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Hydro-Chem Job A299 Hydrogen Plant Operating Manual

Ecogreen Oleochemicals 09/10/13


Batam, Indonesia Issue 1

OPERATING MANUAL

HYDROGEN GENERATING PLANT

FOR

ECOGREEN OLEOCHEMICALS
BATAM ISLAND
INDONESIA

JOB NO. A299

HYDRO-CHEM
A DIVISION OF
LINDE ENGINEERING NORTH AMERICA INC.
Hydro-Chem Job A299 Hydrogen Plant Operating Manual
Ecogreen Oleochemicals 09/10/13
Batam, Indonesia Issue 1

I. INTRODUCTION................................................................................................................. 6

II. PROCESS DESCRIPTION ................................................................................................. 7


A. GENERAL ..................................................................................................................... 7
B. BASIS OF DESIGN........................................................................................................ 8
1. HYDROCARBON FEED AND FUEL.......................................................................... 8
2. HYDROGEN PRODUCT ............................................................................................ 10
3. EXPORT STEAM ........................................................................................................ 10
4. UTILITIES ................................................................................................................... 10
C. PROCESS FLOW OVERVIEW................................................................................... 12
D. DETAILED PROCESS DESCRIPTION...................................................................... 14
1. FEED GAS HEATING ................................................................................................ 14
2. HYDROTREATING .................................................................................................... 14
3. DESULFURIZING (SULFUR REMOVAL) ............................................................... 14
4. REFORMING OF STEAM/HYDROCARBON MIXTURE ....................................... 15
5. CARBON MONOXIDE SHIFT CONVERSION ........................................................ 15
6. PROCESS GAS COOLING SYSTEM ........................................................................ 16
7. HYDROGEN PURIFICATION SYSTEM (PSA) ....................................................... 16
8. PSA TAIL GAS RECOVERY SYSTEM .................................................................... 17
9. REFORMER BURNER SYSTEM .............................................................................. 17
10. STEAM GENERATION AND BLOW DOWN SYSTEM ......................................... 18
III. GENERAL DISCUSSION OF KEY PROCESS POINTS .............................................. 19
A. HYDROTREATING AND DESULFURIZING .......................................................... 19
B. STEAM / HYDROCARBON REFORMING............................................................... 20
1. METHANE LEAKAGE ............................................................................................... 21
C. REFORMER BURNER ............................................................................................... 21
1. REFORMER DRAFT .................................................................................................. 21
2. BURNER FIRING CONDITIONS .............................................................................. 21
D. INDICATIONS OF FAULTY REFORMER / BURNER OPERATION...................... 23
E. CO SHIFT CONVERSION .......................................................................................... 23
E. STEAM GENERATOR WATER TREATMENT OBJECTIVES ............................... 24
1. GENERAL ................................................................................................................... 24
2. CHEMICAL DOSING OF STEAM GENERATOR WATER .................................... 25
IV. HYDROGEN PURIFICATION SYSTEM - PSA ............................................................ 26
A. PSA PROCESS ............................................................................................................ 26
B. DESCRIPTION OF THE PSA STEPS ......................................................................... 27
C. VESSEL STATUS FOR EACH PSA STEP ................................................................. 32
D. PSA CONTROLS AND INDICATIONS ..................................................................... 33
1. START / STOP SELECTOR SWITCH ....................................................................... 33
2. START UP / OPERATE SELECTOR SWITCH ......................................................... 33
Hydro-Chem Job A299 Hydrogen Plant Operating Manual
Ecogreen Oleochemicals 09/10/13
Batam, Indonesia Issue 1

3. LONG CYCLE TIME SHUTDOWN (LCT) ............................................................... 33


4. PAUSE / CONTINUE SWITCH AND MANUAL STEP ........................................... 34
5. VENT / PRODUCT SWITCH ..................................................................................... 34
6. H2 / N2 SWITCH .......................................................................................................... 34
7. PSA MAINTENANCE MODE SWITCH ................................................................... 34
8. PSA TUNING SETTINGS ........................................................................................... 35
9. PSA RUN TIME........................................................................................................... 35
10. ADSORPTION PRESSURE ........................................................................................ 36
11. PSA RATIO FFIC-204 ................................................................................................. 36
12. PSA PRESSURE PROFILE ......................................................................................... 36
E. PSA OPERATION ....................................................................................................... 37
1. PSA START UP ........................................................................................................... 37
2. PSA NORMAL OPERATION ..................................................................................... 37
3. PSA OPERATION WITH LOW PRODUCT PURITY ............................................... 37
4. EFFECT OF ABNORMAL PROCESS CONDITIONS ON THE PSA ...................... 38
F. PSA SHUTDOWN ....................................................................................................... 38
G. CYCLING THE PSA ON NITROGEN ........................................................................ 38
H. TROUBLESHOOTING THE PSA............................................................................... 38
1. CYCLE FAILS TO ADVANCE .................................................................................. 39
2. UNEVEN RUN TIMES OR ABNORMAL PRESSURE PROFILES ......................... 39
3. MALFUNCTION OF A PSA SWITCHING VALVE ................................................. 39
4. PSA SWITCHING VALVE LEAKAGE ..................................................................... 40
V. CONSTRUCTION VERIFICATION AND PRE-COMMISSIONING ........................ 43
A. PRELIMINARY INSPECTION OF EQUIPMENT ..................................................... 43
B. PRE-COMMISSIONING – ELECTRICAL EQUIPMENT ......................................... 43
C. PRE-COMMISSIONING – INSTRUMENTATION ................................................... 44
D. PRE-COMMISSIONING – INSTRUMENT AIR ........................................................ 44
E. PRE-COMMISSIONING – COOLING WATER ........................................................ 44
F. PRE-COMMISSIONING – BOILER FEED WATER ................................................. 45
G. PRE-COMMISSIONING – PROCESS PIPING .......................................................... 45
H. PRE-COMMISSIONING – PIPEWORK LEAK TESTING ........................................ 45
VI. CHARGING THE CATALYSTS AND ADSORBENTS ................................................ 47
A. REFORMER CATALYST ........................................................................................... 47
B. HIGH TEMPERATURE SHIFT CONVERTER CATALYST .................................... 50
C. HYDROTREATER AND DESULFURIZER CATALYST ......................................... 50
D. PSA ADSORBENTS .................................................................................................... 50
VII. PREPARATION FOR PLANT START-UP .................................................................... 52
A. PURGING THE EQUIPMENT .................................................................................... 52
1. PLANT FRONT END PURGE .................................................................................... 52
2. PSA SYSTEM PURGE ................................................................................................ 54
B. STEAM GENERATOR BOIL OUT (PRIOR TO INITIAL START-UP) .................... 55
Hydro-Chem Job A299 Hydrogen Plant Operating Manual
Ecogreen Oleochemicals 09/10/13
Batam, Indonesia Issue 1

VIII. NORMAL OPERATING PROCEDURES .................................................................... 58

IX. OPERATING SCENARIOS – OTHER THAN NORMAL ............................................ 59


A. FLAME OUT SHUTDOWN (FOSD) .......................................................................... 59
B. LOW FIRE SHUTDOWN (LFSD) ............................................................................... 60
C. PSA TRIP ..................................................................................................................... 61
D. EMERGENCY SHUTDOWN PROCEDURE ............................................................. 62
E. GENERAL POWER FAILURE ................................................................................... 63
F. INSTRUMENT AIR FAILURE ................................................................................... 63
G. STEAM FAILURE ....................................................................................................... 64
H. FEED GAS FAILURE .................................................................................................. 64
I. FIRE, EXPLOSION OR RUPTURE ............................................................................ 64
J. REFORMER TUBE RUPTURE .................................................................................. 65
K. TEMPORARY SULFUR POISONING OF REFORMER CATALYST ..................... 66
X. CATALYST REDUCTION ............................................................................................... 67
A. HYDROTREATER/DESULFURIZER CATALYST (711-D-1) ................................. 67
B. REFORMER CATALYST ........................................................................................... 67
1. REDUCTION PROCEDURE WITH NG FEEDSTOCK ............................................ 67
2. REDUCTION PROCEDURE WITH LPG FEEDSTOCK .......................................... 68
C. REDUCTION OF SHIFT CONVERSION CATALYST (711-D-2) ............................ 69
XI. OPERATIONAL ROUTINES AND MAINTENANCE SCHEDULE........................... 70

XII. INSPECTION AND REMOVAL OF PLANT CATALYSTS ........................................ 72


A. HYDROTREATER AND DESULFURIZER CATALYST ......................................... 72
B. REFORMER CATALYST ........................................................................................... 72
C. SHIFT CONVERTER CATALYST............................................................................. 73
D. PSA ADSORBENTS .................................................................................................... 73
XIII. S A F E T Y ....................................................................................................................... 74
A. GENERAL ................................................................................................................... 74
B. SUMMARY OF POTENTIAL HAZARDS ................................................................. 74
1. FIRE AND EXPLOSION ............................................................................................. 75
2. ASPHYXIATION HAZARDS..................................................................................... 76
3. ELECTRICAL SHOCK ............................................................................................... 77
4. FALLS FROM LADDERS OR PLATFORMS ........................................................... 78
5. CHEMICAL HANDLING ........................................................................................... 79
6. EQUIPMENT NOISE .................................................................................................. 81
7. HEAT STRESS ............................................................................................................ 81
C. HAZARDOUS AREA CLASSIFICATION ................................................................. 81
D. GENERAL PROPERTIES OF GASES AND CATALYSTS USED ON SITE............ 81
Hydro-Chem Job A299 Hydrogen Plant Operating Manual
Ecogreen Oleochemicals 09/10/13
Batam, Indonesia Issue 1

APPENDIX A NORMAL OPERATING PROCEDURES


APPENDIX B PLANT READINGS AT 100% CAPACITY
APPENDIX C INITIAL ALARM SETTINGS
APPENDIX D PROCESS FLOW DIAGRAMS/HEAT AND MATERIAL BALANCE
APPENDIX E MECHANICAL FLOW DIAGRAMS
APPENDIX F CAUSE AND EFFECT MATRIX
APPENDIX G PSA STEPPING LOGIC
APPENDIX H HAZARDOUS AREA CLASSIFICATION DRAWING
Hydro-Chem Job A299 Hydrogen Plant Operating Manual
Ecogreen Oleochemicals 09/10/13
Batam, Indonesia Issue 1

I. INTRODUCTION
This Operating Manual and the accompanying procedures are intended as a guide and
reference for personnel connected with the operation and maintenance of the hydrogen
generating plant engineered and built by Hydro-Chem, A Division of Linde Engineering
North America Inc.

While it is not possible to predict in advance each and every variance in normal operating
procedures, these instructions will attempt to;

(1) Explain fully the normal start-up and operation of this plant.

(2) Establish important control points so that any deviation will be readily apparent.

It is expected the site will develop these operating procedures further to take account of
specific operating practices used at the site. In addition, Hydro-Chem start-up personnel may
alter the procedures outlined in this manual due to unforeseen circumstances that may arise
during start-up.

It is recommended that all operating personnel become intimately familiar with plant
operating procedures in order to operate the plant safely and efficiently.

