.
7.7.1 Preliminary Check-out
Check all equipment to ensure that it is properly installed. This will
probably require consulting Manufacturer's literature as well as
construction drawings.
A. Check and lubricate all equipment, in accordance with the
Manufacturer's recommendations.
B. Check the rotation of the following pumps by "bumping" them:
(1) Wash Water Pump.
(2) Rich Amine Pump.
(3) Stripper Reflux Pump.
(4) Lean Amine Pump.
(5) Lean Amine Booster Pump
(6) ATU Skim Oil Pump
(7) MDEA Transfer Pump

C. Check the rotation of the fans on the Lean Amine Cooler and the
Stripper Reflux Condenser, by operating each fan for a short period.
D. Check all piping and equipment to be sure that all blinds have been
removed and that no valves are vented to atmosphere.
E. Place the Instrument Air System in service to all instruments and
check the action of controllers and control valves.
F. Check all relief valves to ensure that they are installed in the proper
locations, the inlet and outlet block valves (if provided) are open, the
bypass valves (if provided) are closed, and the relief valves are set
for the correct relieving pressure.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-31
7.7.2 Shutdown System Check-out
A. Physically check all shutdown activating devices to ensure that they
activate the ESD system.
B. Physically check all devices activated by the ESD system to ensure
that they operate properly.
C. Check all relief valves to ensure that they are installed in the proper
locations and set for the correct relieving pressures.
D. The low-low level shutdowns for the pumps in the wash water and
amine systems will be tested while washing these systems as
described in the following sections.
7.7.3 Leak Testing the Process Piping and Equipment
The process piping and equipment in the ATU can be checked for leaks
by using a temporary nitrogen jumper to pressurize the process side of
the equipment and piping to about 0.6-0.7 kg/cm
2
(g), then checking
flanges, etc. for leaks (usually by applying masking tape or "Snoop" to the
flanges, and by listening for other leaks).
This same procedure can be used to leak test the ATU following
maintenance, before restarting the unit. Whenever plant maintenance
requires opening one or more of the flanged connections in the ATU it is
good practice to leak test the unit before returning it to service. This
allows detecting any leaking connections that may have resulted from the
maintenance operations before sour fuel gas is reintroduced into the unit.
To perform leak testing in the ATU, proceed as follows:
A. Reduce the output from the sour fuel gas hand control in the DCS to
0% to close the Sour Fuel Gas inlet valve.
B. Confirm that the Wash Water Column is isolated from the wash water
circulation loop by confirming that the following valves are all closed:
(1) The bypass valve and downstream block valve at the wash
water flow control valve.
(2) The suction valves at the Wash Water Pumps.
(3) The drain valve on the suction line to the pumps.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-32
(4) The bypass valve and downstream block valve at the make-up
water flow control valve.
C. Confirm that the Amine Absorber is isolated from the solvent
circulation loop by confirming that the following valves are all closed:
(1) The bypass valve and downstream block valve at the lean
solvent flow control valve.
(2) The bypass valve and upstream block valve at the Absorber
level control valve.
(3) The drain valve upstream of the level control valve.
(4) The block valves in the water makeup line.
(5) The bypass valve and upstream block valve at the Absorber
overhead pressure control valve to the SRUs.
(6) The bypass valve and upstream block valve at the Absorber
overhead pressure control valve to the flare.
D. Use a temporary "jumper" to connect a nitrogen supply to one of the
level bridles on the Wash Water Feed Knock-out Drum and establish
a flow of nitrogen into the unit.
E. Continue adding nitrogen until the pressure reaches
0.6-0.7 kg/cm
2
(g).
Due to the volume inside the ATU, it will take several minutes for the
pressure to build up in the unit.
F. Once the desired pressure has been achieved close the valve where
the nitrogen "jumper" is connected to stop the flow of nitrogen. Check
all of the equipment and piping connections for visible or audible
signs of leakage.
G. Disconnect the nitrogen jumper.
H. Re-open valves as necessary to restore the wash water and solvent
circulation loops that were isolated from the columns in the previous
steps.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-33
7.7.4 Washing the Wash Water System
The following procedure is intended to remove grease, rust, scale, dirt,
and trash from the equipment and piping in the Wash Water system
before it is placed in operation. Washing of the system consists of three
steps: an initial water flush to remove dirt and trash from the system; an
acid wash to remove grease, rust, and scale; and a caustic wash to
acclimate the equipment and piping to alkaline pH.
Failure to clean the system properly prior to startup can lead to operating
problems (heat exchanger fouling, rapid filter plugging, etc.).


THIS PROCEDURE REQUIRES WORKING WITH ACIDIC AND
ALKALINE CHEMICALS AND SOLUTIONS. EMPLOYEES MUST
OBSERVE ALL APPLICABLE SAFETY PROCEDURES AND
ENVIRONMENTAL REGULATIONS CONCERNING USAGE OF
PERSONAL PROTECTIVE EQUIPMENT, HANDLING OF
HAZARDOUS MATERIALS, DISPOSAL OF WASTE STREAMS, ETC.
7.7.4.1 Water Flush
A. Place the Wash Water flow controller in the DCS in "manual"
and set its output to 100% to fully open the Wash Water flow
control valve.
B. Place the Wash Water Column level controller in the DCS in
"manual" and set its output to 0% to fully close the level control
valve.
C. Confirm that the Sour Fuel Gas inlet hand control in the DCS is
set to 0% output so that the Sour Fuel Gas inlet valve is fully
closed.
D. Verify that the Wash Water flow control valve is fully open.
Open both of its isolation block valves and its bypass valve.
E. Verify that the Wash Water Column level control valve is fully
closed. Close both of its isolation block valves and its bypass
valve.
WARNING
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-34
F. Verify that the Sour Fuel Gas inlet valve is fully closed. (This
will prevent water from entering the upstream equipment if the
Wash Water Column is accidentally over-filled.)
G. The Wash Water Filters will not be used to filter solids during
this time, but the filter vessels and their piping are to be flushed
and cleaned. Remove the filter elements, then bolt-up the
filters. Open the inlet and outlet block valves on the filters, and
open the bypass valve around the filters.
H. Add water to the top of the Wash Water Column by placing the
Make-up Water flow control valve in manual and setting its
output to 100% to fully open the make-up water flow control
valve.
If make-up water is not available from the Sour Water Stripping
unit, use a temporary jumper to supply water (cold condensate)
to the Wash Water Column.
I. Once there is an adequate level in the column, all the way to
the top of its level gauge open the suction valve on a Wash
Water Pump and use its drain valve to be sure the pump is
flooded with water. Start the pump, then open its discharge
valve.
J. Watch the level in the Wash Water Column while placing the
pump in service to be sure the pump does not lose suction
while filling the downstream piping and equipment. If the level
disappears in the column, shut the pump down until enough
water (or condensate) is added to reestablish the level, then
restart the pump.
K. Once circulation is achieved and the level in the Wash Water
Column is adequate (about halfway up in the level gauge),
discontinue the addition of water (or condensate).
L. Use the low point drain valves to flush out each section of the
system. Leave the drain valves open until the water is clear.
M. Briefly open the bypass valve on the Wash Water Column level
control valve to flush this section of piping to The Sour Water
Stripping Unit. Open the upstream block valve, open the Wash
Water Column level control valve with the level controller in the
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-35
DCS, and use the downstream drain valve to flush the control
station. Once the flush water clears up, close the Wash Water
Column level control valve and the upstream block valve.
N. Circulate the water and blow down the low point drains until all
of the drain water is clear. Add more water ( or condensate) as
necessary to maintain the level in the Wash Water Column.
At some point during the washing procedure, the standby pump
should be placed in service while the other pump is shut down.
This will ensure cleaning out both pumps and their associated
piping.
O. Once the drain water is clear, completely drain the system.
Drain the system as quickly as possible, so that the water
velocity helps to flush the solids from all parts of the system.
P. Allow the pump to continue running while the system drains, but
watch the pump closely to verify that the low-low level shutdown
shuts the pump down below the shutdown setpoint. If the level
drops completely out of the gauge glass before the pump shuts
down, stop the pump manually and correct the problem with the
low-low level shutdown before proceeding further.
7.7.4.2 Acid Wash
A weak (0.1 wt %) citric acid solution is used next to remove grease,
rust, and scale from the equipment and piping. The citric acid will
chelate with the iron in the rust and scale so that it dissolves in the
solution.
A. Reestablish a level in the Wash Water Column.
B. Once a level is established, start a Wash Water Pump to begin
circulating the water.
C. Add concentrated citric acid to the circulating water to make a
0.1 wt % citric acid solution.
D. After circulating for about 3 hours, start the other Wash Water
Pump and shut down the first one.
E. Circulate the solution for a total of about 6 hours, blowing down
the low point drains occasionally. Add more water (or
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-36
condensate) if necessary to maintain the level in the Wash
Water Column.
F. Briefly open the bypass valve on the Wash Water Column level
control valve to flush this section of piping to The Sour Water
Stripping Unit. Then open both block valves and use the level
controller in the DCS to open the Wash Water Column level
control valve briefly and flush the control station. Close the
Wash Water Column level control valve and the block valves.
G. After 6 hours, shut down the pump and completely drain the
system. Drain the system as quickly as possible, so that the
liquid velocity will help flush any remaining solids from the
system.
7.7.4.3 Alkaline Wash
The washing operation is completed by circulating a weak alkaline
solution through the system. This will neutralize any citric acid left in
the system, and acclimate the system to high pH operation so that no
further scale is removed from the equipment and piping when the
normal Wash Water (8.0-9.5 pH) is circulated.
A. Reestablish a level in the Wash Water Column.
B. Once a level is established, start a Wash Water Pump to begin
circulating the water.
C. Add caustic to the circulating water to make a 0.02 wt%
solution. This should give a pH in the range of 11-22.
D. Check the pH of the circulating water. If the pH is less than 11,
add more caustic until the pH is 11 or higher.
E. After circulating for about 1 hour, start the other Wash Water
Pump and shut down the first one.
F. Circulate the solution for a total of about 2 hours, blowing down
the low point drains occasionally. Add more water (or
condensate) if necessary to maintain the level in the Wash
Water Column.
G. Briefly open the bypass valve on the Wash Water Column level
control valve to flush this section of piping to the sour water
header. Then open both block valves and use the level
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-37
controller in the DCS to open the Wash Water Column level
control valve briefly and flush the control station. Close the
Wash Water Column level control valve and the block valves.
H. After 2 hours, shut down the pump and completely drain the
system. Drain the system as quickly as possible, so that the
liquid velocity will help flush any remaining solids from the
system.
7.7.4.4 Initial Water Fill
The Wash Water system should now be clean and ready to place in
service. All that remains is to refill the system with water and
establish the proper operating conditions.
A. Close the inlet and outlet block valves on the Wash Water
Filters (but leave the bypass valve open), then install the proper
element(s) in the filters. Leave the block valves closed for now.
B. Reestablish a level in the Wash Water Column.
C. Once a level is established, start a Wash Water Pump to begin
circulating the water.
D. Place the Wash Water Filters in service as follows:
(1) Open the vent valves on the top of the filters.
(2) "Crack" the filter inlet block valves open slightly and allow
the filters to fill with water. When the filter is full, close the
vent valve.
(3) Open the filter inlet block valves fully and open the outlet
block valves, then close the filter bypass valve.
E. Place the Wash Water flow controller in the DCS in service and
set its setpoint to its normal value. Close the bypass valve on
the Wash Water flow control valve.
F. Confirm that the Wash Water Column level control valve is
closed, then open both of its block valves. Place the level
controller in the DCS in service and set its setpoint to its normal
value.
G. Establish cooling water flow to the Amine Absorber Overhead
Cooler.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-38
The Wash Water system is now ready for service. It can remain in
this operating mode indefinitely while the rest of the ATU is prepared
for startup. Check the system periodically for indications of plugging,
etc. (low flow, erratic pump discharge pressure, high filter pressure
drop), as solid materials may accumulate at various points in the
system over time.
7.7.5 Washing the Amine System
The following procedure is intended to remove grease, rust, scale, dirt,
and trash from the equipment and piping in the solvent system before it is
placed in operation. Washing of the system consists of three steps: an
initial water flush to remove dirt and trash from the system; an acid wash
and rinse to remove grease, rust, and scale; and a weak amine wash and
rinse to acclimate the equipment and piping to alkaline pH.
Failure to clean the system properly prior to startup can lead to operating
problems (column foaming, poor treating, heat exchanger fouling, rapid
filter plugging, etc.).


THIS PROCEDURE REQUIRES WORKING WITH ACIDIC AND
ALKALINE CHEMICALS AND SOLUTIONS. EMPLOYEES MUST
OBSERVE ALL APPLICABLE SAFETY PROCEDURES AND
ENVIRONMENTAL REGULATIONS CONCERNING USAGE OF
PERSONAL PROTECTIVE EQUIPMENT, HANDLING OF
HAZARDOUS MATERIALS, DISPOSAL OF WASTE STREAMS, ETC.
7.7.5.1 Water Flush
A. Place the following controllers in the DCS in "manual" with their
outputs set as indicated:
(1) Set the output from the lean solvent flow controller to
100% to fully open the lean solvent flow control valve.
(2) Open the manual block valve upstream of the lean solvent
filters.
WARNING
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-39
(3) Set the output from the lean solvent filter bypass flow
controller to 100% to fully open the filter bypass flow
control valve.
(4) Set the output from the Amine Absorber level controller to
100% to fully open the Amine Absorber level control valve.
(5) Set the output from the Rich Amine flow controller to 100%
to fully open the rich amine flow control valve.
(6) Set the output from the amine flow controller to the Flash
Gas Contactor to 100% to fully open the flow control valve.
(7) Set the output from the Stripper Reboiler steam flow
controller to 0% to fully close the steam flow control valve.
(8) Set the output from the Stripper Reflux Accumulator level
controller to 0% to fully close the Stripper Reflux
Accumulator level control valve.
(9) Set the output from the bleed water flow controller to 0% to
fully close the bleed water flow control valve.
(10) Set the output from the flow controller on the spill-back line
to the lean amine cooler to 0% to fully close the spill-back
flow control valve.
(11) Set the output from the makeup water flow controller to 0%
to fully close the makeup water flow control valve.
(12) Set the output from the Stripper pressure controller to 0%
to fully close the overhead pressure control valve to the
SRU.
(13) Set the outputs from the two temperature controllers to 0%
to fully close both temperature control valves to the DHT
Unit.
(14) Set the output from the lean solvent flow controller to the
LPG Treating Unit to 0% to fully close the lean solvent flow
control valve to the LPG Treating Unit.
B. Place the other Stripper pressure controller in "automatic" with a
setpoint of 0.85 kg/cm
2
(g). This will open the pressure control
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-40
valve to the flare if pressure builds in the Stripper during this
procedure.
C. Verify that the following control valves are fully open. Open
both of the isolation block valves and the bypass valve (where
applicable) at each control station.
(1) The lean amine flow control.
(2) The lean amine filter bypass.
(3) The Amine Absorber level control, (the rich solvent from
the Amine Absorber).
(4) The rich solvent flow control (the rich solvent from the Rich
Amine Flash tank)
(5) The lean solvent to the Flash Gas Contactor
D. Verify that the following control valves are fully closed. Close
both of the isolation block valves and the bypass valve at each
control station.
(1) The steam flow control valve to the Stripper Reboiler.
(2) The Stripper Reflux Accumulator level control valve.
(3) The bleed water flow control valve from the Stripper reflux.
(4) The spill-back flow controller to the Lean Amine Cooler.
(5) The makeup water flow control valve.
(6) The acid gas pressure control to the SRU.
E. Verify that the bypass valve on the pressure control valve to the
flare is closed. Open both of the isolation block valves at this
control station.
F. The solvent filters will not be used to filter solids during this
time, but the filter vessels and their piping are to be flushed and
cleaned. Remove the filter elements, then bolt-up the individual
filters. Open the inlet and outlet block valves on each filter, and
open the bypass valves for the filters.
G. Verify that the valves in the amine makeup line are closed.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-41
H. Add water (cold condensate) to the Amine Absorber by opening
the flow control valve in the make-up water line.
I. Once there is an adequate level in the Rich Amine Flash Tank,
all the way to the top of its level gauge open the suction valve
on a Rich Amine Pump and use its drain valve to be sure the
pump is flooded with water. Start the pump, then open its
discharge valve.
Watch the level in the Amine Absorber and the Rich Amine
Flash Tank as the pump fills the downstream piping and begins
to fill the Stripper. When the level drops to the low-low level
shutdown it should shut down the pump. If it does not, stop the
pump manually before it loses suction and correct the problem
with the low level shutdown before proceeding.
J. Continue filling the Amine Absorber with condensate and
pumping the water to the Stripper periodically, until the level in
the Stripper is all the way to the top of its level gauge.
K. Once there is an adequate level in the Stripper, open the
suction valve on a Lean Amine Booster Pump and use its drain
valve to be sure the pump is flooded with water. Start the
pump, then open its discharge valve.
L. Once the downstream piping and equipment has been filled
with water, open the suction valve on a Lean Amine Pump and
use its drain valve to be sure the pump is flooded with water.
Start the pump, then open its discharge valve
M. As the pump fills the downstream piping and begins to return
water to the Amine Absorber, watch the level in the Stripper to
be sure the Lean Amine Booster Pump does not lose suction. If
the level disappears in the column, shut both pumps down, add
more condensate to the Amine Absorber and pump it to the
Stripper to reestablish the level, then restart the Lean Amine
Booster Pump and the Lean Amine Pump.
N. As the level begins to rise in the Amine Absorber, restart the
Rich Amine Pump. Watch the levels in both columns, and shut
a pump down if necessary to keep from emptying either
column.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-42
O. Once the levels in both columns are adequate, discontinue the
addition of condensate.
P. At this point, neither the flow into or the level of the Amine
Absorber is being controlled. Both control stations are in
"manual" with the valves fully open to flush the piping as much
as possible. Depending on the hydraulics of the system, it may
be necessary to place either or both of these controls in
"automatic" to prevent losing the level in one of the columns. If
so, leave the bypass valve on the control station "cracked" so
that the bypass piping gets flushed.
Q. Use the low point drain valves to flush out each section of the
system. Leave the drain valves open until the water is clear.
R. Circulate the water and blow down the low point drains until all
of the drain water is clear. Add more condensate as necessary
to maintain the levels in the columns.
At some point during the washing procedure, the standby Rich
Amine Pump, standby Lean Amine Pump, and standby Lean
Amine Booster Pump should be placed in service while the
other pumps are shut down. This will ensure cleaning out both
pumps and their associated piping in each service.
At some point in the washing procedure, open the flow control
valve in the spill-back line to the Lean Amine Cooler to clean
out this section of piping. Then close the control valve again.
S. Once the drain water is clear, shut down the Rich Amine Pump
and completely drain the system. Drain the system as quickly
as possible, so that the water velocity will help flush the solids
from all parts of the system.
T. Allow the Lean Amine Pump and the Lean Amine Booster
Pump to continue running while the system drains, but watch
the pumps closely to verify that the Stripper low-low level
shutdown shuts the pumps down when the level falls to the
shutdown setpoint. If the level drops completely out of the
gauge glass before the pumps shut down, stop the pumps
manually and correct the problem with the low level shutdown
before proceeding further.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-43
U. Confirm that the solvent transfer line (for MDEA makeup) has
been flushed and is ready for service.
7.7.5.2 Acid Wash
A weak (0.1 wt %) citric acid solution is used next to remove grease,
rust, and scale from the equipment and piping. The citric acid will
chelate with the iron in the rust and scale so that it dissolves in the
solution.
A. Use the make-up water line to re-establish the levels in the
Amine Absorber, Rich Amine Flash Tank, and the Stripper as
before, and establish circulation of water in the system.
B. Add concentrated citric acid to the circulating water to make a
0.1 wt % citric acid solution.
C. Begin steam flow to the Stripper Reboiler and gradually raise
the temperature of the circulating solution. For maximum
effectiveness, the solution should be 65-95C throughout the
system, so adjust the steam flow accordingly. The fans on the
Lean Amine Cooler should not be operating at this time.
D. It is unlikely that any steam will leave the top of the Stripper
during this operation, so the Stripper Reflux Accumulator should
remain dry. If a level should develop in this vessel, drain the
water from the vessel using a drain valve on one of the Stripper
Reflux Pumps.
E. After circulating for about 3 hours, start the other Rich Amine
Pump and shut down the first one. Do the same with the Lean
Amine Pumps and the Lean Amine Booster Pumps.
F. Open the flow control valve in the spill-back line to the Lean
Amine Cooler and circulate through this section of piping. Then
close the control valve.
G. Circulate the hot solution for a total of about 6 hours, blowing
down the low point drains occasionally. Add more condensate
if necessary to maintain the levels in the columns.
H. After 6 hours, shut off the steam to the Stripper Reboiler, shut
down the pumps, and completely drain the system. Drain the
system as quickly as possible, so that the liquid velocity will
help flush any remaining solids from the system.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-44
I. Use the condensate makeup line to reestablish the levels in the
Amine Absorber and the Stripper as before, and establish
circulation of water to flush the system.
J. Switch to the other pumps for a few minutes, then shut down
the pumps and completely drain the system.
K. Once again, use the condensate makeup line to reestablish the
levels in the Amine Absorber and the Stripper as before, and
establish circulation of water in the system.
L. Reestablish steam flow to the Stripper Reboiler and gradually
raise the temperature in the column.
M. When the temperature begins to rise in the Stripper overhead
line, start a fan on the Stripper Reflux Condenser and place the
reflux temperature controller in service with a setpoint of 49C.
N. When a level builds in the Stripper Reflux Accumulator, drain it
to the closed drain from the drain on one of the pump cases.
O. Open the downstream block valve at the Stripper Reflux
Accumulator level control valve, then use the drain valve to
blow steam from the column backwards down the reflux line to
remove any debris. Continue until the steam blows clear, then
close the drain valve and the block valve.
P. Continue to circulate water and apply heat in the Stripper
Reboiler, until the water drained from the Stripper Reflux
Accumulator is clear. During this time, blow down the low point
drains occasionally and add more condensate if necessary to
maintain the levels in the columns, and switch to the other Rich
Amine Pump, Lean Amine Booster Pump, and Lean Amine
Pump.
Q. Once the reflux loop has cleared up (the drain water is clear),
shut off the steam to the Stripper Reboiler, shut down the
pumps, and completely drain the system. Drain the system as
quickly as possible, so that the liquid velocity will help flush any
remaining solids from the system.
R. Check the pH of the water draining from the system. If
necessary, repeat Steps K through Q until the pH of the drain
water is about the same as the pH of the condensate makeup.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-45
7.7.5.3 Weak Amine Wash
The washing operation is completed by circulating a weak amine
solution through the system. This will neutralize any citric acid left in
the system, and acclimate the system to alkaline pH operation so
that no further scale is removed from the equipment and piping when
the normal solvent is circulated.
A. Use the condensate makeup line to reestablish the levels in the
Amine Absorber and the Stripper as before, and establish
circulation of water in the system.
B. Add enough MDEA to the circulating water to reach a
concentration of about 1 wt%.
C. Begin steam flow to the Stripper Reboiler and gradually raise
the temperature in the column.
D. When the temperature begins to rise in the Stripper overhead
line, check that at least one of the fans is running on the
Stripper Reflux Condenser.
E. When a level builds in the Stripper Reflux Accumulator, open
the suction valve on one of the Stripper Reflux Pumps and use
its drain valve to be sure the pump is flooded with water. Start
the pump, open its discharge valve, then open the bypass valve
on the Stripper Reflux Accumulator level control valve to pump
the water back into the Stripper.
Watch the level in the Stripper Reflux Accumulator while
pumping it out. Shut the pump down when the vessel is empty,
then close the suction and discharge valves on the pump and
close the bypass valve on the Stripper Reflux Accumulator level
control valve.
F. Continue to circulate the solution and apply heat to the Stripper
Reboiler, pumping out the Stripper Reflux Accumulator as
required by alternating which pump is used. During this time,
blow down the low point drains occasionally and add more
condensate if necessary to maintain the levels in the columns,
and switch to the other Rich Amine Pump, Lean Amine Booster
Pump and Lean Amine Pump.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-46
G. During one of the pumping cycles for the Stripper Reflux
Accumulator, flush out the minimum flow spill-back line by
opening the manual block valve to allow circulation through this
line. Then close the manual block valve.
H. During another pumping cycle, flush out the bleed water piping
by setting the output of the bleed water flow controller to 100%
to fully open the bleed water flow control valve, opening its
upstream and downstream block valves, and opening its
bypass valve. Then close the valves and set the output of the
bleed water flow control valve back to 0%.
I. Take a sample of the circulating solution and run a foam test on
it using the procedure in Section 7.10.
J. Once the solution drained from all the low point drain valves is
clear, shut off the steam to the Stripper Reboiler, shut down the
pumps, and completely drain the system. Drain the system as
quickly as possible, so that the liquid velocity will help flush any
remaining solids from the system.
K. Use the condensate makeup line to reestablish the levels in the
Amine Absorber and the Stripper as before, and establish
circulation of water to flush the system.
L. Open the control valve in the spill-back line to the Lean Amine
Cooler for a few minutes, then close the control valve.
M. Switch to the other pumps for a few minutes, then shut down
the pumps and completely drain the system.
N. If the solvent sample taken in Step I was foamy, repeat Steps A
through M until the solvent is not foamy.
7.7.5.4 Initial Solvent Fill
The solvent system should now be clean, ready to place in service.
All that remains is to fill the system with the proper solvent charge
and establish the proper operating conditions.
NOTE: This procedure prepares the solvent system for operation
in the shortest possible time. However, it does allow the
MDEA to come in contact with oxygen that is in the Amine
Absorber. If a slightly longer startup schedule can be
tolerated, this deficiency can be minimized or eliminated
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-47
by deferring the procedure in this section until nitrogen has
been used to purge the Wash Water Column and Amine
Absorber as described in the following section.
A. Close the inlet and outlet block valves (but leave the bypass
valves open) on the solvent filters, then install the proper
elements and/or carbon in the filters. Leave the block valves
closed on each filter for now.
B. Use the condensate makeup line to reestablish the levels in the
Amine Absorber and the Stripper as before, and establish
circulation of water in the system.
C. Add enough MDEA to the circulating water to reach a
concentration of about 45 wt%.
D. Place in service and adjust the level controller on the Amine
Absorber to maintain its normal setpoint. Stop the condensate
and/or amine makeup when the Stripper level is about 50-60%.
E. Begin steam flow to the Stripper Reboiler and gradually raise
the temperature in the column. Place the steam flow controller
in the DCS on "automatic" with its setpoint set to its normal
value.
F. Open the high point vent valve on the Stripper overhead line
and allow the steam to purge any air from the vessel. As the
pressure builds, the vent valve can be closed.
G. Monitor the stripper pressure, and adjust the overhead pressure
controller if necessary to maintain the stripper pressure at about
0.85 kg/cm
2
(g) as the system is heated to operating
temperatures.
H. Ensure that the fans are running on the Lean Amine Cooler and
the Stripper Condenser.
I. Place the lean solvent temperature controllers in "automatic"
and set their setpoints to their normal values.
J. When a level builds in the Stripper Reflux Accumulator, open
the suction valve on one of the Stripper Reflux Pumps and use
its drain valve to be sure the pump is flooded with water. Open
the block valves upstream and downstream of the reflux flow
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-48
control valve, place the reflux flow controller in "automatic" with
its setpoint set to its normal value, then start the pump and
open its discharge valve.
K. Open the block valves on the Stripper Reflux Accumulator level
control valve and place the level controller in the DCS in
"automatic" with its setpoint set to its normal value. The
Stripper Reflux Accumulator level control valve will now open as
needed to pump water back into the Stripper and maintain the
desired level in the Stripper Reflux Accumulator.
L. If the control loops on the solvent have not already been placed
in service, do so at this time. Switch the Amine Absorber level
controller, and the lean solvent flow controller in the DCS to
"automatic" with their setpoints set to their normal values.
M. Place the Amine flow controller to the Flash Gas Contactor in
automatic and set its setpoint to its normal value.
N. Place the level controller for the Rich Amine Flash Tank in
service as follows:
(1) Confirm that the level controller in the DCS is in
"automatic".
(2) Confirm that the remote setpoint the level controller is
supplying to the rich amine flow controller matches the
current local setpoint on the flow controller.
(3) Switch the rich amine flow controller to "cascade" mode so
that the setpoint for the rich amine flow will now be adjusted
automatically by the level controller.
(4) The setpoint of the level controller will be set at the last
reading. Adjust the setpoint to its normal value.
O. Place each of the solvent filters in service as follows:
(1) Open the vent valve on the top of the filter.
(2) "Crack" the filter inlet block valve open slightly and allow
the filter to fill with solvent. When the filter is full, close its
vent valve.
(3) Open the inlet and outlet block valves on the filter.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-49
(4) Slowly close the valve in the bypass line around the filter.
P. Analyze a sample of the circulating solvent using the procedure
in these guidelines to determine the amine concentration. Add
more fresh MDEA using the solvent transfer line if needed to
bring the concentration up to the design value, 45 wt %.
Q. Confirm that the bleed water flow controller is in "manual' with
its output set at 0% and that the bleed water flow control valve
is closed, then open its upstream and downstream block valves.
The solvent system is now ready for service. It can remain in this
operating mode indefinitely while the rest of the Sulfur Block is
prepared for startup. Check the system periodically for indications of
plugging, etc. (low flow, erratic pump discharge pressure, high filter
pressure drop), as solid materials may accumulate at various points
in the system over time.


Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-50
7.7.6 Purging the Low Pressure Columns
Prior to starting up the using the procedures in Section 7.8 of these
guidelines, nitrogen should be used to purge the Wash Water Column and
the Amine Absorber. This will displace the air introduced into the columns
while washing and filling them earlier.
At this point, the following conditions should exist in the ATU:
The Wash Water system and perhaps the amine system have been
cleaned and loaded with their respective initial fills of water and amine.
(The amine system may be waiting on purging of the Amine Absorber
before the system is loaded with amine.)
7.7.6.1 Purging the Columns
To establish nitrogen flow into the ATU, proceed as follows:
A. Reduce the output from the Sour Fuel Gas hand control in the
DCS to 0% to close the Sour Fuel Gas inlet valve.
B. Confirm that the Wash Water Column is isolated from the wash
water circulation loop by confirming that the following valves are
all closed:
(1) The bypass valve and downstream block valve at the
wash water flow control valve.
(2) The suction valves at the Wash Water Pumps.
(3) The drain valve on the suction line to the pumps.
(4) The bypass valve and downstream block valve at the
make-up water flow control valve.
C. Confirm that the Amine Absorber is isolated from the solvent
circulation loop by confirming that the following valves are all
closed:
(1) The bypass valve and downstream block valve at the lean
solvent flow control valve.
(2) The bypass valve and upstream block valve at the
Absorber level control valve.
(3) The drain valve upstream of the level control valve.
(4) The block valves in the water makeup line.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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Issued 30 August 2011 Amine Treating & Regeneration Page 7-51
(5) The bypass valve and upstream block valve at the
Absorber overhead pressure control valve.
D. Open all of the vent valves on the PI and PDT taps on the
Wash Water Column and the Amine Absorber, and the vent
valves at the tops of the columns.
E. Use a temporary "jumper" to connect a nitrogen supply to one
of the level bridles on the Wash Water Feed Knock-out Drum
and establish a flow of nitrogen into the unit.
F. Allow the nitrogen to continue flowing long enough to reduce
the oxygen concentration in the equipment and piping to less
than 1%. Use a portable oxygen analyzer to determine the
oxygen concentration.
G. Disconnect the nitrogen jumper.
H. Re-open valves as necessary to restore the wash water and
solvent circulation loops that were isolated from the columns in
the previous steps.
NOTE: If the initial solvent fill was not loaded into the solvent
system earlier to avoid exposing the MDEA to oxygen, this
can be accomplished now. Follow the procedure given in
the previous section to fill the solvent system with its initial
solvent charge.

Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-52
7.8 Startup Procedures
The ATU is now ready to accept sour fuel gas from the complex.
7.8.1 Wash Water and Amine Systems
Before routing sour fuel gas into the Wash Water Column and the Amine
Absorber, the wash water and amine systems should be operating and
ready to accept sour gas. The operating conditions described below
should have been established previously at the conclusion of the washing
operations but are repeated below to serve as a "checklist" before
introducing sour fuel gas to the columns as described in the sections that
follow.
A. The H
2
S analyzer has been calibrated.
B. The Wash Water system should be charged with its initial fill of
water, so that the level in the Wash Water Column is at the normal
setpoint for the Wash Water Column level controller.
C. Wash Water should be circulating to the Wash Water Column at the
normal setpoint for the Wash Water flow controller.
D. The Wash Water Filter should be in service.
E. The amine system should be charged with its initial fill of amine, with
the level control in the DCS controlling the level in the Amine
Absorber at its normal setpoint and the level control in the DCS
controlling the level in the Rich Amine Flash Tank at its normal
setpoint.
F. The MDEA concentration in the amine should be close to its design
value (45 wt %). Add more fresh MDEA if necessary to bring the
amine to this strength.
G. Amine should be circulating through the Stripper, the Lean/Rich
Exchanger, and the Lean Amine Cooler to the distributor tray at the
top of the Amine Absorber at the normal setpoint for the flow
controller.
H. The fans should be operating on the Lean Amine Cooler, with the
temperature controllers on the lean amine controlling at their normal
setpoints.
I. The Rich Amine Filters should be in service.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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Issued 30 August 2011 Amine Treating & Regeneration Page 7-53
J. The lean amine filters should be in service, with the bypass flow
controller controlling at its normal setpoint.
K. Steam should be flowing to the Stripper Reboiler at the normal
setpoint for the flow control.
L. The overhead temperature from the Stripper should be above the low
temperature alarm point for the temperature indicator.
M. The fans should be operating on the Stripper Reflux Condenser with
the temperature controller on the outlet from the Stripper Reflux
Condenser controlling at its normal setpoint or lower.
N. The Stripper pressure controller to the SRU, should be in "manual"
with its output set to 0% so that the pressure control valve is fully
closed.
O. The Stripper pressure controller to the flare should be in "automatic"
with a setpoint of 0.85 kg/cm
2
(g).
P. The level in the Stripper Reflux Accumulator should be at the normal
setpoint for the level control.
Q. A Stripper Reflux Pump should be operating with the minimum flow
lined up to allow reflux to spill back into the Stripper Reflux
Accumulator whenever the level valve back to the Stripper is closed.
With these operating conditions established, the ATU is ready to accept
the sour fuel gas and begin treating it.
7.8.2 Sour Fuel Gas Flow to the Columns
The last step in the startup of the ATU is to bring the sour gas from the
rest of the complex into the Wash Water Column and the Amine Absorber.
They will then remove the H
2
S from the gas before sending it to the
treated fuel gas system. The H
2
S removed will be stripped from the
amine and sent to the flare initially. Once operation of the amine system
stabilizes, this acid gas will be routed to the SRUs.
Before introducing sour fuel gas into the columns, confirm that the proper
operating conditions have been established for the Wash Water and
amine systems.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-54
If any of the proper conditions have not been established, do not proceed
until correcting the problem(s). Once all of the conditions are satisfied,
complete the startup of the as follows:
A. Confirm that the sour fuel gas inlet hand control in the DCS is set to
0% output with the Sour Fuel Gas Inlet Valve closed.
B. Slowly increase the output from the sour fuel gas inlet hand control
to 100%, which will open the Sour Fuel Gas Inlet Valve and admit
sour fuel gas to the Wash Water Column.
C. When the output of the sour fuel gas inlet hand control reaches
100%, the Sour Fuel Gas Inlet Valve should be fully open and the
pressure control valve to the flare should be closed to send all of the
sour fuel gas into the Wash Water Column. Visually confirm that
these valves are properly positioned.
D. Once the operation of the Stripper has stabilized, route its acid gas,
which is presently going to the flare through a pressure valve, to the
SRUs as follows:
(1) Confirm that the Stripper pressure controller to the SRUs
in the DCS is in "manual" with its output set to 0%.
(2) Confirm that the setpoint of the Stripper pressure controller
to the SRU is tracking its current reading, then place it in
"automatic".
(3) Slowly raise the setpoint of the Stripper pressure controller
to the flare to 1.0 kg/cm
2
(g).
(4) If, necessary, adjust the setpoint of the Stripper pressure
controller to the SRU to its normal setpoint.
The Stripper pressure controller will now take over control of the
Stripper pressure by opening the pressure valve to send the acid gas
to the Acid Gas Knock-Out Drum in the SRUs. The Stripper
pressure controller to the flare will close the acid gas pressure valve
and stop the flow of acid gas to the flare. If the SRUs shut down (or
some other upset causes the Stripper pressure to rise), the Stripper
pressure controller to the flare will act as an over-ride and divert the
acid gas to the flare.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-55
E. The ATU is now fully on-stream. Before directing your attention
away from the ATU, be sure that:
(1) All controllers are functioning properly.
(2) The steam heating systems are in service and the level
control on the Reboiler condensate pot is functioning
properly.

Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-56
7.9 Shutdown Procedures
The procedures to be used in performing a planned shutdown of the ATU, or the
ATU and ARU, will vary depending on the extent and type of work to be
performed in and around the units during the downtime period. If maintenance
is to be performed on the ATU, there is no need to also shut down the ARU.
This greatly simplifies and shortens the shutdown procedure. Section 7.9.1 that
follows is an example of such a procedure.
If the ARU must also be shut down, then more extensive procedures must be
followed to accomplish a satisfactory shutdown and minimize the time required
for performance of the desired maintenance work. Section 7.9.2 that follows is
an example of a procedure for this circumstance.
Section 7.9.3 is a discussion of emergency shutdown situations. A guide to
troubleshooting the causes of unplanned shutdowns is presented to assist in
quickly identifying and correcting the problem so that the ATU/ARU can be put
back on-line in a minimum amount of time.
The ATU/ARU is affected directly and indirectly by shutdowns and outages that
occur in other systems within the complex. The more important aspects of the
effects these other systems can have on the ATU/ARU are discussed in
Section 7.9.4.
Typical shutdown procedures are outlined and discussed in the sections that
follow for the more common cases. Your existing company procedures and
common sense operational judgment should be used to modify these
procedures as needed to serve the purpose of any given planned shutdown
situation.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-57
7.9.1 Planned Shutdown - ATU
Any equipment to be opened should be properly blinded and purged with
inert gas before admission of air, to avoid exposure to potentially toxic
gases or the formation of flammable vapor mixtures. Any equipment
containing amine solution that is to be opened or entered should be
drained completely, then flushed with condensate or steamed out to avoid
the possibility of skin or eye irritation.
It is generally preferable to shut down the ATU in a controlled fashion to
minimize the impact on the other process units. If time does not allow
performing a controlled shutdown, however, the unit can be shut down by
simply activating the ESD system (using the manual shutdown switch).
This will automatically block the feed into the ATU (sour fuel gas) and
divert the feed gas to the flare system.
To shut the ATU down in a controlled fashion proceed as follows:
A. Slowly reduce the output from the Sour Fuel Gas hand control in the
DCS. As the pressure in the sour fuel gas inlet line begins to
increase, the override pressure controller will open the pressure
control valve and begin diverting the sour fuel gas to the flare
system.
B. When the output of the Sour Fuel Gas hand control reaches 0%, the
pressure control valve should be open and the Sour Fuel Gas inlet
valve should be fully closed to send all of the sour fuel gas to the
flare system.
Visually confirm that these valves are properly positioned. Confirm
that the DCS indicates that the Sour Fuel Gas Inlet Valve is closed.
C. Allow the amine to continue to circulate until the all of the H
2
S and
CO
2
have been stripped from the amine. Once the H
2
S/CO
2
content
of the "rich" amine leaving the Absorber is essentially the same as
the "lean" amine, the ATU can be shut down and isolated from the
ARU.
D. Depending upon the type and extent of the maintenance work to be
done, the wash water can continue to circulate while maintenance is
being performed on the Amine Absorber. However, if desired, the
wash water system can be shut down as follows:
(1) Shut down the Wash Water Pump
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-58
(2) Place the Wash Water flow controller in the DCS in
"manual" and set its output to 0% to fully close the wash
water flow control valve.
(3) Place the Wash Water Column level controller in the DCS
in "manual" and set its output to 0% to fully close the level
control valve.
(4) Place the make-up water flow controller in the DCS in
"manual" and set its output to 0% to fully close the
make-up water flow control valve.
(5) Verify that the wash water flow control valve is fully closed.
Close both of its isolation block valves and its bypass
valve.
(6) Verify that the Wash Water Column level control valve is
fully closed. Close both of its isolation block valves and its
bypass valve.
(7) Verify that the make-up water flow control valve is fully
closed. Close both of its isolation block valves and its
bypass valve.
E. Once the H
2
S/CO
2
content of the "rich" amine leaving the Absorber is
essentially the same as the "lean" amine, the ATU can be shut down
as follows:
(1) Shut down the Lean Amine Pump
(2) Place the lean amine flow controller in the DCS in
"manual" and set its output to 0% to fully close the lean
amine control valve.
(3) Place the amine make-up water flow controller in the DCS
in "manual" and set its output to 0% to fully close the
amine make-up water flow control valve.
(4) Place the Amine Absorber level controller in the DCS in
"manual" and set its output to 100% to fully open the level
control valve.
(5) Allow the amine to drain from the Amine Absorber until the
low-low level shutdown is activated. This should close the
level control valve. Monitor the level in the Amine Absorber
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-59
and be prepared to close the level control valve if the
low-low level shutdown fails to activate.
(6) Monitor the level in the Rich Amine Flash Tank to ensure
that rich amine does not spill over into the hydrocarbon
section of the vessel. Be prepared to take action and close
the Amine Absorber level control valve if the amine level
gets too high in the Rich Amine Flash Tank.
(7) Drain the remaining amine from the Amine Absorber by
opening the manual block valve in the drain line upstream
of the level control valve to send the remaining amine to
the Solvent Drain System.
(8) Verify that the Amine Absorber level control valve is fully
closed. Close both of its isolation block valves and its
bypass valve.
(9) Verify that the lean amine flow control valve is fully closed.
Close both of its isolation block valves and its bypass
valve.
(10) Verify that the make-up water flow control valve is fully
closed. Close both of its isolation block valves and its
bypass valve.
(11) Verify that the spill-back flow control valve is fully closed.
Close both of its isolation block valves and its bypass
valve.
F. The ATU is now ready to be isolated and made safe for entry.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-60
7.9.2 Planned Shutdown - ATU and ARU
Any equipment to be opened should be properly blinded and purged with
inert gas before admission of air, to avoid exposure to potentially toxic
gases or the formation of flammable vapor mixtures. Any equipment
containing amine solution that is to be opened or entered should be
drained completely, then flushed with condensate or steamed out to avoid
the possibility of skin or eye irritation.
To shut the ATU and ARU down in a controlled fashion proceed as
follows:
A. Shutdown and isolate the DHT Unit and the LPG Treating Unit using
the operating procedures for those units.
B. Slowly reduce the output from the Sour Fuel Gas hand control in the
DCS. As the pressure in the sour fuel gas inlet line begins to
increase, the pressure controller will open the pressure control valve
and begin diverting the sour fuel gas to the flare system.
C. When the output of the Sour Fuel Gas hand control reaches 0%, the
pressure control valve should be open and the Sour Fuel Gas inlet
valve should be fully closed to send all of the sour fuel gas to the
flare system.
Visually confirm that these valves are properly positioned. Confirm
that the DCS indicates that the Sour Fuel Gas Inlet Valve is closed.
D. Allow the amine to continue to circulate with steam flowing to the
Stripper Reboiler, until the all of the H
2
S and CO
2
have been stripped
from the amine. Once the H
2
S/CO
2
content of the "rich" amine is
essentially the same as the "lean" amine, the steam can be shut off
to the Stripper Reboiler.
E. Continue to circulate the amine and operate the Lean Amine Cooler
and the Stripper Reflux Condenser until the amine is cool.
F. Depending upon the type and extent of the maintenance work to be
done, the wash water can continue to circulate while maintenance is
being performed on the Amine Absorber or on the equipment in the
ARU. However, if desired, the wash water system can be shut down
as follows:
(1) Shut down the Wash Water Pump
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-61
(2) Place the Wash Water flow controller in the DCS in
"manual" and set its output to 0% to fully close the wash
water flow control valve.
(3) Place the Wash Water Column level controller in the DCS
in "manual" and set its output to 0% to fully close the level
control valve.
(4) Place the make-up water flow controller in the DCS in
"manual" and set its output to 0% to fully close the
make-up water flow control valve.
(5) Verify that the wash water flow control valve is fully closed.
Close both of its isolation block valves and its bypass
valve.
(6) Verify that the Wash Water Column level control valve is
fully closed. Close both of its isolation block valves and its
bypass valve.
(7) Verify that the make-up water flow control valve is fully
closed. Close both of its isolation block valves and its
bypass valve.
G. Once the amine is cool (60C or less throughout the system), shut
down the equipment in the following order:
(1) The Rich Amine Pump.
(2) The Lean Amine Booster Pump
(3) The Lean Amine Pump.
(4) The Stripper Reflux Pump.
(5) The fans on the Lean Amine Cooler and Stripper Reflux
Condenser.
H. The ATU and ARU are now ready to be isolated and made safe for
entry.

Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-62
7.9.3 Emergency Shutdown
The ATU ESD system can be initiated by any of the actuating devices
outlined in Section 7.5.2.1 of these guidelines. The operator must
determine and correct the condition causing the shutdown before the can
be restarted. The problems outlined below should be investigated first by
the operator in his troubleshooting procedure.
S/D Actuation Device Possible Causes
Wash Water Feed Knock-Out
Drum
High-High Level
1. Excessive liquids being received by
the Knock-Out Drum.
2. Malfunction of level control system.
3. Level warning transmitters on the
Knock-Out Drum are plugged or
inoperable.
Amine Absorber Feed
Knock-Out Drum
High-High Level
1. Excessive liquids being received by
the Knock-Out Drum.
2. Malfunction of level control system.
3. Level warning transmitters on the
Knock-Out Drum are plugged or
inoperable.
Amine Absorber
Low-Low Level
1. Malfunction of the Lean Amine
Pump
2. Malfunction of the Lean Amine
Booster Pump
3. Malfunction of the lean amine flow
control system
4. Malfunction of the level control
system.
5. Manual drain valve left open.

Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-63
7.9.4 Effects of Shutdowns and Outages in Other Systems
The ATU/ARU system is directly affected by a shutdown and/or outage in
the LP steam system for the complex. These effects are described below.
7.9.4.1 Steam System Outage
The most immediate impact on the ATU/ARU will be the loss of
LP steam to the Stripper Reboiler if the steam outage lasts long
enough. As the heat input to the reboiler declines, stripping of the
acid gas from the amine will decline and the H
2
S in the treated fuel
gas leaving the Amine Absorber will begin to increase. This will
cause the Treated Fuel Gas analyzer to close the pressure control
valve to the treated fuel gas system to avoid sending off-spec fuel
gas into the complexs fuel gas system. The override pressure
control valve will then open and begin routing the sour fuel gas to the
flare system.

Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-64
7.10 Analytical Procedures
This Section contains analytical procedures for determining:
1. The concentrations of total amine in the ATU/ARU solvent (Section
7.10.2).
2. The concentrations of H
2
S and CO
2
in the ATU/ARU solvent
(Sections 7.10.3 and 7.10.4).
3. The foaming tendency of ATU/ARU solvent (Section 7.10.5).
4. The H
2
S content of the ATU/ARU Amine Absorber overhead gas
(Sections 7.10.6 and 7.10.7).
7.10.1 General Procedures for Analyzing ATU/ARU Solvent
1,2

An amine solution which is to be analyzed should first be inspected
visually. If conducted by an experienced person, such an inspection will
often yield important clues to the identity of a number of contaminants.
For example, a green color in an amine solution usually indicates finely
divided iron sulfide in sub-colloidal particle size (<1 micron), whereas a
finely divided black suspension indicates the presence of larger
(>3 micron) iron sulfide particles. A green or blue solution can indicate the
possibility of either copper or nickel, while an amber colored solution may
contain suspended or dissolved iron oxide. Iron may complex with the
amine an give the solution an amber or dark red color. Thermal
degradation of the amine may give the solution a dark red to brown color.
Amines sometimes display a red or dark brown color resulting from
oxidation, particularly when combined with thermal degradation. An oil
slick on the solution or an oil-like odor is indicative of hydrocarbon
contamination. The presence of these contaminants, however, must be
proven by analysis.
The next step in analyzing an amine solution is the determination of the
percent amine and the acid gas content (H
2
S and CO
2
). Both rich and
lean solutions may be analyzed for these constituents, and from the
analyses the extent of acid gas loading and efficiency of stripping can be
ascertained. Procedures for these analyses are given in Sections 7.10.2
through 7.10.4 that follow.

1
The Dow Chemical Company, Gas Conditioning Fact Book, 1962, pp. 310-311.
2
Dow Chemical U.S.A., Gas Treating from Dow, 1987, pp. 8-1-1 8-1-2.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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In addition to the procedure in Section 7.10.2, the amine concentration of
the solvent can be determined by performing Kjeldahl and Van Slyke
nitrogen analyses. The Kjeldahl determination indicates the total nitrogen
content of the solution, including nitrogen from the amine and from amine
degradation products. The Van Slyke method, on the other hand, shows
amine content, but does not reveal the extent to which the original amine
has been degraded or tied up as heat stable salts. The difference
between the results obtained through Kjeldahl and Van Slyke analyses
usually indicates the degree of amine degradation. As would be
expected, little difference is obtained with initial or unused solution. These
analyses are not commonly performed in plant laboratories, but are
generally left to the chemical solvent supplier.
Heat stable salts can also be determined by a total anion assay. The
amine solution is passed through an ion exchange column containing ion
exchange resin in the hydrogen form. Acid salts are thus broken down
and the acids recovered in the column effluent, while the amine is
absorbed in the column. The acid in the effluent is determined by
potentiometric titration, and from these results plus the original amine
concentration the amount of amine in the form of heat stable salts is
calculated. Again, this type of analysis is commonly left for the chemical
solvent supplier to perform.
The foaming characteristics of an amine solution are determined
empirically in a simple apparatus consisting of an air (or gas) supply,
pressure regulator or gas manometer, graduated glass cylinder, and a gas
dispersion tube. The amine solution is poured into the graduated cylinder
and air passed through at a constant rate. After five minutes, the height of
the foam is recorded, the air flow is interrupted, and the time for the foam
to break is determined. The results thus obtained will indicate whether or
not evaluation of anti-foam agents is desirable. Section 7.10.5 describes
this procedure more completely.
A water analysis can be conducted on the amine solution to obtain a
material balance and serve as an approximate check on the amine
concentration. This is typically determined using the Karl Fischer method
of analysis, but most plant laboratories leave this procedure to the
chemical solvent supplier.
Ordinarily, the above analyses will provide an accurate picture of the
condition of the amine plant solution. At times, however, unusual
operational difficulties may be encountered in amine sweetening units
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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because of contaminants which are not revealed by the usual analytical
methods. When this occurs, infrared spectroscopic analysis may often be
utilized to good advantage.
Infrared spectroscopy is based on the principle that each molecule or
functional group exhibits its own particular absorption characteristics when
exposed to infrared light of a definite wavelength. A wide variety of
functional groups can be readily detected and identified by infrared
techniques. For example, it has been found that degraded or oxidized
amine solutions may contain ammonia, formic acid, a di-functional acid, a
carbonyl compound yielding a glyoxal dinitrophenylhydrazone derivative,
and a high molecular weight material that exhibits the characteristics of a
Jones polymer. Also, both mono- and di-substituted amines have been
identified. Each component exhibits its own particular effects on
corrosion, foaming, and acid gas absorption, effects which can be
determined only by the separate evaluation of each contaminant. Once
these effects are determined, a knowledge of functional groups present
and their relative concentration makes it possible to anticipate which types
of contaminants may be causing difficulties. The chemical solvent
supplier can usually perform this type of analysis more easily than the
plant laboratory.
Steps should be taken to ensure that the amine solution samples taken
are representative of the circulating solvent. Samples should be taken in
glass or plastic containers. Metal containers will cause low results for H
2
S
because sulfides will react with the metal walls of the container. Do not
use copper tubing to withdraw the samples; the copper will contaminate
the amine solution, and H
2
S will react with the copper and give low
results.
Special care should be exercised when taking samples of the rich amine
solution to avoid personnel exposure to H
2
S. Hot, fully loaded amine
solution can flash acid gas when released to atmospheric pressure,
causing low acid gas loading results in addition to the dispersion of H
2
S to
the surroundings. Take samples of the rich solution from the coolest point
in the process (the Amine Absorber outlet, usually), and cool the samples
in a stainless steel coil immersed in an ice bath or cold water to prevent
flashing. The solution should be allowed to flow to a drain in this fashion
for several minutes before taking the sample to be sure that circulating
amine is being taken.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
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Issued 30 August 2011 Amine Treating & Regeneration Page 7-67
In the laboratory procedures that follow, several different reagents are
used that can be harmful if proper care is not exercised. Acids, bases,
and flammable substances are utilized in these procedures, so adherence
to proper laboratory safety practices is necessary to ensure the safety of
all personnel.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-68
7.10.2 Determination of Amine Concentration in ATU/ARU Solvent
The amine concentration in the ATU/ARU solvent can be determined by
acid titration of the lean solution. This technique is not specific for free
amine, however, as amine present in the solution as an amine-acid salt
will also react during the titration. This technique will also give erroneous
results if there are other basic materials in the solution, such as caustic or
soda ash (sometimes used to "neutralize" heat stable salts).
1. Reagents: Distilled or Deionized Water
0.5 N Hydrochloric Acid (HCl)
Bromophenol Blue Indicator
(3',3'',5',5''-tetrabromophenolsulfonephthalein)
2. Procedure:
a. Place about 95 ml of distilled or deionized water in a 250 ml
beaker or Erlenmeyer flask.
b. Add about 5 ml of lean amine solution to the water in the beaker
via pipette, recording the actual quantity.
c. Add 5 drops of Bromophenol Blue indicator to the solution in the
beaker and stir well.
d. Titrate the solution in the beaker with 0.5 N HCl to a faint yellow
color. Alternatively, if a pH meter is available, titrate to a pH of
4.5. Record the amount of HCl used in the titration.
3. Chemical reaction involved:
R
2
HN + HCl R
2
HNH
+
+ Cl


where R
2
HN = CH
3
-N-(CH
2
-CH
2
-OH)
2
= MDEA
(methyldiethanolamine)
As the hydrochloric acid is added to the solution, it reacts with the
amine to form a chloride salt. Once all the amine has reacted, the
continued addition of acid causes the pH of the solution to drop, until
the Bromophenol Blue indicator changes from blue to yellow. Note
that HCl reacts with the amine on a 1:1 molar basis.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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4. Calculation of Weight Percent Amine:
(

(
(

=
Sample Amine
of Gravity Sp.

Sample
of ml
Solution HCl
of Normality

Used
HCl ml

l / ml 1000
100%

Weight
Mole
Amine

Amine
% Weight

The molecular weight of MDEA is 119.17, and the specific gravity of
the solution at room temperature (20C) is about 1.059, assuming
the solution is about 45 wt% MDEA. The equation can then be
simplified to:

Sample
of ml
Solution HCl
of Normality

Used
HCl ml
11.253 Amine % Weight
(

=

Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-70
7.10.3 Determination of Total Acid Gas Loading in ATU/ARU Solvent
The total acid gas (H
2
S + CO
2
) loading, relative to the amine
concentration, in either the lean or rich ATU/ARU solvent can be
determined by base titration of the solution. This procedure does not
distinguish between H
2
S and CO
2
. However, together with the procedure
in Section 7.10.4, the individual concentrations of H
2
S and CO
2
can be
determined.
1. Reagents: Methanol (CH
3
OH), Anhydrous
0.5 N Potassium Hydroxide (KOH) Solution in Methanol
Thymolphthalein Indicator in Methanol
2. Procedure:
a. Place about 125 ml of methanol in a 250 ml beaker or
Erlenmeyer flask.
b. If a pH meter is available, insert the pH meter probe into the
methanol in the beaker and adjust the pH of the methanol to
11.2 by titrating the methanol in the beaker with the 0.5 N KOH.
c. If a pH meter is not available, add 5 drops of Thymolphthalein
indicator to the methanol in the beaker. Titrate the solution in
the beaker with 0.5 N KOH until the solution turns a faint blue
color, indicating a pH of 11.2. The change to faint blue will be
sudden, so add the KOH slowly (one drop at a time).
d. Add about 20 ml of lean amine solution to the methanol in the
beaker via pipette, recording the actual quantity. If rich amine
solution is being tested, use about 10 ml of solution instead.
e. Titrate the solution in the beaker with 0.5 N KOH back to a pH
of 11.2 (or until the solution again turns a faint blue color when
using Thymolphthalein indicator). Record the amount of KOH
used in this titration.
3. Chemical reactions involved:
H
2
S + KOH K
+
+ HS

+ H
2
O
CO
2
+ KOH K
+
+ HCO
3


As the potassium hydroxide is added to the solution, it reacts with the
H
2
S and CO
2
to form potassium hydrosulfide and potassium
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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hydrogen carbonate salts. Once all of the acid gas has reacted, the
continued addition of base causes the pH of the solution to rise, until
the Thymolphthalein indicator changes from colorless to blue. Note
that KOH reacts with H
2
S and CO
2
on a 1:1 molar basis.
4. Calculation of Acid Gas Loading (molar basis):
(

(
(

=
Solvent in
Amine % Wt

Sample
of S.G.

Sample
of ml
Solution KOH
of Normality

Used
KOH ml

l / ml 1000
100%

Weight
Mole
Amine

Amine Mole
Gas Acid Moles

Note that "ml KOH used" refers to the amount used in the second
titration, step 2.e. The "wt % amine in solvent" can be determined
using the procedure in Section 7.10.2.
The molecular weight of MDEA is 119.17, and the specific gravity of
the solution at room temperature (20C) is about 1.059, assuming
the solution is about 45 wt% MDEA. The equation can then be
simplified to:
(

=
Solvent in
Amine % Wt

Sample
of ml
Solution KOH
of Normality

Used
KOH ml
11.253
Amine Mole
Gas Acid Moles

5. Special Considerations:
a. Excess moisture in the equipment will give false readings.
Water may be used to clean the equipment if the equipment is
thoroughly dried prior to use with the anhydrous methanol.
b. The faint blue titration endpoint using Thymolphthalein indicator
is not definite. It may best be determined by comparing the
color of the solution against a reference prepared by titrating a
second sample of methanol-Thymolphthalein to the same color.
c. The KOH solution and Thymolphthalein indicator solution
should be kept tightly closed to prevent loss of methanol by
vaporization. Any vaporization of methanol from the KOH
solution will change the normality of the solution.
d. The Thymolphthalein indicator solution can be prepared by
dissolving 5 grams of thymolphthalein in 100 ml of anhydrous
methanol.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-72
7.10.4 Determination of H
2
S and CO
2
Loading in ATU/ARU Solvent
The H
2
S loading, relative to the amine concentration, in either the lean or
rich ATU/ARU solvent can be determined by titration of the solution with
iodine. Since CO
2
does not react with iodine, this procedure is specific for
H
2
S. Together with the total acid gas loading determined using the
procedure in Section 7.10.3, the individual concentrations of H
2
S and CO
2

can be determined.
1. Reagents: Distilled or Deionized Water
Concentrated Hydrochloric Acid (HCl) or Sulfuric Acid
(H
2
SO
4
)
Standard Starch Solution - 1%
0.1 N Iodine Solution (I
2
)
0.1 N Sodium Thiosulfate Solution (Na
2
S
2
O
3
)
2. Procedure:
a. Measure about 25 ml of chilled iodine solution and place it in a
250 ml beaker or Erlenmeyer flask. Record the amount of
iodine solution used.
b. Carefully add about 25 ml of concentrated acid to the beaker.
c. Add about 5 ml of standard starch solution to the beaker, then
re-chill the beaker in an ice batch for 2-3 minutes.
d. Slowly add 10-20 ml of lean amine solution to the solution in the
beaker via pipette, recording the actual quantity. If rich amine
solution is being tested, use 1-2 ml of solution instead.
e. Use about 25 ml of distilled or deionized water to rinse the
inside of the beaker, then swirl the contents gently to mix the
solution without splashing it.
f. Titrate the excess iodine in the sample with the sodium
thiosulfate solution until the blue color disappears. The end
point is a pale yellow or clear color. The approach of the
endpoint is usually indicated by a milky brown tint at the top of
the liquid surface. As the endpoint nears, slow the rate of
titration and use a small amount of distilled or deionized water
to wash the flask. Record the amount of sodium thiosulfate
solution used in this titration.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
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Issued 30 August 2011 Amine Treating & Regeneration Page 7-73
g. Check the pH of the titrated solution with pH paper to be sure
the solution is acidic. If the solution is not acidic, repeat the
procedure but use more acid in step 2.b.
3. Chemical reactions involved:
H
2
S + I
2
S + 2 HI
I
2
+ Na
2
S
2
O
3
2 S + NaI + NaIO
3

When the solvent is added to the iodine solution, the H
2
S in the
solvent reacts with the iodine to form hydrogen iodide and elemental
sulfur. The solution contains an excess of iodine to ensure that all of
the H
2
S reacts. The iodine solution is chilled prior to adding the
solvent to eliminate or minimize the evolution of H
2
S gas. Note that
H
2
S reacts with iodine on a 1:1 molar basis.
When the sodium thiosulfate solution is added to the solution, it
reacts with the remaining iodine to form sodium iodide and sodium
iodate, along with more elemental sulfur. (It is this elemental sulfur
that may cause the titrated solution to appear pale yellow.) Once the
last bit of iodine is consumed, the starch solution loses its
characteristic blue color. The amount of H
2
S in the solvent sample is
then calculated from the difference between the total iodine and the
iodine that reacts with the sodium thiosulfate. Note that sodium
thiosulfate reacts with iodine on a 1:1 molar basis.
The purpose of the concentrated acid is to neutralize the amine so
that it will release the H
2
S (a weaker acid) so it can react with the
iodine. If the titrated solution is not acidic in step 2.g, then the amine
was not fully neutralized and the H
2
S determination will not be
correct.
4. Calculation of H
2
S Loading (Molar Basis):
(

=
equivalent - g 2
mole - g 1

ml 1000
liter 1

Solution
of Normality

used
ml

Used
moles - g
2
2
2
I
I
I

(

(
(

(
(

=
equivalent - g 2
mole - g 1

ml 1000
liter 1

Solution
O S Na
of Normality

used
O S Na
ml

Used
O S Na
moles - g

3 2 2 3 2 2 3 2 2

Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-74
( )
(


(
(

=
Solvent in
Amine % Wt

Sample
of S.G.

Sample
of ml
Used O S Na
moles - g

Used
moles - g
% 100
Weight
Mole
Amine

Amine Mole
S H Moles
3 2 2 2
2
I

The "wt % amine in solvent" can be determined using the procedure
in Section 7.10.2.
The molecular weight of MDEA is 119.17, and the specific gravity of
the solution at room temperature (20C) is about 1.059, assuming
the solution is about 45 wt% MDEA. Using these values and
substituting the first and second equations into the third, these
equations can be simplified to:
(

(
(

(
(

=
Solvent in
Amine % Wt

Sample
of ml
Solution
O S Na
of Normality

Used
O S Na ml

Solution
of
Normality

Used
ml
5.626
Amine Mole
S H Moles
3 2 2
3 2 2
2
2
2
I
I

5. Calculation of CO
2
Loading (Molar Basis):
Using the total acid gas loading determined with the procedure in
Section 7.10.3, the CO
2
loading of the solvent is determined by
difference:
(

=
Amine Mole
S H Moles

Amine Mole
Gas Acid Moles

Amine Mole
CO Moles
2 2

6. Other Common Units:
The loadings calculated above can be easily converted to other units
commonly used within the industry:
(

=
Sample
of S.G.

Sample in
Amine % Wt

Amine Mole
S H Moles
166.7
Solvent Gallon
S H Grains
2 2

(

=
Sample in
Amine % Wt

Amine Mole
S H Moles
0.2858 S H % Wt
2
2

Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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Issued 30 August 2011 Amine Treating & Regeneration Page 7-75
(

=
Sample
of S.G.

Sample in
Amine % Wt

Amine Mole
CO Moles
0.2653
Solvent Gallon
CO SCF
2 2

(

=
Sample in
Amine % Wt

Amine Mole
CO Moles
0.3693 CO % Wt
2
2

Note that these conversions are specifically for MDEA. Other
amines require different conversion factors.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Amine Treating & Regeneration Page 7-76
7.10.5 Determination of Foaming Tendency of ATU/ARU Solvent
The procedure described in this section is an empirical method for
measuring the foaming tendency of aqueous amine solvents, universally
accepted within the industry.
1. Principle:
Air is bubbled through a solvent sample at a fixed rate for five
minutes, at which time the foam height is measured. The air flow is
stopped and the time for the foam to disappear is measured. The
foam height and "break" time are indicative of how high the foaming
tendency of the solvent is.
2. Equipment: 1000 ml Graduated Cylinder
Aquarium Air Pump (or laboratory air supply) with
Bubble Stone
Stop Watch (or regular watch with a second hand)
3. Procedure:
a. Pour about 200 ml of the sample solution into the graduated
cylinder and insert the bubble stone into the bottom of the
cylinder.
b. Record the level of sample in the cylinder (in ml).
c. Start the air pump or air supply to agitate the sample with
oil-free air at 4 liters per minute (0.2 Nm
3
/H).
d. After five minutes, record the height of the foam in the cylinder
(in ml). Then turn off the air supply and measure the time in
seconds for the foam to "break". For consistency, foam "break"
is defined as the first clear "fish eye" in the surface of the liquid
in the cylinder.
4. Calculation:
Foam Height = Height of Foam - Initial Height of Sample (in ml)
5. Interpretation:
Considerable experience with this test has shown that if the foam
height exceeds 200 ml or the "break" time exceeds 5 seconds, the
plant may be experiencing a foaming problem. The higher the foam
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
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Issued 30 August 2011 Amine Treating & Regeneration Page 7-77
height and/or the longer it takes to "break", the more severe the
problem.
6. Other Considerations:
a. A nitrogen cylinder with the pressure regulated to about
0.35 kg/cm
2
(g), equipped with a flow rotameter, may be used
instead of air. Be sure to keep the tubing and fittings oil-free.
b. This procedure can be used to evaluate the effects of anti-foam
agents on the solvent. However, care must be exercised in
cleaning the equipment between tests since a very small
quantity of residual anti-foam agent will affect the test.
c. Foaming is sometimes caused by contaminants in the solvent
that can be removed by activated carbon treatment. The effect
of activated carbon filtration can be evaluated by running foam
tests on treated and untreated samples. The sample is treated
by mixing it with a quantity of carbon (12-20 mesh) to remove
the contaminant, then filtering the mixture through Whatman
No. 41 filter paper.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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Issued 30 August 2011 Amine Treating & Regeneration Page 7-78
7.10.6 H
2
S Conc. in Amine Absorber Ovhd by the Tutweiler Method
The overhead gas from the Amine Absorber Overhead Knock-out Drum
can be sampled from the sample connection near the sample line for the
H
2
S analyzer.
1. Using a 500 ml Tutweiler apparatus, sample and titrate the treated
gas leaving the Amine Absorber Overhead Knock-out Drum as
outlined in Section 7.10.1 of these guidelines.
2. Chemical reaction involved:
H
2
S + I
2
2 HI + S
The hydrogen sulfide (H
2
S) is converted to small particles of
elemental sulfur by the iodine during the shaking. Good shaking is
required to get good contact between the hydrogen sulfide in the gas
and the iodine in the liquid. When all of the hydrogen sulfide is
converted, the excess iodine causes the characteristic blue color in
the presence of starch. This is a universal test for starch. (Iodine
causes a blue color when it contacts starchy foods, such as potato
for example.)
5. Calculation of Mole (or Volume) percent H
2
S (dry basis):
(

+

(

=
V.P. - P
760

289
T 73 2
(11.85)
Solution Iodine
of Normality

Used Solution
Iodine ml
S H % Mole
2

Where T = sample temperature, C
P = atmospheric pressure at particular location, mm Hg
V.P = vapor pressure of water at sample temperature, mm Hg

The Normality of the standard iodine solution will be 0.1 N. The last
three factors (which correct the actual H
2
S content to compensate for
expansion due to temperature, pressure, and water content) can be
combined and calculated as a function of temperature only. This has
been done for the 500-ml gas sample and is included as the
Tutweiler Factor Chart in Section 7.10.3 of these guidelines
(Chart 2). Therefore, the equation above can be simplified to:
(
(

(
(

(
(

=
Chart Factor
Tutweiler
from Factor

Solution
Iodine of
Normality

Used
Solution
Iodine ml
10,000 S H PPM
2

Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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Issued 30 August 2011 Amine Treating & Regeneration Page 7-79
7.10.7 H
2
S Conc. in Amine Absorber Ovhd Using Gas Detector Tubes
As an alternative to the traditional wet-chemistry method described in the
preceding Section 7.10.6 for determining the concentration of H
2
S in the
Amine Absorber overhead gas, gas detector tubes can be used to quickly
and easily make this determination. Although the discussion that follows
specifically addresses using gas detector tubes manufactured by
Drgerwerk AG of West Germany, there may be suitable detector tubes
available from other manufacturers. Drger tubes can be purchased from
most safety equipment supply companies.
The following Drger tubes can be used with this procedure:
H
2
S 5/b Drger Cat. No. CH 298 01
H
2
S 100/a Drger Cat. No. CH 291 01
7.10.7.1 Operating Principles
Drger tubes and other gas detector tubes measure gas
concentrations by using a sample pump to draw a specific volume of
the gas to be sampled into a glass tube containing a suitable
reagent. The gaseous compound of interest chemically reacts with
the reagent to produce a color change. The length of the "stain" line
is a direct function of the concentration of the compound in the
sample gas. Some detector tubes are calibrated with measured lines
to allow reading the concentration directly on the tube. Others, such
as the two listed above, have reference marks on the tube that can
be multiplied by a factor to compute the concentration.
Drger tubes are designed to be used with a Drger Model 31 gas
detector pump. This is a hand-operated bellows pump that will draw
a 100 cc sample volume for each pump stroke. Some tubes are
designed for a single sample stroke, while others may use 5, 10, or
even 20 strokes. In some cases, a tube may be used for measuring
different concentration ranges by using a different number of strokes.
a. Drger Cat. No. CH 298 01, H
2
S 5/b
This tube will measure H
2
S concentrations in the range of
50 PPM to 600 PPM when one sample stroke is used. If
desired, the range can be reduced to 5 PPM to 60 PPM by
using 10 sample strokes. Each tube contains a substrate of a
white lead compound. When exposed to H
2
S, the lead
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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compound is converted to brown lead sulfide. The H
2
S
concentration in PPM can be read directly from the marks on
the tube according to the length of the brown stain when using
10 sample strokes. If only one sample stroke is used, the tube
reading is multiplied by 10 to give the PPM of H
2
S. This lead
sulfide reaction is not affected by any of the other compounds
normally found in the overhead gas from the ATU/ARU Amine
Absorber.
b. Drger Cat. No. CH 291 01, H
2
S 100/a
This tube will measure H
2
S concentrations in the range of
100 PPM to 2,000 PPM when one sample stroke is used. Each
tube contains a substrate of a white lead compound. When
exposed to H
2
S, the lead compound is converted to brown lead
sulfide. The H
2
S concentration in PPM can be read directly
from the marks on the tube according to the length of the brown
stain. This lead sulfide reaction is not affected by any of the
other compounds normally found in the overhead gas from the
ATU/ARU Amine Absorber.
7.10.7.2 Sampling the Amine Absorber Overhead Gas
The overhead gas from the Amine Absorber Overhead Knock-out
Drum can be sampled from the sample connection near the sample
line for the H
2
/H
2
S analyzer.
a. Before beginning, check the Drger pump for leaks by inserting
an unopened tube into the pump and stroking the pump.
Confirm that the bellows does not re-expand. If it does, either
the pump or its seal around the tube is leaking, and the test
results will not be accurate.
b. Attach a short piece of rubber tubing to the process sample
valve.
c. Break off the tips at each end of a Drger tube and insert it into
the sample pump (with the arrow on the side of the tube
pointing toward the pump).
d. Purge the rubber tubing by venting gas to the atmosphere for a
few seconds. Pinch the rubber tubing closed at the end, close
the gas sample valve, slip the end of the rubber tubing onto the
end of the Drger tube, and reopen the sample valve.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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e. Stroke the sample pump one time (be sure to compress the
bellows until reaching the stops) and allow the pump to draw
the gas sample into the detector tube. The sample stroke is
complete when the metal chain on the bellows is taut.
f. Close the sample valve and remove the rubber tubing from the
end of the Drger tube and from the sample valve.
g. Read the length of the brown stain using the marks on the tube
and record the reading.
7.10.7.3 Calculations
Mole (or Volume) PPM H
2
S (wet basis):
(