For additional and more detailed information concerning any specific piece of equipment,
refer to the mechanical specifications, manufacturer’s instructions, technical data books,
etc., which are included in the Equipment Data Manuals furnished by Hydro-Chem.

NOTE: The hydrogen plant is designed to operate using either natural gas or LPG as the
hydrocarbon feedstock. The basic process is the same whether the plant is operating on
natural gas or LPG, however, the process conditions (temperature, pressures and flows) will
vary depending on the feedstock used.

Page 6 of 85
Hydro-Chem Job A299 Hydrogen Plant Operating Manual
Ecogreen Oleochemicals 09/10/13
Batam, Indonesia Issue 1

II. PROCESS DESCRIPTION


A. GENERAL

The hydrogen generating plant is designed to produce high purity hydrogen using either a
natural gas or LPG feedstock.

Hydrogen is produced by catalytic reforming of the hydrocarbon feedstock and steam at


elevated temperatures in the vertical cylindrical Reformer furnace. Additional hydrogen is
produced by the reaction of carbon monoxide and steam in the Shift Converter.

Impurities such as carbon monoxide, methane, carbon dioxide, nitrogen and water vapor are
removed by the unique adsorption system (PSA), thus producing ultra pure hydrogen.

Fuel for the Reformer furnace is a combination of tail gas from the PSA system and either
natural gas or LPG makeup fuel.

Steam required for the process is generated by recovering waste heat at various points in the
hydrogen plant. Excess steam generated by the plant is exported to the Clients steam system.

Page 7 of 85
Hydro-Chem Job A299 Hydrogen Plant Operating Manual
Ecogreen Oleochemicals 09/10/13
Batam, Indonesia Issue 1

B. BASIS OF DESIGN

This section provides details of the feed, product and utility streams that the plant is designed
for.

1. HYDROCARBON FEED AND FUEL

The design feedstock for the hydrogen generating plant is either natural gas or LPG
having the following characteristics:
Type - Natural Gas
Composition (mol %)
Methane 87.058
Ethane 5.58
Propane 0.98
Butanes 0.49
Pentanes 0.14
Hexane 0.03
Heptane 0.03
Octane 0.02
Nonane 0.002
Carbon Dioxide 4.4
Nitrogen 1.27
Total 100

LHV (Kcal/Nm3) 8,734


HHV (Kcal/ Nm3) 9,669
Total Sulfur (mg/Nm3) max 5
C2 and mercaptans NIL
Temperature at battery limit (°C) for feed 90°C
Pressure at battery limit (Barg) min for feed 23.0
Pressure at battery limit (Barg) max for fuel 12.0
3
Natural Gas Fuel (Nm /hr) 213
3
Natural Gas Feed (Nm /hr) 2,390
3
Total Natural Gas flow (Nm /hr) 2,603

Page 8 of 85
Hydro-Chem Job A299 Hydrogen Plant Operating Manual
Ecogreen Oleochemicals 09/10/13
Batam, Indonesia Issue 1

The fuel flow rate shown above is that required when the PSA Tail Gas burner is in
operation, the ambient temperature is 33C, the relative humidity is 80% and the wind
velocity is zero. During start-up and prior to operating the PSA Tail Gas burner, the natural
gas flow to the burner will be higher. Additionally, if the ambient temperature is below 33°C
and/or the wind velocity is greater than zero, additional natural gas fuel will be required.

Type - LPG
Case 1 Case 2
Composition (mol %):
Propylene 4.0 -
Propane 29.0 32.0
Butenes 8.0 3.0
i-Butane 21.0 23.0
n-Butane 38.0 41.0
Pentane - 1.0
Total 100 100

LHV (Kcal/Nm3) 26,023 26,264


HHV (Kcal/ Nm3) 28,148 28,441
Total Sulfur (ppmw) max 50 50
Temperature at battery limit (°C) 107 107
Pressure at battery limit (Barg) min for feed 23.0 23.0
LPG Fuel (Nm3/hr) 165
LPG Feed (Nm3/hr) 742
Total LPG flow (Nm3/hr) 907

The fuel flow rate shown above is that required when the PSA Tail Gas burner is in
operation, the ambient temperature is 33C, the relative humidity is 80% and the wind
velocity is zero. During start-up and prior to operating the PSA Tail Gas burner, the LPG fuel
flow to the burner will be higher. Additionally, if the ambient temperature is below 33°C
and/or the wind velocity is greater than zero, additional LPG fuel will be required.

Page 9 of 85
Hydro-Chem Job A299 Hydrogen Plant Operating Manual
Ecogreen Oleochemicals 09/10/13
Batam, Indonesia Issue 1

2. HYDROGEN PRODUCT

The hydrogen generating plant is designed to produce a gaseous hydrogen stream of the
following characteristics:
Flow (Nm3/hr) 6,000
Purity - min (mol %) 99.99
Pressure – min (Barg) 17.2
Temperature – max (C) 38
Impurities – max (ppmv)
CO + CO2 10
Nitrogen Balance

3. EXPORT STEAM

The hydrogen generating plant is designed to export steam with the following characteristics:
Flow – Natural Gas Feedstock (Kg/hr) 4,639
Flow – LPG Case 1 Feedstock (Kg/hr) 4,064
Pressure – nom (Barg) 17.9
Temperature (C) Saturated
Solids content – max (ppm) 5

4. UTILITIES

Instrument Air
Quality Clean, dry, oil free
Particle Size – max (micron) 3
Dew Point at atmospheric pressure (C) -20
Pressure – min (Barg) 5.0
Temperature (C) Ambient
Cooling Water
Total Chlorides – max (ppmw) 5
Pressure – min (Barg) 3.5
Supply Temperature (C) 34
Return Temperature (C) 39

Page 10 of 85
Hydro-Chem Job A299 Hydrogen Plant Operating Manual
Ecogreen Oleochemicals 09/10/13
Batam, Indonesia Issue 1

Nitrogen (for purging and startup)


Quality Clean, dry, oil free
Purity – min (mol %) 99.5
Oxygen – max (mol %) 0.5
Pressure (Barg) 4.0
Temperature (C) Ambient
Electric Power
Motors 380V, 3 phase, 50Hz
Lighting / power supplies 220V, 1 phase, 50 Hz
Instrument and controls 24V DC
Boiler Feed Water
pH Range 8-10
Conductivity – max (uS/cm) 12
Total Hardness – max (ppm CaCO3) 1
SiO2 – max (ppm) 0.5
Chlorides NIL
Phosphates Traces
Iron – max (ppm) 0.2
Pressure (Barg) 29
Temperature (C) 105
Hydrogen Import (for Hydrotreating)
Flow – LPG Case 1 Feedstock (Nm3/hr) 148
Purity 99.99
Pressure – min (Barg) 22.0
Temperature – max (C) 38
Impurities – max (ppmv)
CO + CO2 10

Page 11 of 85
Hydro-Chem Job A299 Hydrogen Plant Operating Manual
Ecogreen Oleochemicals 09/10/13
Batam, Indonesia Issue 1

C. PROCESS FLOW OVERVIEW

The hydrogen plant is designed to operate using either natural gas or LPG as the hydrocarbon
feedstock. The basic process is the same whether the plant is operating on natural gas or
LPG, however, the process conditions (temperature, pressures and flows) will vary
depending on the feedstock used

If natural gas is used as the feedstock it is supplied to the battery limit at 24 barg and 90C
and if LPG is used as the feedstock it is supplied to the battery limit at 24 Barg and 107C.
The hydrocarbon feed stream then enters the Feed Heater (711-E-2) where it is heated to
343C (NG) / 316C (LPG). The feed stream exiting the Feed Heater is then mixed with a
small quantity of import hydrogen which is available at the battery limit at 22 Barg

NOTE: It is critical the heated hydrocarbon feed is mixed with import hydrogen when the
feedstock is LPG to ensure satisfactory hydrotreating and desulfurization occurs in the
downstream equipment. If natural gas is used as the feedstock and it contains no sulfur or
olefins then import hydrogen is not required.

The feed gas stream then enters the Hydro-desulfurizer (711-D-1) at the bottom of the vessel.
The lower (hydrotreating) section of this vessel is packed with hydrotreating catalyst which,
at these temperatures, converts organic sulfur compounds to H2S and hydrogenates any
olefins present in the feed gas. The upper (desulfurizing) section of the vessel is packed with
desulfurizing catalyst which retains the newly converted H2S, as zinc sulfide, in the catalyst.
H2S is a poison for the reforming catalyst.

The feed gas exits the top of Hydro-desulfurizer at 316C (NG) / 382C (LPG) and is mixed
with saturated steam from the Steam Drum (711-F-3) before entering the Feed Superheater
(711-E-6), where the stream is heated to 538C (NG) / 504C (LPG). This superheated
stream is then passed to the Reformer tubes.

In the tubes of the Reformer, the hydrocarbon and steam are heated further and react in the
presence of a catalyst to produce a mixture of hydrogen, carbon dioxide, carbon monoxide,
water, and methane. To obtain good conversion to hydrogen the Reformer tubes are heated
to achieve a process gas exit temperature from the tubes of 843C (at the end of the reformer
catalyst life).

From the Reformer tubes the stream enters the Reformer Effluent Steam Generator
(711-E-1) where the temperature is reduced from 816C to approximately 407C (NG) /
387C (LPG). The stream then passes to the Feed Heater (711-E-2), where the temperature is
further reduced by heat exchange with the feed gas from the battery limit, before being routed
to the Shift Converter (711-D-2).

The temperature of the stream entering the Shift Converter (711-D-2) is set to 343C, which
is the temperature required to achieve good conversion in the Shift Converter at the end of
the Shift Converter catalyst life.

Page 12 of 85
Hydro-Chem Job A299 Hydrogen Plant Operating Manual
Ecogreen Oleochemicals 09/10/13
Batam, Indonesia Issue 1

In the Shift Converter (711-D-2), steam and carbon monoxide react in the presence of a
catalyst to form more hydrogen and carbon dioxide. The reaction is exothermic and so there
will be a temperature rise across the Shift Converter. This temperature rise will vary
according to the plant rate, but at 100% load it will be approximately 70C (NG) / 65C
(LPG). Based on a Shift Converter inlet temperature of 343C and a plant load of 100%, it is
estimated that the process gas will exit the Shift Converter at 413C (NG) / 408C (LPG).

The process gas then flows to the Shift Effluent Steam Generator (711-E-3) where it is
cooled to 235C. The stream is then further cooled to 146C (NG) / 157C (LPG) in the
Boiler Feed Water Exchanger (711-E-4) before being passed to the Process Cooler (711-E-5)
where the gas is cooled to 38C and excess water in the stream is condensed.

The gas and condensed water then enters the Cold Condensate Separator (711-F-2), where
the condensate is collected and discharged under level control to the client’s drain system.

The gas stream exiting the Cold Condensate Separator (711-F-2) is cleaned using the five
bed PSA (Pressure Swing Adsorption) purification system, which uses the adsorption process
to produce a high purity hydrogen product stream. The waste gas produced by the
purification process is burned in the Reformer burner (711-X-1) and provides the majority of
the heat required by the endothermic reaction in the Reformer tubes. The additional heat for
this reaction is provided by a make up fuel stream.

If natural gas is used as the plant feedstock then natural gas fuel is provided to the plant
battery limit at 12 Barg and 40C. This fuel source is reduced in pressure to 2.75 Barg before
being passed to the Reformer burner (711-X-1) as the make up fuel stream. If LPG is used as
the feedstock the make up fuel stream is derived by taking a slipstream from the main LPG
feed line, reducing the pressure to 2.75 Barg and then passing it to the Reformer burner (711-
X-1) as the make up fuel stream.

Boiler feed water for the steam generating system is provided to the plant battery limit at 29
Barg and 105C by the client. The boiler feed water is pre-heated in the Boiler Feed Water
Exchanger (711-E-4) to 177C on route to the Steam Drum (711-F-3).

All of the steam needed by the process is produced by recovering waste heat from various
points in the process using the Flue Gas Steam Generator (711-E-7), Reformer Effluent
Steam Generator (711-E-1) and Shift Effluent Steam Generator (711-E-3). In addition the
waste heat recovery section has been optimized so that the plant produces excess steam,
which is exported to the Clients system. Facilities are provided on the Steam Drum (711-F-3)
for the Client to provide chemical treatment to the steam generator systems.

To ensure efficient combustion, the Reformer (711-D-8) is held at a small negative pressure
of -6.35 mm WG by Induced Draft Fan 711-G-3. Combustion air is provided to the burner by
Combustion Air Fan 711-G-4. To increase overall plant thermal efficiency the combustion
air is pre-heated to 246C in Combustion Air Pre-heater 711-E-8 and then further heated to
399C in Combustion Air Pre-heater 711-E-9, before being passed to the Reformer burner.

Page 13 of 85
Hydro-Chem Job A299 Hydrogen Plant Operating Manual
Ecogreen Oleochemicals 09/10/13
Batam, Indonesia Issue 1

D. DETAILED PROCESS DESCRIPTION

1. FEED GAS HEATING

The feed gas (natural gas or LPG and import hydrogen) flows to the Feed Heater (711-E-
2) where it is heated before entering the Hydro-desulfurizer (711-D-1). The Feed Heater
is a double pipe, multi-tube type exchanger with feed gas on the shell side and process
gas from the Reformer Effluent Steam Generator (711-E-1) on the tube side. The feed
gas is heated to 343C (NG) / 316C (LPG) by the process gas, which enters the Feed
Heater at 407C (NG) / 387C (LPG) and exits at 343C.

2. HYDROTREATING

The heated feed gas (feed gas and hydrogen) from the Feed Heater (711-E-2), which is at
approximately 343C (NG) / 316C (LPG), is passed through the Cobalt-Molybdenum
catalyst located in the bottom bed of the Hydro-desulfurizer (711-D-1). Any organic
sulfur or sulfur compounds in the feedstock are converted to hydrogen sulfide in the
presence of this catalyst at these temperatures. In addition, any olefins present are
hydrogenated. The reactions in the Hydrotreater are represented by the following
equations:
Sulfur Compound Conversion: RHS + H2 ↔ RH + H2S (1)
Olefin Conversion: CnH2n + H2 ↔ CnH2n+2 (2)

Reaction (1) is slightly exothermic but reaction (2) creates a significant exotherm of
approximately 20C per mol% in the feedstock. Both reactions are necessary as sulfur
compounds are poisonous to the Reformer catalyst and olefin slip can cause carbon
deposition on downstream equipment and catalysts.

NOTE: The hydrotreating step is critical when operating the plant on LPG feedstock as
it is expected that the feed will contain both sulfur compounds and olefins. If natural gas
is used as the feedstock and it contains no sulfur or olefins then the hydrotreating step is
redundant. However, it should be noted that operating the Hydrotreater on low sulfur
feeds (< 2 ppmv) for extended periods of time can lead to permanent partial deactivation
of the catalyst.

3. DESULFURIZING (SULFUR REMOVAL)

The heated feed gas (feed gas and hydrogen) then passes through the zinc oxide catalyst
(top bed) in the Hydro-desulfurizer (711-D-1). The hydrogen sulfide reacts with the zinc
oxide to form zinc sulfide and is absorbed by the catalyst. The reaction in non reversible
and is represented by the following equation:
ZnO + H2S → ZnS + H2O

Page 14 of 85
Hydro-Chem Job A299 Hydrogen Plant Operating Manual
Ecogreen Oleochemicals 09/10/13
Batam, Indonesia Issue 1

4. REFORMING OF STEAM/HYDROCARBON MIXTURE

The hydro-desulfurized feed gas is mixed with a controlled amount of saturated steam
before flowing to the Feed Superheater (711-E-6) and onto the catalyst tubes in the
Reformer (711-D-8). The Reformer is cylindrical in design with catalyst tubes arranged
in a circle near the insulated refractory wall. A single upfired burner is located in the base
of the Reformer to provide heat energy for the reaction within the catalyst tubes. Process
gas flow through the catalyst tubes is upwards.

The Reformer is the heart of the hydrogen generating plant. The reaction of hydrocarbon
gas with steam in the presence of a nickel reforming catalyst produces hydrogen, carbon
monoxide, carbon dioxide and methane. The Steam Methane Reforming reaction is
represented by the following equations:
General: CmHn + nH2O ↔ (n/2 + m)H2 +mCO
Methane: CH4 + H2O ↔ 3H2 + CO
The reforming reaction is highly endothermic (i.e. requires a large heat supply) and must
take place under carefully controlled external firing conditions. In addition to the
reforming reaction, a partial water gas shift reaction occurs in the Reformer. The water
gas shift reaction is represented by the following equation:
CO + H2O ↔ CO2 + H2
To obtain good conversion to hydrogen the Reformer tubes are heated so that the process
gas exiting the tubes is at approximately 843C (at the end of the reformer catalyst life).
This exit temperature can be lowered and good conversion still achieved when the
catalyst is new.

Flue gas leaves the Reformer at 1,010C and is used to superheat the feed gas / steam
mixture in the Feed Superheater (711-E-6) before being used to preheat the combustion
air in Combustion Air Pre-heaters (711-E-9 and 711-E-8) and raise steam in the Flue Gas
Steam Generator (711-E-7). The flue gas is then discharged to atmosphere at 144C (NG)
/ 147C (LPG).

5. CARBON MONOXIDE SHIFT CONVERSION

The hot process gas exiting the Reformer flows to the Reformer Effluent Steam
Generator (711-E-1) and then passes through Feed Heater (711-E-2), before entering the
Shift Converter (711-D-2). The temperature of the stream entering the Shift Converter is
controlled at approximately 343C (at the end of the Shift Converter catalyst life). The
Shift Converter (711-D-2) is packed with chromium promoted iron oxide catalyst, which
at this temperature promotes the water-gas shift reaction, and converts carbon monoxide
in the process gas stream to carbon dioxide and hydrogen as follows:
CO + H2O ↔ CO2 + H2

Page 15 of 85
Hydro-Chem Job A299 Hydrogen Plant Operating Manual
Ecogreen Oleochemicals 09/10/13
Batam, Indonesia Issue 1

The water-gas shift reaction is exothermic and so there will be a temperature rise across
the Shift Converter in operation. This temperature rise will vary according to the plant
rate, and at 100% load will be approximately 70C (NG) / 65C (LPG). Based on a Shift
Converter inlet temperature of 343C and a plant load of 100%, it is estimated that the
process gas will exit the Shift Converter at 413C (NG) / 408C (LPG).

NOTE: The Shift Converter catalyst can become “temperature set” when operated at a
given temperature for an extended period of time, although newer shift converter
catalysts are less prone to this that some older catalysts. Irrespective of whether the
catalyst is susceptible to ‘temperature set’ or not it is recommended that the Shift
Converter is always operated at the lowest possible temperature to achieve the design
conversion. This enables the temperature of the Shift Converter to be increased when the
conversion rate falls, as the catalyst ages, and thereby prolong the life of the catalyst.

6. PROCESS GAS COOLING SYSTEM

From the Shift Converter the process gas flows to the Shift Effluent Steam Generator (711-
E-3) where it is cooled to 235C. The process gas then enters the exchanger train where it
is progressively cooled.

The first exchanger in the exchanger train is the Boiler Feed Water Exchanger (711-E-4),
which is a double pipe, multi-tube type exchanger with BFW on the shell side and process
gas on the tube side. The BFW is pre-heated by the process gas from 105C to 177C on
route to the Steam Drum (711-F-3). The process gas exiting the exchanger is cooled to
146C (NG) / 157C (LPG) before entering the Process Cooler (711-E-5).

The Process Cooler (711-E-5) is the final exchanger in the train and is a shell and tube type
exchanger, with process gas on the shell side and cooling water on the tube side. The
process gas is cooled in the exchanger to 38C and excess water in the stream is condensed.

The gas and condensed water then enters the Cold Condensate Separator (711-F-2), where
the condensate is collected, before the crude hydrogen gas stream is passed to the PSA
purification system.

The process condensate is discharged from the Cold Condensate Separator (711-F-2) under
level control to the client’s drain system.

7. HYDROGEN PURIFICATION SYSTEM (PSA)

For details of the PSA process refer to the PSA PROCESS section of the manual.

After purification by the PSA, the high purity hydrogen product is available to the Client at
approximately 17.2 Barg.

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8. PSA TAIL GAS RECOVERY SYSTEM

Waste gas produced when the PSA is regenerated (from the blow down and purge steps)
is collected in the Tail Gas Drum (711-F-1) and is used as the primary fuel for the
Reformer burner (711-X-1). The Tail Gas Drum (711-F-1) is designed to minimize the
fluctuations in waste gas pressure imposed by the PSA as it cycles, with the expected
pressure variation during normal operation being from approximately 0.2 Barg to 1.0
Barg.

In addition, as the waste gas from the PSA varies in composition, the Tail Gas Drum
(711-F-1) also provides mixing of the waste gas stream, using an internal distribution
pipe within the vessel, to ensure the waste gas fuel to the Reformer burner is of a near
uniform calorific value.

Whenever the PSA is offline, no waste gas is available for the burner. Facilities are
therefore provided to route a slipstream of crude hydrogen directly from the Cold
Condensate Separator (711-F-2) to the Tail Gas Drum (711-F-1) to cater for these
circumstances.

9. REFORMER BURNER SYSTEM

The Reformer burner (711-X-1) consists of a single upfired burner located in the floor of
the Reformer and is used to provide heat to the Reformer tubes. The burner is capable of
firing either natural gas (or LPG gas) and hydrogen rich PSA waste gas simultaneously.
The burner operates in conjunction with a single Induced Draft Fan (711-G-3) and a
single Forced Draft Fan (711-G-4). The Reformer is held at a negative pressure of -6.35
mmWG by the Induced Draft Fan (711-G-3) during operation. The combustion air to the
burner is first heated to 246C in Combustion Air Preheater (711-E-8) by heat exchange
with the hot flue gas exiting the Flue Gas Steam Generator (711-E-7) and then further
heated to 399C in Combustion Air Preheater (711-E-9) by heat exchange with the hot
flue gas exiting the Feed Superheater (711-E-6).