=
mbar Pres., Baro.
1013

Factor
Tube

Length
Stain
S H PPM
2

The last factor corrects the measurement for pressure effects when
samples are taken at elevations above sea level. Note that the
average barometric pressure at the compex is
14.7 PSIA = 1013 mbar.
The "Tube Factor" depends on the type of Drger tube used and the
number of sample strokes:
Drger Tube Catalog No. Sample Strokes Tube Factor

H
2
S 5/b CH 298 01 1 10
H
2
S 5/b CH 298 01 10 1
H
2
S 100/a CH 291 01 1 1


Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sour Water Stripping Page 8-i
Table of Contents
8. SOUR WATER STRIPPING ......................................................................................... 8-1
8.1 PURPOSE OF SYSTEM ....................................................................................... 8-1
8.2 SAFETY ................................................................................................................. 8-1
8.3 PROCESS DESCRIPTION .................................................................................... 8-2
8.3.1 General ........................................................................................................... 8-2
8.3.2 Sour Water Collection ..................................................................................... 8-2
8.3.3 Sour Water Stripping ...................................................................................... 8-3
8.4 EQUIPMENT DESCRIPTION ................................................................................ 8-5
8.4.1 Sour Water Stripper, A2-DA1520 ................................................................... 8-5
8.4.2 Sour Water Stripper Packing and Internals, A2-DB1520 ................................ 8-5
8.4.3 Stripper Trays, A2-DB1521 ............................................................................ 8-5
8.4.4 SWS Cross Exchanger, A2-EA1520 .............................................................. 8-5
8.4.5 Sour Water Stripper Reboiler, A2-EA1521 ..................................................... 8-6
8.4.6 SWS Quench Water Cooler, A2-EC1520 ....................................................... 8-6
8.4.7 SWS Bottoms Cooler, A2-EC1521 ................................................................. 8-6
8.4.8 Sour Water Flash Drum, A2-FA1520 .............................................................. 8-6
8.4.9 SWS Skim Oil Sump, A2-FA1522 .................................................................. 8-7
8.4.10 SWS Skim Oil Pump Sump, A2-FA1523A/B .................................................. 8-7
8.4.11 Sour Water Tank, A2-FB1520 ........................................................................ 8-7
8.4.12 Sour Water Filter, A2-FD1520A/B .................................................................. 8-7
8.4.13 Sour Water Transfer Pump, A2-GA1520A/B .................................................. 8-7
8.4.14 SWS Feed Pump, A2-GA1521A/B ................................................................. 8-8
8.4.15 SWS Quench Water Pump, A2-GA1522A/B .................................................. 8-8
8.4.16 SWS Bottoms Pump, A2-GA1523A/B ............................................................ 8-8
8.4.17 SWS Skim Oil Pump, A2-GA1524A/B ............................................................ 8-8
8.5 INSTRUMENTATION AND CONTROL SYSTEMS ............................................... 8-9
8.5.1 SWS Shutdowns and Alarms ......................................................................... 8-9
8.6 PROCESS PRINCIPLES AND OPERATING TECHNIQUES ............................. 8-11
8.6.1 SWS Stripper Operation ............................................................................... 8-11
8.6.2 Quench Water Circulation ............................................................................ 8-12
8.6.3 pH Control .................................................................................................... 8-13
8.7 PRECOMMISSIONING PROCEDURES ............................................................. 8-14
8.7.1 Preliminary Check-out .................................................................................. 8-14
8.7.2 Washing the Sour Water System ................................................................. 8-15
8.8 STARTUP PROCEDURES .................................................................................. 8-19
8.8.1 Initial Startup of the SWS ............................................................................. 8-19
8.8.1.1 Initial Water Fill ...................................................................................... 8-19
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
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Issued 30 August 2011 Sour Water Stripping Page 8-ii
8.8.1.2 Exporting Treated Water ....................................................................... 8-21
8.8.2 Normal Startup of the SWS .......................................................................... 8-23
8.8.2.1 Initial Water Fill ...................................................................................... 8-23
8.8.2.2 Exporting Treated Water ....................................................................... 8-26
8.9 SHUTDOWN PROCEDURES ............................................................................. 8-29
8.9.1 Planned Shutdown ....................................................................................... 8-29
8.9.2 Effects of Shutdowns and Outages in Other Systems .................................. 8-31
8.9.2.1 Steam System Outage .......................................................................... 8-31
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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Issued 30 August 2011 Tailgas Cleanup Page 8-1
8. SOUR WATER STRIPPING
8.1 Purpose of System
The purpose of the Sour Water Stripping (SWS) system is to remove H
2
S and
ammonia (NH
3
) from various sour water streams produced in the Sulfur Block
and elsewhere in the aromatics complex. The resulting treated water
(containing less than 20 PPMW of H
2
S and less than 20 PPMW of NH
3
) is
returned to the aromatics complex for reuse elsewhere, while the SWS off-gas
(NH
3
, H
2
S, and water vapor) is routed to the Sulfur Recovery Units (SRUs).
8.2 Safety


ALL PIPING AND VESSELS INCLUDED IN THIS UNIT EITHER CONTAIN
OR HAVE THE POTENTIAL FOR CONTAINING HAZARDOUS GASES
THAT MAY CAUSE SERIOUS INJURY OR DEATH. THE TWO GASES
THAT ARE MOST COMMON AND HAZARDOUS IN A TOXIC WAY ARE
HYDROGEN SULFIDE AND AMMONIA. CLOSE ATTENTION SHOULD
BE PAID TO THE "GENERAL SAFETY" SECTION OF THESE
GUIDELINES AS TO THE NATURE AND ABILITY OF THESE GASES TO
CONTAMINATE OTHER ELEMENTS IN THIS UNIT.
AN EMPLOYEE'S KNOWLEDGE OF THE HAZARDOUS CHEMICALS AND
COMPOUNDS WITH WHICH HE WILL BE WORKING IS ONE OF THE
MOST BASIC PREREQUISITES FOR HIS OWN SAFETY, THE SAFETY
OF OTHERS, AND THE PROTECTION OF EQUIPMENT. ALL
EMPLOYEES SHOULD REVIEW THE "GENERAL SAFETY" SECTION
OCCASIONALLY TO REFRESH THEIR MEMORIES. NEW EMPLOYEES
SHOULD STUDY IT UNTIL THE INFORMATION IS THOROUGHLY
UNDERSTOOD. PEOPLE WHO HAVE NOT BEEN PROPERLY TRAINED
SHOULD NOT BE ALLOWED TO OPERATE OR WORK IN AND AROUND
THIS PLANT.
WARNING
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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8.3 Process Description
8.3.1 General
The Systems Diagram, Material Balance and Process Flow Diagram,
Dwg. Nos. 507000-7000-01, and 507000-7000-05 through -06, are
contained in the "Process Flow Diagrams" Section of the Basic
Engineering Package. Please refer to these drawings to follow this
description of the process.
The Sour Water Stripping Unit (SWS) receives sour water streams
containing ammonia (NH
3
) and hydrogen sulfide (H
2
S) from other units in
the No. 2 Aromatics Complex. These sour water streams are combined
with sour water produced in the Sulfur Block (predominately Sour Water
from the ATU and excess quench water from the SWS) and steam
stripped to remove essentially all of the NH
3
and H
2
S from the water. The
resulting treated water (containing less than 20 PPMW of H
2
S and less
than 20 PPMW of NH
3
) is returned to the complex for reuse elsewhere,
while the SWS off-gas (NH
3
, H
2
S, and water vapor) is routed to the SRUs.
8.3.2 Sour Water Collection
Sour water from other units within the complex is combined with the sour
water streams generated within the Sulfur Block and flows to the Sour
Water Flash Drum, A2-FA1520, at 54C [129F]. This vessel is operated
at low pressure (1.05 kg/cm
2
(g) [15 PSIG]) to maximize the vaporization
and removal of any light hydrocarbons that may be entrained or dissolved
in the sour water. Any flash gases are directed to the flare header for
disposal.
The flash drum is large enough to provide 30 minutes or more of
residence time for the sour water. This allows time for any heavy
hydrocarbons entrained in the water to separate as a second liquid phase
that spills over the internal weir at the inlet end of the drum, collecting in
the SWS Skim Oil Sump, A2-FA1522. The SWS Skim Oil,
A2-GA1524A/B, sends the collected hydrocarbon to the Condensate Feed
Tank on start/stop level control.
After removal of any liquid hydrocarbon, the heavier water phase passes
under the internal weir at the outlet end of the drum to be pumped to the
Sour Water Tank, A2-FB1520, by the Sour Water Transfer Pump,
A2-GA1520A/B, on level control. This tank is large enough to provide
3-4 days of residence time to allow "working off " an accumulation of sour
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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water after an outage. The tank also provides time for mixing which
minimizes Sour Water Stripper feed composition fluctuations due to the
many sources of sour water in the complex.
8.3.3 Sour Water Stripping
After residing in the Sour Water Tank for several days, the sour water is
pumped by the SWS Feed Pump, A2-GA1521A/B, on flow control through
the tube side of the SWS Cross Exchanger, A2-EA1520. The sour water
is preheated to 100C [211F] by cooling the treated water before flowing
to the Sour Water Stripper, A2-DA1520, to enter the column above the
first valve tray, tray #2.
Traditional reflux systems do not work well for strippers in this service
because of the highly corrosion nature of concentrated NH
3
-H
2
S aqueous
systems. For this reason, these systems often employ a direct-contact
condenser instead, using a circulating stream of quench water to provide
cooling for the upper section of the column. The Sour Water Stripper
contains an upper section of packing to provide contact between the
quench water and the stripped gases, and a lower section of valve trays to
provide contact between the sour water and the stripping steam.
The stripping section of the column contains 30 valve trays and one
chimney draw tray. As the sour water flows down the column, the NH
3

and H
2
S are stripped from the water by countercurrent contact with
stripping steam rising upward. This stripping steam is generated in the
Sour Water Stripper Reboiler, A2-EA1521, using LP (3.5 kg/cm
2
(g)
[50 PSIG]) steam on flow control as the heat input. The stripping steam
strips the NH
3
and H
2
S from the water and carries it upward to the quench
section of the column. The SWS Bottoms Pump, A2-GA1523A/B, pumps
the treated water from the bottom of the column through the shell side of
the SWS Cross Exchanger, cooling the treated water from 123C [254F]
to 54C [130F] by countercurrent heat exchange with the cool sour
water. The SWS Bottoms Cooler, A2-EC1521, provides final cooling to
49C [120F] before the treated water is returned to the complex for reuse
elsewhere.
The quench section of the column contains a packed bed and a chimney
draw tray. As the stripping steam rises upward in this section, it is
countercurrently contacted by the circulating quench water, cooling the
off-gas to 85C [185F] as it condenses most of the steam. The chimney
tray below the packed bed that collects the quench water leaving the
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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bottom of the bed has overflow pipes to direct the condensed water onto
the valve tray (tray #2) below. The quench water collecting on the
chimney tray is pumped by the SWS Quench Water Pump,
A2-GA1522A/B, to the SWS Quench Water Cooler, A2-EC1520, to cool
the water from 99C [210F] to 66C [150F] to reject the heat removed
from the stripping steam in the quench section of the column. The cooling
rate is adjusted as necessary to control the column overhead temperature
at 85C [185F]. This allows the NH
3
and H
2
S stripped from the water to
leave the column at 0.85 kg/cm
2
(g) [12 PSIG]and flow to the SRUs.

Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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8.4 Equipment Description
8.4.1 Sour Water Stripper, A2-DA1520
The upper section of the Sour Water Stripper contains a chimney draw
tray and a single bed of random packing to provide good contact between
the circulating quench water and the stripped gases. The stripping section
of the column contains 30 valve trays and one chimney draw tray. The
valve trays provide good contact between the sour water and the reboiler
vapors to strip H
2
S and NH
3
from the water.
A chimney tray is located below the bottom valve tray to gather all of the
column liquids to feed the Sour Water Stripper Reboiler. The column
section located below this chimney tray serves to separate the outlet
steam and treated water from the reboiler.
8.4.2 Sour Water Stripper Packing and Internals, A2-DB1520
This bed of random packing provides good contact between the stripped
gases entering below it and the quench fed above it inside the Sour Water
Stripper. The packing has a bed limiter above it and rests on a bed
support. The quench water is distributed over the packing by a distributor
tray. The packing is aluminum; the other internals are 316L S.S.
8.4.3 Stripper Trays, A2-DB1521
These 1-pass valve trays provide good contact between the sour water
fed above them and the reboiler vapors fed below them inside the Sour
Water Stripper. The tray decks for Trays #1 and #2 are 316L S.S. with
316 S.S. valves and bolting. For the remaining trays, the tray decks are
carbon steel and the valves are fabricated from 316 S.S. to resist
corrosion and to prevent "sticking" to the tray decks. The bottom valve
tray has a seal pan for its downcomer to maintain a liquid seal and prevent
gas from blowing up the downcomer.
The chimney tray gathers the tower liquids to feed the reboiler. The outlet
from the reboiler reenters the column below the chimney tray, with the
vapor produced by the reboiler flowing upward through the chimneys in
order to reach the valve trays above.
8.4.4 SWS Cross Exchanger, A2-EA1520
This shell and tube exchanger conserves energy by providing heat
exchange between the stripped sour water and the sour water feed
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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stream, so that the hot water leaving the Sour Water Stripper can preheat
the sour water before it feeds the Sour Water Stripper. This cross
exchange saves reboiler duty by preheating the sour water, and reduces
the load on the SWS Bottoms Cooler by partially cooling the hot stripped
water.
8.4.5 Sour Water Stripper Reboiler, A2-EA1521
The Sour Water Stripper Reboiler is a fixed tubesheet shell and tube heat
exchanger. The exchanger is arranged as once-through vertical
thermosiphon reboiler, mounted on the side of the Sour Water Stripper.
The static head of the water above the inlet nozzle on the lower channel
provides the driving force to circulate the water through the tubes.
LP steam on the shell of the exchanger heats the water inside the tubes,
partially vaporizing it to create stripping steam to remove the H
2
S and the
NH
3
from the sour water flowing down the Sour Water Stripper.
8.4.6 SWS Quench Water Cooler, A2-EC1520
This forced-draft aerial exchanger is used to cool a circulating stream of
quench water which enters above the packed section of the Sour Water
Stripper and provides cooling for the upper section of the column. Fans
are used to circulate air across the finned tubes to remove heat from the
circulating quench water.
8.4.7 SWS Bottoms Cooler, A2-EC1521
This forced-draft aerial exchanger provides the final cooling of the stripped
sour water stream leaving the bottom of the Sour Water Stripper. Fans
are used to circulate air across the finned tubes to remove heat from the
water.
8.4.8 Sour Water Flash Drum, A2-FA1520
This horizontal vessel allows for the removal of hydrocarbons that may be
carried out of the various upstream processes with the sour water. The
sour water enters the vessel through a slotted, vertical distributor. Any
hydrocarbon that may be carried with the sour water from the upstream
processes will accumulate in the center section of this vessel. When a
sufficient amount of hydrocarbon has accumulated, the hydrocarbon will
overflow the partition and flow into the hydrocarbon section. Lighter
hydrocarbons are disengaged from the sour water and routed to the
battery limits on pressure control. Hydrocarbon-free sour water then
passes under another partition, at the opposite end of the vessel, and into
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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the sour water outlet section, where the sour water is pumped to the Sour
Water Tank.
8.4.9 SWS Skim Oil Sump, A2-FA1522
This horizontal vessel is located in a below-ground concrete vault. It
collects the heavy hydrocarbons from the Sour Water Flash Tank. The
collected hydrocarbon liquid is pumped back to the Condensate Feed
Tank on stop/start level control.
8.4.10 SWS Skim Oil Pump Sump, A2-FA1523A/B
These vertical vessels house the SWS Skim Oil pumps. Hydrocarbon
liquids from the SWS Skim Oil Sump flow into this vessel and are pumped
out by the SWS Skim Oil Pump.
8.4.11 Sour Water Tank, A2-FB1520
The Sour Water Tank is an above-ground vertical cylindrical tank with a
floating roof. This tank is large enough to provide 2-3 days of residence
time to allow "working off " an accumulation of sour water after an outage.
It has two level transmitters to indicate the sour water level, with a low
level alarm to alert the operators of a low level, and a low level shutdown
which will shut down the SWS Feed Pump if the level in the tank drops too
low. The tank also has multiple connections to the closed drain system
which can be used to route hydrocarbons to the closed drain if a layer of
hydrocarbon should form in the tank.
8.4.12 Sour Water Filter, A2-FD1520A/B
These full-flow filters are designed to remove solid particles 5 microns and
larger from the sour water, which will help prevent fouling of the
downstream heat exchangers.
8.4.13 Sour Water Transfer Pump, A2-GA1520A/B
These centrifugal pumps are used to transfer the sour water from the Sour
Water Flash Drum to the Sour Water Tank. Each pump is designed for
the total duty; the other pump is a 100% spare. These pumps are
equipped with tandem seals to reduce the likelihood of releasing H
2
S to
the surroundings.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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8.4.14 SWS Feed Pump, A2-GA1521A/B
These centrifugal pumps are used to send the sour water from the Sour
Water Tank to the Sour Water Stripper. Each pump is designed for the
total duty; the other pump is a 100% spare. These pumps are equipped
with tandem seals to reduce the likelihood of releasing H
2
S to the
surroundings.
8.4.15 SWS Quench Water Pump, A2-GA1522A/B
These centrifugal pumps are used to circulate quench water to cool the
stripped gases in the upper section of the Sour Water Stripper. Each
pump is designed for the total duty; the other pump is a 100% spare.
These pumps are equipped with tandem seals to reduce the likelihood of
releasing H
2
S to the surroundings.
8.4.16 SWS Bottoms Pump, A2-GA1523A/B
These centrifugal pumps are used to send the stripped water from the
Sour Water Stripping Unit to the battery limits for use elsewhere in the
complex. Each pump is designed for the total duty; the other pump is a
100% spare.
8.4.17 SWS Skim Oil Pump, A2-GA1524A/B
These vertical sump-type pump is mounted in the SWS Skim Oil Pump
Sump to transfer the recovered hydrocarbons back to the Condensate
Feed Tank.










Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Tailgas Cleanup Page 8-9
8.5 Instrumentation and Control Systems
8.5.1 SWS Shutdowns and Alarms
There are several interlocks of significance in the SWS Unit that either
generate an alarm or shut down an individual piece of equipment. These
devices/interlocks and their effects are described in this section.
a. Sour Water Flash Drum Low-Low Level, A2-LT15209A/B/C
The Sour Water Transfer Pump (A2-GA1520A/B) could be damaged
if the pump loses suction because the level in the Sour Water Flash
Drum drops too low. This device will protect the pump by stopping it
before this can occur. The setpoint is 530 mm above the bottom of
the vessel. Note that there are three independent transmitters and
2oo3 voting logic is used for the shutdown.
b. Sour Water Tank Low-Low Level, A2-LT15218A/B/C
The SWS Feed Pump (A2-GA1521A/B) could be damaged if the
pump loses suction because the level in the Sour Water Tank drops
too low. This device will protect the pump by stopping it before this
can occur. The setpoint is 300 mm above the bottom of the vessel.
Note that there are three independent transmitters and 2oo3 voting
logic is used for the shutdown.
c. SWS Bottoms Cooler Fan High Vibration, A2-WSH15234
Each fan on the SWS Bottoms Cooler (A2-EC1521) is provided with
its own vibration switch. If the vibration sensed by the switch
exceeds the preset level, the switch will trip to stop the associated
fan and activate an alarm in the DCS.
d. Sour Water Stripper Low-Low Level, A2-LT15247A/B/C
The SWS Bottoms Pump (A2-GA1523A/B) could be damaged if the
pump loses suction because the level in the Sour Water Stripper
drops too low. This device will protect the pump by stopping it before
this can occur. The setpoint is 300 mm above the bottom seam of
the column. Note that there are three independent transmitters and
2oo3 voting logic is used for the shutdown.


Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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e. SWS Quench Water Cooler Fan High Vibration, A2-WSH15263
Each fan on the SWS Quench Water Cooler (A2-EC1520) is
provided with its own vibration switch. If the vibration sensed by the
switch exceeds the preset level, the switch will trip to stop the
associated fan and activate an alarm in the DCS.

Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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8.6 Process Principles and Operating Techniques
8.6.1 SWS Stripper Operation
The stripped water must be comparatively free of H
2
S and NH
3
to assure
attainment of the treated water specification. These contaminates are
removed from the sour water in the Sour Water Stripper by stripping them
out with steam.
The stripping steam is produced by vaporizing some of the water in the in
the Sour Water Stripper Reboiler, using LP (3.5-4.2 kg/cm
2
(g)) steam for
the heat input. The steam rate to the reboiler (and, hence, the stripping
rate) is controlled by the steam flow controller. Adjust this steam rate as
needed to keep the H
2
S and NH
3
in the treated water low, i.e., less than
20 PPMW of H
2
S and less than 20 PPMW of NH
3
.


THE DESIGN STRIPPING STEAM RATE SHOWN ON THE
PROCESS FLOW DIAGRAM SHOULD BE CLOSE TO OPTIMUM.
ALTHOUGH IT MAY BE POSSIBLE TO REDUCE THIS SOMEWHAT
WITHOUT GOING OUT OF COMPLIANCE, REDUCING THE
STRIPPING STEAM RATE SIGNIFICANTLY CAN CAUSE THE
CONCENTRATION OF H
2
S AND AMMONIA IN THE TREATED
WATER TO EXCEED THE ALLOWABLE CONCENTRATION IN THE
TREATED WATER SPECIFICATION.
IF IT IS NECESSARY TO OPTIMIZE THE STEAM TO THE SOUR
WATER STRIPPER REBOILER, REDUCE THE STEAM BY SMALL
INCREMENTS AND CHECK THE CONCENTRATION OF AMMONIA
AND H
2
S AFTER EACH CHANGE. DO NOT REDUCE THE STEAM
FURTHER IF EITHER CONCENTRATION BEGINS TO RISE
SIGNIFICANTLY.
CAUTION
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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8.6.2 Quench Water Circulation
The operating conditions shown on the Process Flow Diagram for this
system (in terms of the quench water circulation rate and water
temperature) should generally be maintained. The quench water
circulation rate is controlled by the quench water flow controller in the
DCS, while the temperature is controlled by a temperature controller on
the Sour Water Stripper overhead gas line adjusting the speed of one of
the fans on the SWS Quench Water Cooler, A2-EC1520.
In general, decreasing the quench water circulation rate will increase the
quench water temperature upstream of the cooler (which increases the
corrosion rate) and may increase the Sour Water Stripper Overhead
temperature if the cooler cannot cool the quench water sufficiently. Care
should be taken when reducing the quench water circulation rate to
ensure that the corrosion rate in the quench water circulation loop does
not become excessive.
As the feed rate to the SWS Stripper decreases, the quench water
circulation rate can decrease in proportion with the feed flow rate down to
about 50% of design flow rate. Below this point, the quench water rate
cannot be allowed to drop any further without risking poor performance in
the packed section of the SWS Stripper due to uneven liquid distribution
and wetting of the packing. At lower feed rates (below 50%) simply setting
the quench water flow rate to the column at about 50% of design should
maintain adequate performance. (It should be noted, however, that there
is really no detrimental effect if the quench water circulation is simply left
at the design value at all times. The only drawback is slightly higher
power consumption by the pump and aerial cooler.)
Increasing the quench water temperature will increase the overhead gas
temperature and water content which increases the load on the
downstream SRUs (since water is a product of the Claus reaction, higher
water content in the SWS feed gas can negatively impact the recovery of
in the SRUs). However, decreasing the quench water temperature (and
correspondingly the overhead gas temperature) may lead operating
issues including salt deposition and plugging in the downstream piping
and equipment. Ammonium salts can form in the gas stream leaving the
top of the Sour Water Stripper if the gas temperature falls below about
70C. These salts can plug the mist eliminator in the top of the Sour Water
Stripper as well as the downstream piping and equipment. In addition,
decreasing the overhead gas temperature below about 82C may prevent
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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the ammonia from leaving the top of the column. Instead it may become
trapped in the column where it will concentrate, or it may leave in the
stripped water causing the treated water to exceed the specification for
ammonia.
The flow rate and temperatures shown on the Process Flow Diagram are
usually a good compromise between minimizing corrosion, minimizing the
load on the downstream SRUs, and minimizing operating issues within the
SWS unit.
8.6.3 pH Control
High pH water tends to hold H
2
S in solution and aids in releasing
ammonia from sour water. Conversely, low pH water tends to hold
ammonia in solution and improves the stripping of H
2
S. By injecting a
small amount of caustic near the tower bottom, ammonia stripping in the
bottom of the Sour Water Stripper can be improved while the H
2
S is still
stripped in the upper part of the tower.
Injection points for caustic addition have been supplied in the lower
section of the Sour Water Stripper. In the event that the stripped water
cannot meet the low ammonia specification, caustic can be added to the
tower to increase the pH and improve the ammonia stripping in the tower.
If caustic is added, injection control is critical to limit the pH of the stripped
water to about 8.0.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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8.7 Precommissioning Procedures
Prior to the initial startup, there are a number of precommissioning activities that
are necessary to ensure that the newly constructed plant is ready to be placed
in service. The activities outlined below should serve as a guide, but there may
be others required as a part of your normal plant procedures.
8.7.1 Preliminary Check-out
Check all equipment to ensure that it is properly installed. This will
probably require consulting Manufacturer's literature as well as
construction drawings.
A. Check and lubricate all equipment, in accordance with the
Manufacturer's recommendations.
B. Check the rotation of the following pumps by "bumping" them:
(1) Sour Water Transfer Pump.
(2) SWS Feed Pump
(3) SWS Quench Water Pump
(4) SWS Bottoms Pump
(5) SWS Skim Oil Pump

C. Check the rotation of the fans on the SWS Quench Water Cooler and
the SWS Bottoms Cooler, by operating each fan for a short period.
D. Check all piping and equipment to be sure that all blinds have been
removed and that no valves are vented to atmosphere.
E. Place the Instrument Air System in service to all instruments and
check the action of controllers and control valves.
F. Check all relief valves to ensure that they are installed in the proper
locations, the inlet and outlet block valves (if provided) are open, the
bypass valves (if provided) are closed, and the relief valves are set
for the correct relieving pressure.
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8.7.2 Washing the Sour Water System
The following procedure is intended to remove grease, rust, scale, dirt,
and trash from the equipment and piping in the Sour Water Stripping
system before it is placed in operation.
Failure to clean the system properly prior to startup can lead to operating
problems (heat exchanger fouling, rapid filter plugging, etc.).
A. Place the following controllers in the DCS in "manual" with their
outputs set as indicated:
(1) Set the output from the Sour Water Flash Drum level controller
to 0% to fully close the Sour Water Flash Drum level control
valve.
(2) Set the output from the SWS Inlet flow controller to 100% to
fully open the SWS Inlet flow control valve.
(3) Set the output from the SWS level controller to 100% to fully
open the level control valve.
(4) Set the output from the Quench Water flow controller to 100%
to fully open the Quench Water flow control valve.
(5) Set the output from the SWS Stripper Reboiler steam flow
controller to 0% to fully close the steam flow control valve.
(6) Set the output from the SWS pressure controller to 0% to fully
close the overhead pressure control valve to the SRUs.
B. Place the other SWS pressure controller in "automatic" with a
setpoint of 0.85 kg/cm
2
(g). This will open the pressure control valve
to the flare if pressure builds in the Sour Water Stripper during this
procedure.
C. Verify that the bypass valve on the pressure control valve to the flare
is closed. Open both of the isolation block valves at this control
station.
D. Place the H.P. Nitrogen supply to the Stripper overhead line in
service and open the manual block valve. This will prevent a vacuum
from forming in the Sour Water Stripper during this procedure.
E. Set the Treated Water hand control in the DCS is to 0% output to
fully open the automated valve in the Startup/Re-run line to the Sour
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Water Tank, and fully close the automated valve in the Treated
Water line downstream of the SWS Bottoms Cooler. Visually confirm
that these valves are properly positioned.
F. Verify that the manual block valve at the inlet to the Sour Water Tank
is open.
G. Verify that the manual block valve in the fill line for the Quench Water
Loop is closed.
H. Verify that the SWS Inlet flow control valve is fully open. Open both
of its isolation block valves and its bypass valve.
I. Verify that the SWS level control valve is fully open. Open both of its
isolation block valves and its bypass valve.
J. Verify that the Quench Water flow control valve is fully open. Open
both of its isolation block valves and its bypass valve.
K. Verify that the Sour Water Flash Drum level control valve is fully
closed. (This will prevent water from entering the upstream
equipment if the Sour Water Tank is accidentally over-filled.)
L. The Sour Water Filters will not be used to filter solids during this
time, but the filter vessels and their piping are to be flushed and
cleaned. Remove the filter elements, then bolt-up the filters. Open
the inlet and outlet block valves on the filters, and open the bypass
valve around the filters.
M. Use a temporary jumper to add cold condensate to the Sour Water
Tank.
N. Once there is an adequate level in the tank, open the suction valve
on a SWS Feed Pump and use its drain valve to be sure the pump is
flooded with water. Start the pump, then open its discharge valve.
Watch the level in the Sour Water Tank as the pump fills the
downstream piping and begins to fill the Sour Water Stripper. When
the level drops to the low-low level shutdown it should shut down the
pump. If it does not, stop the pump manually before it loses suction
and correct the problem with the low level shutdown before
proceeding.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Tailgas Cleanup Page 8-17
O. Continue filling the Sour Water Tank with condensate and pumping
the water to the Sour Water Stripper periodically, until the level in the
Stripper is all the way to the top of its level gauge.
P. Once there is an adequate level in the Stripper, open the suction
valve on a SWS Bottoms Pump and use its drain valve to be sure the
pump is flooded with water. Start the pump, then open its discharge
valve.
Watch the level in the Sour Water Stripper as the pump fills the
downstream piping and begins to circulate back to the Sour Water
Tank. When the level drops to the low-low level shutdown it should
shut down the pump. If it does not, stop the pump manually before it
loses suction and correct the problem with the low level shutdown
before proceeding.
Q. Once circulation is achieved and the level in the Sour Water Stripper
is adequate (about halfway up in the level gauge), discontinue the
addition of condensate.
R. Circulate the water and blow down the low point drains until all of the
drain water is clear. Add more condensate as necessary to maintain
the level in the Sour Water Stripper.
At some point during the washing procedure, the standby SWS Feed
Pump and the standby SWS Bottoms pump should be placed in
service while the other pumps are shut down. This will ensure
cleaning out all pumps and their associated piping.
S. When the drain water begins to clear, open the manual block valve in
the Quench Water fill line, open the suction valve on a SWS Quench
Water Pump and use its drain valve to be sure the pump is flooded
with water. Start the pump, then open its discharge valve.
Watch the level in the Sour Water Stripper as the pump fills the
quench water circulation loop. Add additional condensate to the Sour
Water Tank if necessary and pump the water to the Sour Water
Stripper.
T. Once circulation is achieved in the Quench Water loop and the level
in the Sour Water Stripper is adequate (about halfway up in the level
gauge), discontinue the addition of condensate and close the manual
block valve in the Quench Water fill line.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Tailgas Cleanup Page 8-18
U. Circulate the water in the Quench Water loop and blow down the low
point drains until all of the drain water is clear.
At some point during the washing procedure, the standby SWS
Quench Water Pump should be placed in service while the other
pump is shut down. This will ensure cleaning out both pumps and
their associated piping.
V. Once the drain water is clear in the main circulation loop and Quench
Water loop, shutdown the pumps and completely drain the system.
Drain the system as quickly as possible, so that the water velocity
helps to flush the solids from all parts of the system.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Tailgas Cleanup Page 8-19
8.8 Startup Procedures
8.8.1 Initial Startup of the SWS
The SWS system should now be clean, ready to place in service. All that
remains is to fill the system with water and establish the proper operating
conditions.
8.8.1.1 Initial Water Fill
A. Close the bypass valves around the following control stations:
(1) SWS Inlet flow control
(2) SWS level control
(3) Quench water flow control
B. Close the inlet and outlet block valves (but leave the bypass
valves open) on the Sour Water Filters, then install the proper
elements in the filters. Leave the block valves closed on each
filter for now.
C. Use a temporary jumper to add cold condensate to the Sour
Water Tank and reestablish the level in the Sour Water Stripper
as before.
D. Establish circulation of water in the system (including the
Quench Water loop) using the procedures in Section 8.7.2.
E. Start a fan on the SWS Bottoms Cooler and place the bottoms
temperature controller in service with a setpoint of 60C.
F. Begin steam flow to the Sour Water Stripper Reboiler and
gradually raise the temperature in the column. Place the steam
flow controller in the DCS on "automatic" with its setpoint set to
its normal value.
G. Open the high point vent valve on the Stripper overhead line
and allow the steam to purge any air from the vessel. As the
pressure builds, the vent valve can be closed.
H. When the temperature begins to rise in the SWS overhead line,
start a fan on the SWS Quench Water Cooler and place the
overhead temperature controller in service with a setpoint of
85C.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Tailgas Cleanup Page 8-20
I. Monitor the stripper pressure, and adjust the overhead pressure
controller if necessary to maintain the stripper pressure at about
0.85 kg/cm
2
(g) as the system is heated to operating
temperatures.
J. Ensure that the fans are running on the SWS Bottoms Cooler
and the SWS Quench Water Cooler.
K. If the control loops for the Sour Water Stripper have not already
been placed in service, do so at this time. Switch the SWS
level controller, and the SWS Inlet flow controller in the DCS to
"automatic" with their setpoints set to their normal values.
L. Place the Quench Water flow controller in automatic and set
its setpoint to its normal value.
M. Place each of the sour water filters in service as follows:
(1) Open the vent valve on the top of the filter.
(2) "Crack" the filter inlet block valve open slightly and allow
the filter to fill with sour water. When the filter is full, close
its vent valve.
(3) Open the inlet and outlet block valves on the filter.
(4) Slowly close the valve in the bypass line around the filter.
Note: At this point the sour water system is ready for service. It
can remain in this operating mode indefinitely while the
rest of the Complex is prepared for startup. Check the
system periodically for indications of plugging, etc. (low
flow, erratic pump discharge pressure, high filter pressure
drop), as solid materials may accumulate at various points
in the system over time.
N. Once there is an adequate level of Sour Water in the Sour
Water Flash Drum, open the suction valve on a Sour Water
Transfer Pump and use its drain valve to be sure the pump is
flooded with water. Start the pump, then open its discharge
valve.
Watch the level in the Sour Flash Drum as the pump fills the
downstream piping and begins to flow to the Sour Water Tank.
When the level drops to the low-low level shutdown it should
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Tailgas Cleanup Page 8-21
shut down the pump. If it does not, stop the pump manually
before it loses suction and correct the problem with the low
level shutdown before proceeding.
O. Place the Sour Water Flash Tank level controller in the DCS in
automatic and set its setpoint to its normal value.
P. Once a level of hydrocarbons has built up in the hydrocarbon
side of the Sour Water Flash Tank, the oil level controller can
also be placed automatic and its setpoint set to its normal
value.
The sour water will continue to circulate from the Sour Water Tank to
the Sour Water Stripper and back to the tank. The Sour Water Tank
is large enough to provide 3-4 days of residence time for the
produced sour water in the event the Sour Water System is not ready
to export treated water at this time.
8.8.1.2 Exporting Treated Water
Stripped sour water may not be routed to the complexs treated water
system until the temperature in the bottom of the Sour Water Stripper
is high enough to satisfy the Stripped Water Low Temperature
Interlock. This interlock disables the hand control in the DCS to
prevent the operator from routing the stripped water to the complexs
treated water system until the temperature in the bottom of the Sour
Water Stripper is sufficiently high.
Once the temperature in the bottom of the Sour Water Stripper is
high enough to satisfy the low-temperature interlock, and the
complex is producing a sufficient quantity of sour water for
processing:
A. Slowly increase the output from the Treated Water hand
control to 100%, which will open the automated valve in the
Treated Water line downstream of the SWS Bottoms Cooler
and close the automated valve in the Startup/Re-run line to the
Sour Water Tank.
B. When the output of the Treated Water hand control reaches
100%, the automated valve in the Treated Water line
downstream of the SWS Bottoms Cooler should be fully open
and the automated valve in the Startup/Re-run line fully closed
to send all of the treated water to the complexs treated water
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Tailgas Cleanup Page 8-22
system. Visually confirm that these valves are properly
positioned.
C. Once the operation of the Sour Water Stripper has stabilized,
route its acid gas, which is presently going to the flare through a
pressure valve to the SRUs as follows:
(1) Confirm that the Sour Water Stripper pressure controller to
the SRUs in the DCS is in "manual" with its output set to
0%.
(2) Confirm that the setpoint of the Sour Water Stripper
pressure controller to the SRUs is tracking its current
reading, then place it in "automatic".
(3) Slowly raise the setpoint of the Sour Water Stripper
pressure controller to the flare to 1.0 kg/cm
2
(g).
(4) If, necessary, adjust the setpoint of the Sour Water
Stripper pressure controller to the SRU to its normal
setpoint.
The Sour Water Stripper pressure controller will now take over
control of the Sour Water Stripper pressure by opening the
pressure valve to send the acid gas to the SWS Gas Knock-Out
Drums in the SRUs. The Sour Water Stripper pressure
controller to the flare will close the acid gas pressure valve and
stop the flow of acid gas to the flare. If the SRUs shut down (or
some other upset causes the Sour Water Stripper pressure to
rise), the Sour Water Stripper pressure controller to the flare will
act as an over-ride and divert the acid gas to the flare.
D. The SWS is now fully on-stream. Before directing your
attention away from the SWS, be sure that:
(1) All controllers are functioning properly.
(2) The steam heating systems are in service and the level
control on the Reboiler condensate pot is functioning
properly.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Tailgas Cleanup Page 8-23
8.8.2 Normal Startup of the SWS
The procedure for startup of the SWS after it has been shut down will be
very similar to the procedure for the initial startup, except that condensate
will not be used to fill the system. For ease of reference, the steps to be
performed are written in this Section to serve as a "check list" that can be
easily followed on subsequent startups. Refer to the previous Sections for
the reasons and details pertaining to the different steps performed.
Prior to commencing SWS startup, check for the completion of all
maintenance work (connecting lines, removing blinds, etc.) if such work
was performed.
8.8.2.1 Initial Water Fill
A. Confirm that the Treated Water hand control in the DCS is to
0% output to fully open the automated valve in the Startup/Re-
run line to the Sour Water Tank, and fully close the automated
valve in the Treated Water line downstream of the SWS
Bottoms Cooler. Visually confirm that these valves are properly
positioned.
B. Place the following controllers in the DCS in "manual" with their
outputs set as indicated:
(1) Set the output from the SWS Inlet flow controller to 100%
to fully open the SWS Inlet flow control valve.
(2) Set the output from the SWS level controller to 100% to
fully open the level control valve.
(3) Set the output from the Quench Water flow controller to
100% to fully open the Quench Water flow control valve.
C. Confirm that the output from the SWS Stripper Reboiler steam
flow controller is set to 0% and the steam flow control valve is
fully closed.
D. Confirm that the output from the SWS pressure controller is set
to 0% and the overhead pressure control valve to the SRUs is
fully closed.
E. Place the other SWS pressure controller in "automatic" with a
setpoint of 0.85 kg/cm
2
(g). This will open the pressure control
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Tailgas Cleanup Page 8-24
valve to the flare if pressure builds in the Sour Water Stripper
during this procedure.
F. Verify that the bypass valve on the pressure control valve to the
flare is closed and that both of the isolation block valves are
open.
G. If not already in service, place the H.P. Nitrogen supply to the
Stripper overhead line in service and open the manual block
valve.
H. Verify that the manual block valve at the inlet to the Sour Water
Tank is open.
I. Verify that the manual block valve in the fill line for the Quench
Water loop is closed.
J. If the Sour Water Flash Drum is already in service and sending
sour water to the Sour Water Tank, proceed to Step L.
Otherwise, if the Sour Water Flash Drum is not in service, open
the isolation valves upstream of the flash drum to allow sour
water to enter the flash drum from the upstream Units.
K. Once there is an adequate level of sour water in the Sour Water
Flash Drum, open the suction valve on a Sour Water Transfer
Pump and use its drain valve to be sure the pump is flooded
with water. Start the pump, then open its discharge valve.
Watch the level in the Sour Flash Drum as the pump fills the
downstream piping and begins to send sour water to the Sour
Water Tank. When the level drops to the low-low level
shutdown it should shut down the pump. If it does not, stop the
pump manually before it loses suction and correct the problem
with the low level shutdown before proceeding.
L. Confirm that there is an adequate level of sour water in the
Sour Water Tank, then open the suction valve on a SWS Feed
Pump and use its drain valve to be sure the pump is flooded
with water. Start the pump, then open its discharge valve.
Watch the level in the Sour Water Tank as the pump fills the
downstream piping and begins to fill the Sour Water Stripper.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Tailgas Cleanup Page 8-25
M. Continue pumping sour water to the Sour Water Stripper until
the level in the Stripper is all the way to the top of its level
gauge.
N. When there is an adequate level in the Stripper, open the
suction valve on a SWS Bottoms Pump and use its drain valve
to be sure the pump is flooded with water. Start the pump, then
open its discharge valve to begin circulating sour water back to
the Sour Water Tank.
O. Once circulation is achieved and the level in the Sour Water
Stripper is adequate, open the manual block valve in the
Quench Water fill line, open the suction valve on a SWS
Quench Water Pump and use its drain valve to be sure the
pump is flooded with water. Start the pump, then open its
discharge valve.
Watch the level in the Sour Water Stripper as the pump fills the
quench water circulation loop. If the level in the stripper falls
below the low level alarm point, stop the SWS Quench Water
Pump and pump additional sour water to the Stripper from the
Sour Water Tank to bring the level in the level back up before
restarting the SWS Quench Water Pump.
P. Once circulation is achieved in the Quench Water loop and the
level in the Sour Water Stripper is adequate (about halfway up
in the level gauge), close the manual block valve in the Quench
Water fill line.
Q. Start a fan on the SWS Bottoms Cooler and place the bottoms
temperature controller in service with a setpoint of 60C.
R. Begin steam flow to the Sour Water Stripper Reboiler and
gradually raise the temperature in the column. Place the steam
flow controller in the DCS on "automatic" with its setpoint set to
its normal value.
S. When the temperature begins to rise in the SWS overhead line,
start a fan on the SWS Quench Water Cooler and place the
overhead temperature controller in service with a setpoint of
85C.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Tailgas Cleanup Page 8-26
T. Monitor the stripper pressure, and adjust the overhead pressure
controller if necessary to maintain the stripper pressure at about
0.85 kg/cm
2
(g) as the system is heated to operating
temperatures.
U. Ensure that the fans are running on the SWS Bottoms Cooler
and the SWS Quench Water Cooler.
V. If the control loops for the Sour Water Stripper have not already
been placed in service, do so at this time. Switch the Sour
Water Flash Tank level controllers, the SWS level controller,
and the SWS Inlet flow controller in the DCS to "automatic" with
their setpoints set to their normal values.
W. Place the Quench Water flow controller in automatic and set
its setpoint to its normal value.
The sour water will continue to circulate from the Sour Water Tank to
the Sour Water Stripper and back to the tank. The Sour Water Tank
is large enough to provide 3-4 days of residence time for the
produced sour water in the event the Sour Water System is not ready
to export treated water at this time.
8.8.2.2 Exporting Treated Water
Stripped sour water may not be routed to the complexs treated water
system until the temperature in the bottom of the Sour Water Stripper
is high enough to satisfy the Stripped Water Low Temperature
Interlock. This interlock disables the hand control in the DCS to
prevent the operator from routing the stripped water to the complexs
treated water system until the temperature in the bottom of the Sour
Water Stripper is sufficiently high.
Once the temperature in the bottom of the Sour Water Stripper is
high enough to satisfy the low-temperature interlock, and the
complex is producing a sufficient quantity of sour water for
processing:
A. Slowly increase the output from the Treated Water hand
control to 100%, which will open the automated valve in the
Treated Water line downstream of the SWS Bottoms Cooler
and close the automated valve in the Startup/Re-run line to the
Sour Water Tank.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Tailgas Cleanup Page 8-27
B. When the output of the Treated Water hand control reaches
100%, the automated valve in the Treated Water line
downstream of the SWS Bottoms Cooler should be fully open
and the automated valve in the Startup/Re-run line fully closed
to send all of the treated water to the complexs treated water
system. Visually confirm that these valves are properly
positioned.
C. Once the operation of the Sour Water Stripper has stabilized,
route its acid gas, which is presently going to the flare through a
pressure valve to the SRUs as follows:
(1) Confirm that the Sour Water Stripper pressure controller to
the SRUs in the DCS is in "manual" with its output set to
0%.
(2) Confirm that the setpoint of the Sour Water Stripper
pressure controller to the SRUs is tracking its current
reading, then place it in "automatic".
(3) Slowly raise the setpoint of the Sour Water Stripper
pressure controller to the flare to 1.0 kg/cm
2
(g).
(4) If, necessary, adjust the setpoint of the Sour Water
Stripper pressure controller to the SRU to its normal
setpoint.
The Sour Water Stripper pressure controller will now take over
control of the Sour Water Stripper pressure by opening the
pressure valve to send the acid gas to the SWS Gas Knock-Out
Drums in the SRUs. The Sour Water Stripper pressure
controller to the flare will close the acid gas pressure valve and
stop the flow of acid gas to the flare. If the SRUs shut down (or
some other upset causes the Sour Water Stripper pressure to
rise), the Sour Water Stripper pressure controller to the flare will
act as an over-ride and divert the acid gas to the flare.
D. The SWS is now fully on-stream. Before directing your
attention away from the SWS, be sure that:
(1) All controllers are functioning properly.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Tailgas Cleanup Page 8-28
(2) The steam heating systems are in service and the level
control on the Reboiler condensate pot is functioning
properly.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Tailgas Cleanup Page 8-29
8.9 Shutdown Procedures
Typical shutdown procedures for the Sour Water Stripping Unit are outlined and
discussed in the sections that follow for the more common cases. Your existing
company procedures and common sense operational judgment should be used
to modify these procedures as needed to serve the purpose of any given
planned shutdown situation.
8.9.1 Planned Shutdown
Any equipment to be opened should be properly blinded and purged with
inert gas before admission of air, to avoid exposure to potentially toxic
gases or the formation of flammable vapor mixtures.
To shut the SWS down in a controlled fashion proceed as follows:
A. Slowly reduce the output from the Treated Water hand control in the
DCS is to 0% output to fully open the automated valve in the
Startup/Re-run line to the Sour Water Tank, and fully close the
automated valve in the Treated Water line downstream of the SWS
Bottoms Cooler. Visually confirm that these valves are properly
positioned.
B. Place the stream flow controller in manual and set its output to 0% to
close the stream flow control valve and stop the steam flow to the
Sour Water Stripper Reboiler.
C. Continue to circulate the sour water and operate the SWS Bottoms
Cooler and the SWS Quench Water Cooler until the sour water is
cool.
D. Once the sour water is cool, shut down the SWS Feed Pump to stop
the flow of sour water to the Sour Water Stripper and close the block
valves in the pump suction lines.
E. Place the SWS flow controller in the DCS in "manual" and set its
output to 0% to fully close the sour water inlet flow control valve.
F. Shutdown the SWS Quench Water Pumps and shut down the fans
on the SWS Quench Water Cooler.
G. Place the quench water flow controller in the DCS in "manual" and
set its output to 0% to fully close the quench water flow control valve.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Tailgas Cleanup Page 8-30
H. Use the SWS Bottoms pump to pump the sour water from the Sour
Water Stripper to the Sour Water Tank until the low-low level
shutdown is activated. This should shut down the SWS Bottoms
Pump. Monitor the level in the Sour Water Stripper and be prepared
to shut down the pump if the low-low level shutdown fails to activate.
I. Place the SWS level controller in the DCS in "manual" and set its
output to 0% to fully close the SWS level control valve.
J. Shut down the fans on the SWS Bottoms Cooler
K. Drain the remaining sour water in the SWS equipment to the Closed
Drain System.
L. Verify that the SWS level control valve is fully closed. Close both of
its isolation block valves and its bypass valve.
M. Verify that the SWS flow control valve is fully closed. Close both of
its isolation block valves and its bypass valve.
N. Verify that the quench water flow control valve is fully closed. Close
both of its isolation block valves and its bypass valve.
O. The SWS is now ready to be isolated and made safe for entry.

Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Tailgas Cleanup Page 8-31
8.9.2 Effects of Shutdowns and Outages in Other Systems
The SWS system is directly affected by a shutdown and/or outage in the
LP steam system for the complex. These effects are described below.
8.9.2.1 Steam System Outage
The most immediate impact on the SWS will be the loss of LP steam
to the Stripper Reboiler if the steam outage lasts long enough. As
the heat input to the reboiler declines, stripping of the acid gas from
the sour water will decline and the H
2
S and NH
3
in the treated water
leaving the Sour Water Stripper will begin to increase. If this
happens, use the Treated Water hand control in the DCS to route the
treated water back to the Sour Water Tank until the LP steam system
can be brought back on-line.








Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-1
Table of Contents
9. SULFUR RECOVERY .................................................................................................. 9-4
9.1 PURPOSE OF SYSTEM ....................................................................................... 9-4
9.2 SAFETY ................................................................................................................. 9-4
9.3 PROCESS DESCRIPTION .................................................................................... 9-5
9.3.1 Overview ......................................................................................................... 9-5
9.3.2 General ........................................................................................................... 9-6
9.3.3 Feed Gas Processing ..................................................................................... 9-6
9.3.4 Thermal Processing ........................................................................................ 9-7
9.3.5 Catalytic Processing ....................................................................................... 9-8
9.3.6 Air Control System .......................................................................................... 9-9
9.3.7 Molten Sulfur Handling ................................................................................. 9-10
9.3.8 Steam Production ......................................................................................... 9-10
9.4 EQUIPMENT DESCRIPTION .............................................................................. 9-11
9.4.1 Reactor Furnace, A2-BA1530 (A2-BA1540) ................................................. 9-11
9.4.2 Acid Gas Burner Assembly, A2-BA1531 (A2-BA1541) ................................ 9-12
9.4.3 Acid Gas Knock-Out Drum, A2-FA1530 (A2-FA1540) ................................. 9-12
9.4.4 SWS Gas Knock-Out Drum, A2-FA1531 (A2-FA1541) ................................ 9-12
9.4.5 Reactor, A2-DC1530 (A2-DC1540) .............................................................. 9-13
9.4.6 Catalyst for Sulfur Plant Reactors, A2-MC1530 (A2-MC1540) ..................... 9-13
9.4.7 Acid Gas Preheater, A2-EA1530 (A2-EA1540) ............................................ 9-13
9.4.8 Sulfur Condenser, A2-EA1531 (A2-EA1541) ............................................... 9-13
9.4.9 Reactor No. 1 Feed Heater, A2-EA1532 (A2-EA1542) ................................ 9-14
9.4.10 Reactor No. 2 Feed Heater, A2-EA1533 (A2-EA1543) ................................ 9-14
9.4.11 Reactor No. 3 Feed Heater, A2-EA1534 (A2-EA1544) ................................ 9-15
9.4.12 Sulfur Surge Tank, A2-FB1530 (A2-FB1540) ............................................... 9-15
9.4.13 Acid Gas Knock-Out Drum Pump, A2-GA1530A/B (A2-GA1540A/B) .......... 9-16
9.4.14 SWS Gas Knock-Out Drum Pump, A2-GA1531A/B (A2-GA1541A/B) ......... 9-17
9.4.15 Sulfur Storage Tank Vent Ejector, A2-EE1530 (A2-EE1540) ....................... 9-17
9.4.16 Process Air Blower, A2-GB1530A/B (A2-GB1540A/B) ................................. 9-18
9.4.17 Air Blower Suction Screen/Silencer, A2-FD1530A/B (A2-FD1540A/B) ........ 9-19
9.4.18 Process Air Vent Silencer, A2-FG1530A/B (A2-FG1540A/B) ....................... 9-19
9.4.19 Sulfur Drain Seal Assembly, A2-ME1530A-D (A2-ME1540A-D) .................. 9-19
9.4.20 Refractory for Reactor Furnace and Waste Heat Boiler, A2-MR1530
(A2-MR1540) .............................................................................................................. 9-20
9.4.21 Ceramic Ferrules for Waste Heat Boiler, A2-MR1532 (A2-MR1542) ........... 9-20
9.4.22 Refractory for Waste Heat Boiler, A2-MR1533 (A2-MR1543) ...................... 9-20
9.4.23 Refractory for Sulfur Condenser, A2-MR1534 (A2-MR1544) ....................... 9-20
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-2
9.4.24 Refractory for Reactor, A2-MR1535 (A2-MR1545) ...................................... 9-21
9.4.25 Rainshield for Reactor Furnace, A2-ME1531 (A2-ME1541) ........................ 9-21
9.4.26 Ceramic Ferrule for Reactor Furnace, A2-MR1531 (A2-MR1541) ............... 9-21
9.4.27 Waste Heat Boiler, A2-BF1530 (A2-BF1540) ............................................... 9-22
9.5 INSTRUMENTATION AND CONTROL SYSTEMS ............................................. 9-24
9.5.1 SRU Air:Acid Gas Ratio Control Loop .......................................................... 9-24
9.5.2 Acid Gas Burner Management System ........................................................ 9-30
9.5.3 Process Air Blower Controls ......................................................................... 9-34
9.5.4 Reactor Furnace Temperature Control ......................................................... 9-39
9.5.5 Knock-Out Drum Pump Control .................................................................... 9-41
9.5.6 "Ride-Through" System Considerations ....................................................... 9-41
9.5.7 Boiler Low-Low Level S/D Transmitter Testing ............................................ 9-44
9.5.8 SRU Emergency Shutdown Systems ........................................................... 9-46
9.6 PROCESS PRINCIPLES AND OPERATING TECHNIQUES ............................. 9-56
9.6.1 Equipment Damage ...................................................................................... 9-56
9.6.2 Cold Catalyst Bed Startup ............................................................................ 9-58
9.6.3 Sulfur Solidification ....................................................................................... 9-60
9.6.4 Ammonia Salt Formation .............................................................................. 9-61
9.6.5 Catalyst Fouling ............................................................................................ 9-62
9.6.6 Operation of SRUs in Parallel ....................................................................... 9-62
9.6.7 Process air Blower Operation ....................................................................... 9-65
9.6.8 Reactor Furnace Temperature ..................................................................... 9-70
9.6.9 Ammonia Destruction Considerations .......................................................... 9-73
9.6.10 Sulfur Recovery Efficiency ............................................................................ 9-76
9.6.11 Operation at Low Flow Rates ....................................................................... 9-78
9.6.12 Pressure Drop Surveys ................................................................................ 9-82
9.6.13 Boiler Water Treatment ................................................................................ 9-84
9.7 PRECOMMISSIONING PROCEDURES ............................................................. 9-86
9.7.1 Preliminary Check-out .................................................................................. 9-86
9.7.2 Shutdown System Check-out ....................................................................... 9-87
9.7.3 Leak Testing the Process Piping and Equipment ......................................... 9-88
9.7.4 Purging the Inlet Knock-Out Drums .............................................................. 9-93
9.7.5 Commissioning Fuel Gas and Instrument Air to the Process ....................... 9-95
9.7.6 Commissioning Nitrogen to the Process ...................................................... 9-99
9.7.7 Commissioning the Sulfur Surge Tank Heating and Ventilation ................. 9-102
9.7.8 Pre-filling the Sulfur Drain Seal Assemblies ............................................... 9-104
9.8 STARTUP PROCEDURES ................................................................................ 9-105
9.8.1 Initial Firing / Refractory Cure-out ............................................................... 9-105
9.8.2 Amine Acid Gas Flow ................................................................................. 9-117
9.8.3 SWS Gas Flow ........................................................................................... 9-124
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-3
9.8.4 Routing SRU Tailgas to the TGCU ............................................................. 9-127
9.8.5 Normal Startup - Cold System .................................................................... 9-129
9.8.6 Normal Startup - Hot System ...................................................................... 9-146
9.8.7 Firing Supplemental Fuel Gas .................................................................... 9-158
9.9 SHUTDOWN PROCEDURES ........................................................................... 9-164
9.9.1 Planned Shutdown - No Reactor Entry ....................................................... 9-165
9.9.2 Planned Shutdown for Reactor Entry ......................................................... 9-170
9.9.3 Shutting Down When Boiler Tubes Are Leaking ........................................ 9-180
9.9.4 Emergency Shutdown ................................................................................ 9-181
9.9.5 Effects of Shutdowns and Outages in Other Systems ................................ 9-183
9.10 ANALYTICAL PROCEDURES .......................................................................... 9-187
9.10.1 Procedure for Sampling and Titrating with a Tutweiler Apparatus ............. 9-187
9.10.2 H
2
S Concentration in Acid Gas by the Tutweiler Method ........................... 9-189
9.10.3 H
2
S and SO
2
Concentration in Tailgas by the Tutweiler Method ................ 9-192
9.10.4 Tailgas Analysis Table ................................................................................ 9-196
9.10.5 Tailgas Analysis Operating Chart ............................................................... 9-197
9.10.6 Essential Apparatus for Tutweiler Analysis ................................................ 9-199
9.10.7 Materials for Tutweiler Analysis .................................................................. 9-200
9.10.8 H
2
S and SO
2
Conc. in Tailgas Using Gas Detector Tubes ......................... 9-200
9.11 ADJUSTING STACKMATCH

IGNITOR/PILOTS ............................................. 9-205


Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-4
WARNING
WARNING
9. SULFUR RECOVERY
9.1 Purpose of System
The purpose of the Sulfur Recovery Units (SRUs) is to dispose of H
2
S-laden
acid gas. This gas is produced by the new Amine Regeneration Unit and Sour
Water Stripping Unit. Acid gases of this type are not allowed into the
atmosphere, as they are highly toxic. If burned in a flare system, the pollutants
would exceed emission standards. Each Sulfur Recovery Unit can take enough
H
2
S out of the acid gas so that the remaining tailgas can be processed in a
Tailgas Cleanup Unit to meet the emission standards after incineration. Also,
the byproduct of pure sulfur is a marketable product.
9.2 Safety


ALL PIPING AND VESSELS INCLUDED IN THIS UNIT EITHER CONTAIN
OR HAVE THE POTENTIAL FOR CONTAINING HAZARDOUS GASES
THAT MAY CAUSE SERIOUS INJURY OR DEATH. THE TWO GASES
THAT ARE MOST COMMON AND HAZARDOUS IN A TOXIC WAY ARE
HYDROGEN SULFIDE AND SULFUR DIOXIDE. CLOSE ATTENTION
SHOULD BE PAID TO THE "GENERAL SAFETY" SECTION OF THESE
GUIDELINES AS TO THE NATURE AND ABILITY OF THESE GASES TO
CONTAMINATE OTHER ELEMENTS IN THIS UNIT.
AN EMPLOYEE'S KNOWLEDGE OF THE HAZARDOUS CHEMICALS AND
COMPOUNDS WITH WHICH HE WILL BE WORKING IS ONE OF THE
MOST BASIC PREREQUISITES FOR HIS OWN SAFETY, THE SAFETY
OF OTHERS, AND THE PROTECTION OF EQUIPMENT. ALL
EMPLOYEES SHOULD REVIEW THE "GENERAL SAFETY" SECTION
OCCASIONALLY TO REFRESH THEIR MEMORIES. NEW EMPLOYEES
SHOULD STUDY IT UNTIL THE INFORMATION IS THOROUGHLY
UNDERSTOOD. PEOPLE WHO HAVE NOT BEEN PROPERLY TRAINED
SHOULD NOT BE ALLOWED TO OPERATE OR WORK IN AND AROUND
THIS PLANT.
WARNING
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-5
9.3 Process Description
9.3.1 Overview
The Systems Diagram, Material Balance and Process Flow Diagrams,
Dwg. Nos. 507000-7000-01, and 507000-7000-07 through -09, are
contained in the "Process Flow Diagrams" Section of the Basic
Engineering Package. Please refer to these drawings to follow this
description of the process.
The new Sulfur Recovery Units, consisting of SRU Train 1 and
SRU Train 2, are designed to operate in parallel and recover elemental
sulfur from the off-gases produced by the new Amine Regeneration and
Sour Water Stripper Units. It is intended that the Sulfur Recovery Facility
convert and recover 99.9% or more of the hydrogen sulfide (H
2
S)
contained in the feed streams as elemental sulfur in compliance with
environmental requirements.
The acid gases produced by the new Amine Regeneration Unit (ARU) and
the new Sour Water Stripping Unit (SWS) are routed to two parallel Claus
Sulfur Recovery Units (SRUs) using technology licensed from BP Amoco
Corporation. The H
2
S is converted into molten elemental sulfur and
routed to the common Sulfur Degassing Unit (SDU) that uses technology
licensed from BP Amoco Corporation to reduce the H
2
S content of the
sulfur to less than 10 PPMW. The combined tailgas from the sulfur plants
is processed in a Tailgas Cleanup Unit (TGCU) using the Shell Claus
Off-gas Treating (TGCU) process licensed by Shell Global Solutions (US)
Inc. to produce an acid gas stream that is recycled back to the Claus plant
so that the overall sulfur recovery is 99.9 wt. % or better.
The effluent gas from the TGCU is thermally incinerated in a Tailgas
Thermal Oxidation Unit (TTO) to convert all of the remaining sulfur
compounds into sulfur dioxide (SO
2
) before dispersion of the gas to the
atmosphere. Due to the sulfur removal by the TGCU process, the
incinerated effluent gas will contain less than 200 PPMV of SO
2
on a dry,
0% oxygen basis.
The two process trains are identical, so all of the information that follows
applies to both trains. Where references to equipment or instrument tag
numbers are given, the SRU Train 1 tag number is given first followed by
the SRU Train 1 tag number in parentheses.

Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-6
9.3.2 General
Each sulfur plant processes 1,181 Nm
3
/H of acid gas from the Amine
Regeneration Unit and 33 Nm
3
/H of off-gas from Sour Water Stripping
(SWS) Unit, plus 50% of the recycle acid gas from the Tailgas Cleanup
Unit. Each sulfur plant will recover 94-96% of the sulfur contained in the
total acid gas feed as elemental sulfur, producing about 34.6 MT/D of
molten sulfur product. The tailgas leaving each sulfur plant is routed to
the common TGCU.
Each sulfur plant uses the modified straight-through Claus process
licensed from BP Amoco Corporation, with a number of special design
features to accomplish the required recovery performance while providing
exceptionally good on-stream reliability and ease of operation. The Claus
process utilizes the following chemical reactions to convert hydrogen
sulfide to elemental sulfur:
(1) H
2
S + 3/2 O
2
SO
2
+ H
2
O
(2) 2 H
2
S + SO
2
3/n S
n
+ 2 H
2
O
The overall reaction for the process is:
(3) 3 H
2
S + 3/2 O
2
3/n S
n
+ 3 H
2
O
The sulfur plant contains one non-catalytic conversion stage and three
catalytic conversion stages in series. The Claus reaction is highly
exothermic, releasing a great deal of heat energy that is recovered as HP
and LP steam in heat exchangers following the conversion stages.
9.3.3 Feed Gas Processing
Acid gas from the Amine Regeneration Unit is combined with the recycle
acid gas from the Tailgas Cleanup Unit and is routed to the Acid Gas
Knock-Out Drum, A2-FA1530 (A2-FA1540), at 49C [120F] and
0.74 kg/cm
2
(g) [10.5 PSIG]. Entrained liquids are separated and
automatically routed back to the Rich Amine Flash Drum by Acid Gas
Knock-Out Drum Pump, A2-GA1530A/B (A2-GA1540A/B), on start/stop
level control. The scrubbed acid gas stream flows through the Acid Gas
Preheater, A2-EA1530 (A2-EA1540), where a portion of the LP
(4.2 kg/cm
2
(g) [60 PSIG]) steam generated elsewhere in the SRU heats
the acid gas to 126C [259F]. Preheating the amine acid gas allows it to
be mixed with the SWS gas without causing ammonium salt precipitation.
The preheater is also an energy conservation device, as preheating with
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-7
LP steam allows more HP (48.5 kg/cm
2
(g) [690 PSIG]) steam to be
produced in the sulfur plant.
SWS gas from the Sour Water Stripping Unit is routed to the SWS Gas
knock-Out Drum, A2-FA1531 (A2-FA1541), at 85C [185F] and
0.70 kg/cm
2
(g) [10.0 PSIG]. Entrained liquids are separated and
automatically routed back to the Sour Water Flash Drum by the SWS Gas
Knock-Out Drum Pump, A2-GA1531A/B (A2-GA1541A/B), on start/stop
level control. The scrubbed SWS gas mixes with the majority of the
preheated amine acid gas and flows to the Acid Gas Burner, A2-BA1531
(A2-BA1541). The remainder of the amine acid gas is routed into the
sides of the Reactor Furnace, A2-BA1530 (A2-BA1540), on flow ratio
control to ensure proper destruction of the ammonia in the first zone of the
furnace as described below.
9.3.4 Thermal Processing
One-third of the hydrogen sulfide in the feed stream must be converted to
sulfur dioxide before the Claus reaction (2) can be utilized to produce
elemental sulfur. Accordingly, the acid gas feed stream flows to the Acid
Gas Burner to be combusted with air provided by the Process Air Blower,
A2-GB1530A/B (A2-GB1540A/B). The amount of air is controlled to
combust one-third of the hydrogen sulfide to sulfur dioxide via reaction (1).
Sufficient air is also provided to combust the ammonia and hydrocarbons
entering with the acid gas.
The combustion products pass into the first combustion zone of the
Reactor Furnace, which provides the necessary residence time to allow
these reactions to reach equilibrium. At 1370C [2500F] or above (with
the proper residence time), ammonia is almost completely destructed to
nitrogen and water. The first combustion zone is controlled at or above
this temperature by adjusting the amount of amine acid gas bypassing the
burner. Combustion of the SWS gas at or above this temperature in a
reducing atmosphere is essential for destruction of the ammonia, and
avoids formation of undesirable and troublesome compounds such as
sulfur trioxide.
The first combustion zone of the Reactor Furnace is separated from the
second zone by a refractory checker wall. The amine acid gas bypassing
the burner is injected into the Reactor Furnace immediately downstream
of the checker wall, where it mixes with the burner effluent. The second
zone is large enough to provide sufficient residence time for the
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-8
sulfur-forming and hydrocarbon-oxidizing reactions to reach equilibrium.
The Reactor Furnace functions as a non-catalytic conversion stage, as
67% of the hydrogen sulfide is converted to elemental sulfur.
The effluent from the Reactor Furnace enters the tubes in the Waste Heat
Boiler, A2-BF1530 (A2-BF1540), where the gas is cooled to 328C
[622F] by producing HP steam. The gas is then routed through the first
condensing pass of the Sulfur Condenser, A2-EA1531 (A2-EA1541), and
further cooled to 165C [329F] by producing LP steam. The outlet
channel of the Sulfur Condenser is extended and contains a compartment
that serves as a separator for the condensed sulfur that is formed as the
gases are cooled. About 65% of the sulfur entering the sulfur plant is
recovered as condensed liquid sulfur here.
9.3.5 Catalytic Processing
The vapor from the first condensing pass of the Sulfur Condenser flows to
the Reactor No. 1 Feed Heater, A2-EA1532 (A2-EA1542), and is heated
by a portion of the HP steam generated in the Waste Heat Boiler, which
circulates in a thermosiphon loop. The reheated stream then enters the
first catalyst chamber in the Reactor, A2-DC1530 (A2-DC1540), at 232C
[450F].
In this first catalytic conversion stage, the majority of the remaining sulfur
compounds are converted to elemental sulfur vapor by reaction (2). In
addition, much of the organic sulfur compounds formed by side reactions
in the Reactor Furnace, carbonyl sulfide (COS) and carbon disulfide
(CS
2
), are hydrolyzed back to H
2
S in this catalyst bed. Hydrolysis of the
organic sulfur compounds helps achieve high sulfur recovery by
converting the organic sulfur compounds into sulfur species that will react
via the Claus reaction to produce sulfur. Special promoted catalysts are
often employed for higher COS/CS
2
conversion, and this catalytic stage is
often operated at higher temperatures since this also increases
conversion.
The sulfur vapor produced the first catalyst bed is then condensed at
about 161C [322F] in the second condensing pass of the Sulfur
Condenser by generating additional LP steam. About 20% of the inlet
sulfur is condensed and recovered as liquid sulfur in the separator
chamber at the outlet of this condenser pass. The vapor from the second
condensing pass is reheated to 210C [410F] using HP steam in the
Reactor No. 2 Feed Heater, A2-EA1533 (A2-EA1543), and is routed to the
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-9
second catalyst chamber in the Reactor where further conversion of H
2
S
and SO
2
occurs. The reactor effluent is then cooled to 157C [314F] in
the third condensing pass of the Sulfur Condenser by generating
additional LP steam. About 7% of the inlet sulfur is recovered as
condensed liquid sulfur in the separator chamber at the outlet of this
condensing pass.
The vapor leaving the third condensing pass is reheated to 204C [400F]
using HP steam in the Reactor No. 3 Feed Heater, A2-EA1534
(A2-EA1544), and flows to the third catalyst chamber in the Reactor, the
final conversion stage. More conversion occurs in this third catalytic stage
before the gas is cooled in the fourth pass of the Sulfur Condenser by
generating additional LP steam. An additional 2% of the total sulfur is
recovered in the separator chamber at the outlet of this fourth and final
condensing pass, bringing the total sulfur recovery to approximately 94%
in the Claus sulfur plant. The remaining vapor leaves the fourth pass of
the Sulfur Condenser at about 156C [313F] and flows to the TGCU.
9.3.6 Air Control System
For optimum sulfur recovery, the hydrogen sulfide:sulfur dioxide ratio of
the process gas at all points downstream of the Reactor Furnace should
be exactly 2:1. This ratio depends on the amount of air sent to the Acid
Gas Burner by the Process Air Blower. A combination of
feed-forward/feed-back control is used in the sulfur plant to control the
proper quantity of air.
The amine acid gas flow rate and SWS gas flow rate (and fuel gas flow
rate, if any) are measured, summed together, and sent to the ratio
controller which adjusts the air flow, yielding feed-forward control that
allows the sulfur plant to compensate for changes in the amine acid gas
and SWS gas flow rates (and the fuel gas flow rate, also).
The H
2
S:SO
2
ratio of the gas from the fourth condensing pass of the
Sulfur Condenser is continuously analyzed by the air demand analyzer.
This analyzer signal is then used to change the setpoint of the flow ratio
controller, thus providing feed-back control to allow the sulfur plant to
adjust to variations in amine acid gas and/or SWS gas composition,
temperature, and pressure.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
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Issued 30 August 2011 Sulfur Recovery Page 9-10
9.3.7 Molten Sulfur Handling
Liquid sulfur from each of the four condensing passes is routed to an
individual Sulfur Drain Seal Assembly, A2-ME1530A-D (A2-ME1540A-D),
in the below-ground Sulfur Surge Tank, A2-FB1530 (A2-FB1540). Each
drain seal has a "U"-tube that uses static head from a column of liquid
sulfur to serve as a seal and prevent the process gases from escaping.
The drain seals are steam-jacketed to prevent sulfur from freezing and
have view hatches to allow verifying that each rundown line is flowing.
The Sulfur Surge Tank provides storage for about 160 metric tons of raw
sulfur production from the sulfur plant. The Sulfur Surge Tank is a
horizontal cylindrical tank resting in a concrete vault. The tank is
constructed of carbon steel and is equipped with internal steam coils. The
Sulfur Surge Tank Vent Ejector, A2-EE1530 (A2-EE1540), uses HP
motive steam to route the tank vapors to the Tailgas Thermal Oxidation
system.
9.3.8 Steam Production
The Sulfur Recovery Unit produces steam at two pressure levels. High
pressure steam is generated at 48.5 kg/cm
2
(g) [690 PSIG] in the Waste
Heat Boiler. A portion of this steam is used to reheat the reactor feed
streams and in the TGCU Reactor Feed Heater, A2-EA1560. The
remaining HP steam from the SRU is routed to the Tailgas Thermal
Oxidation system to be superheated in the Thermal Oxidizer Waste Heat
Boiler, A2-BF1570.
Low pressure steam at 4.2 kg/cm
2
(g) [60 PSIG] is produced in the Sulfur
Condenser. Part of this steam is used to preheat the amine acid gas, heat
the Sulfur Storage Tank, heat the steam-jacketed lines, and for steam
tracing services. The remainder is routed to the complex's LP steam
header.

Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-11
9.4 Equipment Description
9.4.1 Reactor Furnace, A2-BA1530 (A2-BA1540)
The Reactor Furnace is a combustion and non-catalytic reaction chamber.
The furnace shell is internally lined with refractory insulation to protect it
against the extreme process temperatures inside. The maximum
operating temperature is about 1600C. Although the furnace can
withstand short excursions above this temperature, prolonged operation
above this temperature will damage the refractory. The refractory is
designed to keep the furnace shell at 200-340C to protect it from acid
corrosion on its interior. Periodic surveys of the temperature all along the
shell of the furnace should be conducted (using a hand-held infrared
pyrometer) to ensure that the shell is always in the desired temperature
range.
The furnace is divided into two combustion/reaction zones by a refractory
checker wall. In the first zone, the SWS gas and most of the amine acid
gas are combusted with process air to destroy the ammonia, oxidize the
hydrocarbons, produce sulfur dioxide, and form sulfur. The remaining
amine acid gas enters the furnace through side injection nozzles and
mixes with the combustion products flowing through the checker wall into
the second zone of the furnace. This second zone provides additional
residence time for the sulfur-forming and hydrocarbon-oxidizing reactions
to reach equilibrium.
The furnace is covered by a protective metal shroud to prevent thermal
shock to the hot metal shell by severe weather, such as heavy rains.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
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Issued 30 August 2011 Sulfur Recovery Page 9-12
9.4.2 Acid Gas Burner Assembly, A2-BA1531 (A2-BA1541)
The burner assembly is specifically designed to burn the acid gas stream
for this facility. The unit consists of an acid gas burner tip, a fuel gas
burner ring with multiple tips for combusting fuel gas during plant warmup,
a pilot gas burner with an integral ignitor, two flame scanners, two
viewports, and specially designed air distribution baffles for proper
combustion. This complete unit is installed in the front of the Reactor
Furnace
The StackMatch

ignitor/pilot assembly is designed to be retracted or


extracted after the main fuel gas burner ring or the acid gas burner tip has
been lit. If the assembly is extracted, the block valve can be closed to
isolate it from the furnace atmosphere. The assembly includes filters for
the incoming fuel gas and air, which should be checked (and cleaned, if
necessary) after each use so that there is no chance of a plugged filter
causing delays during the next startup.
9.4.3 Acid Gas Knock-Out Drum, A2-FA1530 (A2-FA1540)
This vertical vessel is installed in the inlet amine acid gas line to remove
liquids from the gas stream before it is routed to the Acid Gas Burner and
Reactor Furnace. The liquid produced in this vessel is pumped on
automatic start/stop control to the Rich Amine Flash Drum. The vessel is
equipped with high level alarms to warn of a rising level in the drum, and a
high-high level shutdown to activate the SRU ESD system before liquids
can reach the hot furnace. The shutdown requires that 2 out of 3
transmitters have a high-high level indicated.
9.4.4 SWS Gas Knock-Out Drum, A2-FA1531 (A2-FA1541)
This vertical vessel is installed in the inlet SWS gas line to remove liquids
from the gas stream before it is routed to the Acid Gas Burner. The liquid
removed in this vessel is pumped on automatic start/stop control to the
Sour Water Flash Drum. The vessel is equipped with high level alarms to
warn of a rising level in the drum, and a high-high level shutdown to
block-in the SWS gas before liquids can reach the hot furnace.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-13
9.4.5 Reactor, A2-DC1530 (A2-DC1540)
The Reactor is a single horizontal vessel divided by two vertical partitions
into three separate catalyst chambers. This reactor is of the axial
down-flow type, with the feed gas entering the top of each chamber (via a
standpipe from the bottom of the vessel) and proceeding vertically
downward through its catalyst bed. These standpipes discharge the feed
gases against the top of the vessel shell to distribute the gases over the
length of each chamber and prevent the inlet gas streams from impinging
directly on the catalyst beds.
A catalyst support grating is installed in each chamber to support its
catalyst bed in the center of the vessel. The support grating is covered
with a stainless steel screen to prevent the catalyst from sifting through
the grating. A small bead of castable refractory is used to seal the edges
of the support grating to prevent catalyst leaks between the grating and
the vessel shell.
9.4.6 Catalyst for Sulfur Plant Reactors, A2-MC1530 (A2-MC1540)
Refer to the Basic Engineering Package for the type of catalyst used in
the Reactor.
9.4.7 Acid Gas Preheater, A2-EA1530 (A2-EA1540)
This shell and tube exchanger uses LP steam to heat the inlet amine acid
gas stream before it mixes with the SWS gas and is combusted in the
Acid Gas Burner and the Reactor Furnace. This minimizes the possibility
of having ammonia salts precipitate when the amine acid gas mixes with
the high ammonia content SWS gas. The preheating also increases the
production of HP steam in the Waste Heat Boiler.
9.4.8 Sulfur Condenser, A2-EA1531 (A2-EA1541)
The Sulfur Condenser contains four different sets of tubes. Divider plates
in the inlet and outlet channels segregate the four different gas streams
flowing through this exchanger.
The four sets of condensing pass tubes are immersed in the water-filled
section of the shell, allowing them to cool the hot gases leaving the Waste
Heat Boiler and the three catalyst beds in the Reactor. The boiling water
in the shell of the exchanger cools the gases and condenses sulfur from
the process streams. The steam produced will be controlled at about
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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Issued 30 August 2011 Sulfur Recovery Page 9-14
4.2 kg/cm
2
(g). The outlet channel of the exchanger is extended to serve
as gas/liquid separators to remove entrained sulfur droplets from the gas
streams by gravity separation. The separator chambers also contain
woven wire mist eliminators to assist in removing sulfur from the gas
streams. Steam-jacketed sulfur drains are located in the bottom of each
separator chamber to remove the liquid sulfur produced.
The boiler is equipped with level transmitters that will shut down the SRU
should the water level fall to within 75 mm of the top row of condensing
tubes. The shutdown requires that 2 out of 3 transmitters have a low-low
level indicated. Operation of the boiler without a sufficient water level
could possibly damage the tubes.
9.4.9 Reactor No. 1 Feed Heater, A2-EA1532 (A2-EA1542)
This shell and tube exchanger uses HP steam to heat the process gas
stream leaving the first condensing pass of the Sulfur Condenser before it
enters the first catalyst bed in the Claus Reactor. This exchanger
operates in a thermosiphon loop with the Waste Heat Boiler using a
portion of the steam produced by the Waste Heat Boiler to provide the
heat input. The temperature of the gas leaving the exchanger is controlled
at the desired value by adjusting a control valve in the condensate outlet
line. This control valve can raise the level of condensate in the exchanger
shell to submerge some of the tubes in condensate to reduce the heat
input.
9.4.10 Reactor No. 2 Feed Heater, A2-EA1533 (A2-EA1543)
This shell and tube exchanger uses HP steam to heat the process gas
stream leaving the second condensing pass of the Sulfur
Condenser before it enters the second catalyst bed in the Claus Reactor.
This exchanger operates in a thermosiphon loop with the Waste Heat
Boiler using a portion of the steam produced by the Waste Heat Boiler to
provide the heat input. The temperature of the gas leaving the exchanger
is controlled at the desired value by adjusting a control valve in the
condensate outlet line. This control valve can raise the level of
condensate in the exchanger shell to submerge some of the tubes in
condensate to reduce the heat input.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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Issued 30 August 2011 Sulfur Recovery Page 9-15
9.4.11 Reactor No. 3 Feed Heater, A2-EA1534 (A2-EA1544)
This shell and tube exchanger uses HP steam to heat the process gas
stream leaving the third condensing pass of the Sulfur Condenser before it
enters the third catalyst bed in the Claus Reactor. This exchanger
operates in a thermosiphon loop with the Waste Heat Boiler using a
portion of the steam produced by the Waste Heat Boiler to provide the
heat input. The temperature of the gas leaving the exchanger is controlled
at the desired value by adjusting a control valve in the condensate outlet
line. This control valve can raise the level of condensate in the exchanger
shell to submerge some of the tubes in condensate to reduce the heat
input.
9.4.12 Sulfur Surge Tank, A2-FB1530 (A2-FB1540)
This horizontal vessel is installed in a below-ground concrete vault. It
receives the produced liquid sulfur from the SRU and holds it in a molten
state for pumping to the Sulfur Degassing Unit. There are steam coils
installed in the bottom of the tank to keep the sulfur molten, each with its
own steam supply and trap. Should a steam coil develop a leak, it can be
shut off while the others keep the sulfur hot.
The tank is installed below ground to accept the sulfur production by
gravity flow. Liquid-sealed Sulfur Drain Seal Assemblies are provided to
allow draining of the produced liquid sulfur while preventing passage of
the process gases. Liquid sulfur flows through these drain seals and then
into the tank.
The primary ventilation system for the Sulfur Storage Tank is the Sulfur
Surge Tank Vent Ejector, A2-EE1530 (A2-EE1540). It uses HP steam as
the motive force to circulate air through the tank. Ambient air enters
through the breather vents at each end of the tank and is educted to the
ejector suction. The discharge from the ejector is routed to the TTO for
disposal. This air circulation dilutes the H
2
S that "weathers off" from the
liquid sulfur so that the concentration remains below the lower explosive
limit. The circulation also prevents accumulation of water in the tank that
could cause rapid corrosion.
In addition to the steam-powered ejector, there is a backup natural-draft
ventilation system provided for the Sulfur Storage Tank when the ejector
is out of service. The tank vapors are vented from the tank through a
heated vent stack mounted on the top of the tank. Air to displace these
vapors enters through the breather vents at each end of the tank and
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-16
sweeps through the tank before entering the vent stack. The
steam-jacketing on the vent stack heats the air in the stack, providing the
natural-draft driving force that makes the system work.


IT IS VERY IMPORTANT TO KEEP HEAT (STEAM) ON THE VENT
STACK TO MAINTAIN THE NATURAL DRAFT. IN ADDITION, THE
STEAM JACKET ON THE VENT STACK MUST VENTED
PERIODICALLY TO PREVENT NON-CONDENSIBLES FROM
ACCUMULATING AND "BLANKING OFF" THE STEAM HEATING
SURFACES. A VENT LINE IS PROVIDED EXPRESSLY FOR THIS
PURPOSE.
9.4.13 Acid Gas Knock-Out Drum Pump, A2-GA1530A/B
(A2-GA1540A/B)
These pumps send liquids that accumulate in the Acid Gas Knock-Out
Drum to the Rich Amine Flash Drum. The pumps are designed to start
and stop automatically when the level rises in the vessel. Level
transmitters mounted on the vessel alert the operator if the level in the
vessel exceeds the automatic start point. These pumps are equipped with
tandem seals to reduce the likelihood of releasing H
2
S to the
surroundings.



THE LIQUID IN THESE PUMPS CONTAINS DISSOLVED H
2
S. THIS
H
2
S CAN BE RELEASED TO THE SURROUNDINGS WHEN LIQUID
IS DRAINED FROM THESE PUMPS OR FROM THE PIPING
CONNECTED TO THE PUMPS. ALWAYS OBSERVE PROPER
PROCEDURES AND PRECAUTIONS WHEN DRAINING LIQUID
FROM THESE PUMPS OR PERFORMING MAINTENANCE ON
THEM. THE "GENERAL SAFETY" SECTION OF THESE
GUIDELINES SHOULD BE CONSULTED IF THERE IS ANY DOUBT
ABOUT HOW TO WORK SAFELY WHEN H
2
S MAY BE PRESENT.
WARNING
WARNING
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-17
9.4.14 SWS Gas Knock-Out Drum Pump, A2-GA1531A/B
(A2-GA1541A/B)
These pumps send liquids that accumulate in the SWS Gas Knock-Out
Drum to the Sour Water Flash Drum. The pumps are designed to start
and stop automatically when the level rises in the vessel. Level
transmitters mounted on the vessel alert the operator if the level in the
vessel exceeds the automatic start point. These pumps are equipped with
tandem seals to reduce the likelihood of releasing H
2
S to the
surroundings.


THE LIQUID IN THESE PUMPS CONTAINS DISSOLVED H
2
S AND
NH
3
. THIS H
2
S AND/OR NH
3
CAN BE RELEASED TO THE
SURROUNDINGS WHEN LIQUID IS DRAINED FROM THESE
PUMPS OR FROM THE PIPING CONNECTED TO THE PUMPS.
ALWAYS OBSERVE PROPER PROCEDURES AND PRECAUTIONS
WHEN DRAINING LIQUID FROM THESE PUMPS OR
PERFORMING MAINTENANCE ON THEM. THE "GENERAL
SAFETY" SECTION OF THESE GUIDELINES SHOULD BE
CONSULTED IF THERE IS ANY DOUBT ABOUT HOW TO WORK
SAFELY WHEN H
2
S AND/OR NH
3
MAY BE PRESENT.

9.4.15 Sulfur Storage Tank Vent Ejector, A2-EE1530 (A2-EE1540)
This jet ejector uses HP motive steam to circulate air through the Sulfur
Surge Tank and route it to the Thermal Oxidizer. This air dilutes the H
2
S
that "weathers off " from the liquid sulfur product so that the H
2
S
concentration in the Sulfur Surge Tank is well below the lower explosive
limit (LEL). The ejector body is steam-jacketed to prevent sulfur contained
in the circulating air from freezing and plugging the ejector.
Whenever motive steam to the ejector is not available, the ejector
discharge valve should be closed. This will prevent back-flow of Thermal
Oxidizer gases into the Sulfur Surge Tank.
WARNING
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-18


NEVER BLOCK-IN THE EJECTOR COMPLETELY (CLOSING BOTH
THE SUCTION AND DISCHARGE VALVES) WHILE THE HP
MOTIVE STEAM IS CONNECTED TO THE EJECTOR. A LEAK IN
THE MOTIVE STEAM BLOCK VALVE COULD ALLOW THE HP
STEAM TO OVER-PRESSURE THE EJECTOR BODY.

9.4.16 Process Air Blower, A2-GB1530A/B (A2-GB1540A/B)
These multi-stage centrifugal blowers provide the combustion air required
to combust the amine acid gas and SWS gas in the Acid Gas Burner. The
air flow rate is controlled by throttling a valve in each blower suction line.
A vent valve on each blower discharge line is used to vent air to the
atmosphere when the process air flow is low so that the blower does not
go into "surge".


THE BOLT HOLES IN THE BLOWER/MOTOR BASEPLATES ARE
PROVIDED FOR SHIPPING AND POSITIONING PURPOSES ONLY.
DO NOT BOLT THE BASEPLATES DOWN TIGHTLY. EITHER
LEAVE THE NUTS OFF, OR HAND-TIGHTEN THEM ONLY.
EXCESSIVE TIGHTENING MAY DISTORT THE BASEPLATES AND
CAUSE MISALIGNMENT AND/OR VIBRATION DAMAGE TO THE
UNITS.
THE BASEPLATES ARE TO REST ON RESILIENT FOUNDATION
PADS. DO NOT GROUT UNDER THE BASEPLATES. RIGIDLY
CONNECTING THE BASEPLATES TO THEIR FOUNDATIONS WILL
INCREASE THE BLOWER VIBRATION LEVELS AND LEAD TO
BLOWER DAMAGE.
WARNING
CAUTION
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-19
9.4.17 Air Blower Suction Screen/Silencer, A2-FD1530A/B
(A2-FD1540A/B)
This filter/silencer is designed to keep rainwater and large solid particles
from entering the Process Air Blower. It also helps reduce the noise
produced by the Process Air Blowers.
9.4.18 Process Air Vent Silencer, A2-FG1530A/B (A2-FG1540A/B)
These silencers help reduce the noise produced when the blow-off valves
on the discharge of the Process Air Blowers are being used to prevent the
blowers from "surging".
9.4.19 Sulfur Drain Seal Assembly, A2-ME1530A-D (A2-ME1540A-D)
Ortloff's proprietary Sulfur Drain Seal Assemblies are designed to drain
liquid sulfur from the four outlet channels of the Sulfur Condenser. The
seals are built as "U-type" traps that use liquid sulfur to seal and prevent
process gases from flowing to the Sulfur Surge Tank along with the liquid
sulfur product. The drain seals are sized to provide a seal leg which
should not blow out at the maximum discharge pressure of the Process
Air Blower.
The seals are fully steam-jacketed and designed to be installed in the top
of the Sulfur Surge Tank. Each seal has a hinged inspection hatch to
allow observation and sampling of the flow from each condenser pass.
The liquid sulfur from the inspection basin flows down to the bottom of the
Sulfur Surge Tank through a drain pipe to prevent free-fall of the liquid
sulfur, which could cause static electricity to build up. The drain seals are
mostly carbon steel, except for the inspection hatches which are
aluminum.
Each drain seal has removable blind flanges to allow "rodding" its
rundown line and its dip leg. Before removing either flange, close the
block valve in the rundown line to prevent the escape of process gas to
the surroundings when the plugging is cleared. When the rodding
operation is complete and the flange(s) are back in place, remember to
reopen the block valve.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-20
9.4.20 Refractory for Reactor Furnace and Waste Heat Boiler,
A2-MR1530 (A2-MR1540)
The firing chamber of the Reactor Furnace and the transition piece on the
Waste Heat Boiler have a refractory lining consisting of alumina firebrick
backed heavy duty firebrick. The checker wall in the Reactor Furnace is
also constructed from alumina firebrick. Mortar used for installing the
brick is alumina air-setting mortar. The inlet tubesheet on the Waste Heat
Boiler is covered with a layer of alumina castable refractory.
9.4.21 Ceramic Ferrules for Waste Heat Boiler, A2-MR1532
(A2-MR1542)
The ceramic ferrules are inserted into the inlet ends of the tubes in the
Waste Heat Boiler, then a layer of castable refractory is installed over the
tubesheet. The ceramic ferrules are flush with the outside of the
refractory and extend into each tube. The ferrules and refractory protect
the tube ends from being directly exposed to the hot combustion gas and
give very long operating life to the Waste Heat Boiler.
9.4.22 Refractory for Waste Heat Boiler, A2-MR1533 (A2-MR1543)
The outlet channel of the Waste Heat Boiler is covered with a lining of
castable refractory. This refractory protects the steel surfaces of the
channel from accelerated sulfide corrosion rates due to the high process
gas temperature.
9.4.23 Refractory for Sulfur Condenser, A2-MR1534 (A2-MR1544)
The inlet channel of the first pass of the Sulfur Condenser is covered with
a lining of castable refractory. This refractory protects the steel surfaces
of the channel from accelerated sulfide corrosion rates due to the high
process gas temperature. The refractory is built up on the bottom of the
channel so that it is flush with the bottom of the inlet nozzle and with the
bottom of the tubes in the lowest row of tubes, so that the entire inlet
channel free-drains from the inlet nozzle into the tubes and liquid sulfur
cannot "puddle" in the inlet channel.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-21
9.4.24 Refractory for Reactor, A2-MR1535 (A2-MR1545)
A 50 mm bead of castable refractory is installed around the edges of the
catalyst bed supports inside each chamber of the Reactor. This seals the
edges of the bed supports so that the small catalyst pellets cannot escape
from the beds.
9.4.25 Rainshield for Reactor Furnace, A2-ME1531 (A2-ME1541)
The Reactor Furnace shell is internally lined with refractory insulation to
protect it against the extreme process temperatures inside. The refractory
is designed to keep the furnace shell at 200-340C to protect it from
corrosion on its interior. Shell temperatures higher than this can result in
high temperature sulfidic corrosion of the steel shell, while temperatures
lower than this can cause the steel to drop below the acid dewpoint of the
process gas and suffer acid corrosion.
The upper 240 of the Reactor Furnace is covered by a metal rainshield to
prevent over-cooling of the furnace shell by rain and/or wind, which would
cause shorter refractory life (due to thermal cycling) and corrosion of the
furnace shell (due to acid condensation). The rainshield is mounted on
stand-off rings to protect the furnace shell from direct exposure to the
elements without restricting the free circulation of cooling air over the
furnace shell. The rainshield is formed from corrugated galvanized steel.
9.4.26 Ceramic Ferrule for Reactor Furnace, A2-MR1531 (A2-MR1541)
These ceramic ferrules are inserted into the side ports on the Reactor
Furnace where the bypassed acid gas is to be injected into the second
zone of the furnace. The ceramic ferrules extend to the outside of the
refractory lining inside the furnace so that essentially no part of the nozzle
is directly exposed to the hot furnace gases or to radiation from the hot
furnace. This will help protect the nozzles from overheating whenever the
bypass acid gas is not flowing.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-22
9.4.27 Waste Heat Boiler, A2-BF1530 (A2-BF1540)
The Waste Heat Boiler contains the cooling pass tubes which cool the hot
gases leaving the Reactor Furnace. The cooling pass tubes are immersed
in the water-filled section of the shell, allowing them to cool the hot gases
leaving the Reactor Furnace from by boiling water in the shell of the
exchanger. The steam produced will be controlled at about
48.5 kg/cm
2
(g). Because of the high inlet temperature to these tubes, the
inlet tubesheet is refractory-lined and the inlet of each tube contains a
ceramic ferrule insert.
Most of the steam produced by the Waste Heat Boiler is routed to the
Thermal Oxidizer Waste Heat Boiler, A2-BF1570, to be superheated
before it is exported to the HP Steam header. The remaining portion of
this steam is withdrawn and directed to the three heaters for the Reactor
feeds, the Reactor No. 1 Feed Heater, the Reactor No. 2 Feed Heater,
and the Reactor No. 3 Feed Heater, which operate in a thermosiphon loop
with the Waste Heat Boiler. The steam flows over and condenses on the
outside of the tubes in these exchangers, heating the gas within the tubes
to raise the temperatures of the gas streams to the desired feed
temperatures for the catalyst beds. The condensate from these three
exchangers returns to the Waste Heat Boiler by gravity flow.
The boiler is equipped with level transmitters that will shut down the SRU
should the water level fall to within 75 mm of the top row of tubes. The
shutdown requires that 2 out of 3 transmitters have a low-low level
indicated. Operation of the boiler without a sufficient water level will result
in severe damage to the tubes and the shell.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-23


AS DISCUSSED ABOVE, THE BOILING WATER IN THE SHELL
KEEPS THE COOLING PASS TUBES FROM OVERHEATING. IF
THE WATER LEVEL IN THE BOILER DROPS BELOW THESE
TUBES, THE HOT COMBUSTION GAS INSIDE WILL DESTROY
THE TUBES. ALTHOUGH LOW LEVEL SHUTDOWN SHOULD
ACTIVATE THE SRU ESD IF THE WATER LEVEL FALLS TO 75 MM
ABOVE THE COOLING PASS TUBES, THE LOW LEVEL ALARMS
IN THE DCS ARE EARLY WARNINGS OF BFW LOSS. THESE LOW
LEVEL ALARMS SHOULD RECEIVE IMMEDIATE ATTENTION TO
MINIMIZE THE POTENTIAL FOR DAMAGE TO THE BOILER. THE
LEVEL GAUGES SHOULD ALSO BE MONITORED CLOSELY BY
THE OUTSIDE OPERATOR.

WARNING
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-24
9.5 Instrumentation and Control Systems
9.5.1 SRU Air:Acid Gas Ratio Control Loop
The chemistry of the Claus reaction dictates that optimum sulfur recovery
is achieved when the ratio of hydrogen sulfide (H
2
S) to sulfur dioxide
(SO
2
) in the process gases is maintained at 2:1. This ratio is determined
by the amount of H
2
S in the acid gas feed that is combusted to SO
2
by the
oxygen in the process air stream fed to the burner. Each sulfur plant uses
a combination of feed-forward and feed-back control to adjust the ratio of
the air flow rate to the acid gas and fuel gas flow rates and maintain the
optimum 2:1 H
2
S:SO
2
ratio. The loop diagram on page 9-29 illustrates the
components of this control scheme when implemented in a distributed
control system (DCS). (All of the instrument tag numbers used below
refer to the instruments as they are numbered in the Train 1 SRU. The
control algorithm and the relay settings for the Train 2 SRU will be
identical.)
The feed-forward portion of the control loop uses the acid gas and fuel
gas flow rates to compute the setpoint for the air flow controller,
A2-FIC15370. Since the amine acid gas, SWS gas, and fuel gas require
different amounts of air, the three flow rates are metered separately and
then summed by A2-FY15345 and A2-FY15349. The three signals are
also biased (by A2-FY15320, A2-FY15331, and A2-FY15355) to allow for
the differences in air requirements. In this manner, the setpoint for
A2-FIC15370 will be properly adjusted as the individual gas flow rates
vary.
A special photometric analyzer samples the process gas in the sulfur plant
tailgas to determine the relative amounts of H
2
S and SO
2
in the gas. The
analyzer provides an output signal that is proportional to the amount the
air flow rate must change in order to bring the H
2
S:SO
2
ratio to the
optimum 2:1 value. This signal is the feed-back part of the control loop,
and is used to make minor adjustments to the air:acid gas ratio and allow
the control system to respond to compositional variations in one or more
of the acid gas feeds.
The control loop is discussed in detail in the sections that follow. The
discussions are divided into five sections: air requirement computation for
the acid gas streams, air:acid gas ratio adjustment, air requirement
computation for fuel gas, air flow control, and local/remote control.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-25
9.5.1.1 Air Requirement Computation for the Acid Gas Streams
The purpose of the acid gas bias/summing circuit is to compute the
theoretical process air required for the acid gas streams, properly
adjusted to account for the differing amounts of oxygen that the two
streams require. The amine acid gas and SWS gas flow rate signals
are linearized and input to the DCS by A2-FT15320 and
A2-FT15331, respectively. Flow indicators A2-FI15320 and
A2-FI15331 in the DCS indicate these flow rates in engineering units.
Each flow rate is multiplied by a scale factor (relays A2-FY15320 and
A2-FY15331, respectively) to compute the process air required by
each stream, then added together by summing relay A2-FY15345 to
give the theoretical air flow requirement for the acid gas streams.
The two bias calculation blocks multiply each gas flow rate by a gain
factor equal to the process air required per unit of flow for that
stream. The appropriate gain factors are 2.563 Nm
3
/Nm
3
for the
amine acid gas (A2-FY15320) and 2.186 Nm
3
/Nm
3
for the SWS gas
(A2-FY15331). A2-FY15345 then sums the two outputs from the
bias relays, providing an output that (at design conditions) is equal to
the required air flow rate for the acid gas streams. This output is
then supplied to the ratio adjustment relay, A2-AY15348. These
factors can be revised periodically if changes in feedstocks, etc.
cause long-term changes in the compositions of one or both of the
acid gas streams.
Note that each bias relay has a "zero" switch (A2-HS15320 for
A2-FY15320 and A2-HS15331 for A2-FY15331). These switches
can be used to "turn off " their respective relays when there is no flow
of the corresponding gas stream. This prevents an erroneous
reading from a flow transmitter causing errors in the theoretical air
flow computations. A similar switch (A2-HS15356) is included for the
fuel gas bias relay (A2-FY15355) discussed in Section 9.5.1.3.
9.5.1.2 Air:Acid Gas Ratio Adjustment
By choosing the appropriate gain factors for A2-FY15320 and
A2-FY15331, the output from A2-FY15345 (the theoretical air flow
rate) is equal to the required process air flow rate for the acid gas
streams, assuming the composition and conditions of the amine acid
gas and SWS gas streams remain constant. This will seldom be
true, however, so there must be a means to adjust the air:acid gas
ratio for temporary changes in composition, such as increased
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
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Issued 30 August 2011 Sulfur Recovery Page 9-26
hydrocarbon content. This is the reason for including the ratio
adjustment relay, A2-AY15348.
The "coarse" ratio adjustment is set manually by the DCS operator in
the range of 0.0-2.0 via A2-HIC15347. This ratio setting is then "fine
tuned" by the air demand controller, A2-AIC15347. The action of
limit relay A2-AY15347 is to allow A2-AIC15347 to vary the "coarse"
ratio setting up or down by about 10%, so that the controller acts as
a "trim" on the control loop. This is accomplished with two
calculation blocks: bias relay A2-AY15347 and summing relay
A2-HY15347.
The bias relay, A2-AY15347, reduces the magnitude of the
A2-AIC15347 output signal and centers it around zero by multiplying
the signal by a gain factor of 0.002 and adding a constant of -0.1.
Thus, as the output from A2-AIC15347 varies from 0% to 100%, the
output from A2-AY15347 will vary from -0.1 to +0.1. Summing relay
A2-HY15347 then adds this output to the output from A2-HIC15347
to yield the ratio adjustment setting that is input to A2-AY15348 and
indicated by A2-HI15347.
The ratio adjustment relay, A2-AY15348, multiplies the ratio
adjustment setting from A2-HY15347 by the theoretical air flow rate
from A2-FY15345 to produce the corrected air flow rate for the acid
gas streams. The effective ratio at A2-AY15348 will vary from 0.0 to
2.0 as the output from A2-HY15347 varies from 0.0 to 2.0. For
example, if the output from A2-HY15347 is 1.1, the effective ratio
applied to the theoretical air flow by A2-AY15348 will be 1.1, and the
corresponding corrected air flow rate will be 1.1 times the theoretical
air flow rate. The output from A2-AY15348 (the corrected air flow
rate for the acid gas streams) is then supplied to the fuel gas
summing relay, A2-FY15349. The design setting for A2-HIC15347 is
1.0 (i.e., a ratio adjustment multiplier of 1.0, which is no adjustment).
9.5.1.3 Air Requirement Computation for Fuel gas
If an SRU is operating at very low load, it may be necessary to burn
supplemental fuel gas in its Acid Gas Burner. When operating in this
mode, the air flow control scheme must also add the air required to
burn the fuel gas. Since most fuel gas has a nearly constant
composition, it is not necessary to adjust the air:fuel gas ratio like it is
with the acid gas streams. Instead, the fuel gas flow rate can simply
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-27
be multiplied by a gain factor to compute its air requirement, then
summed together with the corrected air flow described earlier that is
computed by A2-AY15348.
The fuel gas flow rate is linearized and input to the DCS by
A2-FT15355. Flow controller A2-FIC15355 in the DCS converts this
linear signal into a flow rate in engineering units. Bias relay
A2-FY15355 then multiplies the fuel gas flow rate by the appropriate
gain factor for this fuel gas, 32.509 Nm
3
/Nm
3
(For the C4 LPG), to
give the computed air flow for the fuel gas. This is added to the
corrected air flow for the acid gas streams by summing relay
A2-FY15349, giving the total air flow rate that is then supplied to the
air flow controller, A2-FIC15370, as a remote setpoint.
For reference, the total theoretical air flow requirement is also
computed and displayed in the DCS. This is accomplished by
summing relay A2-FY15346, which sums the theoretical air flow rate
for the acid gas streams (the output from A2-FY15345) with the
theoretical air flow rate for the fuel gas (the output from
A2-FY15355). The output from A2-FY15346 is the total theoretical
air flow requirement, which is displayed on A2-FI15346 in the DCS.
9.5.1.4 Air Flow Control
All of the complicated parts of the control loop are contained in the
calculation blocks discussed above. The resulting output from
A2-FY15349 is the required air flow rate, so it is simply supplied to
the air flow controller, A2-FIC15370, as its setpoint. A2-FIC15370 is
a standard PID controller with remote setpoint adjustment. Its output
controls the Process Air Blower suction valve, either A2-FV15333A
on A2-GB1530A or A2-FV15333B on A2-GB1530B.
Note that the signal from A2-FIC15370 actually controls
A2-FV15333A or A2-FV15333B together with the control valves on
the blower discharge lines using split ranges. This split-range action
is discussed in later sections as its details are not important to this
discussion.
9.5.1.5 Local/Remote Control
The initial startup of an Acid Gas Burner is performed by an outside
operator stationed at the local control panel near the burner. Since
the operator must be able to control the air flow rate while purging
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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the furnace and lighting the burner, a hand controller (A2-HIC15370)
is mounted on the local Train 1 SRU control panel to allow manual
control of the air flow valve, A2-FV15333A or A2-FV15333B, and the
other blower control valves. After startup, control is then switched
back to the DCS.
A2-HS15370 in the DCS selects whether A2-FV15333A/B is
controlled by the local operator or by the controller in the DCS,
A2-FIC15370. During startup, when the outside operator has control,
A2-HS15370 is positioned such that the signal from A2-HIC15370 is
supplied to A2-FV15333A/B. When the DCS operator is ready to
assume control, the output of A2-FIC15370 can be matched to that
of A2-HIC15370 (as indicated by A2-HI15370 in the DCS) and
A2-HS15370 repositioned to send the output of A2-FIC15370 to
A2-FV15333A/B, resulting in a "bump-less" transfer.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
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Issued 30 August 2011 Sulfur Recovery Page 9-29