The burner consists of three components, namely:

 Pilot burner

 Make-up Gas burner, which refers to the make-up gas firing part of the burner and
can be fired with either natural gas or LPG make up fuel. The make up fuel used
depends on whether the plant feedstock is natural gas or LPG.

 PSA Tail Gas burner, which refers to the hydrogen rich PSA waste gas firing part of
the burner.

The pilot burner is configured as a single interrupted gas pilot and is used to light the
Make-up Gas Burner at start-up.

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The Make-up Gas Burner is made up of a number of gas pokers located around the
circumference of the burner tile. The design heat release of the Make-up Gas burner is
6.25MW (NG) / 6.51MW (LPG) based on the expected lower heating value (LHV) of the
fuel gas.

The PSA Tail Gas burner consists of a single gas poker located in the centre of the burner
tile. The PSA Tail Gas burner is only used whilst the Make-up Gas burner is in operation.
Facilities are provided to allow crude hydrogen to be fired by the PSA Tail Gas burner
when the Reformer is in service but no PSA tail gas is available. The design heat release
of the PSA Tail Gas burner is 12.82 MW based on the lower heating value (LHV) of the
hydrogen rich PSA tail gas.

A single self checking UV flame scanner (BE-700) is used to supervise the Pilot Burner
and Make-up Gas Burner during operation when the Reformer firebox temperature is
below 760C. No separate flame monitoring system is provided or required on the PSA
Tail Gas Burner.

10. STEAM GENERATION AND BLOW DOWN SYSTEM

Heat is recovered from various parts of the process and used to generator steam in the
Flue Gas Steam Generator (711-E-7), the Reformer Effluent Steam Generator (711-E-1)
and the Shift Effluent Steam Generator (711-E-3). The generated steam is used for the
process, with any excess steam produced being exported to the Clients steam system.

As steam is continuously being liberated from the Steam Generators, the dissolved solids
in the Steam Generator makeup water are left behind and will begin to concentrate in the
Steam Generators. A continuous blow down is provided on the Steam Drum (711-F-3)
and bottom blow downs are provided at the low point of each of the Steam Generators to
keep the build up of solids under control. The frequency and length of use of the bottom
blow downs should be determined by a specialist water treatment company with expertise
in steam systems.

The blow down effluent liberated from the system is routed to the Blowdown Drum (711-
F-4) where the flash steam is released to atmosphere and the residual condensate is
collected and discharged to the client’s open drain system.

Deaerated BFW for the steam system is provided to the plant battery limit by the client at
29 Barg and 105C. The BFW is pre-heated by process gas in the Boiler Feed Water
Exchanger (711-E-4) to 177C on route to the Steam Drum (711-F-3).

Facilities are provided to enable chemicals to be injected into the Steam Drum (711-F-3)
to control the quality of the water in the steam system. A specialist water treatment
company with expertise in steam systems should be engaged by the Client to determine a
suitable chemical treatment regime and ongoing monitoring of the Steam Generator
water quality.

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III. GENERAL DISCUSSION OF KEY PROCESS POINTS


A. HYDROTREATING AND DESULFURIZING

The hydrotreating catalyst (lower bed) in the Hydro-desulfurizer (711-D-1) contains cobalt
oxide / molybdenum oxide, which in the presence of hydrogen and at a temperature of
approximately 300C to 399C will convert any organic sulfur compounds in the feed gas to
hydrogen sulfide. In addition, the catalyst will convert any olefins in the feed gas to saturated
hydrocarbons. Both of these conversions are desirable and necessary.

The desulfurizer catalyst upper bed in the Hydro-desulfurizer (711-D-1) contains zinc oxide,
which at a temperature of approximately 300C to 399C will convert the hydrogen sulfide
generated by the hydrotreating catalyst to zinc sulfide. The zinc sulfide is then retained in the
catalyst bed.

The following operating variables affect the performance of the hydrotreating and
desulfurizing catalysts:

a. Flow rate of feed gas.

b. Type and amount of sulfur and olefins in the feed gas.

c. Pressure of operation.

d. Temperature of operation.

e. Hydrogen (hydrotreating) flow rate.

The control of the above operating variables is largely determined by factors not associated
with the hydrotreating or the desulfurization process. For example, the type and amount of
olefins and sulfur compounds are determined by the composition of the feedstock and the
flow rate in the vessel is determined by the capacity at which the hydrogen plant is operated.

However, it should be noted that the efficiency of the hydrotreating and the desulfurization
process increases greatly as the feed gas flow is decreased or the operating pressure is
increased. The amount of sulfur absorption is enhanced if the sulfur compounds are in the
form of mercaptans and disulfides. If large quantities of sulfur compounds are in the feed,
this will necessitate the replacement of the desulfurizing catalyst in a shorter period than
originally expected.

Temperature is the main operating variable that can be used to optimize the performance of
the hydro-desulfurizer. With all other conditions remaining constant, an increase in the
operating temperature results in an increase in the amount and type of sulfur compounds
converted to hydrogen sulfide, which subsequently increases the sulfur removal capability of
the desulfurizer.

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However, temperatures above 400C should be avoided due to the potential for hydrocarbon
cracking on the surface of the catalyst and absorbent.

It is also evident that if the olefins content of the feedstock increases the hydrogen injection
flow must also increase to ensure complete hydrogenation and avoid olefin drive carbon
formation reactions in the downstream equipment. As the hydrogenation reaction is
exothermic the overall quantity of olefins that can be processed by the hydrotreater is limited
to ensure the maximum bed temperature remains below 400C.

The hydrotreating catalyst bed has been sized for 5 years operation and the desulfurizer bed
for 1 year operation, based on continuous plant operation at 100% load with the worst case
design feedstock. The sulfur loading of the desulfurizer bed must be checked periodically
using the sample points provided on vessel 711-D-1 and the zinc oxide catalyst replaced
before any sulfur breakthrough occurs, as sulfur breakthrough will poison the Reformer
catalyst. In addition, periodic checks should be made on the amount of olefins leaking from
the hydrotreating bed to prevent olefin driven carbon formation reactions in the downstream
equipment.

The pressure drop across the catalyst beds should also be checked periodically. An increase
in pressure drop may indicate catalyst breakdown or fouling and the beds should then be
inspected and replaced as necessary.

NOTE: The hydrotreating step is critical when operating the plant on LPG feedstock as it is
expected that the feed will contain both sulfur compounds and olefins. If natural gas is used
as the feedstock and it contains no sulfur or olefins then the hydrotreating step is redundant.
However, it should be noted that operating the Hydrotreater on low sulfur feeds (< 2 ppmv)
for extended periods of time can lead to permanent partial deactivation of the catalyst.

B. STEAM / HYDROCARBON REFORMING

The operation of the Reformer (711-D-8) is the most critical in the operation of the plant. If
the Reformer is not operated properly, significant load is put on the purification system and
this is then likely to affect hydrogen product purity. The major variables in the operation of
the Reformer are:

a. Reformer outlet temperature

b. Reformer outlet pressure

c. Steam/carbon ratio

The best indication of whether the Reformer is operating satisfactorily is the percentage of
methane in the Reformer outlet. The design value of methane leakage from the Reformer is
3.8 mol% (NG) / 1.9mol% (LPG) on a wet basis, which equates to 5.9 mol% (NG) /
3.3mol% (LPG) on a dry basis.

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1. METHANE LEAKAGE

The percent of methane in the Reformer outlet is closely related to the operating pressure
and temperature of the Reformer outlet gas and the steam/carbon ratio of the Reformer
feed.

The following general operating trends can be observed, with all other conditions
constant.

a. As the Reformer outlet pressure is increased, methane leakage from the Reformer
increases.

b. As the Reformer outlet temperature is increased, methane leakage from the Reformer
decreases.

c. As the steam/carbon ratio in the Reformer inlet is increased, methane leakage from
the Reformer decreases.

The Reformer operating pressure, temperature, and feed gas steam/carbon ratio are all
controlled variables.

C. REFORMER BURNER

The reaction in the catalyst tubes is highly endothermic and therefore requires additional heat
to be added to the Reformer. This is achieved using a single, upfired burner mounted in the
Reformer base.

1. REFORMER DRAFT

The burner requires a minimum draft to meet the heat liberation requirement. The draft is
controlled by PDIC-601, which adjusts the speed of the Induced Draft Fan (711-G-3) to
maintain the required draft. The Induced Draft Fan (711-G-3) sucks the Reformer flue
gas through the Feed Superheater (711-E-6), the Combustion Air Preheater (711-E-9),
the Flue Gas Steam Generator (711-E-7) and the Combustion Air Preheater (711-E-8)
and discharges it to the atmosphere at 144C (NG) / 147C (LPG).

2. BURNER FIRING CONDITIONS

The burner should be operated to provide a flame that is as short and slender as possible.
The burner should, at no time be fired, in a manner that causes the flame to impinge on
the catalyst tubes.

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The burner is designed to be fired using ten percent excess air to achieve satisfactory
combustion. It is possible to operate the burner with lower excess air rates and this may,
in fact, be desirable as it increases Reformer efficiency. However, if the flue gas analysis
indicates that carbon monoxide is present then the amount of excess air should be
increased to ensure complete combustion.

If carbon monoxide is present in the flue gas, after-burning can occur in the waste heat
section of the plant, and is normally evident by a rapid increase in temperature in this part
of the plant. Immediate steps should be taken to correct this condition, or severe damage
could result to the equipment and structures. In this case the firing rate of the burner
should be reduced or the combustion air flow increased. The firing rate may then be
increased back to the desired rate when the after burning stops. If this does not solve the
problem, then the firing rate must be reduced substantially until after-burning ceases,
before the rate can be increased.

If the firing rate has to be increased beyond the normal rate to maintain plant output, with
no other signs of malfunction, loss of catalyst activity is indicated. If it is determined that
sulfur poisoning is the source of this trouble, refer to the operating procedure on
temporary sulfur poisoning of the catalyst which details what actions to take.

Note: As the Reformer catalyst ages and loses activity the Reformer outlet temperature
will need to be increased to maintain the required hydrogen product rate. Operating
Reformer tubes at the lowest temperature possible to achieve the desired hydrogen
product rate will extend the catalyst life as well as the expected Reformer tube life.
Excessive temperatures will decrease both of these.

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D. INDICATIONS OF FAULTY REFORMER / BURNER OPERATION

The following table provides general information on typical problems encountered with the
Reformer and possible causes.

Indication Reasons

High Reformer firebox pressure Heat release too high / insufficient or


excess combustion air

High pressure drop across Reformer tubes Carbon build-up / high flow rate /
catalyst attrition / steam carryover -
solids on catalyst

Low pressure drop across Reformer tubes Low feed / steam flow

Tube hot spots Uneven catalysts packing / carbon


build-up / catalyst attrition / loss of
catalyst activity

Positive pressure in firebox Reformer draft set too low /


excessive firing rate

Over firing to maintain production Loss of catalyst activity

Excessive temperature in firebox Over firing / incorrect combustion air

E. CO SHIFT CONVERSION

The high temperature Shift Converter (711-D-2) converts approximately 68% (NG) / 73%
(LPG) of the CO in the Reformer effluent outlet gas to H2 and CO2. The water-gas shift
reaction is dependent upon temperature, the quantity of excess steam and process gas flow
and is moderately exothermic. Pressure has no effect on the reaction.