Air:Acid Gas Ratio Control Loop (SRU Train 1)
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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Issued 30 August 2011 Sulfur Recovery Page 9-30
9.5.2 Acid Gas Burner Management System
The burner management system (BMS) for the Acid Gas Burner in each
SRU is controlled by a sequential logic controller (most commonly a
programmable logic controller or PLC). The ESD reset, BMS, and
Startup/Run Logic Flowcharts for the Train 1 SRU, contained in the
Instrumentation and Controls Diagrams section of the Basic Engineering
Package, describe the sequence of steps required before permitting
ignition to ensure a safe firing order. The function of the various system
components is described below. (All of the instrument tag numbers used
below refer to the instruments as they are numbered in the Train 1 SRU.
The logic for the Train 2 SRU is identical.)
9.5.2.1 Startup/Run Interlocks
The "startup" and "run" interlock logic for the Train 1 SRU is shown
on the Startup/Run Logic Flowcharts. The purpose of this logic is to
simplify lighting the Acid Gas Burner and switching to acid gas firing
in the Train 1 SRU by automatically positioning the process gas
switching valves in the proper sequence for safe operation:
(1) Before attempting ignition of the burner, the catalyst beds
should be bypassed so that air cannot reach them and cause
sulfur fires. Setting selector switch A2-HS15314 on the local
Train 1 SRU control panel to "STARTUP" will open the two
Warmup Bypass Valves, A2-HV15441 and A2-HV15454, close
the Tailgas Valve to the TTO, A2-HV15457, and close the
Tailgas Valve to the TGCU, A2-HV15462, so that air and/or
combustion products from the Reactor Furnace are diverted
upstream of the first catalyst bed in the Reactor to flow directly
to the TTO.
(2) Once the pilot burner in the Acid Gas Burner has been lit and
the SRU is ready to accept acid gas (furnace up to temperature,
etc.), the Warmup Bypass Valves must be closed before acid
gas can be introduced into the SRU. However, in order to avoid
activating the "complete flowpath interlock" alarm and possibly
tripping the Reactor Furnace high-high pressure S/D, there
must be an open flowpath through the SRU before the bypass
valves are closed.
(3) Setting selector switch A2-HS15314 to "RUN" will automatically
open the Tailgas Valve to the TTO, prove the valve open, then
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close the two bypass valves and initiate the nitrogen purge,
A2-HV15453, between the two valves. By automating the valve
switching steps and including checks of the limits switches in
the logic, the chance of accidentally causing an SRU1 ESD due
to over-pressure during startup are greatly reduced.
While the switching valves are moving, the corresponding status
lights on the local Train 1 SRU control panel should blink to provide
feedback to the operator. If a switching valve does not move to the
proper position, its status light should continue to blink. This will alert
the operators to investigate the problem and take any required
corrective action so that the BMS then allows proceeding.
9.5.2.2 Flame Scanners
The flame scanners, A2-BE15369A and A2-BE15369B, monitor the
pilot, warmup, and acid gas burners. If a scanner detects a flame,
the associated "flame proven" signal will indicate. If neither scanner
detects a flame, the SRU1 ESD system is activated. Since a "flame
proven" signal from either scanner satisfies the ESD system,
maintenance may be performed on one flame scanner while the
other remains in service. Note that a third flame scanner,
A2-BE15368, is furnished with the pilot to detect its flame, but it is
used only to activate its status light (A2-GL15368) on the local
Train 1 SRU control panel and a status indicator (A2-BL15368) in the
DCS.
9.5.2.3 Purge Cycle
To ensure the unit is safe for firing, a purge cycle must be completed
before the pilot can be ignited. To purge the Reactor Furnace, a
Process Air Blower is used to send a high flow rate of air through the
furnace for 25 seconds to satisfy the purge timer. The air flow must
then be reduced to a low rate to allow ignition of the pilot.
9.5.2.4 Ignition Cycle
After the purge cycle is complete, pressing the "IGNITION"
push-button (A2-HPB15368) on the local Train 1 SRU control panel
causes the BMS to initiate an attempt to ignite the pilot. The BMS
closes the pilot burner purge gas valve (A2-HV15381), opens the
pilot air block valve (A2-NV15367), closes the vent valve in the fuel
gas to the pilot (A2-NV15364), opens the pilot fuel gas block valves,
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(A2-NV15363 and A2-NV15365), and energizes the ignition system,
(A2-BX15368).
After a 15 second ignition trial, the ignition system is de-energized. If
a pilot flame is established, one or both flame scanners will indicate
"flame proven" and the block valves in the air and fuel gas supplies
to the pilot will remain open. Otherwise, the air and fuel gas supplies
to the pilot are blocked-in and the purge cycle must be repeated.
9.5.2.5 Fuel gas Firing
After the pilot burner is lit, the main fuel gas supply is enabled.
Pressing push-button A2-HPB15391 on the local Train 1 SRU control
panel will close the main burner purge gas valve, (A2-HV15382),
close the vent valve in the fuel gas to the main burner (A2-NV15358),
and open the main fuel gas block valves (A2-NV15357 and
A2-NV15359). The fuel gas control valve (A2-FV15355) can then be
adjusted using either A2-HIC15355 on the local SRU control panel or
A2-FIC15355 in the DCS to manually fire fuel gas on the warmup
burner ring in the Acid Gas Burner to heat the refractory in the
Reactor Furnace and heat the water in the Waste Heat Reclaimer
and Sulfur Condenser.
9.5.2.6 Acid Gas Firing
After the pilot burner is lit, the acid gas controls can also be enabled.
Turning startup/run selector switch A2-HS15314 on the local Train 1
SRU control panel to "RUN" will open the Tailgas Valve to the TTO,
A2-HV15457, prove it open, then close the two Warmup Bypass
Valves, A2-HV15441 and A2-HV15454, and establish a nitrogen
purge between them. Turning acid gas firing selector switch
A2-HS15315 on the local Train 1 SRU control panel to "ENABLED" will
then allow using the manual acid gas controls, A2-HIC15320 and
A2-HIC15331, on the local Train 1 SRU control panel to introduce
amine acid gas and SWS gas, respectively, into the Train 1 SRU.
9.5.2.7 Pilot and Main Fuel gas On/Off Switches
Push-buttons A2-HPB15390 and A2-HPB15391 on the local Train 1
SRU control panel are used to turn the pilot burner and main fuel gas
burner, respectively, on and off. If the burner is already "on",
pressing its push-button will extinguish the burner by closing the two
block valves and opening the vent valve in its fuel gas supply, and
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then open the valve in its purge gas supply to begin purging the
burner. For the pilot burner, the block valve in its air supply is also
closed and the ignition system, A2-BX15368, is de-energized.
If the burner is "off " (and the "flame proven" is already satisfied by
one of the other burner tips), pressing its push-button will ignite the
burner by closing the valve in its purge gas supply to cease purging
the burner, and closing the vent valve and opening the two block
valves in its fuel gas supply. For the pilot burner, the block valve in
its air supply is also opened and its ignition system, A2-BX15368, is
energized for 15 seconds.
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9.5.3 Process Air Blower Controls
The depiction of the controls for the Process Air Blower (A2-GB1530A/B)
shown on P&ID 507000-7100-23 is fairly straightforward in how the control
elements are to be arranged. What may not be clear, however, is why the
controls are implemented in this manner. The discussion that follows will
describe what purposes these controls serve. (The Train 1 SRU blower
controls for A2-GB1530A are used as examples below. The concepts for
the "B" blower and for the Train 2 SRU blower controls are the same.)
In general, the process air flow to the Train 1 SRU is controlled at a
specified ratio to the acid gas and fuel gas flows by A2-FIC15370.
A2-FIC15370 is given a remote setpoint computed from the amine acid
gas flow rate, the SWS gas flow rate, the fuel gas flow rate, and the air
demand reading. A2-FIC15370 then adjusts the blower suction valve,
A2-FV15333A, to control the desired air flow rate.
9.5.3.1 Blower Operation at Low Air Flow
At low flow rates, the air flow can drop below the blower's surge line.
If this is allowed to occur, the air flow will become erratic and the
blower may be damaged. To prevent this from happening, the
blower is equipped with a blow-off valve, A2-FV15335A, on its
discharge line. When the air flow to the SRU is low, the blow-off
valve will open and allow some of the air from the blower to vent to
the atmosphere, increasing the air flow through the blower to keep it
above the surge line.
The discharge pressure from the air blower depends on the
back-pressure from the SRU, the TGCU, and the TTO, which is a
function of plant throughput. At low plant throughput, the pressure
drop through these units is low and the resulting back-pressure on
the air blower is low. If the back-pressure gets low enough, it can
limit the air flow through the blow-off valve and cause the blower to
drop below its surge line. To prevent this from happening, the air
blower discharge valve, A2-FV15334A, is designed to begin throttling
the blower discharge at very low flow rates, so that the discharge
pressure from the blower will remain high enough to allow the
blow-off valve to keep the blower from surging.
The three valves on the A2-GB1530A blower operate together over
the following controller ranges to give the response described above:
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A2-FV15333A: Fully open at 100% output from A2-FIC15370
33.3% open at 0-66.7% output from A2-FIC15370
(software "min. stop" keeps valve from closing
further)
A2-FV15334A: Fully open at 100% output from A2-FIC15370
Fully closed at 0% output from A2-FIC15370
A2-FV15335A: Fully closed at 66.7-100% output from
A2-FIC15370
Fully open at 0% output from A2-FIC15370
This results in the following actions by the blower control valves:
1. At 100% output from A2-FIC15370, the suction valve and discharge
valve will be fully open, the blow-off valve will be fully closed, and all
of the air will be flowing to the SRU.
2. As the output from A2-FIC15370 drops from 100% to 66.7%, the
suction valve will begin throttling from 100% open to 33.3% open,
the discharge valve will begin closing and going from fully open to
throttling at 66.7% open, the blow-off valve will still be fully closed,
and all of the air will still be flowing to the SRU.
3. As the output drops below 66.7%, the suction valve will not close
any further (to prevent starving the blower for air), the discharge
valve will continue to throttle, and the blow-off valve will begin to
open and vent part of the air to the atmosphere instead of flowing to
the process.
4. At 0% output, the suction valve will still be 33.3% open, the
discharge valve will be fully closed, the blow-off valve will be 100%
open, and all of the air will be venting rather than flowing to the SRU.
These split-range control actions are accomplished by the function
relays in the DCS shown on the P&ID. For the A2-GB1530A blower,
the actions of the relays are as follows:
A2-FY15333A: For an input of 66.7-100%, the output from this
relay varies linearly from 33.3-100%. For an input
below 66.7%, the output is constant at 33.3%
(minimum output limit).
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A2-FY15334A: For an input of 0-100%, the output from this relay
is direct.
A2-FY15335A: For an input of 0-66.7%, the output from this relay
varies linearly from 100% to 0%, providing reverse
action for the fail-closed control valve. For an
input above 66.7%, the output is constant at 0%.
The output signals from the DCS to each of the control valves should
be displayed on the DCS console. The I/P transducers mounted on
the valves in the field are direct (i.e., 4-20 mA to the transducer gives
an output of 0-100% from the valve positioner).
The split-range values on the P&IDs are the suggested initial settings
for the control schemes on these blowers. These values may need
adjustment once the SRUs are placed in operation, depending on
the operating characteristics of each particular air blower and its
control valves. These adjustments can be made during plant startup.
9.5.3.2 Blower "Swapping" Controls
While the SRUs are operating, it is sometimes necessary to "swap"
air blowers for maintenance purposes, etc. This means switching
from A2-GB1530A to A2-GB1530B or vice versa in the Train 1 SRU,
for instance. The DCS provides controls for slowly reducing the air
flow from the on-line blower while increasing the air flow from the
off-line blower, so that switching from one blower to the other can be
accomplished without disturbing SRU operations. (Although we have
attempted to automate this concurrent ramping operation on a couple
of past projects, we have not found this to be very satisfactory. The
way that the blower controls need to be ramped will depend on the
current plant throughput and whether or not the blower suction valve
is still in control. This is classic "fuzzy logic", something that is easy
for a human to do but very difficult for a computer.)
Bias controller A2-HIC15339A and bias relay A2-HY15339A in the
DCS adjust the controller output to the control valves on
A2-GB1530A. A setting of 1.0 on A2-HIC15339A results in
multiplying the output of A2-FIC15370 by 1.0 before sending the
signal to the valves on A2-GB1530A (i.e., no change). A setting of
0.0 on A2-HIC15339A results in multiplying by 0.0, so zero signal is
sent to the valves on A2-GB1530A (resulting in all its air venting to
atmosphere with no air flow to the process). At settings between 0.0
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and 1.0 on A2-HIC15339A, the output to the valves on A2-GB1530A
is the corresponding fraction of the output from A2-FIC15370. The
bias controllers and relays (A2-HIC15339B and A2-HY15339B) for
the other blower (A2-GB1530B) work in the same fashion.
With these controls in the DCS, it is a relatively simple matter to
swap air blowers by gradually shifting the air flow control from one
blower to the other. After the off-line blower has been started, the
DCS operator can begin to reduce the control signal to the on-line
blower while increasing the control signal to the off-line blower,
making changes as needed to maintain a stable air flow to the SRU.
Once all of the control signal is going to the off-line blower and none
is going to the on-line blower, the off-line blower has become the
on-line blower. What was the on-line blower is now the off-line
blower, and it can then be shut down without affecting the SRU.
9.5.3.3 Blower Start Interlocks and Controls
The interlocks and control actions for starting a Process Air Blower
are shown on the BMS Logic Flowchart contained in the
Instrumentation and Controls Diagrams section of the Basic
Engineering Package. These interlocks and actions ensure that
these blowers are started in a safe manner while minimizing the
starting load on the blowers and motors:
a. It is best to start a blower in an unloaded condition, with its
suction valve partially open and its blow-off valve wide open.
The "blower start permissive" relays, A2-HSL15338A/B, require
that the control signal to the blower in question be set to 0% in
order to start that blower. As described earlier in
Section 9.5.3.1, this will place the suction valve and blow-off
valve in the proper positions.
b. There is always the potential to have acid gas in the process air
piping, so having the blower suction and blow-off valves open
while its blower is not running should be minimized to reduce
the risk of releasing acid gas to the atmosphere. When the
operator presses the "permit to start" push-button,
A2-HPB15338A/B, for a blower, its suction and blow-off valves
will open for 30 seconds to allow time for the operator to start
the blower using the local start/stop control.
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If the blower is not started within this time, the suction and
blow-off valves are closed and the "permit to start" is disabled.
The operator will have to press A2-HPB15338A/B again before
the blower can be started.
c. If the operator starts the blower and the motor starter contacts
for the blower indicate that the blower is running within this
time, the solenoid valve on the blower discharge valve is then
energized so that the operator can increase the control signal to
the blower to open the discharge valve and commence air flow
to the process.
The solenoid valve for the fail-closed discharge valve on each
blower is not energized unless that blower is running. This
minimizes the potential to have acid gas "back down" the
process air line and be released to the atmosphere.
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9.5.4 Reactor Furnace Temperature Control
The temperature in the first combustion zone of each Reactor Furnace,
A2-BA1530 and A2-BA1540, must be 1370C [2500F] or higher to insure
maximum ammonia destruction. The temperature in each furnace can be
controlled at this value by varying the amount of amine acid gas
bypassing its Acid Gas Burner, A2-BA1531 or A2-BA1541, respectively.
Increasing the portion of bypassed acid gas increases the flame
temperature at an Acid Gas Burner, which is the opposite of what would
be expected for typical burner systems. However, remember that an Acid
Gas Burner operates at substoichiometric conditions - combustion is
limited by the amount of process air provided, not by the amount of acid
gas (i.e., the fuel) at the burner. The process air rate is determined by the
total acid gas inlet flow rate to an SRU, not by the amount of acid gas
routed to its burner.
Claus plant operation is based on converting one-third of the H
2
S in the
total feed gas to SO
2
at the burner. Any hydrocarbons and ammonia
present are also oxidized, but the rest of the H
2
S passes through
un-oxidized. Bypassing some of the acid gas around the burner permits
combustion of a larger fraction of the H
2
S in the feed to the burner,
resulting in a higher flame temperature.
For a simplified example, consider the case where there is no SWS acid
gas flow. Without any amine acid gas bypassed, only 33% of the H
2
S at
the burner would be burned. If one-third of the total amine acid gas
bypasses the burner, then 50% of the H
2
S in the amine acid gas sent to
the burner must be burned in order to convert one-third of the total H
2
S to
SO
2
. Thus, a larger fraction of the H
2
S entering the burner is combusted
when part of the acid gas bypasses the burner, which raises the flame
temperature.
The furnace temperature control loop for the Train 1 SRU consists of: the
optical pyrometer, A2-TT15375; the Reactor Furnace temperature
controller, A2-TIC15375; the acid gas bypass flow ratio controller,
A2-FFIC15350; the acid gas valve to the burner, A2-FV15351, and the
acid gas bypass valve, A2-FV15350. (Note that an optical pyrometer
does not actually measure temperature. Instead, it infers the furnace
temperature by measuring the infrared radiation inside the Reactor
Furnace. Experience has shown that the temperature indicated by an
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optical pyrometer is usually 100-200C lower than the calculated
temperature for a given set of conditions.)
The furnace temperature is not directly controlled. Instead, it is controlled
indirectly via remote setpoint adjustment of A2-FFIC15350. (Past
experience has shown that measurement of the front zone temperature
using optical pyrometers is not always consistent and/or repeatable, and
flow ratio control of the bypass amine acid gas has proven to be more
stable for control purposes.) By placing A2-FFIC15350 in "cascade",
A2-TIC15375 can adjust its ratio setpoint within the range of 0.00:1 to
0.65:1. Thus, if the temperature in the first zone of the Reactor Furnace is
too low, A2-TIC15375 will raise the ratio setpoint of A2-FFIC15350, which
will then bypass more amine acid gas around the Acid Gas Burner and
raise the furnace temperature.
The 1370C furnace temperature for ammonia destruction discussed
earlier is a calculated temperature. As stated earlier, the temperature
indicated by an optical pyrometer is usually 100-2300C lower than the
calculated temperature for a given set of conditions, so a normal operating
temperature of 1200C as indicated by the pyrometer is suggested for the
first zone in the Reactor Furnace. Operating experience will dictate the
minimum indicated furnace temperature at which SWS gas can be
admitted to the furnace.
When the Train 1 SRU is operating at low flow rates, there may not be
enough pressure drop in its Acid Gas Burner to give good control of the
bypass acid gas with A2-FV15350. For this reason A2-FV15351 is
designed to work together with A2-FV15350 over split ranges of the
A2-FFIC15350 controller output. If A2-FV15350 goes fully open at lower
flow rates, the controller output will continue to increase so that
A2-FV15351 begins to "throttle" in the amine acid gas line to the burner
and force more of the acid gas to flow through A2-FV15350.
It is critical that A2-FV15351 never closes completely, as there should
always be some amine acid gas flowing to the burner to be sure that the
front zone of the Reactor Furnace does not become an oxidizing
atmosphere. The DCS limit relay, A2-FY15351, will prevent this fail-open
valve from closing completely by limiting the output to the valve to 75%
and below.
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9.5.5 Knock-Out Drum Pump Control
Under ordinary conditions, little (if any) liquid will drop out in the Acid Gas
Knock-Out Drum, A2-FA1530. During upsets, however, liquid can rapidly
accumulate in the drum. For this reason, the Acid Gas Knock-Out Drum
Pump, A2-GA1530A/B has been designed to automatically start and stop
as required by the liquid level in the drum, based on the level signal sent
to the DCS. Level signals are provided to the PLC by three LTs for use as
a 2oo3 voting shutdown if the level continues to rise.
The local H-O-A switches near the pumps allow the operator to place
these pump in "auto" start mode. The DCS should start the pump when
the liquid level reaches the "pump start" level in the drum. After the liquid
is pumped out, the DCS should stop the pump when the level reaches the
"pump stop" level. If the pump fails to start, or the liquid level is rising
faster than the pump can keep up with, the DCS should give a LAH. If the
level continues to rise, the PLC will activate the SRU ESD system when
the level reaches the LAHH setpoint to prevent carry-over of liquids into
the Acid Gas Burner and the Reactor Furnace. If the pump fails to stop,
the DCS should give a LAL.
Similarly, little (if any) liquid will drop out in the SWS Gas Knock-Out
Drum, A2-FA1531 under normal conditions. It can also have liquids
accumulate rapidly during an upset, however, so the SWS Gas Knock-Out
Drum Pump, A2-GA1531A/B has also been designed to automatically
start and stop as required by the liquid level in the drum, based on the
level signal sent to the DCS. Level signals are provided to the PLC by
three LTs for use as a 2oo3 voting shutdown.
The local H-O-A switches near the pumps allow the operator to place
these pumps in "auto" start mode. The DCS should start the pump when
the liquid level reaches the "pump start" level in the drum. After the liquid
is pumped out, the DCS should stop the pump when the level reaches the
"pump stop" level. If the pump fails to start, or the liquid level is rising
faster than the pump can keep up with, the DCS should give a LAH. If the
level continues to rise, the PLC will close the SWS gas inlet valve when
the level reaches the LAHH setpoint to prevent carry-over of liquids to the
Acid Gas Burner. If the pump fails to stop, the DCS should give a LAL.
9.5.6 "Ride-Through" System Considerations
Field experience has shown that a brief interruption in the electric power
to a typical air blower will not cause a substantial drop in the air flow as
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long as power is restored before the blower "spins down" too much. The
rotors in Process Air Blowers have relatively large moments of inertia so it
takes a relatively long time (usually many seconds) for the rotational
speed to decline to the point that the air flow drops enough to extinguish
the flame in the associated burner.
It is possible to take advantage of this phenomenon by including
provisions in the emergency shutdown (ESD) systems that will allow the
blowers in the SRUs to "ride-through" momentary power interruptions. If
power is restored quickly enough, the blower in a unit will come back up to
speed before enough air flow is lost to cause a "flame failure" shutdown,
so that the unit will not have to be restarted. If the power loss lasts long
enough, of course, the unit will shut down on "flame failure" and will have
to be restarted manually. For power "blips", however, there is a good
chance the unit will stay on-line.
In order for the blowers to "ride-through", the motor starter circuit must
include an auxiliary contact that is held-in during a power outage, so that if
power is restored the starter contactor will re-engage. The generic motor
starter schematic below shows one way of accomplishing the
"ride-through".



The key features on the schematic are:
There is a "run permissive" contact from the PLC in the main power
supply to the starter circuit. If the unit ESD is activated for any reason
("flame failure", for instance), this contact opens so that the blower is
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stopped. If the ESD is activated during a power interruption, the blower
will not restart when power is restored because this contact will be open.
There is a "ride-through" contact from the PLC that parallels the usual
"m" latch relay in the starter circuit. The PLC closes this contact when it
receives the "run" status from the blower. If power is restored before the
ESD is activated, this closed contact allows the starter contact to
re-engage and restore the "m" latch to keep the motor going.
The start/stop control for the motor is interlocked, and has a
momentary "start" contact and a maintained "stop" contact. This ensures
that the blower remains off when an operator stops a blower using its local
start/stop control station, regardless of what the "ride-through" logic may
be doing at that time.
Within the PLC logic for each ESD system, the "run" status for each
blower is connected to a TDO (time delay off) timer set for 10 seconds.
Normally-open contacts from the TDO are used in the PLC logic that
determines whether a particular blower is running, as well as the logic that
determines whether any blowers are running. Thus, if power is lost to a
blower and the starter contactor disengages, the TDO contacts will
continue to maintain the "blower running" logic as "true" for up to
10 seconds. If power is restored to the blower within this time and the
starter contactor re-engages, the ESD logic will remain satisfied and the
unit will not shut down. If power is not restored to the blower within this
time, the TDO contacts will open and cause the "blower running" logic to
become "false" and activate the unit ESD.
While the TDO timer is running, all of the unit shutdowns besides "no
blower running" are still active. If any of these other shutdowns are
tripped, the ESD will be activated immediately to shut down the unit. For
example, if the flame is lost in the burner during this time, "flame failure"
will activate the ESD and the unit will shut down immediately. Among
other things, the ESD will then remove the "run permissive" from the
blowers so that the blowers cannot restart.
The logic for an air blower "run permissive" is similar to the ESD logic for
that ESD system, but there are a couple of key differences. First, each
unit ESD includes all of the shutdowns, while the "run permissive" does
not include the "no blower running" or "flame failure" S/Ds to allow starting
an air blower in the first place. Second, the unit ESD requires that the
"MANUAL RESET" push-button be pressed to reset the unit ESD, but the
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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"run permissive" is auto-resetting since it must occur before the "MANUAL
RESET" push-button is pressed. The auto-resetting should be inhibited for
20 seconds after an ESD event by an internal timer in the PLC to allow
time for the 10 second blower "ride-through" relays and timers to time out,
plus other inherent time delays such as flame scanner delays and valve
travel times.
9.5.7 Boiler Low-Low Level S/D Transmitter Testing
Both of the boilers in each SRU (the Waste Heat Boiler and the Sulfur
Condenser) have three independent level transmitters connected to the
PLC that activate the SRU ESD system before the water level can get low
enough to cause tube damage. The shutdown in activated when two out
of three transmitters show a low-low level. These transmitters should be
tested periodically to determine that they are functioning properly. Since
2oo3 voting is used for the low-low level shutdowns in the SRU ESDs, the
level transmitters can be tested one at a time without having to bypass the
ESD system.
Consider A2-LT15401A on the SRU Train 1 Waste Heat Boiler, for
example. The procedure for testing A2-LT15401B and A2-LT15401C will
be similar, as will A2-LT15431A/B/C on the Sulfur Condenser. The
procedure for testing A2-LT15401A is as follows:
(1) The outside operator notifies the DCS operator that he is preparing
to test shutdown level transmitter "A" on the Waste Heat Boiler.
(2) The DCS operator confirms that A2-LI15401B and A2-LI15401C are
both indicating adequate level in the boiler, then notifies the outside
operator to proceed.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-45


DO NOT PROCEED UNLESS THE OTHER TWO LEVEL
INDICATORS SHOW ADEQUATE LEVEL IN THE BOILER.
OTHERWISE THE LOW-LOW LEVEL SHUTDOWN IN THE SRU
ESD WILL BE ACTIVATED AS SOON AS THE OUTSIDE
OPERATOR BEGINS DRAINING THE LEVEL TRANSMITTER IN
THE NEXT STEP.
(3) After being notified to proceed by the DCS operator, the outside
operator blocks-in A2-LT15401A by closing its block valves, then
opens the drain valve on the bottom of the transmitter to drain the
water from the instrument.
(4) If the transmitter is operating properly, the DCS will alarm that there
is a low level in the Waste Heat Boiler on A2-LI15401A. The DCS
operator acknowledges the alarm on the DCS and reports it to the
outside operator.
(5) After being notified of the alarm, the outside operator closes the drain
valve on A2-LT15401A, slowly opens its bottom block valve to allow
the transmitter to fill with water then opens its top block valve. This
should clear the low level alarm on A2-LI15401A in the DCS.
(6) After confirming that the low level alarm has cleared, the other level
transmitters can be tested in a similar fashion.
NOTE: The DCS operator must not begin another task until confirming
that the low level alarm has cleared. This is to guard against
having a level transmitter malfunction that causes an SRU ESD
when the other transmitters are tested.
CAUTION
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-46
9.5.8 SRU Emergency Shutdown Systems
The purpose of the Sulfur Recovery Unit Emergency Shutdown systems
(Train 1 SRU ESD and Train 2 SRU ESD) is to shut off the flow of amine
acid gas, SWS gas, fuel gas, and process air to the affected SRU when
serious problems occur. The Cause and Effect Diagram for the Train 1
SRU, contained in the Instrumentation and Controls Diagrams section of
the Basic Engineering Package, describes the SRU1 ESD system in block
format. For reference, the causes and effects of the SRU1 ESD system
shown on this diagram are explained below. (All of the instrument tag
numbers used below refer to the instruments as they are numbered in the
Train 1 SRU. The logic for the Train 2 SRU is identical.)
As noted on the Cause and Effect Diagram, it is recommended that a
5 second delay be used for most of the process parameters included in
the causes of the ESD system. This is to prevent the "nuisance"
shutdowns that are sometimes caused by momentary fluctuations in the
process or the sensing elements.
9.5.8.1 Causes
Any one of the causes listed below will activate the SRU1 ESD
system:
d. Manual Shutdown Switches, A2-HS15310 and A2-HS15313
An operator can activate the SRU1 ESD system using either of
two manual shutdown switches:
(1) A2-HS15310 is a NORMAL / ESD selector switch in the
DCS.
(2) A2-HS15313 is a NORMAL / ESD selector switch mounted
on the local Train 1 SRU control panel.
(3) Acid Gas Scrubber High-High Liquid Level,
A2-LT15305A/B/C
These devices prevent liquids in the Acid Gas Scrubber from
flowing into the hot combustion chamber of the Reactor
Furnace and causing an explosion. They are set to actuate if
the liquid level reaches 1,280 mm above the bottom seam of
the vessel. Note that there are three independent transmitters
and 2oo3 voting logic is used for the ESD (i.e., at least two
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-47
transmitters must show high-high level) to avoid spurious "trips"
due to the malfunction of a single transmitter.
e. No Process Air Blower Running, A2-GB1530A and
A2-GB1530B starter contacts
If neither Process Air Blower is sending air to the Train 1 SRU,
acid gas could flow backwards down the process air line and
escape from either the blowers or their suction screens. The
motor starter contacts on A2-GB1530A/B are used to determine
whether a blower is running, and will activate the SRU1 ESD
system if neither blower is running.
f. Acid Gas Burner Flame Failure, A2-BY15369A and
A2-BY15369B
Dual flame scanners are aimed to observe the flames from the
pilot, warmup, and main acid gas burners. If neither scanner
detects a flame (2oo2), a "flame failure" occurs and activates
the SRU1 ESD system. If only one scanner detects a flame
(1oo2), a malfunction alarm is activated in the DCS, but the
SRU1 ESD system is not activated. A third flame scanner,
A2-BY15368, is furnished with the pilot to detect its flame, but it
is used only to activate its status light (A2-GL15368) on the
local Train 1 SRU control panel and a status indicator
(A2-BL15368) in the DCS.
g. Reactor Furnace High-High Pressure, A2-PT15372A/B/C
These devices protect against over-pressuring the SRU and
blowing out its Sulfur Drain Seal Assemblies (which would emit
toxic H
2
S to the atmosphere) due to plugging by solid sulfur
somewhere in the plant, a surge in acid gas flow to the furnace,
etc. by activating the SRU1 ESD system before the pressure
gets too high. The sensing lines for the pressure transmitters
are mounted on the process air line to avoid corrosion and/or
plugging with sulfur. The shutdown setpoint is 0.85 kg/cm
2
(g).
Note that there are three independent transmitters and 2oo3
voting logic is used for the ESD.
h. Waste Heat Reclaimer Low-Low Water Level,
A2-LT15401A/B/C
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Issued 30 August 2011 Sulfur Recovery Page 9-48
These devices activate the SRU1 ESD system to prevent the
water level from dropping below the top of the cooling pass
tubes in this boiler while hot gas is flowing through the tubes.
Hot furnace combustion gas flows inside the tubes and will
destroy these tubes if they are not cooled by water boiling
outside the tubes. These devices are set to actuate if the level
falls to within 75 mm of the top of the cooling pass tubes. Note
that there are three independent transmitters and 2oo3 voting
logic is used for the ESD.
i. Reactor 1st Bed Outlet High-High Temperature,
A2-TT15419A/B/C
These devices shut down the Train 1 SRU if a temperature of
400C or higher is measured at the outlet from the first catalyst
bed in the Reactor. Such a temperature would indicate a sulfur
fire inside this catalyst bed, which could cause damage by
overheating the equipment if allowed to continue burning. Free
oxygen can leave the Reactor Furnace and reach this catalyst
bed if burner performance becomes poor due to burner
damage, low H
2
S concentration in the acid gas, etc. Note that
there are three independent transmitters and 2oo3 voting logic
is used for the ESD.
j. Sulfur Condenser Low-Low Water Level, A2-LT15431A/B/C
These devices activate the SRU1 ESD system to prevent the
water level from dropping below the top of the condensing pass
tubes in this boiler while hot gas is flowing through the tubes,
thereby averting high effluent temperatures and higher than
normal tube wall temperatures. High effluent temperatures
would result in lower sulfur recovery due to insufficient
condensing of liquid sulfur, and high tube wall temperatures
could possibly damage the tubes due to differential expansion.
These devices are set to actuate if the level falls to within
75 mm of the top of the condensing pass tubes. Note that there
are three independent transmitters and 2oo3 voting logic is
used for the ESD.
k. Neither Warmup Bypass Valve Closed, A2-ZSC15441,
A2-ZSC15454
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
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Issued 30 August 2011 Sulfur Recovery Page 9-49
Amine acid gas or SWS gas should not be fed to the Train 1
SRU if its warmup bypass line to the TTO is in use. Otherwise,
very high concentrations of H
2
S would be sent to the TTO,
possibly leading to a high-high temperature S/D of the TTO and
venting of un-combusted H
2
S to the atmosphere. The "closed"
limit switches on the warmup bypass valves (A2-HV15441 and
A2-HV15454) must indicate that at least one of these valves is
closed, or the SRU1 ESD system will be activated.
Note that the SRU1 ESD system is not to be activated if the
Train 1 SRU is firing supplemental fuel gas in its Acid Gas
Burner. The amine acid gas and SWS gas shutdown valves,
A2-HV15320 and A2-HV15331, respectively, are to be closed
automatically and an alarm is to be generated, but the ESD
system is not to be activated since the Train 1 SRU can
continue to fire on fuel gas through its warmup bypass line.
Example logic to accomplish this is shown below:

l. Pilot Ignition Safety Interlock Timer Expired, BMS logic
Once the pre-ignition steps have been completed and the BMS
gives a "PERMIT TO IGNITE" for the pilot burner in the Acid Gas
Burner (signaled by illuminating status indicator light
A2-AL15394 on the local Train 1 SRU control panel), an ignition
safety interlock timer is started in the BMS. If an ignition
attempt is not made within 5 minutes, the SRU1 ESD system
will be activated to shut down the sulfur plant. This prevents a
potentially unsafe condition from persisting, where a leaking
fuel gas valve could cause an explosive mixture to form in the
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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Issued 30 August 2011 Sulfur Recovery Page 9-50
Reactor Furnace, since the air flow is low at this point in the
startup procedure.
9.5.8.2 Effects
An SRU1 ESD shutdown, activated either manually or automatically,
has the following effects on the Train 1 Sulfur Recovery Unit:
a. Shuts off the amine acid gas flow to the Acid Gas Burner by
closing the acid gas shutdown valve, A2-HV15320.
b. Shuts off the SWS gas flow to the Acid Gas Burner by closing
the SWS gas shutdown valve, A2-HV15331.
c. Shuts down the Process Air Blower, A2-GB1530A/B.
d. Closes the air blower suction valves, A2-FV15333A/B, to
prevent possible venting of any hazardous gases to the
atmosphere.
e. Closes the air blower discharge valves, A2-FV15334A/B, to
prevent back-flow and possible venting of any hazardous gases
to the atmosphere.
f. Closes the air blower vent valves, A2-FV15335A/B, to prevent
possible venting of any hazardous gases to the atmosphere.
g. Initiates the Train 1 SRU Fuel Gas Burner Shutdown system,
which performs the following actions:
(1) Shuts off and depressurizes the main fuel gas supply by
closing block valves A2-NV15357 and A2-NV15359 and
opening vent valve A2-NV15358.
(2) Shuts off the pilot air supply by closing block valve
A2-NV15367.
(3) Shuts off and depressurizes the pilot fuel gas supply by
closing block valves A2-NV15363 and A2-NV15365 and
opening vent valve A2-NV15364.
(4) De-energizes the ignition system, A2-BX15368.
(5) Begins purging the pilot burner with nitrogen by opening
block valve A2-HV15381.
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Issued 30 August 2011 Sulfur Recovery Page 9-51
(6) Begins purging the warmup burner with nitrogen by
opening block valve A2-HV15382.
h. Sends the Train 1 SRU S/D status to the TGCU ESD system.
(The TGCU ESD system will shut down the TGCU if neither
SRU is running and the TGCU is not in "startup" mode.)
i. Cancels the "slow transfer over-ride" switch in the DCS,
A2-HS15464, for the tailgas valves.
j. Initiates purging of the Acid Gas Burner, A2-BA1531, and the
Reactor Furnace, A2-BA1530, with nitrogen by opening block
valve A2-KV15377 for 5 minutes.
When the amine acid gas flow to the Train 1 SRU is blocked, the
pressure control system on the stripper in the upstream ARU should
automatically divert acid gas to the flare as required. When the SWS
gas flow to the Train 1 SRU is blocked, the pressure control system
on the stripper in the upstream SWS should also automatically divert
SWS gas to the flare as required.
9.5.8.3 Non-ESD Shutdowns and Alarms
In addition to the devices listed in Section 9.5.10.1 that activate the
SRU1 ESD system, there are several interlocks of significance that
either generate an alarm or shut down an individual piece of
equipment. These devices/interlocks and their effects are described
in this section.
a. SWS Gas Scrubber High-High Liquid Level, A2-LT15325A/B/C
These devices prevent liquids in the SWS Gas Scrubber from
flowing into the hot combustion chamber of the Reactor
Furnace and causing an explosion by closing the SWS gas
shutdown valve. They are set to actuate if the liquid level
reaches 1,490 mm above the bottom seam of the vessel. Note
that there are three independent transmitters and 2oo3 voting
logic is used for the S/D.
Unlike the level transmitters on the Acid Gas Scrubber, this
interlock does not activate the SRU1 ESD system. Instead,
it closes only the SWS gas shutdown valve, A2-HV15331, to
stop the flow of SWS gas. This valve does not re-open
automatically when the level drops down and the shutdown
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
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Issued 30 August 2011 Sulfur Recovery Page 9-52
resets. The plant operators must use A2-HIC15331 on the local
control panel to open A2-HV15331 to reintroduce SWS gas into
the SRU in a controlled fashion.
b. Process Air Blower Operation while in "Startup" Mode
During normal operation, activating the SRU1 ESD system will
shut down the Process Air Blower and close the suction,
discharge, and blow-off valves on the blower. However, if the
Train 1 SRU is firing on fuel gas through its Warmup Bypass
Valves, the air blower will remain running (with its valves open)
if the "flame failure" S/D (see Section 9.5.10.1.f) is tripped or
one of the fuel gas pressures is not satisfied (see
Sections 9.5.8.3.c and 9.5.8.3.d) All other shutdown devices
(see Section 9.5.8.2) go to their shutdown positions.
By leaving the air blower running when a fuel gas flame is lost,
fewer blower restarts are necessary while re-lighting the burner,
resulting in less "wear and tear" on the large motors driving
these blowers.
c. Acid Gas Burner Fuel Gas Supply Low-Low Pressure,
A2-PT15354
During warmup while the Train 1 SRU is firing on fuel gas, loss
of the fuel gas supply would cause the fuel gas pressure to
drop. This device will shut off the fuel gas to the Acid Gas
Burner before flame instability creates the potential for an
explosion. The shutdown setpoint is 0.35 kg/cm
2
(g).
Note that if the Train 1 SRU is firing on acid gas, the transmitter
only activates the Train 1 SRU Fuel gas Burner Shutdown
system (pilot fuel gas and main fuel gas), so the Train 1 SRU
will continue running on acid gas. If, however, the Train 1 SRU
is firing only fuel gas (as indicated by its acid gas firing selector
switch, A2-HS15315, being set to "DISABLED"), the SRU1 ESD
system is activated and the low-low pressure is reported to the
"first out" alarm logic. Example logic to accomplish this is shown
below:
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
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Issued 30 August 2011 Sulfur Recovery Page 9-53