Temperature is an important operating variable that can be used to optimize performance of


the Shift Converter. The higher the temperature, the faster the rate of reaction, but the lower
the equilibrium is. Hence, for a given catalyst activity, there is an optimum temperature. At
the start of operation it is possible, and desirable, to operate the Shift Converter at relatively
low inlet temperatures (310 - 315C) and still achieve design CO conversion due to the high
activity of the new catalyst. Operation with the lowest possible inlet temperature will extend
the life of the shift catalyst. As the catalyst ages the inlet temperature should then be
increased to maintain the design conversion.

An increase in excess steam also favors the forward water-gas shift reaction to generate more
hydrogen.

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Periodic checks should be made on the pressure drop over the Shift Converter. The normal
pressure drop is very low (0.07 - 0.2 Barg), however, over a period of time, catalyst
breakdown and/or fouling can cause this to increase.

Condensate should be avoided at all times on the catalyst bed. During start-up, with the Shift
Converter cold, care should be taken to minimize condensation build up in the vessel by
either pre-heating the vessel with nitrogen and/or draining any condensate through the drain
valve downstream of the vessel.

E. STEAM GENERATOR WATER TREATMENT OBJECTIVES

1. GENERAL

Boiler feed water, regardless of the type and extent of external treatment, may contain
contaminants that can cause deposits, corrosion, and carryover. Deposits will reduce heat
transfer, resulting in higher fuel consumption, higher metal temperatures, and could lead to
eventual equipment failure. Whilst deposits are most serious in the heat recovery units
themselves, they may also cause problems in equipment located either before or after the
Steam Generator systems.

Corrosion not only results in failure at the point of attack, but also produces serious levels of
metal oxide contamination, which may cause deposits elsewhere in the steam system.
Problems of deposit formation and corrosion are present in any water-steam system. These
conditions must be carefully controlled to achieve satisfactory results. Poor control of the
deaerated water treatment will inevitably result in oxygen pitting in the steam system.

Water carryover from the Steam Generators to the Reformer catalyst can easily occur due to
foaming in the Steam Drum (711-F-3). Even low levels of carryover may damage the catalyst
and result in a reduction of plant capacity.

Therefore, the three main objectives of Steam Generator water treatment can be summarized
as follows:

a. Prevent formation of deposits by application of chemical treatments.

b. Reduce corrosion of metals by removal of dissolved oxygen and carbon dioxide.

c. Prevent boiler water carryover to catalyst by application of dispersants and anti-


foaming agents.

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2. CHEMICAL DOSING OF STEAM GENERATOR WATER

It is recommended that a local company with expertise in water treatment is engaged by the
Client to provide a suitable chemical treatment regime and ongoing monitoring of the Steam
Generator water quality.

Typically, the chemical dosing regime will consist of the following elements:

(1) An oxygen scavenger to eliminate any residual oxygen in the water after
deaeration.

(2) pH control to maintain a basic pH in the boiler.

(3) Internal treatment and iron control to minimize corrosion.

(4) Filming chemicals to protect the steam condensate systems.

It is extremely important that this treatment is started when the steam system is
commissioned to ensure proper clean up of the entire steam system and provide corrosion
protection for all plant metal surfaces that the steam will come into contact with, including
the plant catalysts.

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IV. HYDROGEN PURIFICATION SYSTEM - PSA


A. PSA PROCESS

The purification system is a five bed system which uses the adsorption process to produce a
high purity hydrogen product stream. Crude hydrogen from the Cold Condensate Separator
(711-F-2) flows upwards through an adsorber vessel filled with adsorbent material. The
adsorbent is a granular material that attracts and traps (adsorbs) the impurities in the crude
hydrogen allowing clean hydrogen to be discharged from the top of the vessel. The adsorbent
can only adsorb a given quantity of impurity and once the adsorbent becomes saturated with
impurities it must be taken off line and cleaned. The adsorption process is reversible and
depressurizing the vessel causes the adsorbent to release the impurities. The adsorption
process is exothermic and the desorption process is endothermic. The loading of the
adsorbent material is both pressure and temperature dependent, with an increase in loading
capability being favored by lower temperatures and higher pressures.

The PSA system uses five identical adsorber vessels (711-D-3, 711-D-4, 711-D-5, 711-D-6
and 711-D-7) to maintain a continuous flow of pure hydrogen. One vessel is always online
whilst the other four are in various stages of regeneration.

Each vessel contains three adsorbent beds in series:

 The first (lower) bed contains alumina. The purpose of this bed is to remove water
from the gas stream as the subsequent adsorbent beds strongly adsorb water. Any
water slippage from this bed will be preferentially adsorbed in the subsequent beds.
The binding forces of the water molecules to the adsorbent material in the
downstream beds are strong causing difficulties in regenerating the adsorbent during
the desorption steps. Water slippage from the alumina bed can therefore lead to a
permanent deactivation of the adsorber bed.

 The second (middle) bed contains activated carbon. The purpose of this bed is to
remove CO2, CH4, C2 and N2.

 The third (top) bed contains zeolithical molecular sieve. The purpose of this bed is to
remove CO and N2.

The design RUN period (Adsorption time for each PSA vessel) is 4.5 minutes when
operating at a plant capacity of 100%. This RUN period is extended when the plant is
operating at less than 100% capacity to increase plant efficiency. The following provides an
overview of the 15 steps which each PSA vessel will automatically cycle through when the
PSA is in operation. Note that the step descriptions correspond to the operation of adsorber
vessel 711-D-3.

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Step 1 - Run (adsorption of impurities; hydrogen goes to product).

Step 2 - Run (adsorption of impurities; hydrogen goes to product).

Step 3 - Run (adsorption of impurities; hydrogen goes to product).

Step 4 - First depressurization (HP equalize to another vessel).

Step 5 – Hold (all PSA valves on the vessel closed).

Step 6 - Second depressurization (LP equalize to another adsorber).

Step 7 - Hold (all PSA valves on the vessel closed).

Step 8 - Third depressurization (provide purge to another vessel).

Step 9 - Fourth depressurization (Blow down to the Tail Gas Drum 711-F-1).

Step 10 - Blowdown (vessel is pressure equalized with Tail Gas Drum 711-F-1).

Step 11 - Receive Purge (purge with hydrogen from another vessel).

Step 12 - First repressurization (LP equalize from another adsorber).

Step 13 - Second repressurization (HP equalize from another adsorber).

Step 14 - Third repressurization (repressurize using product hydrogen).

Step 15 - Final Repressurization (repressurize using product hydrogen).

B. DESCRIPTION OF THE PSA STEPS

Each PSA vessel will automatically cycle through a series of 15 steps, which consist of a
number of adsorption steps and regeneration steps. The following sections describe the PSA
steps in further detail. Where the description refers to co-current flow it means that flow is in
the same direction as the PSA feed flow (i.e. from the bottom of the vessel to the top).
Conversely when it refers to counter-current flow it means in the opposite direction to the
PSA feed flow (i.e. from the top of the vessel to the bottom). Reference should also be made
to the PSA Stepping Logic drawing 2910A299-000-P-FP-1017.

ADSORPTION – RUN (3 STEPS)

The adsorption steps for each vessel are as follows:

 Vessel 711-D-3 steps 1,2,3

 Vessel 711-D-4 steps 4,5,6

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 Vessel 711-D-5 steps 7,8,9

 Vessel 711-D-6 steps 10,11,12

 Vessel 711-D-7 steps 13,14,15

During the adsorption step the PSA feed gas enters the adsorber at the bottom of the vessel
and flows upward to the top. Impurities are selectively retained (adsorbed) within the
adsorbent beds and clean hydrogen flows from the top of the vessel. As more feed gas is
processed by the vessel the impurity front will advance towards the top of the vessel. The
adsorber must therefore be taken offline for regeneration before the impurity front reaches
the outlet of the vessel, otherwise impurities will be seen in the hydrogen product.

FIRST DEPRESSURIZATION – HP EQUALISATION

To make the PSA process more efficient, as much hydrogen as possible is saved from the
vessel that has completed its RUN cycle by progressively decanting the clean hydrogen into
other vessels. The first of these steps is the high pressure equalization step. The high pressure
equalization step for each of the vessels is as follows:

 Vessel 711-D-3 equalizes to 711-D-5 on step 4

 Vessel 711-D-4 equalizes to 711-D-6 on step 7

 Vessel 711-D-5 equalizes to 711-D-7 on step 10

 Vessel 711-D-6 equalizes to 711-D-3 on step 13

 Vessel 711-D-7 equalizes to 711-D-4 on step 1

During this step the adsorber that has just completed its RUN cycle is depressurized co-
currently to an intermediate pressure (HP equalization pressure), and the hydrogen gas used
to partially repressurize a lower pressure vessel. The impurity front in the depressurizing
vessel will advance further to the top of the vessel.

The pressures in the two vessels should equalize within 43 to 45 seconds, with the overall
step time set to 45 seconds. If the equalization occurs too quickly then the adsorbents can be
damaged leading to a loss of PSA capacity. PSA valves KV-503A/B/C/D/E are automatically
throttled to adjust the equalization time. Opening these valves will result in faster pressure
equalization, and conversely closing these valves will result in slower pressure equalization.
The valve openings will be set at commissioning and unless the PSA valves are serviced,
should need no further adjustment.

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SECOND DEPRESSURIZATION – LP EQUALIZATION

Following the HP equalization step all the PSA valves on the depressurizing vessel are
closed and the vessel is held in this condition for a step waiting for the LP equalization step.
Once the LP equalization step is initiated, the adsorber that was on HOLD is depressurized
co-currently to an intermediate pressure (LP equalization pressure), and the hydrogen gas
used to partially repressurize a lower pressure vessel. The impurity front in the
depressurizing vessel will advance further to the top of the vessel.

The low pressure equalization step for each of the vessels is as follows:

 Vessel 711-D-3 equalizes to 711-D-6 on step 6

 Vessel 711-D-4 equalizes to 711-D-7 on step 9

 Vessel 711-D-5 equalizes to 711-D-3 on step 12

 Vessel 711-D-6 equalizes to 711-D-4 on step 15

 Vessel 711-D-7 equalizes to 711-D-5 on step 3

The pressures in the two vessels should equalize within 43 to 45 seconds, with the overall
step time set to 45 seconds. PSA valves KV-503A/B/C/D/E are automatically throttled to
adjust the equalization time. Opening these valves will result in faster pressure equalization,
and conversely closing these valves will result in slower pressure equalization. The valve
openings will be set at commissioning and unless the PSA valves are serviced, should need
no further adjustment.

THIRD DEPRESSURIZATION – PROVIDE PURGE

Following the LP equalization step all the PSA valves on the depressurizing vessel are closed
and the vessel is held in this condition for a step waiting for the PROVIDE PURGE step.
Once the PROVIDE PURGE step is initiated, the adsorber that was on HOLD then provides
a hydrogen purge to a lower pressure vessel. The steps are:

 Vessel 711-D-3 provides purge to 711-D-7 on step 8

 Vessel 711-D-4 provides purge to 711-D-3 on step 11

 Vessel 711-D-5 provides purge 711-D-4 on step 14

 Vessel 711-D-6 provides purge to 711-D-5 on step 2

 Vessel 711-D-7 provides purge to 711-D-6 on step 5

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During this step the high pressure vessel is depressurized co-currently until the purge end
pressure is reached. The hydrogen flows into the top of the vessel being purged and sweeps
the impurities collected by the adsorbents to the bottom of this vessel and out to the Tail Gas
Drum (711-F-1). The impurity front in the depressurizing vessel will advance further to the
top of the vessel.

The time available for the purge step is 3 minutes at 100% PSA capacity. PSA valves KV-
503A/B/C/D/E are throttled to set the purge time and PSA valves KV-504A/B/C/D/E are
ramped open during this step.

FOURTH DEPRESSURIZATION – BLOW DOWN

The blow down steps for each of the vessels is as follows:

 Vessel 711-D-3 blows down on step 9

 Vessel 711-D-4 blows down on step 12

 Vessel 711-D-5 blows down on step 15

 Vessel 711-D-6 blows down on step 3

 Vessel 711-D-7 blows down on step 6

During the blow down step the vessel is depressurized counter-currently to the Tail Gas
Drum (711-F-1), where the residual hydrogen and some impurities in the adsorber vessel are
collected.

The blow down is completed at the same time as the LP equalization of two other vessels is
occurring (45 seconds). PSA valves KV-504A/B/C/D/E are opened to enable blow down to
711-F-1.

Following the initial BLOW DOWN the PSA valve (KV-504A/B/C/D/E) of the vessel that
has just blown down remains open for the next step to ensure the PSA vessel pressure and
Tail Gas Drum pressure are equalized.

RECEIVE PURGE

The vessel that has just been depressurized to, and pressure equalized with, the Tail Gas
Drum (711-F-1) is now purged. The steps are:

 Vessel 711-D-3 receives purge from 711-D-4 on step 11

 Vessel 711-D-4 receives purge from 711-D-5 on step 14

 Vessel 711-D-5 receives purge from 711-D-6 on step 2

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 Vessel 711-D-6 receives purge from 711-D-7 on step 5

 Vessel 711-D-7 receives purge from 711-D-3 on step 8

During this step the vessel receiving the purge is cleaned by a flow of hydrogen from the top
of the vessel to the bottom and out to the Tail Gas Drum (711-F-1). The impurity front is
returned to the bottom of the vessel.

The time available for the purge step is 3 minutes at 100% PSA capacity. PSA valves KV-
503A/B/C/D/E are throttled to set the purge time and PSA valves KV-504A/B/C/D/E are
ramped open during this step.

VESSEL REPRESSURIZATION

Once the adsorber has been purged it must be returned to operating pressure before it can be
placed back into service. This is achieved in three stages as follows:

FIRST REPRESSURIZATION

Equalizing with another vessel during the LP equalization step (see previous description
of this step). The flow of hydrogen into the vessel being re-pressurized is from the top of
the vessel (counter-current).

SECOND REPRESSURIZATION

Equalizing with another vessel during the HP equalization step (see previous description
of this step). The flow of hydrogen into the vessel being re-pressurized is from the top of
the vessel (counter-current).

THIRD REPRESSURIZATION

The final repressurization is achieved by using a slip stream of pure hydrogen from the
hydrogen product line. The flow of hydrogen into the vessel being re-pressurized is from
the top of the vessel (counter-current). Once the vessel is repressurized to the operating
pressure it is then placed back into service. The repressurizing hydrogen flow is
controlled with FIC-204 and it is the setting on this controller that will ultimately
determine the PSA cycle time. Increasing the repressurization flow will cause the vessel
to be repressurized quicker and reduce the cycle time. Conversely reducing this flow will
cause the vessel to take longer to repressurize and thereby increase the cycle time. When
the PSA is operating at 100% capacity the repressurization time is expected to be 3.75
minutes. During normal operation the setting of FIC-204 will be automatically adjusted
to increase or decrease the PSA capacity to match the plant capacity.

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Hydro-Chem Job A299 Hydrogen Plant Operating Manual
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C. VESSEL STATUS FOR EACH PSA STEP
The following table provides details of the status of each vessel on the 15 PSA steps.
STEP 711-D-3 STATUS 711-D-4 STATUS 711-D-5 STATUS 711-D-6 STATUS 711-D-7 STATUS STEP TIME AT 100%
No CAPACITY (Sec)
Pressure (Barg) Pressure (Barg) Pressure (Barg) Pressure (Barg) Pressure (Barg)
RUN HP EQ FROM 711-D-7 HOLD HOLD HP EQ TO 711-D-4
1 45
17.93 6.51 TO 12.68 0.34 6.51 17.93 TO 12.68
RUN REPRESS PURGE FROM 711-D-6 PURGE TO 711-D-5 HOLD
2 180
17.93 12.68 TO 17.00 0.34 6.51 TO 2.76 12.68
RUN REPRESS LP EQ FROM 711-D-7 BLOW DOWN LP EQ TO 711-D-5
3 45
17.93 17.00 TO 17.93 0.34 TO 6.51 2.76 TO 0.34 12.68 TO 6.51
HP EQ TO 711-D-5 RUN HP EQ FROM 711-D-3 HOLD HOLD
4 45
17.93 TO 12.68 17.93 6.51 TO 12.68 0.34 6.51
HOLD RUN REPRESS PURGE FROM 711-D-7 PURGE TO 711-D-6
5 180
12.68 17.93 12.68 TO 17.00 0.34 6.51 TO 2.76
LP EQ TO 711-D-6 RUN REPRESS LP EQ FROM 711-D-3 BLOW DOWN
6 45
12.68 TO 6.51 17.93 17.00 TO 17.93 0.34 TO 6.51 2.76 TO 0.34
HOLD HP EQ TO 711-D-6 RUN HP EQ FROM 711-D-4 HOLD
7 45
6.51 17.93 TO 12.68 17.93 6.51 TO 12.68 0.34
PURGE TO 711-D-7 HOLD RUN REPRESS PURGE FROM 711-D-3
8 180
6.51 TO 2.76 12.68 17.93 12.68 TO 17.00 0.34
BLOW DOWN LP EQ TO 711-D-7 RUN REPRESS LP EQ FROM 711-D-4
9 45
2.76 TO 0.34 12.68 TO 6.51 17.93 17.00 TO 17.93 0.34 TO 6.51
HOLD HOLD HP EQ TO 711-D-7 RUN HP EQ FROM 711-D-5
10 45
0.34 6.51 17.93 TO 12.68 17.93 6.51 TO 12.68
PURGE FROM 711-D-4 PURGE TO 711-D-3 HOLD RUN REPRESS
11 180
0.34 6.51 TO 2.76 12.68 17.93 12.68 TO 17.00
LP EQ FROM 711-D-5 BLOW DOWN LP EQ TO 711-D-3 RUN REPRESS
12 45
0.34 TO 6.51 2.76 TO 0.34 12.68 TO 6.51 17.93 17.00 TO 17.93
HP EQ FROM 711-D-6 HOLD HOLD HP EQ TO 711-D-3 RUN
13 45
6.51 TO 12.68 0.34 6.51 17.93 TO 12.68 17.93
REPRESS PURGE FROM 711-D-5 PURGE TO 711-D-4 HOLD RUN
14 180
12.68 TO 17.00 0.34 6.51 TO 2.76 12.68 17.93
REPRESS LP EQ FROM 711-D-6 BLOW DOWN LP EQ TO 711-D-4 RUN
15 45
17.00 TO 17.93 0.34 TO 6.51 2.76 TO 0.34 12.68 TO 6.51 17.93

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Hydro-Chem Job A299 Hydrogen Plant Operating Manual
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D. PSA CONTROLS AND INDICATIONS

The following PSA functions are provided to the Operator to be able to control the operation
of the PSA. Once the PSA is online no Operator input should be necessary as the stepping
sequence is fully automatic.

1. START / STOP SELECTOR SWITCH

A selector switch is provided for the Operator to stop and start the PSA. When the PSA is
selected to STOP all the PSA switching valves will close and the PSA sequence will halt at
the current step. When the PSA is selected to START the sequence will commence cycling
from the current step and the PSA switching valves will automatically open and close based
on the step that the sequence is operating in (see the PSA Stepping Logic drawing).

2. START UP / OPERATE SELECTOR SWITCH

During normal operation the PSA is set to OPERATE mode. In this mode the HP and LP
equalization steps will only be completed when the equalization timer has expired and the
pressure within the two equalizing vessels falls within a preset maximum and minimum
limit, which should normally occur within the equalization time. If the equalizing pressure is
not within the preset limits once the equalization time has expired, the step will automatically
be extended until it is.

When in START UP mode the HP and LP steps will be completed based on the equalization
timer only. This is to ensure that when the PSA is started it will cycle correctly even if the
vessel pressures are not at the pressure expected for normal operation.

Also when the PSA is set to START UP mode it is not possible to select the PSA to
PRODUCT mode (see VENT / PRODUCT SWITCH section) and the long cycle time shut
down (see next section) is bypassed. The START UP mode is selected automatically when
the PSA stops.

3. LONG CYCLE TIME SHUTDOWN (LCT)

A long cycle time is considered to be when a PSA vessel remains on the RUN step for 15%
longer than the expected run time for that PSA capacity. This can happen when a particular
pressure required to step the PSA on is not satisfied and is mainly caused by PSA switching
valve malfunctions. If a vessel remains in RUN for too long, impurities will leak from the top
of the vessel and contaminate the hydrogen product. Therefore the system detects a long
cycle time and automatically shuts down the PSA.

The LCT shut down is active when the PSA is in OPERATE mode and automatically
bypassed when the PSA is in START UP mode.

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4. PAUSE / CONTINUE SWITCH AND MANUAL STEP

When PAUSE mode is selected the PSA sequence will stop at the current step and not cycle
any further. If the PSA is operating at the time PAUSE is selected all the PSA switching
valves maintain their positions.

NOTE: Leaving the PSA in PAUSE for periods longer than the normal RUN time will cause
an impurity break through from the PSA.

If the START / STOP selector switch is set to STOP and the PAUSE / CONTINUE selector
set to PAUSE a MANUAL STEP facility will be enabled, which will cause the PSA to be
advanced one step each time it is operated.

These facilities are provided to enable the PSA to be started up and for maintenance purposes
only. Care must be taken when using these facilities that large pressure differentials are not
imposed on the PSA beds as this could lead to adsorbent degradation. There should be no
requirement to use these controls during normal PSA operation.

Setting the selector switch to CONTINUE will exit the PAUSE mode and return the PSA to
normal cycling.

5. VENT / PRODUCT SWITCH

When this switch is set to VENT mode the hydrogen product valve (PV-603A) is locked
closed. Selecting PRODUCT mode will release PV-603A and enable hydrogen to be sent to
the product system. The VENT mode is selected automatically when the PSA stops.