d. Acid Gas Burner Fuel Gas High-High Burner Pressure,
A2-PT15361
During warmup while the Train 1 SRU is firing on fuel gas,
malfunction of the fuel gas pressure control could cause
excessive firing of the warmup burner in the Acid Gas Burner.
This device will prevent this unsafe condition by shutting off the
fuel gas to the Acid Gas Burner. The shutdown setpoint is
3.5 kg/cm
2
(g).
Note that if the Train 1 SRU is firing on acid gas, the transmitter
only activates the Train 1 SRU Fuel gas Burner Shutdown
system (pilot fuel gas and main fuel gas), so the SRU will
continue running on acid gas. If, however, the Train 1 SRU is
firing only fuel gas (as indicated by its acid gas firing selector
switch, A2-HS15315, being set to "DISABLED"), the SRU1 ESD
system is activated and the high-high pressure is reported to
the "first out" alarm logic, as shown by the example logic for the
previous item.
e. Complete Flowpath Interlock (see Logic Flow Diagrams for the
limit switch tag numbers)
In order for the Train 1 SRU to operate without over-pressuring
its drain seals, there must be a complete flowpath from the SRU
to the TTO. The ESD logic can determine whether such a
complete flowpath exists by examining the status of the limit
switches on the process gas valves. There are basically three
different paths that the Train 1 SRU can take to reach the TTO:
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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(1) Both of its Warmup Bypass Valves, A2-HV15441 and
A2-HV15454, are fully open to the TTO.
(2) Its manual tailgas block valve, A2-HV15455, and its
Tailgas Valve to the TTO, A2-HV15457, are both fully
open to send the tailgas directly to the TTO.
(3) Its manual tailgas block valve and its Tailgas Valve to the
TGCU, A2-HV15462, are both fully open and the TGCU
Complete Flowpath Interlock is satisfied, allowing the
tailgas to flow through the TGCU and then to the TTO.
If the "open" limit switches do not indicate that at least one of
these flowpaths is valid, the "complete flowpath interlock" alarm
is activated. However, the SRU1 ESD system is not activated
by this interlock. Because this interlock depends on a number
of valve limit switches to determine whether a complete
flowpath exists, there is always the potential for spurious "trips"
even though all of the valves are actually in the proper
positions. Since the SRUs are already protected against
over-pressure (see Section 9.5.10.1.g), this interlock will alarm
in the DCS (A2-QA15458) but is not included in the ESD.
To prevent releasing excessive amounts of hazardous gases to
the atmosphere from the TTO and/or possibly damaging the
Thermal Oxidizer, the interlocks for the Train 1 SRU require that
at least one of its Warmup Bypass Valves be closed before
opening A2-HV15320 or A2-HV15331 and admitting amine acid
gas or SWS gas, respectively, to the Train 1 SRU. Therefore,
its Tailgas Valve to the TTO, A2-HV15457, must be open
before closing its Warmup Bypass Valves when switching from
fuel gas firing to acid gas firing.
When the TGCU is already on-line processing tailgas from one
of the SRUs, switching the tailgas from the other SRU into the
TGCU requires gradually diverting its tailgas from the TTO to
the TGCU. For the Train 1 SRU, this requires "throttling" both
tailgas valves, A2-HV15457 and A2-HV15462, at the same time
to make the switch without upsetting the TGCU.
When throttling the tailgas valves in this manner, the limit
switches on the valves will be indicating that neither of the
tailgas valves is fully open, so the Complete Flowpath Interlock
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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logic will not be satisfied for the Train 1 SRU. For this reason,
there is a "slow transfer over-ride" switch in the DCS,
A2-HS15464. When this switch is toggled to "OVER-RIDE", the
limit switches on the two tailgas valves are ignored by the
Complete Flowpath Interlock logic until the DCS operator
finishes routing the Train 1 SRU tailgas into the TGCU to
deactivate the over-ride. During this time, the DCS operator is
responsible for ensuring that there is always a complete
flowpath for the Train 1 SRU.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
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Issued 30 August 2011 Sulfur Recovery Page 9-56
9.6 Process Principles and Operating Techniques
The more important considerations involved in startup, operation, shutdown,
maintenance, and emergency procedures for the Sulfur Recovery Units are
discussed in the remaining sections of this portion of the operating guidelines.
The operator should also be thoroughly acquainted with the equipment and the
"Process Description" section in these guidelines before attempting to operate
the plant in accordance with the operating techniques that follow. If the function
of each portion of the plant equipment is understood, the sequence of steps
outlined in the "procedures" sections will be more easily understood. In
addition, the following general discussion of principles and techniques will clarify
the reasons for some of the procedures.
9.6.1 Equipment Damage
The refractory installed in the Reactor Furnaces can be damaged by too
rapid heating or cooling. The Initial Cure and Normal Warmup schedules
for the refractory should be provided by the refractory vendor. These
schedules should be adhered to quite closely.
After the initial startup, the sulfur plants will contain some sulfur
throughout the system, and especially in the catalyst beds. Sulfur fires will
ignite at temperatures as low as 150C if sufficient oxygen is available.
For this reason, it is very important to minimize the time periods when air
(or combustion gas containing oxygen) is routed through the catalyst
beds. Localized temperatures in excess of 150C can exist in a catalyst
bed even though the temperatures measured around the Reactor are less
than 150C. Because of this, sulfur ignition sometimes occurs in the
catalyst beds when it is not anticipated by temperatures that are readily
available for observation.
Under ordinary circumstances, the only time when oxygen-bearing gases
will be flowing through a Reactor is during the transition when switching
from firing fuel gas for warmup to firing acid gas. During this time,
observe the Reactor temperatures frequently. If the temperatures are
rising more than 5C to 10C in a 30 minute period after the temperatures
have reached 200C, then there is possibly a fire present. The high
temperature shutdown on the outlet of the first catalyst bed in each SRU
will protect that SRU against excessive temperatures in its piping;
however, localized excessive temperatures can occur in the catalyst beds
prior to being indicated in the Reactor outlet lines. Steps should be taken
to prevent the temperatures rising high enough to activate the shutdown
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
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as it will require some time to cool down the hot spot before proceeding
with startup.
Do not use water to quickly cool a Reactor after a fire. Not only will this
damage the catalyst, the rapid cooling may cause structural damage to
the Reactor. The acidic water that forms may cause corrosion damage to
the Reactor or other equipment. Nitrogen is available in each SRU for use
in cooling a hot catalyst bed.
Explosive mixtures of air (oxygen) and gases in the equipment are a
potential danger. During an automatic shutdown all air, oxygen, fuel gas,
and acid gas flows are shut off simultaneously. Any malfunction of these
devices could leak an explosive mixture into the unit. For this reason, the
PLC requires purging of the Reactor Furnace before attempting pilot
ignition, and requires re-purging the furnace if the burner does not light but
fuel gas was admitted.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
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Issued 30 August 2011 Sulfur Recovery Page 9-58


NEVER "HYDROBLAST" THE TUBES (OR ANY OTHER STEEL
SURFACES) IN THE SULFUR PLANT EQUIPMENT. NOT ONLY
DOES THIS REMOVE THE PROTECTIVE SULFIDE FILM THAT
FORMS ON CARBON STEEL AND PREVENTS CORROSION, THE
WATER WILL REACT WITH THE SULFUR COMPOUNDS PRESENT
IN THE EQUIPMENT TO FORM A VARIETY OF ACIDS
(SULFUROUS, POLYTHIONIC, ETC.) THAT RAPIDLY CORRODE
THE STEEL.
THERE HAVE BEEN NUMEROUS INSTANCES OF SULFUR PLANT
BOILERS BEING BLASTED DURING A TURNAROUND TO CLEAN
THEM UP, THEN HAVING THE TUBES BEGIN LEAKING AS SOON
AS THE BOILER IS RETURNED TO SERVICE.
IF THE BOILER TUBES HAVE BECOME PLUGGED, THE BEST
WAY TO CLEAR THE TUBES IS TO MECHANICALLY "ROD" THEM.
IT IS OFTEN HELPFUL TO APPLY HEAT TO THE TUBES BEFORE
"RODDING", AS THIS WILL MELT ANY SULFUR THAT MAY BE
PART OF WHAT HAS PLUGGED THE TUBES. ONE WAY TO DO
THIS IS TO DRAIN THE WATER FROM THE BOILER AND PUT
STEAM ON THE SHELL, THEN DRAIN THE CONDENSATE
PERIODICALLY TO KEEP LIVE STEAM ON THE TUBES.
9.6.2 Cold Catalyst Bed Startup
Each sulfur plant is designed to be started up without first warming the
Reactor catalyst. In the cold bed startup procedure, warmup gases are
not routed through the Reactor catalyst beds. Fuel gas is burned with
excess air on the warmup burner tips of the Acid Gas Burner mounted on
each Reactor Furnace. The hot combustion products flow through the
Reactor Furnace, through the Waste Heat Boiler tubes and the first
condensing pass tubes of the Sulfur Condenser, and then to the warmup
bypass line that is upstream of the first catalyst bed. This warms the
furnace refractory lining and the process heat exchange surfaces up to
normal operating temperatures.
CAUTION
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
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The combustion gases are routed to the atmosphere via the Thermal
Oxidizer. Therefore, normal operating procedures require that the
Thermal Oxidizer also be warming up according to its refractory warmup
schedule (or already be on-line) during the period when the SRU(s) is(are)
being brought up to operating temperatures. Do not admit acid gas to an
SRU until the Thermal Oxidizer is at operating temperature and ready to
accept SRU tailgas.
The cold bed startup procedure includes the following steps:
A. Open the Warmup Bypass Valves, and close the Tailgas Valve to the
Thermal Oxidizer and the Tailgas Valve to the TGCU. Startup
cannot be attempted unless this flow path is open.
B. Ignite the warmup burner in the Acid Gas Burner and fire on fuel gas
with excess air, adjusting air and fuel gas rates to follow the
appropriate warmup schedule.
C. Once the Waste Heat Boiler and Sulfur Condenser start to make
steam, their back-pressure controllers should be placed in service.
The other tube passes in the Sulfur Condenser and the tube passes
in the reactor feed heaters will come up to temperature as these
boilers begin producing steam.
D. When the furnace and all process heat exchangers are warmed up to
normal operating temperatures and the Thermal Oxidizer is ready to
accept SRU tailgas, reduce the fuel gas and air flow rates. Open the
Tailgas Valve to the Thermal Oxidizer, then close the Warmup
Bypass Valves. Add amine acid gas and reduce fuel gas in equal
increments until the fuel gas is shut off.
E. Gradually admit the full amine acid gas flow rate. Adjust the air flow
to the proper air:amine acid gas ratio. Follow the procedures in
these guidelines for introducing SWS gas into the SRU. Gradually
admit the full SWS gas flow rate and readjust the air:acid gas ratio if
necessary.
There are several advantages to using the cold bed startup procedure.
First, the catalyst beds are not exposed to warmup gases containing free
oxygen. This reduces the chance of fires in the catalyst bed during
warmup, which can cause overheating damage to both equipment and
catalyst.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-60
Second, the catalyst beds are not exposed to warmup gases that contain
free carbon (soot). This reduces the chance of contaminating and
plugging the beds with soot.
Third, the cold bed startup procedure reduces catalyst sulfation and,
therefore, keeps the catalyst active longer. Deactivation has been shown
to be caused primarily by sulfate contamination of the catalyst surface.
Sulfation occurs most readily at conditions encountered during a startup
procedure which uses combusted fuel gas for catalyst heating.
An additional benefit of having the warmup bypass line is that a sulfur
plant can be kept on hot stand-by, firing on fuel gas, without exposing the
catalyst beds to overheating, carbon deposition, or sulfation damage. The
hot fuel gas combustion products will keep all process heat exchange
surfaces at normal operating temperatures. Since most corrosion damage
in sulfur plants occurs when the plants are allowed to cool down and stand
cold, using the warmup bypass can greatly extend the service life of sulfur
plants which require considerable stand-by time.
9.6.3 Sulfur Solidification
Sulfur melts at 119C. All surfaces in the SRUs must be maintained
above this temperature during normal sulfur production operating periods.
However, temperatures around the Sulfur Surge Tanks and the Sulfur
Storage Tank should be kept below 158C since sulfur undergoes a phase
change at this temperature that can result in a tremendous increase in
viscosity, which could overload any of the sulfur pumps. Maintaining the
steam coil pressure in the Sulfur Surge Tank and the Sulfur Storage Tank
at 5.0 kg/cm
2
(g) or less will ensure that the sulfur does not get too hot.
All of the piping and valves in liquid sulfur service are steam-jacketed, as
are the valves in sulfur vapor service and the vent stacks on the Sulfur
Surge Tanks. The steam traps serving these heating systems should be
checked regularly to verify proper operation. The simplest method to do
this is to verify that sulfur will melt on the steam trap inlet; if the
condensate there is hot enough to melt sulfur, then the steam in the
jackets will be hot enough, too. It is also important to periodically sweep
the non-condensibles out of the jackets and coils by giving their vent
valves a good "blow". This will prevent the accumulation of
non-condensibles that could create localized "cold" spots where sulfur can
freeze.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-61
9.6.4 Ammonia Salt Formation
Hydrogen sulfide reacts with ammonia at low temperature to form
ammonium hydrosulfide:
NH
3
+ H
2
S NH
4
HS
If the temperature is low enough, this ammonium hydrosulfide will
precipitate as a solid salt. The temperature at which the solid phase will
form is a function of the NH
3
and H
2
S concentrations and the gas
pressure, but generally ranges from 15C to 40C for most acid gas
streams. It is recommended that all surfaces in contact with NH
3
-H
2
S be
maintained 20-25C above the solid formation temperature, so all of the
equipment, piping, and instruments in the SRUs that is exposed to SWS
gas are electric traced, steam traced or steam jacketed to keep them
above 65C.


TO PREVENT PLUGGING OF EQUIPMENT, PIPING, OR
INSTRUMENTS WITH AMMONIA SALTS, THE TRACING OR
STEAM JACKETING IN CERTAIN SECTIONS OF THE SRUS MUST
BE LEFT IN SERVICE YEAR ROUND. THESE ARE ANY PIPING,
EQUIPMENT AND INSTRUMENTATION IN SWS GAS SERVICE.

Essentially all of the ammonia in the SWS gas will be destroyed in the
Reactor Furnace during normal operation. If, however, amine acid gas
flow is interrupted (due to upsets in the ARU, etc.) and the SRUs are
processing only SWS gas, the ammonia may not be completely destroyed
and salts could begin to form in the downstream equipment (particularly
the Sulfur Condensers). Loss of amine acid gas flow can also cause
excessively high furnace temperatures, poor sulfur recovery, and poor
operation or equipment damage in the TGCU or the Thermal Oxidizer
downstream. For this reason, the operator must closely observe the
SRUs if their amine acid gas flow is interrupted, and be ready to activate
the SRU ESD systems if necessary to prevent equipment damage.
CAUTION
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-62
9.6.5 Catalyst Fouling
The catalyst beds in the Reactors may be severely fouled by carry-over of
hydrocarbon liquids or vapors from the ARU and/or Sour Water Stripper
Units into the SRUs. This will cause permanent damage to the catalyst
and is to be avoided if at all possible, even if shutting down the SRUs for
periods is required.
The catalyst may also be fouled by passing fuel gas combustion products
through the beds when insufficient air to burn all of the fuel gas is being
supplied to the Acid Gas Burner. This causes soot (carbon) formation
which coats the catalyst and causes loss of activity. The catalyst beds in
this plant will be warmed with fuel gas combustion products only during
the initial startup. Excess air will be used during this warmup period, so
the chances of fouling the catalyst in this manner are remote.
The catalyst may also temporarily lose activity due to molten sulfur
condensing on the beds. This can be corrected by raising the Reactor
inlet temperatures by approximately 15-20C for a few hours, then
readjusting to the normal operating range. The catalyst activity will be
completely restored in this manner by re-vaporizing the deposited sulfur.
The reactor feed temperatures can be raised by appropriate adjustment of
the temperature controllers on the gas outlet lines from the reheat
exchangers.
9.6.6 Operation of SRUs in Parallel
Train 1 SRU and Train 2 SRU are designed to operate in parallel with
each other to provide maximum acid gas processing capacity. The SRUs
are connected at their inlets, with the amine acid gas and SWS gas
feedstocks split to flow through the units in parallel. Due to the relatively
low pressure drops through the SRUs (normally 0.5-0.7 bar(g) at full rates,
when the pressure drop of the associated TGCU is included), operating
changes in one unit can significantly impact the other units because of the
flow hydraulics.
The acid gas flow controls for Train 1 SRU and Train 2 SRU are designed
to allow automatic operation of the parallel units in a fashion that
maximizes processing capacity and maximizes sulfur recovery efficiency.
There are two basic schemes for operating SRUs in parallel: "base-load"
operation of all-but-one SRU, or "cascade" operation of all SRUs. Each
scheme has advantages and disadvantages relative to the other,
depending on the operating characteristics of the particular feed units and
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-63
SRUs, current operating conditions, and other factors. As a result, the
choice of which operating mode to use is best determined based on field
experience with the specific units.
9.6.6.1 "Base-Load" Operation on All-But-One SRU
One operating mode is to "base-load" all but one SRU, and let the
remaining SRU take the "swing." That is, the flow controllers are
used to feed a fixed quantity of amine acid gas and/or SWS gas to
one SRU, while a pressure controller is used to control the feed
valves to the remaining SRU (either directly or via setpoint
adjustment of the flow controllers). This mode allows one SRU to
operate at steady feed rates, but requires that the remaining SRU
take all of the variation in the flow of the amine acid gas and/or SWS
gas feed to the sulfur facilities.
The main advantage of this operating mode is that the "base-load"
SRU has very steady feed gas rates, which in turn allows its
air:acid gas ratio control scheme to keep the plant trimmed very
close to optimum H
2
S:SO
2
ratio under most circumstances. This
means that the sulfur recovery efficiency of the "base-load" SRU is
generally very high.
The primary disadvantage of this operating mode is that the "swing"
SRU can see very large fluctuations in its amine acid gas and/or
SWS gas feed rates, since this unit has to take all of the flow
variation. Consequently, the sulfur recovery efficiency can be
considerably lower for this SRU than for the "base-load" unit because
the air:acid gas ratio control scheme on the "swing" unit is unable to
keep the plant as close to optimum H
2
S:SO
2
ratio, resulting in wider
and more frequent deviations from the optimum ratio.
The impact of this disadvantage can be minimized if the total amount
of acid gas to be processed is less than the maximum capacity of the
units. By setting the "base-load" SRU to process its full capacity, a
smaller quantity of acid gas will be processed in the "swing" SRU.
This means that a larger portion of the total acid gas is processed in
the SRU operating at the higher recovery.
Depending on the quantity of SWS gas to be processed, it may be
possible to send all of the SWS gas to one of the SRUs and process
only amine acid gas in the remaining SRU. In this case, the SRU
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-64
processing the SWS gas would be operated as the "base-load" unit
for amine acid gas. This should give steadier operating conditions
for this SRU, allowing better sulfur recovery efficiency and more
reliable ammonia destruction in the SRU. And, since the "swing"
SRU is processing only amine acid gas, its sulfur recovery efficiency
will be higher than for a "swing" SRU processing both amine acid gas
and SWS gas. The net result may be higher overall sulfur recovery
efficiency for the SRUs than if SWS gas was processed in both the
units (although this may not always be the case).
9.6.6.2 "Cascade" Operation of All SRUs
The other operating mode is to place both the SRUs in "cascade"
operation. Rather than feeding a fixed flow rate to one SRU and
forcing the remaining SRU to take all of the "swing", the acid gas can
be split in relative proportions between the SRUs. As the amount of
available acid gas changes, the feed rates to both the SRUs will be
adjusted proportionally. This mode spreads the variations in the flow
of amine acid gas and/or SWS gas feed between the SRUs so that
no unit is experiencing as much change as when operated as a
"swing" unit. However, none of the units is operating on steady flow
rates, as both the units must absorb the fluctuations in flow from the
feed units.
The primary advantage of this operating mode is that no SRU is
experiencing large variations in feed flow rates, so there is less
variation in sulfur recovery efficiency compared to operating as a
"swing" SRU. This operating mode is generally also more reliable
when the amount of SWS gas to be processed is high enough that
both the SRUs must process SWS gas.
The main disadvantage of this operating mode is that none of the
units is processing at steady feed rates, so neither SRU can maintain
its sulfur recovery efficiency as high as it can when operating as a
"base-load" SRU. If the feed units are producing acid gas at
reasonably steady rates, however, the magnitude of this loss in sulfur
recovery efficiency from operating with both the SRUs in "cascade"
mode can be relatively minor.
The overall sulfur recovery efficiency for the SRUs as a whole will depend
on how much acid gas is to be processed, the relative amounts of amine
acid gas and SWS gas to be processed, relative catalyst activities within
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-65
the reactors of the plants, and many other factors. As a result, the choice
of which operating mode to use will often depend on the particular
circumstances at any given time. As operating experience is gained with
the units, past experience will probably serve as the best tool for choosing
the operating mode in different situations.
9.6.7 Process air Blower Operation
The Process air Blower is actually a multi-stage, low-head, centrifugal
compressor. Although this air blower is less complicated to operate than
conventional centrifugal compressors (like those used in fuel gas service,
for instance), the blower does require some special attention when
operating at low flow rates. These cases are discussed in the sections
below.
9.6.7.1 Preventing "Surge" in the Process air Blower
When centrifugal compressors are operated at low flow rates, they
may enter a range of flow instability known as "surge."
The startup air flow rate to an SRU is primarily controlled by throttling
a valve in the blower suction. This method of flow control is
preferred because suction throttling reduces the inlet air density and
maintains a higher volumetric flow rate through the blower when the
mass flow rate is lower. Because of this effect, the blower should be
able to operate down to a lower flow rate before going into surge.
Operating experience will establish what the stable operating range
is for this blower.
The primary indication of blower surge is erratic air flow rate. The
first sign of this is usually audible the check valve in the blower
discharge line begins to "clatter." The air pressure gauge on the inlet
to the Acid Gas Burner will usually fluctuate rapidly, and the burner
flame can often be observed to "puff" back and forth, when the
blower is in surge. If the surge is severe enough, it will cause high
vibration levels on the blower. If the blower is in surge for an
extended period, the blower casing will overheat due to re-circulation
of hot air between stages of the machine. Regardless of the
symptoms, the result of allowing a blower to operate in surge for long
periods of time is physical damage to the blower, either from high
vibration or from high temperature. For this reason, do not allow an
air blower to remain in surge.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-66
To prevent the blower from surging at low flow rates, the discharge
piping on each blower has a "blow-off" valve installed. The action of
the blow-off valve is controlled by relays in the DCS. When the air
flow is low, the PLC will open the blow-off valve and allow some of
the air from the blower to vent to the atmosphere, increasing the air
flow through the blower to keep it above the surge line. A silencer
has been installed in the vent line to reduce the noise level around
the blower when the blow-off is used. If the blower is surging, then
adjust its blow-off valve to open more until the blower stops surging. It
does no harm to open the blow-off more than necessary, although it
does waste power by forcing the blower to compress more air than
necessary. Adjusting the amount that the blow-off opens is simply a
matter of making the appropriate configuration change in the DCS.
9.6.7.2 "Swapping" Process Air Blowers During Operation
While a sulfur plant is running, it is often necessary to "swap" air
blowers to bring the off-line blower on-line so that the other blower
can be shut down. This can usually be accomplished with only a
slight "bobble" to the process by starting and stopping the blowers in
the proper manner. The procedure given below is one technique for
swapping blowers.
Since each SRU must remain on-ratio at all times for optimum sulfur
recovery, it is important that the air flow to an SRU not be disturbed
while swapping blowers. If the air flow fluctuates, the best that can
happen is a minor disturbance in air:acid gas ratio and a small drop
in sulfur recovery. At worst, the Acid Gas Burner may lose its flame,
the SRU will shut down on "flame failure", and the acid gases will be
diverted to the flare (a reportable emission episode). The "bias"
controllers in the DCS together with the bias and flow control relays
in the DCS, are designed to make swapping blowers relatively simple
and avoid these problems.
One of the complicated aspects associated with swapping blowers is
the impact that starting the off-line blower can have on air flow. Each
air blower has its own suction valve. Since the DCS will be sending
the same control signals to the valves on both blowers, there is a
potential to suddenly double the air flow when the off-line blower is
first started. This would not only disturb the process, it could
possibly blow out the flame in the burner.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-67
The bias relays in the DCS allow the DCS operator to slowly ramp up
the flow from the off-line blower while ramping down the flow from
the on-line blower. Although we have attempted to automate this
concurrent ramping operation on a couple of past projects, we have
not found this to be very satisfactory. The way that the blower
controls need to be ramped will depend on the current plant
throughput and whether or not the blower suction valve is still in
control of the air flow from the blower. This is classic "fuzzy logic",
something that is easy for a human to do but very difficult for a
computer.
The procedure below describes how to switch an SRU from the "A"
blower to the "B" blower. That is, the "A" blower is running to the
SRU and the "B" blower is not currently running. The procedure to
switch from the "B" blower to the "A" blower in the SRU is similar.
Make sure the SRU is operating stably before proceeding.
A. In the DCS, confirm that the A blower hand controller is
currently set to 100% output so the blower relay is multiplying
the signal it receives from the process air flow controller by 1.0
(i.e., no change). (If the setting is not already 100%, slowly
increase it to 100% before proceeding, allowing time for the
controls to respond.)
B. Set the B blower hand controller in the DCS to 0% output.
This means that its relay will be multiplying the signal it receives
from the process air flow controller by 0.0, so all of the flow
relays for the valves on the B blower will be receiving 0% as
their inputs. After transformation by the suction, discharge, and
vent relays in the DCS, this means that the positioners on the
suction valve, discharge valve, and vent valve will be receiving
control signals of 33%, 0%, and 100%, respectively.
C. Switch the process air flow controller to "manual".
This ensures that the input to the "bias" relays does not change
during the blower swap procedure, so that the DCS operator
can see the impact on air flow while adjusting the relays.
D. On the off-line blower (B), confirm that:
(1) Its suction valve is closed.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-68
(2) Its discharge valve is closed.
(3) Its blow-off valve is closed.
E. Start the off-line blower as follows:
(1) Press the local push-button to give the blower a "permit to
start" and energize the solenoid valves on its suction and
vent valves for 30 seconds.
(2) Start the blower using its local start/stop control station.
(3) Once the blower is running, the solenoid valve on its
discharge valve is also energized.
The blower suction valve will open 33%, its vent valve will open,
and its discharge valve will remain closed. The valves will all
return to being closed if the blower is not started before the
"permit to start" times out.
Since the discharge valve will still be fully closed when the
blower starts, there will be no change in the air flow to the SRU
even though air will be flowing through the blower. All of the air
will be flowing out of the blow-off valve and venting atmosphere.
F. In the DCS, begin to increase the output from the B blower
hand controller.
This will begin to increase the multiplier in the B relay from
0.0, and the output to the discharge valve will begin to increase
as the output to the vent valve begins to decrease.
G. Continue to increase the output from the B blower hand
controller until the B blower develops enough discharge
pressure to open its check valve and the air flow to the SRU
begins to increase.
Depending on current operating conditions in the SRU, this may
happen as soon as the discharge valve begins to open, or it
may not happen until the suction valve begins to open more.
Once the discharge check valve on the B blower opens, the
air flow to the SRU will begin to increase as the B blower
starts to contribute to the air flow.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-69
H. Begin to decrease the output from the A blower hand
controller.
This will begin to reduce the multiplier in A relay from 1.0 and
begin to reduce the flow from the A blower. Depending on
current operating conditions in the SRU, this may be due to
throttling the suction valve more, or may be due to closing of
the discharge valve.
I. Continue to increase the output from the B blower hand
controller and reduce the output from the A blower hand
controller as necessary to control the air flow, until the B
blower hand controller has 100% output and the A blower
hand controller has 0% output.
This will increase the air flow from the B blower and reduce
the air flow from the A blower until all the flow to the SRU is
from the B blower and the A blower is just venting air to the
atmosphere.
J. Switch the air flow controller back to "automatic".
K. Shut down the A blower using the local start/stop control
station.
L. The blower swap is now complete. Before leaving the area,
visually confirm that:
(1) The off-line blower is stopped.
(2) The suction, discharge, and v valves on the off-line blower
are closed.
(3) The on-line blower is running smoothly.
(4) The process has returned to steady operation.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-70
9.6.8 Reactor Furnace Temperature
Each Reactor Furnace is designed to destroy the ammonia contained in
the SWS gas feed by maintaining a high-temperature, reducing
atmosphere in the front zone of the furnace. In order to control the
temperature in the front zone of the furnace, a portion of the amine acid
gas bypasses the Acid Gas Burner and flows to side injection ports on the
Reactor Furnace, where the bypass gas mixes with the burner combustion
products as they enter the second zone of the furnace. If less of the
amine acid gas is routed to a burner, a greater portion of the H
2
S fed to
that burner is actually combusted, raising the flame temperature and
increasing the temperature in the front zone of that furnace. If more
amine acid gas is routed to a burner, a smaller fraction of the H
2
S entering
that burner is combusted, lowering the temperature in the front zone of
that furnace.
The amount of amine acid gas that is fed to the burner in the SRU is
controlled using the flow ratio controller in the DCS to adjust bypass gas
control valve to regulate the amine acid gas flowing to the side injection
ports on its furnace (the bypass gas flow rate). In theory, the optical
pyrometer mounted on the side of the furnace should measure the
temperature inside the first zone of the Reactor Furnace and make
appropriate adjustments to the bypass gas flow by changing the ratio
setting on the flow ratio controller to control the desired temperature.
In practice, however, the temperatures measured by optical pyrometers
on similar furnaces have often given erratic responses to process
changes. It is suspected that the cool bypass gas entering the side
injection ports is influencing the temperature measurement, either due to a
cooling effect on the refractory as the gas flows through the openings in
the lining, or due to back-mixing caused by eddies arising from the "jet"
effect of the combustion products leaving the Acid Gas Burner.
If the temperature response of the pyrometers does prove to be
unreliable, then the bypass gas ratio can be used for control purposes
instead. The graph below shows the bypass gas ratio as a function of the
ratio of SWS gas flow to amine acid gas flow. The bypass gas ratio is the
amine acid gas bypassing the burner as indicated in the DCS versus the
total amine acid gas as indicated in the DCS. Combustion of the
ammonia in the SWS gas is very exothermic, so less of the amine acid
gas must be bypassed to maintain the same front zone temperature as
the ratio of SWS gas to amine acid gas increases.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-71
0.205
0.206
0.207
0.208
0.209
0.210
0.211
0.212
0.213
0.214
0.215
0.00 0.01 0.02 0.03 0.04 0.05
B
y
p
a
s
s

G
a
s

R
a
t
i
o
,

N
m
3
/
N
m
3
SWS Gas:Amine Acid Gas Ratio, Nm
3
/Nm3
Design Point (Normal Operation)

The setpoint for the flow ratio controller can be set by the operator using
the graph above. When operating in this mode, the temperature indicated
on the optical pyrometer can be monitored to determine if changes to the
setpoint on the flow ratio controller are necessary. If the temperature
reading is lower than normal, raise the setpoint on the flow ratio controller
to bypass more amine acid gas around the burner and raise the
temperature. If the temperature reading is higher than normal, lower the
setpoint on the flow ratio controller to bypass less amine acid gas around
the burner and bring the temperature down.
If field experience shows that the temperature measurement of the optical
pyrometers on these SRUs will give acceptable control. Placing the flow
ratio controller in "cascade" will allow the temperature controller to adjust
its ratio setpoint, so that the amount of bypass gas is controlled
appropriately with the flow ratio controller.
Whether the bypass gas ratio is controlled directly or is set by the action of
the temperature controller adjusting the bypass gas ratio, the following
considerations apply to the bypass gas flow rate:
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-72
(7) The total bypass acid gas flow rate should never be allowed to
exceed 67% (i.e., ) of the total amine acid gas flow rate, as this will
ensure that at least of the total acid gas feed is always flowing to
the burner regardless of the SWS gas flow rate. If less that of the
total H
2
S is fed to the burner, all of the oxygen in the process air fed
to the burner may not be consumed. If this happens, free oxygen
may enter the downstream catalyst beds and catch them on fire,
leading to catalyst (and possibly equipment) damage.
(8) 65% is the recommended maximum bypass acid gas ratio to allow a
safety margin for flow measurement errors, slow control response,
plant upsets, etc.
(9) It is always desirable to minimize the bypass acid gas ratio, as
sending more of the amine acid gas feed to the burner means less
chance of contaminating the downstream catalyst beds with
hydrocarbons or carbon. Even the best-run amine systems will
always pick up small amounts of hydrocarbon, which can
subsequently contaminate the catalyst beds. Hydrocarbon fouling is
the most common cause of poor catalyst life in refinery sulfur plants.
(10) The pressure drop through the Acid Gas Burner is the driving force
that allows the bypass gas control valve to bypass part of the amine
acid gas around the burner and into middle of the furnace instead.
When the SRU is operating at low flow rates, there may not be
enough pressure drop through the burner to give good control of the
bypass acid gas. In such cases, the flow ratio controller will "pinch"
the control valve in the acid gas line to the burner, increasing the
pressure drop available for the bypass gas control valve.
The DCS relay is designed to limit the output to the control valve in
the acid gas line to the burner so that this valve is never
completely closed. There should always be at least

of the amine
acid gas flowing to the burner to be sure that the front zone of the
Reactor Furnace does not begin to operate in an oxidizing
atmosphere.
(11) When an SRU is not processing SWS gas, it is not necessary to
bypass any amine acid gas around its burner. When operating in
this mode, place the flow ratio controller in "manual" and set its
output to 0% to fully close the bypass gas control valve and send all
the amine acid gas to the burner. With all of the amine acid gas
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-73
flowing through the burner, it is less likely that hydrocarbons in the
acid gas will leave the furnace un-combusted, so there is less
chance of fouling the downstream catalyst beds.