6. H2 / N2 SWITCH

The H2 / N2 switch is provided to enable the PSA to be cycled on nitrogen to purge the
adsorbers. When this switch is set to N2 mode the low inlet pressure shut down (PSLL-602)
is disabled. In addition, different PSA switching valve open settings (for KV-503A/B/C/D/E)
are used in the PSA sequence in N2 mode. This is necessary as the molecular weight of
nitrogen is significantly more than hydrogen and the PSA would cycle too slowly if the valve
open positions were left unchanged.

The PSA must always be set to H2 mode while the plant is operating. N2 mode can not be
selected if the pressure in any of the PSA adsorbers is above 5.0 Barg or the burner is
operating.

7. PSA MAINTENANCE MODE SWITCH

The PSA maintenance mode switch is provided to enable PSA switching valves to be stroked
for maintenance. Maintenance mode can not be selected unless the PSA is shutdown and is
never required to be used during normal plant operation.

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NOTE: It is the Operators sole responsibility to ensure the safety of plant and personnel
when operating valves in maintenance mode. Opening valves when high differential
pressures exist across the valve can lead to higher than design flows in the PSA vessel and
damage the PSA adsorbents.

8. PSA TUNING SETTINGS

The PSA tuning settings are provided to enable the PSA to be set up at commissioning and
whenever the PSA switching valves are serviced or replaced. They are never used to operate
the plant and therefore no further explanation is included.

NOTE: Only personnel with a full understanding of the PSA operation should adjust these
setting. Inappropriate changes may lead to the PSA adsorbents being damaged.

9. PSA RUN TIME

The PSA RUN time is the amount of time that the PSA is on the adsorption step. At 100%
capacity the design RUN time is 4.5 minutes. Each PSA vessel is capable of holding a fixed
quantity of impurities before the impurities break through to the product. If the rate at which
impurities are delivered to the PSA is reduced then each PSA vessel can stay in the RUN
mode longer without affecting product purity. Therefore as the PSA capacity is reduced the
RUN time is automatically extended.

It is also evident that if more impurities are present in the PSA feed gas (but the flow rate to
the PSA remains unchanged) the loading on the PSA beds will increase. This will necessitate
the PSA RUN time to be reduced, even though the PSA capacity is unchanged. If the
Reformer or Shift Converter are not operated correctly or the catalyst activation decreases,
the feed gas to the PSA can contain more impurities, which will require the PSA to be
operated on a faster cycle and thereby reduce the PSA efficiency.

The overall PSA RUN time is controlled by the repressurization flow controller (FIC-204).
Increasing the repressurization flow will cause the repressurization of the next adsorber to
occur quicker, enabling it to go to RUN mode sooner and so reduce the cycle time.
Conversely reducing this flow will cause the vessel to take longer to repressurize and thereby
increase the cycle time. When the PSA is operating at 100% capacity the repressurization
time is expected to be 3.75 minutes. During normal operation the setting of FIC-204 will be
automatically adjusted.

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10. ADSORPTION PRESSURE

The PSA should always be operated at the design adsorption pressure of 17.93 Barg. Whilst
operating at other pressures than design may be feasible the knock on effect is that the
equalization times and pressures will be changed along with the quantity of hydrogen
available for the purge step. Depending on the extent of these changes, this may lead to
problems in achieving product purity or may even prevent the PSA stepping. If the PSA
operating pressure is changed for any reason the tuning parameters will need to be modified
for the new pressure.

11. PSA RATIO FFIC-204

The PSA ratio FFIC-204 is a calculated ratio based on the plant capacity versus the PSA
capacity as follows:

PSA RATIO FFIC-204 = PLANT CAPACITY / PSA CAPACITY

Where
PLANT CAPACITY = Feed flow controller SP at current rate / Feed flow controller SP at 100% capacity.
Note: Feed flow controller is FIC-200A when the plant is operating on NG feed and FIC-200B when the plant is operating
on LPG feed.
PSA CAPACITY = Repress flow controller SP at current rate / Repress flow controller SP at 100% capacity
Note: Repress flow controller is FIC-204.

For maximum plant efficiency the plant should be operated at a PSA ratio of 1.0.

NOTE: Once FIC-204 is placed into CASCADE mode the Operator can set a target PSA
ratio which is then used to adjust the repressurization flow. If the target PSA ratio is set
below 1.0 the repressurization flow will be increased causing the PSA cycle time to be
reduced. This will decrease the hydrogen product flow as more hydrogen is used for
repressurization. However, it will also decrease the likelihood of an impurity breakthrough
from the PSA as the vessel loading is reduced. The reverse is true if the target PSA ratio is
set to above 1.0.

12. PSA PRESSURE PROFILE

The pressure profile (trends) of all five adsorbers is permanently available to the Operator on
a dedicated trend page. These trends provide the best source of information to the Operator
on whether the PSA is operating satisfactorily or not. All five trends should look identical to
each other and repeat as the PSA cycles.

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Hydro-Chem Job A299 Hydrogen Plant Operating Manual
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Batam, Indonesia Issue 1

E. PSA OPERATION

1. PSA START UP

See APPENDIX A for the PSA start up procedure.

2. PSA NORMAL OPERATION

When the PSA is operating normally it will automatically cycle through each of the 15 steps
and produce a continuous flow of high purity hydrogen whilst periodically blowing down
waste gas to the Tail Gas Drum (711-F-1). In addition, the PSA cycle time will be
automatically adjusted to optimize the PSA efficiency as the plant rate changes.

During normal operation the Operator should not need to make any adjustments to the PSA.

3. PSA OPERATION WITH LOW PRODUCT PURITY

During times of plant upset or abnormal process conditions, the PSA may become
overloaded and impurities appear in the hydrogen product. This situation, although not
desirable, is reversible by reducing the load on the PSA and cycling it quicker so that the
regeneration steps are initiated on a more frequent basis. The severity of the impurity break
through will largely determine the corrective actions and time required to return the PSA to a
normal operating condition.

If a small impurity break through is detected it can be rectified by increasing the PSA
repressurization flow rate (FIC-204). If FIC-204 is in CASCADE mode then reducing the
PSA ratio will cause the repressurization rate to increase. Doing this will make the PSA cycle
quicker (thereby processing less gas per cycle) and initiate the regeneration steps more
frequently. Once the PSA is clean the repressurization rate can then be returned to normal,
noting that it may have to be set higher than before the break through occurred to prevent the
break through from re-occurring.

NOTE: The RUN time should not be reduced to less than 3.5 minutes. If the PSA is not
being cleaned, or is being cleaned too slowly, with a RUN time of 3.5 minutes then
additional measures must be taken to clean the PSA.

The PSA load can be reduced further by decreasing the product flow from the PSA by
closing in PV-603A/B. Doing this effectively reduces the amount of PSA feed gas to be
processed by forcing some of the PSA feed gas through PV-602, located upstream of the
PSA. The maximum cleaning capabilities are obtained when all product flow is stopped and
the only feed gas processed by the PSA is used by repressurization flow controller (FIC-204).
Setting these conditions will enable the PSA to be cleaned in the shortest possible time. Once
the PSA is cleaned it can be returned to normal operation.

Note: When reducing product flow the set point on PIC-602 must be adjusted to maintain the
PSA pressure at 17.93 Barg.

Page 37 of 85
Hydro-Chem Job A299 Hydrogen Plant Operating Manual
Ecogreen Oleochemicals 09/10/13
Batam, Indonesia Issue 1

4. EFFECT OF ABNORMAL PROCESS CONDITIONS ON THE PSA

The PSA has been designed to provide high purity hydrogen from a PSA feed gas
composition in accordance with the heat and material balance. Deviations from these design
conditions can put an increased load on the PSA and adversely affect its performance. The
following list provides details of some of these abnormal conditions and their consequences:

 Operating the PSA at higher than design temperatures will reduce the adsorption
capabilities of the adsorbents, which can lead to impurity break through.

 Operating the PSA with increased concentrations of impurities in the PSA feed gas
can overload the adsorbent, which can lead to impurity break through.

 High molecular weight impurities or entrained liquids in the PSA feed will be
strongly adsorbed by the adsorbent and become difficult to remove during the
regeneration steps. This can cause the adsorption capabilities of the adsorbents to be
reduced, leading to impurity break through.

 The PSA is designed to operate with a Tail Gas Drum (711-F-1) pressure of between
0.2 Barg and 0.8 Barg and during the purge step it is expected this pressure will be at
approximately 0.34 Barg. If the Tail Gas Drum is operated at a higher pressure, this
imposes a back pressure on the PSA, which reduces the efficiency of the regeneration
steps. Reducing the efficiency of the PSA regeneration steps reduces the capabilities
of the adsorbents during the RUN step, leading to impurity break through, unless the
RUN time is reduced. Therefore the Tail Gas Drum (711-F-1) should always be
operated at the lowest possible pressure consistent with reliable PSA Tail Gas burner
operation.

F. PSA SHUTDOWN

See APPENDIX A for the PSA shutdown procedure.

Refer to the Cause and Effects matrix for the process conditions that cause an automatic shut
down of the PSA (PSASD)

G. CYCLING THE PSA ON NITROGEN

Refer to the PREPARATION FOR PLANT START-UP section of the manual.

H. TROUBLESHOOTING THE PSA

The following sections provide some information on typical problems encountered with the
PSA and detail some suggestions to diagnose the cause of the problem. Years of experience
with PSA operation indicates that if the process conditions remain unchanged then the most
likely cause of any PSA problem is a failure of the instrumentation, particularly the switching
valves.

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1. CYCLE FAILS TO ADVANCE

When in OPERATE mode the successful completion of each step requires preset pressures to
be achieved in specific vessels. If the cycle fails to advance then it is very likely that the
correct pressure was not achieved for that step. Firstly determine the step on which the failure
occurred and then:

 If the cycle fails to advance from steps 2, 5, 8, 11 or 14, check whether the bed that is
on REPRESS is being repressurized and, if not, check FV-204 and the relevant KV-
505 switching valve for correct operation. Leakage through other switching valves
(from HP vessel to any LP vessel) may also be suspected.

 If the cycle fails to advance from steps 1, 3, 4, 6, 7, 9, 10, 12, 13 or 15 then suspect
that one of the KV-503 valves has not operated correctly or a switching valve is
leaking.

2. UNEVEN RUN TIMES OR ABNORMAL PRESSURE PROFILES

During normal operation the RUN time of each PSA adsorber should be the same to within
+/- 15 seconds and the trends for each vessel should look identical to each other and repeat as
the PSA cycles. If this is not the case suspect a PSA valve leakage or malfunction.

3. MALFUNCTION OF A PSA SWITCHING VALVE

If a PSA switching valve malfunction is suspected the responsible valve needs to be


identified. This can usually be done by a general inspection of the actual valve positions
compared to the expected valve positions, as the PSA cycles. The PAUSE / CONTINUE
selector can be used to stop the PSA from advancing from a step while the valves are
checked.

NOTE: Holding a PSA vessel on RUN for too long will cause an impurity break through.

Once the problem valve is identified the cause of the malfunction must be determined and
rectified. The likely causes are:

 A problem with the valve itself.