IT IS POSSIBLE FOR THE SIDE INJECTION PORT NOZZLES
ON A REACTOR FURNACE TO OVERHEAT IF THERE IS NO
BYPASS ACID GAS FLOWING THROUGH THE NOZZLES.
ALTHOUGH THE HOT FURNACE GASES SHOULD NOT
"BACK" INTO THE NOZZLES, THE INTENSE RADIANT HEAT
FROM THE HOT FURNACE INTERIOR MAY CAUSE
OVERHEATING OF THE NOZZLES.
TO PREVENT ANY SUCH OVERHEATING, THE NITROGEN
PURGE FOR THE INJECTION PORTS SHOULD BE PLACED
IN SERVICE WHENEVER THERE IS NO BYPASS ACID GAS
FLOW.
9.6.9 Ammonia Destruction Considerations
It is generally accepted within the industry that sulfur plants processing
ammonia-bearing streams (sour water stripper off-gas, for instance) must
be designed to destroy essentially all of the ammonia, probably down to
PPM levels, to avoid plugging with ammonia salts in the downstream
equipment. For this reason, many sulfur plant designers impose upper
limits on the ratio of SWS gas to amine acid gas to ensure successful
operation of their SRUs. We do not believe this is necessary, however, if
the reactor furnace is designed for ammonia destruction in a reducing
atmosphere like the furnace in this SRU is.
Years ago, ammonia was destroyed in one section of a reactor furnace by
literally burning it in the presence of excess air. A notable number of
undesirable side effects result when the ammonia is destroyed in this
oxidizing atmosphere, as a significant amount of sulfur trioxide (SO
3
) is
formed in this oxidizing step since the ammonia-bearing feed stream also
contains sulfur compounds. This SO
3
can cause significant problems
throughout the process. First, it readily reacts with any free ammonia
WARNING
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-74
throughout the process to form heat-stable salts that deposit and
accumulate. (Frequently, small amounts of ammonia enter the process in
the amine acid gas stream to participate in this salt accumulation
problem.) Second, the SO
3
can react with the Claus catalyst surface to
form sulfate salts that deactivate the catalyst. Third, the SO
3
can
condense on and corrode the cooler surfaces in the unit very rapidly
during upset periods. Fourth, the SO
3
absorbs in the sulfur product and
causes it to be corrosive.
As these problems were diagnosed and studied, Amoco and others
discovered and demonstrated that the ammonia could be successfully
destroyed in a Claus SRU by thermal decomposition in a reducing
atmosphere. This process change essentially eliminated the formation of
SO
3
in the unit. Amoco found that large quantities of ammonia could be
destroyed in a reducing atmosphere at elevated temperatures, and
obtained patents covering this mode of operation in 1973. As Amoco
licensees, our SRUs are designed for reducing-atmosphere ammonia
destruction in a two-zone reactor furnace, with careful attention to
controlling the front zone temperature at or above 1370C to ensure near
complete ammonia destruction.
Surprisingly, though, we have found that our clients do not always operate
our SRUs in strict accordance with the published operating procedures
regarding such matters as minimum furnace temperature, feedstock
ratios, etc. In fact, some of our clients have operated their SRUs on just
sour water stripper off-gas for days at a time because of operating
problems in the amine unit. Although there was undoubtedly ammonia
escaping from the furnace when operated in this manner, there has never
been any plugging with salts during this time.
This has led us to conclude that avoiding SO
3
formation, not complete
ammonia destruction, is the critical element in the reliability of our
reducing-mode SRUs. If you examine the melting points of the various
salts that can result from ammonia and the sulfur compounds that might
be found in a sulfur plant, only ammonium sulfate, (NH
4
)
2
SO
4
, has a
melting point that is higher than the freezing point of sulfur. Since all of
the surfaces in a sulfur plant must be maintained above the sulfur freezing
point, none of the other salts can precipitate under normal operating
temperatures. Thus, as long as the furnace is operated in a reducing
atmosphere so that there is no SO
3
to combine with water and the
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-75
residual ammonia to form ammonium sulfate, salt precipitation should not
occur in the SRU.
Since these SRUs are followed by an amine-based tailgas cleanup unit,
though, there will be cooler pieces of equipment downstream of the SRU.
However, the first cool section is the quench water system in the TGCU,
which will easily scrub the ammonia from the gas streams since ammonia
dissolves readily in water. Because this serves to raise the pH of the
quench water and counteract the drop in pH as H
2
S, CO
2
, and trace
quantities of SO
2
dissolve in the water, this ammonia is actually beneficial
to the process. Depending on the amount of ammonia in the gas, some
may escape from a quench tower and dissolve in the downstream amine
solution, but periodically purging a small amount of water from the stripper
reflux system will prevent the ammonia from concentrating enough to
cause salt problems.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-76
9.6.10 Sulfur Recovery Efficiency
The sulfur recovery efficiency of an SRU depends on a number of factors.
These sulfur plants are designed to achieve an average sulfur recovery of
at least 94-96%, but should be capable of recoveries somewhat higher
than this. Operator attention to the following aspects of sulfur plant
operation will ensure consistently good recovery levels in these SRUs.
9.6.10.1 H
2
S:SO
2
Ratio
Maximum sulfur recovery is obtained when the H
2
S to SO
2
ratio in
the process gas upstream of the first catalyst bed is exactly 2:1. It is
virtually impossible to maintain this exact ratio, but efforts should be
made to control near 0% air demand on the air demand analyzer.
For instance, the changing air temperature and relative humidity
between day and night will cause some variation in the air flow rate,
resulting in variations in percent air demand (a function of the
H
2
S:SO
2
ratio).
The air demand analyzer will continuously analyze the process gas
and calculate the percent air demand, allowing the air demand
controller to automatically trim the air:acid gas ratio to stay close to a
2:1 H
2
S:SO
2
ratio. If the analyzer is out of service or needs to be
checked, the procedures in Section 9.10 of these guidelines can be
used to manually sample the process gas and determine the
H
2
S:SO
2
ratio, so that the appropriate change can be made to the
air:acid gas ratio.
9.6.10.2 Reactor Feed Temperatures
The optimum feed temperature to a Claus reactor is a complex
function of several factors, which often have conflicting effects on
overall sulfur recovery. Some general guidelines used by sulfur plant
designers are:
(1) Catalytic conversion is favored by lower operating
temperatures.
(2) Hydrolysis (conversion) of organic sulfur compounds (such as
COS and CS
2
, which are formed by side reactions in the
Reactor Furnace) back into H
2
S is favored by higher operating
temperatures.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-77
(3) Liquid sulfur will be adsorbed in the catalyst pores (rendering
the catalyst temporarily inactive) if the reactor operating
temperature is too close to the sulfur dewpoint.
These factors were carefully considered when these SRUs were
designed and the temperatures shown on the process flow diagram
were chosen, but provisions have been included to control and/or
change these temperatures. If desired, the optimum reactor feed
temperatures can be determined for the actual operating conditions
by making changes and observing whether the amount of sulfur in
the tailgas goes up or down. The H
2
S and SO
2
concentrations in the
SRU tailgas indicated by the air demand analyzer for the SRU in
question will give a direct indication of whether the sulfur recovery
has improved (i.e., a lower total concentration for the two) or suffered
(i.e., a higher total concentration for the two) when a change is
made.
The sulfur recovery is affected by the catalyst bed feed
temperatures. Maximum sulfur recovery is usually obtained when
the catalyst bed inlet temperatures are controlled at the lowest level
that will allow the reaction to continue. The feed temperatures must
be sufficiently high to prevent catalyst deactivation due to
condensation and deposition of liquid sulfur on the catalyst. The
catalyst bed feed temperatures should be controlled at 230C or
higher during startup periods, and during other periods of upset or
unusual operating conditions. Calculations indicate that catalyst bed
feed temperatures may be reduced to 200-210C or slightly lower
during periods of stable operation without causing problems,
particularly in the second and third catalyst beds.
However, lowering the feed temperature to the first catalyst bed may
not increase recovery, due to lower hydrolysis of organic sulfur
compounds in this catalyst bed. Calculations indicate that the
optimum sulfur recovery for these SRUs is obtained then the first
catalyst bed is operated at high temperature, due to the higher
conversion of the organic sulfur compounds to H
2
S, which is
subsequently recovered in the downstream catalyst beds. As shown
on the Process Flow Diagram, the feed temperature to the first
catalyst bed will normally be around 225-235C. Operating
experience will show whether lower reactor outlet temperatures still
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-78
give satisfactory performance with the catalyst used in this catalyst
bed.
9.6.11 Operation at Low Flow Rates
Generally speaking, most sulfur plants can operate down to about 20-25%
of design throughput without much loss in recovery efficiency and without
requiring much operator attention. This is often referred to as the
turndown range or turndown ratio of the plant. Turndown to 20-25% of
design rate corresponds to a turndown ratio of 5:1 to 4:1. When an SRU
must operate at rates lower than 20-25% of design, there are several
operating problems that often occur. These problems, and ways to solve
them, are discussed below.
9.6.11.1 Loss of Sulfur Recovery Efficiency
The H
2
S:SO
2
ratio in the process gas is the single factor that most
affects sulfur recovery. This ratio is a function of the air:acid gas flow
ratio. At low flow rates, the flow meters on the amine acid gas, SWS
gas, and process air become less accurate, due to the low
differential pressures the flow transmitters must measure. This loss
of accuracy in measuring the flows to the SRU reduces the
effectiveness of the feed-forward part of the air ratio control loop,
requiring the feed-back part of the loop (the Air Demand Analyzer) to
make bigger corrections to try to keep the H
2
S:SO
2
ratio at 2:1. The
result is a loss in recovery because the H
2
S:SO
2
ratio oscillates more
widely from the optimum 2:1 ratio.
This poor sulfur recovery performance due to flow meter limitations
can be corrected by adjusting the flow meters for the lower rates.
Depending on the particular circumstances, this can be
accomplished in a number of ways:
(4) If the SRU must operate at low flow rates permanently, or for
long periods of time, installing new orifice plates with smaller
bores may be an attractive solution. This will increase the
differential pressures measured by the meters to put the flow
transmitters back into good operating ranges. The
disadvantages of this technique are that a plant shutdown is
required to make the change, and that the plant cannot operate
at high flow rates again without changing orifice plates.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-79
(5) If the SRU must operate at low flow rates temporarily,
re-calibrating the flow transmitters to span lower differential
pressure ranges may be a better method since this change can
be made while the plant is running. In fact, with "smart"
transmitters and the required I/O modules in the DCS, this
change can be made from the control room.
(6) If the SRU must operate at variable flow rates, using dual flow
transmitters calibrated for low and high differentials can provide
accurate flow measurement over a much wider range. With
proper programming in the DCS, the dual transmitters allow
"seamless" metering of the flow.
9.6.11.2 Deactivation of Catalyst Beds by Sulfur "Fog"
As a sulfur condenser is operated at lower and lower rates, it
reaches a point where the bulk gas cooling rate caused by radiation
and conduction heat transfer exceeds the dewpoint reduction rate
caused by sulfur condensation on the tube walls. Instead of
condensing along the walls of the tubes, sulfur begins to condense
into tiny droplets out in the gas. Due to the low flow rates, there is
not enough turbulence in the gas to make the droplets coalesce
along the tube walls. The droplets come out of the tubes as a "fog"
that cannot be removed in the downstream separator section, and
are carried over into the reactor feed heaters.
The feed heaters cannot vaporize all of the carry-over liquid sulfur,
probably because the small surface area of the droplets (relative to
their volume) causes slow mass transfer of vaporized sulfur away
from the droplets that impedes heat transfer. This causes the liquid
sulfur droplets to enter the reactor catalyst beds. The liquid sulfur is
then adsorbed into the pores of the catalyst where it blocks the active
sites, rendering the catalyst inactive. The catalyst activity can be
restored by raising the reactor feed temperature and vaporizing the
liquid sulfur out of the pores, but this can be very hard to do when the
condensers are carrying over liquid sulfur.
The symptom of sulfur carry-over into the catalyst beds is a gradual
decline in the temperature rises across the beds. Since the Claus
reaction is exothermic (heat releasing), the catalyst bed AT is a direct
indication of the amount of reaction occurring. As the liquid sulfur
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-80
deactivates the catalyst, there will a gradual decrease in the reactor
bed temperatures, starting at the top and moving downward.
Experience has shown that when the condenser passes begin to fog,
the liquid sulfur will accumulate in the outlet channels of the heating
passes in this style of sulfur plant. Due to the arrangement of these
"package" sulfur plants, the heating pass outlet channels are low
spots in the flow paths from the condenser outlets to the reactor
inlets. It is believed that as the gas flowing out of the heating pass
tubes turns 90 to exit through the channel outlet nozzles, centrifugal
force causes the sulfur droplets to impinge upon the endplates of the
channels with enough force to make the small droplets coalesce into
droplets too large to leave with the gas. Over a period of time, sulfur
will accumulate to the point where it begins to cause fluctuations in
the operating pressure of the affected SRU. The pressure drop will
build up enough to "lift" some of the sulfur into the downstream
catalyst bed, at which point the pressure drop will immediately
become much lower.
These SRUs have been designed to take advantage of this
phenomenon and drain the liquid sulfur out of the reheat passes
before it builds up enough to cause pressure drop problems and be
carried into the Reactor. Each heating pass outlet channel has a
steam-jacketed sulfur drain valve on it. The drain valves are
connected together in a steam-jacketed line that is connected to the
cooling pass outlet line. At low flow rates, the pressure drop through
an SRU is very low, so the static head of the accumulated liquid
sulfur is enough to cause the sulfur to drain into the cooling pass
outlet line, where it can flow into the first condensing pass and then
drain into the Sulfur Collection Header.
If sulfur carry-over is suspected (due to a gradual decline in Reactor
bed temperatures or because of SRU pressure fluctuations), these
drain valves can be used to drain sulfur from the heating passes by
opening them periodically to allow the sulfur to drain. Open each
drain valve, one at a time, for one or two minutes, then close the
valve. Do this every 4 to 8 hours, using the Reactor bed
temperatures as an indication of whether to use the drains more or
less frequently. Do not leave the drain valves open. Once the
sulfur has drained out of the heating pass channels, hot gas from the
cooling pass outlet will flow back up the drain line and disturb the
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-81
operation of the downstream catalyst beds if the drain valves are left
open.
9.6.11.3 Loss of Steam Pressure in Boilers
The heat released in the tubes of the Waste Heat Boiler is
proportional to the amount of feed gas processed. At very low flow
rates, generally less than 10% of the original design, the heat loss to
the surroundings can be more than this heat release, to the point
where the Waste Heat Boiler is no longer producing steam. When
this happens, the reheat exchangers will not be able to keep the
reactor feeds as hot as desired and liquid sulfur can begin to
condense on the catalyst beds and render the catalyst inactive.
The heat release in the Waste Heat Boiler can be increased by
burning supplemental fuel gas on the warmup ring of the Acid Gas
Burner. This burner is designed to burn fuel gas without forming soot
while processing acid gas. The warmup burner tips are installed in
the air plenum of the burner upstream of the acid gas tip so that the
fuel gas burns in an air-rich atmosphere, and the oxygen remaining
after combusting the fuel gas then reacts with the acid gas.
To make firing supplemental fuel gas easier, the air flow control
system is designed to automatically add air for the fuel gas like it does
for the acid gas. The air:acid gas ratio control system will
automatically add more process air for the fuel gas when firing
supplemental fuel gas. The air demand analyzer in the SRU will
continue to keep the air flow at the proper rate via the air controller.
Since the supplemental fuel gas requires an increase in the process
air flow to the sulfur plant, burning supplemental fuel gas will also
increase the mass flow rate through that plant. As a result, this
mode of operation can be used to help prevent sulfur "fog" problems
discussed earlier from occurring in a Sulfur Condenser. If the plant
throughput is near the range at which fogging occurs, firing some
supplemental fuel gas may be enough to avoid the problem.
9.6.11.4 Long Term Low-Flow Operation
Should the need arise for an SRU to operate at inlet rates below
15 to 20% for extended periods of time, consideration may be given
to plugging some of the condensing pass tubes in the Sulfur
Condenser. This will increase the flow rates through the remaining
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-82
tubes so that they are then above the "fog" formation rate and sulfur
carry-over is eliminated. Soft iron plugs can be inserted into the inlet
ends of the tubes for this purpose. (Do not plug the outlet ends of
the tubes. Since the boiler slopes from its inlet end to its outlet end,
liquid sulfur would accumulate in the tubes and could cause localized
corrosion, plugging, etc.)
9.6.12 Pressure Drop Surveys
A commonly encountered problem in sulfur plants (and Tailgas Cleanup
Units and Thermal Oxidizers) is a flow restriction due to high pressure
drop. High pressure drop is typically caused by a restriction at one point
in the equipment or piping, due to:
5. Accumulation of liquid (sulfur, etc.) in equipment or piping
6. Partial plugging of a catalyst bed (soot, carbon, polymers, etc.)
7. Partial plugging of a mist eliminator (sulfur, soot, catalyst, etc.)
The first step in identifying the cause of the high pressure drop is to
determine which equipment pass or section of piping contains the
restriction. (It is unusual to have more than one area of high pressure
drop at any one time.) This is best accomplished by making a pressure
survey of the process side of the SRU (and Tailgas Cleanup Unit and
Thermal Oxidizer, if necessary).
Due to the low operating pressure in a sulfur plant (generally
0.7 kg/cm
2
(g) or less) and the low pressure drop in each equipment pass
(generally 0.00-0.04 bar per pass), a single pressure gauge must be used
to make the pressure survey in order to get meaningful results. The
gauge should be a low-pressure gauge for best results (a -1 0
+1.5 kg/cm
2
gauge is recommended).
Beginning at the front end of the sulfur plant of interest, use the pressure
tap valves on the inlet and outlet lines from each equipment pass to
measure the pressure at each point in the process. Proceed toward the
back end of the process until the pass with the high pressure drop is
found. Note that some of the pressure tap valves may be plugged with
solid sulfur. Rod-out the sample valves as necessary to obtain an
accurate pressure reading.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-83



ALWAYS OBSERVE PROPER PROCEDURES AND PRECAUTIONS
WHEN USING THE PRESSURE TAP VALVES, PARTICULARLY IF
THE VALVES ARE PLUGGED AND MUST BE CLEARED.
ALTHOUGH THE VALVES ARE ORIENTED TO MINIMIZE THE
POSSIBILITY OF FILLING WITH MOLTEN SULFUR, HOT SULFUR
MAY SUDDENLY BE EXPELLED FROM A VALVE WHEN THE PLUG
IS CLEARED. RELEASE OF TOXIC GASES (H
2
S AND SO
2
, IN
PARTICULAR) IS ALSO A POSSIBILITY. THE "GENERAL SAFETY"
SECTION OF THESE GUIDELINES SHOULD BE CONSULTED IF
THERE IS ANY DOUBT ABOUT HOW TO WORK SAFELY WHEN
H
2
S, SO
2
, OR MOLTEN SULFUR MAY BE PRESENT.
When troubleshooting problems of this nature, it is very helpful to have
pressure survey information taken previously when the units were
operating properly. It is recommended that one or more pressure surveys
be performed early in the operating life of the plants, for comparison
purposes later if problems are encountered. Since the pressure drop of a
sulfur plant is a function of plant throughput (pressure drop is roughly
proportional to the square of the flow rate), it is even more helpful for
troubleshooting purposes if the early pressure surveys are performed at
different plant throughput rates. It is also important to record the gas flow
rates (amine acid gas, SWS gas, process air) during each pressure
survey, since pressure drop depends so strongly on plant throughput.
WARNING
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-84
9.6.13 Boiler Water Treatment
SAMSUNG TOTAL PETROCHEMICALS CO., LTD. IS
RESPONSIBLE FOR ESTABLISHING AND MONITORING THE
BOILER AND WATER CHEMICAL TREATMENT PROGRAM.
Proper boiler water chemical treatment is essential to achieving long
service life for the Waste Heat Boilers and Sulfur Condensers. Without
good day-to-day control of the water quality, solids buildup, corrosion, and
attack by the treating chemicals themselves can occur. It is Samsung
Total Petrochemicals Co., Ltd.s responsibility to see that a proper
chemical treating program is initiated prior to startup and that the program
is properly monitored and refined throughout the service life of the plant.
There are many qualified boiler and water treatment companies that can
advise the owner/operator on chemical treatment testing and controls. It
is recommended that only those companies that have local technicians
with extensive experience specifically in boiler water treatment be
selected to assist with Samsung Total Petrochemicals Co., Ltd.s program.
The design details incorporated in the boilers in these SRUs have proven
to be very reliable when combined with good operator practice regarding
water treatment. However, even properly designed equipment can be
severely damaged during a short period of operation if the water treatment
program is inadequate or improper.
The Waste Heat Boilers and the Sulfur Condensers are equipped with
continuous blowdowns to remove suspended and dissolved solids from
the water inside the boilers. In addition, these boilers are equipped with
intermittent blowdown connections on the bottom of their shells. These
intermittent blowdown valves should be used on a regular basis to give
the boilers a good "blow" to prevent sludge from accumulating in the
bottom of the shells. This is particularly important for the Waste Heat
Boiler because sludge must not be allowed to coat the tubes. The
consequence of fouling the outside of the tubes is tube failure from
overheating, as the fouling will impair the heat transfer and allow the hot
combustion gases to destroy the tubes.
Prior to using the intermittent blowdown valves, use the level controllers in
the DCS to raise the water level up to the high level alarm point. Then
open the intermittent blowdown valves, one at a time, until the level drops
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-85
back to the normal liquid level. Watch the boiler level in the sight glasses
throughout this operation to ensure that the level is not lost (which would
activate the SRU ESD and shut down that plant). Remember to reset the
level controllers at the conclusion of this procedure.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-86
9.7 Precommissioning Procedures
Prior to the initial startup, there are a number of precommissioning activities that
are necessary to ensure that the newly constructed plant is ready to be placed
in service. The activities outlined below should serve as a guide, but there may
be others required as a part of your normal plant procedures.
9.7.1 Preliminary Check-out
A. Check all equipment to ensure that it is properly installed. This will
probably require consulting the Manufacturer's literature as well as
construction drawings.
B. Check and lubricate all equipment in accordance with the
Manufacturer's recommendations.
C. Check the rotation of the Process Air Blowers, the Acid Gas
Knock-Out Drum Pumps, and the SWS Gas Knock-Out Drum
Pumps:
(1) Operate each Process Air Blower for a short period
(20 seconds or less) with its discharge valve closed.
(2) "Bump" each Acid Gas Knock-Out Drum Pump and check for
proper rotation.
(3) "Bump" each SWS Gas Knock-Out Drum Pump and check for
proper rotation.
D. Check all piping and equipment to be sure that all blinds have been
removed and that no valves are vented to atmosphere.
E. Place the Instrument Air System in service to all instruments and
check the action of controllers and control valves.
F. Turn on the steam supplies to all of the steam-jacketed sulfur vapor
valves and use the vent valves on each jacket section to vent the air
from the jackets. "Stroke" each valve to confirm it moves freely.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-87
9.7.2 Shutdown System Check-out
G. Fill the Waste Heat Boilers and the Sulfur Condensers with treated
boiler feed water up to the high-level alarm points. As the level is
rising, check the level transmitters and the high level alarms for
proper operation.
H. Use the quick-opening blowdown valves to lower the water levels in
the boilers and check for proper operation of the level transmitters,
the low level alarms, and the low-low level shutdowns.
I. Fill the boilers with treated boiler feed water back up to the normal
liquid levels.
J. Physically check all shutdown activating devices to ensure that they
activate the SRU ESD system.
K. Physically check all devices activated by the SRU ESD system to
ensure that they operate properly.
L. Check all relief valves to ensure that they are installed in the proper
locations and set for the correct relieving pressures.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-88
9.7.3 Leak Testing the Process Piping and Equipment


THE LOW PRESSURE PROCESS PIPING (ACID GAS, SULFUR
VAPOR, PROCESS AIR) AND LOW PRESSURE PROCESS
EQUIPMENT IN THESE SRUS ARE NOT DESIGNED TO BE FILLED
WITH WATER AFTER INSTALLATION OF REFRACTORY AND
CATALYST. ONLY THE EQUIPMENT AND PIPING UPSTREAM OF
AMINE ACID GAS AND SWS GAS SHUTDOWN VALVES CAN BE
FILLED WITH WATER AND HYDROTESTED. USE THE
FOLLOWING PROCEDURE TO LEAK-TEST THE REST OF THE
SRUS.
The process piping and equipment in each SRU can be checked for leaks
by using a Process Air Blower to pressurize the process side of the
equipment and piping to about 0.6-0.7 kg/cm
2
(g), then checking flanges,
etc. for leaks (usually by applying masking tape or "Snoop" to the flanges,
and by listening for other leaks). In order to develop this pressure, the
blower can be operated with the tailgas block valves and the warmup
bypass valves in the SRU closed, and the blow-off valve on the blower
"pinched". This procedure requires some special preparations to operate
the blower in this manner, as detailed below.
The Complete Flowpath Interlock must be temporarily disabled in order to
operate the SRU in this manner. The Leak Test switch on each local SRU
control panel is used to position the process gas valves as described
above and also directs the PLC to bypass most of the unit shutdowns.
This means that "jumpers" on the limits switches and "forces" in the PLC
are not necessary to perform this test. It also means that it is not
necessary to have water in the boilers (Waste Heat Boiler and Sulfur
Condenser) during the test since the low-low water level S/Ds are also
bypassed.
This same procedure can be used to leak test each SRU before restarting
it following maintenance. Whenever plant maintenance requires opening
one or more of the flanged connections in an SRU, it is good practice to
leak test that SRU before returning it to service. This allows detecting any
CAUTION
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-89
leaking connections that may have resulted from the maintenance
operations before acid gas is reintroduced into that unit. Although the
SRU is pressurized with air to perform the leak test, there is no air flow
through the units during the testing procedure so there is very little
jeopardy of having sulfur fires in the catalyst beds.
Note that the SRU warmup bypass line is not leak tested during this
procedure. This line can be checked for leaks using the nitrogen purge on
the piping as described in a later section of these guidelines.
To perform leak testing in the SRU, proceed as follows:
M. Switch the process air flow hand switch in the DCS to "local" to give
control of the valves on the air blower to the air flow controller (HIC)
on the local SRU control panel.
N. Confirm that the Reactor Cool-Down switch on the local SRU control
panel is set to "NORMAL".
O. Confirm that the manual block valve in the SRU Tailgas line is open.
P. Switch the Startup/Run selector switch on the local SRU control
panel to "STARTUP".
The PLC and DCS should perform the following actions:
(1) The two Warmup Bypass Valves are opened.
(2) The nitrogen purge valve between the warmup bypass valves is
closed.
(3) The Tailgas Valve to the Thermal Oxidizer is closed.
(4) The Tailgas Valve to the TGCU is closed.
Confirm that the "WARMUP OPEN" light on the panel is illuminated, and
that the "TTO OPEN" and the "TGCU OPEN" lights on the panel are
extinguished.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-90
Q. Turn the Leak Test key switch on the local SRU control panel to
"TEST".
The PLC should perform the following actions:
(1) The two Warmup Bypass Valves are closed.
(2) The nitrogen purge valve is opened.
(3) All of the ESDs for that SRU are bypassed, except for the
high-high furnace pressure S/D and the manual S/D switches.
Confirm that the "WARMUP OPEN" light on the local SRU control panel
is now extinguished.
R. Set the air flow controller on the local SRU control panel to 0%
output and confirm that the suction, discharge, and blow-off valves
on the air blowers are fully closed.
S. Start a Process Air Blower:
(1) Press the local "permit to start" push-button for the selected
blower.
(2) Start the blower using its local start/stop control station.
The blower suction valve will open 33%, its vent valve will open, and
its discharge valve will remain closed when the "permit to start"
push-button is pressed. Once the blower is started and comes up to
speed, a flow of air will be established out of the blow-off valve and
its silencer.
T. Use the local air flow controller as needed to open the discharge
valve on the blower and send air to the SRU to begin pressurizing it.
Although the blower discharge valve will begin to open as the output
from the controller is increased, air will not flow through the sulfur
plant once pressure builds because the warmup bypass valves and
the tailgas valves are all closed.
At this point, two operators will be necessary to control and monitor the
Process Air Blower. One operator should be stationed at the local SRU
control panel, and one stationed near the blower area.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-91


DO NOT LET THE AIR BLOWER GO INTO SURGE. THE
OPERATOR STATIONED NEAR THE BLOWER SHOULD LOOK
AND LISTEN FOR INDICATIONS OF SURGE. IF SURGE IS
DETECTED, REDUCE THE OUTPUT ON THE AIR FLOW
CONTROLLER TO OPEN THE BLOW-OFF VALVE MORE AND
INCREASE THE AIR FLOW ENOUGH TO BRING THE BLOWER
OUT OF SURGE. IT MAY NOT BE POSSIBLE TO RAISE THE
DISCHARGE PRESSURE ALL THE WAY TO 0.6-0.7 KG/CM
2
(G)
WITHOUT CAUSING THE BLOWER TO SURGE.
U. Slowly increase the output from air flow controller to "pinch" the
blow-off valve on the air blower until the discharge pressure from the
blower reaches 0.6-0.7 kg/cm
2
(g) as measured by the pressure
gauge on the process air line to the burner.
Due to the volume inside the SRU, it will take several minutes for the
pressure to build up in the SRU.
V. Once the desired discharge pressure has been achieved, and the
blower is operating stably, check all of the equipment and piping
connections for visible or audible signs of leakage. Continue to
monitor the air blower to be sure it is operating stably.
NOTE: Do not allow the pressure to reach the high-high pressure
S/D, since this shutdown is still active and will activate the
SRU ESD system if this happens.
W. After the leak test has been completed, press the ESD push-button
on the local SRU control panel to activate the SRU ESD system and
shut down the air blower.
X. Turn the Leak Test switch on the local SRU control panel to
"NORMAL".
The PLC should perform the following actions:
(1) The two Warmup Bypass Valves are opened.
(2) The nitrogen purge valve is closed.
CAUTION
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-92
(3) All of the ESDs for the SRU are enabled again.
Confirm that the "WARMUP OPEN" light on the local SRU control panel
is now illuminated.
Y. Confirm the following:
(1) The air blower is shut down, and its suction, discharge, and
blow-off valves are closed.
(2) The two Warmup Bypass Valves are both open.
(3) The Tailgas Valve to the Thermal Oxidizer and the Tailgas
Valve to the TGCU are both closed.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-93
9.7.4 Purging the Inlet Knock-Out Drums
Since inert nitrogen gas is available in the SRU area, it can be used to
purge the Acid Gas Knock-Out Drum and the SWS Gas Knock-Out Drum
prior to removing the blinds in their inlet lines. One procedure for doing so
is as follows.


UNTIL THE AIR IS PURGED FROM THE KNOCK-OUT DRUMS,
THERE MAY BE FLAMMABLE GAS MIXTURES PRESENT IN THE
VESSELS AND THEIR PIPING. ENSURE THAT ALL IGNITION
SOURCES, INTERNAL AND EXTERNAL TO THE VESSELS, HAVE
BEEN REMOVED BEFORE PROCEEDING.
A. Verify that the blinds are in place in the inlet amine acid gas line and
the inlet SWS gas line. Do not attempt this procedure if these lines
are not blinded from their respective acid gas sources.
B. The sulfur plant downstream of the drums does not need to be
purged with nitrogen. Verify that the amine acid gas and SWS gas
flow controllers on the local SRU panel are set to 0% output and that
the inlet amine acid gas valve and the inlet SWS gas valve are
closed.
C. Open the suction valve and close the discharge valve on each Acid
Gas Knock-Out Drum Pump.
D. Open all of the vent and drain valves on the level and pressure
instruments on the Acid Gas Knock-Out Drum and each Acid Gas
Knock-Out Drum Pump, and the vent and drain valves on each Acid
Gas Knock-Out Drum Pump.
E. Remove the blind from the drain valve on the pump suction line and
use a hose or other means to temporarily connect nitrogen to the
valve. Commence the flow of nitrogen into the Acid Gas Knock-Out
Drum and each Acid Gas Knock-Out Drum Pump, so that nitrogen is
flowing out of all of the open valves. Be sure to include the acid gas
inlet line from the Amine Regeneration Unit.
WARNING
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-94
F. Allow the nitrogen to continue flowing long enough to reduce the
oxygen concentration in the vessel and piping to less than 1%. Use
a portable oxygen analyzer to determine the oxygen concentration.
G. When the oxygen concentration is below 1%, begin closing the vent
and drain valves. Close the valves on each Acid Gas Knock-Out
Drum Pump first, then the valves on the Acid Gas Knock-Out Drum
level instruments. Leave the sample connection valve open on the
outlet line from the Acid Gas Knock-Out Drum.
H. Close the valve where the nitrogen hose is connected to stop the
flow of nitrogen, then close the sample connection valve.
I. Repeat Steps C through H for the SWS Gas Knock-Out Drum and
the SWS Gas Knock-Out Drum Pump. The sample connection valve
on the outlet line from the SWS Knock-Out Drum should be the last
valve closed, after stopping the flow of nitrogen.
Leave each system blocked-in like this until ready to bring acid gas into
the SRU.
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-95
9.7.5 Commissioning Fuel Gas and Instrument Air to the Process
The fuel gas and instrument air supplies to the process side of an SRU
must be made ready for use prior to starting up the SRU using the
procedures in Section 9.8 of these guidelines. This requires blowing down
each section of piping to ensure that there are no liquids and/or
construction debris in the headers and supply lines. The procedure below
can be used to make sure that these gas utility systems are ready for
service.
A. Select local manual control for the main fuel gas control valve by
switching the fuel gas hand switch in the DCS to "local".
B. Set the fuel gas controller on the local SRU control panel to 0%
output.
C. Confirm that the following fuel gas and instrument air valves are
closed:
(7) The manual block valve in the main fuel gas supply line.
(8) The two automated block valves and the flow control valve
downstream of the manual block valve in the main fuel gas line
to the Acid Gas Burner.
(9) The upstream manual block valve, the two automated block
valves, and the downstream manual block valve in the fuel gas
supply line to the pilot.
(10) The manual block valve(s), and the automated block valve in
the air supply line to the pilot.
(11) The manual block valve in the instrument air supply line to the
Air Demand Analyzer.
(12) The block valves in the instrument air supplies to the level
transmitters, on the Sulfur Surge Tank.
D. Confirm that all of the manual vent/drain valves in the main fuel gas,
pilot fuel gas, and pilot air piping are closed.
E. If the orifice plate has already been installed in the fuel gas flow
meter remove it for now.
F. Disconnect the fuel gas and instrument air from the burner systems
by performing the following steps:
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-96
(1) Unbolt the flanged connection at the burner in the main fuel gas
supply line.
(2) Disconnect the fuel gas supply tubing where it connects to the
pilot.
(3) Disconnect the instrument air supply tubing where it connects to
the pilot.
(4) Cover the open ends of these connections on the burner and
pilot to prevent debris from entering when the upstream piping
is blown down.
G. Remove the following pressure regulators, then cover the
downstream piping to prevent debris from entering when the
upstream piping is blown down:
(1) The main fuel gas supply regulator.
(2) The pilot instrument air supply regulator.
(3) The pilot fuel gas supply regulator.
H. "Force" the PLC to open the following valves:
(1) The automated block valves in the main fuel gas supply line.
(2) The automated block valves in the fuel gas supply line to the
pilot.
(3) The automated block valve in the instrument air supply line to
the pilot.
I. Confirm that these automated valves have moved to the proper
positions.
J. "Crack" the manual block valve in the main fuel gas supply line and
allow fuel gas to blow through the piping until it is clear. Then close
the gate valve, reinstall the main fuel gas pressure regulator, and
reopen the block valve.
K. Using the pressure gauge and the vent valve downstream of the
main fuel gas pressure regulator, adjust the main fuel gas regulator
to its specified setpoint.
L. Use the main fuel gas flow controller on the local control panel to
fully open the fuel gas flow control valve in the main fuel gas line,
Operating Guidelines Samsung Total Petrochemicals Co., Ltd.
Fall 2011 Daesan, Korea
SULFUR BLOCK
Issued 30 August 2011 Sulfur Recovery Page 9-97
then use the downstream vent valve to blow out this section of
piping. Close the vent valve when the piping is clear.
M. "Crack" the manual block valve downstream of the fuel gas flow
control valve and allow fuel gas to blow through the piping until it is
clear. Then close the manual block valve and the control valve.
N. "Crack" the upstream manual block valve in the fuel gas supply line
to the pilot and allow fuel gas to blow through the piping until it is
clear. Then close the ball valve, reinstall the pilot fuel gas pressure
regulator and reopen the block valve.
O. Using the pressure gauge and the vent valve downstream of the pilot
fuel gas pressure regulator, adjust the pilot fuel gas regulator to its
specified setpoint.
P. "Crack" the manual block valve downstream of pilot fuel gas
automated block valves and allow fuel gas to blow through the piping
until it is clear. Then close the manual block valve.
Q. "Crack" the upstream manual block valve in the instrument air supply
line to b