 A problem with the solenoid or I/P positioner (experience suggests this is the most
common cause).

 Problem with the control system (PLC or power supply).

 Problem with the instrument air supply or vent connection on the valve.

Page 39 of 85
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Batam, Indonesia Issue 1

4. PSA SWITCHING VALVE LEAKAGE

If the RUN time for each PSA vessel is significantly different or the pressure profile of each
vessel is not consistent, the PSA switching valves should be checked for leakage. Any valve
leaks detected should be repaired as soon as possible. It is recommended an initial leak test is
done in situ using hydrogen gas, noting that many of the PSA switching valves are required
to be leak tight in both directions. The following procedure can be used.

NOTE: Although the following procedure is presented in a stepwise fashion, some of these
checks can be carried out simultaneously.

Checking the PSA Inlet Valves (KV-501A/B/C/D/E)

With the PSA on a PURGE step, stop the PSA by selecting the START / STOP selector to
STOP. Depressurize the hydrogen product header. Monitor the PSA inlet pressure (PIC-602)
and the pressure in the vessel on the PURGE step for 5 minutes. If the pressure in the vessel
on the PURGE step increases during this time then it is likely that the PSA inlet valve is
leaking.

 On step 11, 711-D-3 is on PURGE and 711-D-4 is providing PURGE. Check KV-
501A and KV-501B.

 On step 2, 711-D-5 is on PURGE and 711-D-6 is providing PURGE. Check KV-


501C and KV-501D.

 On step 8, 711-D-7 is on PURGE and 711-D-3 is providing PURGE. Check KV-


501E and 66-KV-501A.

Checking the PSA Outlet Valves (KV-502A/B/C/D/E) and Repress Valves (KV-
505A/B/C/D/E)

With the PSA on a RUN step, stop the PSA by selecting the START / STOP selector to
STOP. Depressurize the hydrogen product header and close FV-204. Monitor the PSA outlet
pressure (PIC-603A) and the pressures in the vessels for 5 minutes. If the pressures in the
vessels decrease during this time then it is likely that a PSA outlet valve is leaking.

 On step 1, 711-D-3 is on RUN and 711-D-4 and 711-D-7 are equalizing. Check KV-
502A/B/E.

 On step 7, 711-D-5 is on RUN and 711-D-4 and 711-D-6 are equalizing. Check KV-
502C/B/D.

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Then check for valve leakage in the opposite direction. With the PSA on a RUN step stop the
PSA by selecting the START / STOP selector to STOP. Leave the hydrogen product header
pressurized, close the manual valve downstream of PV-603A and upstream of PV-603B and
on the line to the CO analyzer AT-722 and close FV-204. Monitor the PSA outlet pressure
(PIC-603A) and the pressures in the vessels for 5 minutes. If the hydrogen product pressure
decreases during this time then it is likely that a PSA outlet valve is leaking.

 On step 1, 711-D-3 is on RUN. If the hydrogen product pressure decreases and there
are no flange leaks or valve stem leaks, suspect a leakage at one or more of the
product valves KV-502B/C/D/E.

 On step 10, 711-D-6 is on RUN. If the hydrogen product pressure decreases and there
are no flange leaks or valve stem leaks, suspect a leakage at one or more of the
product valves KV-502A/B/C/E.

Once the PSA outlet valves are confirmed not to leak repeat the same procedure but with
FV-204 open. This will check the PSA repress valves KV-505A/B/C/D/E.

Checking the PSA Blow Down Valves (KV-504A/B/C/D/E)

With the PSA on a RUN step, stop the PSA by selecting the START / STOP selector to
STOP. Monitor the PSA vessel pressure and also the Tail Gas Drum (711-F-1) pressure PIC-
606A for 5 minutes. If the pressures in the vessels decrease during this time and the Tail Gas
Drum pressure increases then it is likely that a PSA blow down valve is leaking.

 On step 1, 711-D-3 is on RUN and 711-D-4 and 711-D-7 are equalizing. Check KV-
504A/B/E.

 On step 7, 711-D-5 is on RUN and 711-D-4 and 711-D-6 are equalizing. Check KV-
504C/B/D.

Checking the PSA Equalization Valves (KV-503A/B/C/D/E)

With the PSA on a RUN step, stop the PSA by selecting the START / STOP selector to
STOP. In turn force equalization valves open and check for pressure increases / decreases in
each of the PSA vessels.

NOTE: Extreme caution needs to be shown when forcing PSA valves open not to
accidentally blow down a PSA vessel from high pressure to low pressure, which could
damage the adsorbents. For this reason it is recommended the valves are forced open at the
skid using instrument air directly connected to the valve. It is possible to force the valves
open by connecting a 4-20mA signal generator and if this method is chosen it is
recommended that the signal generator is connected at the valve. Remote connection may
lead to a valve being incorrectly opened.

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 On step 1, 711-D-3 is on RUN. Force open KV-503A. Check the pressure in 711-D-3
does not decrease and the pressure in vessels 711-D-4/5/6/7 does not increase. This
will check KV-503B/C/D/E. Then close KV-503A and force open KV-503C. Check
the pressure in 711-D-3 does not decrease and the pressure in 711-D-5 does not
increase. This will check KV-503A. Remove forces from all valves.

 Repeat this same procedure at steps 4, 7, 10, 13 forcing the relevant KV-503 valves
at each step. This will check all the KV-503 valves in both flow directions.

Page 42 of 85
Hydro-Chem Job A299 Hydrogen Plant Operating Manual
Ecogreen Oleochemicals 09/10/13
Batam, Indonesia Issue 1

V. CONSTRUCTION VERIFICATION AND PRE-COMMISSIONING


Whilst an Operating manual is not the place to include detailed construction verification and
pre-commissioning procedures, brief details are included in the following sections as an aid
to understanding the type and extent of activities that should be undertaken. It can not be
stressed enough that the key to successfully commissioning a plant in the shortest possible
time lies largely in the thoroughness with which these activities are completed.
A. PRELIMINARY INSPECTION OF EQUIPMENT
After installation of the skids, connection of process piping and instrumentation, but prior to
loading the vessels with catalyst or adsorbent, a detailed inspection of the plant should be
conducted to ensure the plant has been constructed in accordance with the design documents.
The following list, whilst not exhaustive, provides general guidelines on the inspection
requirements:
1. Check every line, vessel, valve, pump, instrument, etc. to see that they conform to the
P&ID’s, mechanical diagrams, electrical and instrument diagrams and design
specifications.

2. Remove all shipping braces and break any temporary shipping welds.

3. Check that the feed lines, product line, and utilities are tied in properly at the battery
limits.

4. Remove any dirt, welding slag, etc. that may be in the field fabricated equipment by
flushing with water or blowing with nitrogen or clean dry air.

5. Check to see that all catalysts and adsorbents have been received at the plant site and
stored in a safe, dry location.

6. Make sure that the sliding end of each exchanger is free to grow by ensuring the holding
down bolts are loose. Also ensure all piping that is designed to move during plant
operation is free to move.

7. Check all insulation is complete as per the design documents.

8. Check all debris and flammable materials are removed off site.

B. PRE-COMMISSIONING – ELECTRICAL EQUIPMENT

The following items should be checked during the pre-commissioning of the electrical
equipment.

1. Ensure all electrical protection devices such as fuses and overloads are set in accordance
with the design requirements.

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2. Check direction of rotation of all motors.

3. Check the alignment of all electric motors and couple up.

4. Grease and lubricate rotating machines as per the vendor instructions.

5. Ensure any electric tracing required is installed and working.

C. PRE-COMMISSIONING – INSTRUMENTATION

The following items should be checked during the pre-commissioning of the instrument and
control system.

1. Check all instrumentation is calibrated in accordance with the design documents.

2. Loop check all instrumentation to the control system and stroke check all control valves,
including confirming the air failure action of each valve is in accordance with the design
documents.

3. Function check the control system for correct operation.

4. Perform a proof test on the safety instrumented system.


NOTE: A proof test of the safety instrumented system must be performed periodically to
maintain the integrity of the system.

D. PRE-COMMISSIONING – INSTRUMENT AIR

The following procedure can be used to pre-commission the instrument air system.

1. Ensure that the supply line to each individual instrument is closed.

2. Open the drain valve on each air header, pressurize the header and blow each one down
until the header is clean.

3. Disconnect the instrument air to each instrument and blow each line clean. Once clean re-
connect each line.

E. PRE-COMMISSIONING – COOLING WATER

The following procedure can be used to pre-commission the cooling water system.

1. Break the cooling water supply line at the Process Cooler (711-E-5) and Sample Cooler
(SP-1930).

2. Flush the supply lines until clean.

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3. Reconnect the lines. Break the cooling water return line at a suitable point and flush
through the equipment until the lines are clean.

F. PRE-COMMISSIONING – BOILER FEED WATER

The following procedure can be used to pre-commission the boiler feed water system.

1. Break the boiler feed water supply line at the BFW Exchanger (711-E-4). Open LV-400
and flush the line until clean and then reconnect the line.

2. Break the boiler feed water supply line at the Steam Drum (711-F-3) and flush the line
until clean and then reconnect the line.

3. Open the low point drains on the Steam Generators 711-E-1, 711-E-3 and 711-E-7. Open
LV-400 to supply BFW to the Steam Drum and allow the Steam Generators to be
flushed.

G. PRE-COMMISSIONING – PROCESS PIPING

All piping installed on the skids should have been cleaned before installation, if there are any
questions about any piping not being clean then it should be cleaned. All interconnecting
piping between skids and client piping must be cleaned before connecting to the skids.

The normal method used to clean the process pipes is to blow the pipes with high velocity air
or nitrogen. This exercise should be undertaken before any of the catalysts or adsorbents are
charged as this allows the vessels on the plant to be used as volume tanks to generate the
high velocities needed to clean the lines.

NOTE: Blowing the pipes with low velocity air or nitrogen will NOT adequately clean
them.

H. PRE-COMMISSIONING – PIPEWORK LEAK TESTING

Once the process pipework is clean and reassembled a leak test should be conducted to
ensure that all flange joints are leak tight. This leak test is not intended to check the integrity
of welded joints, which should already have been confirmed during the construction process.
It is normal practice to use either air or nitrogen to conduct the leak test. The following
procedure can be used:

1. Pressurize the system to be leak tested. Each system should be pressurized to as close to
the normal operating pressure as practical.

2. Test each flanged joint, valve packing, etc for leakage using a leak detection solution.

3. Tighten any leaks and repeat the leak test.

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4. If tape is used on the flange joints during the leak test ensure that all tape is removed once
the testing is complete. Tape can present a fire hazard during plant operation when the
pipes are operating at elevated temperatures.

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VI. CHARGING THE CATALYSTS AND ADSORBENTS


Prior to charging catalysts and adsorbents the vessels and catalyst tubes must be inspected to
ensure they are clean and free from debris. In addition, vessel screens located on either the
inlet or outlet nozzles of the vessels must be inspected to ensure they are not plugged or
damaged.
A. REFORMER CATALYST

A number of methods are available for charging the Reformer catalyst and there are specialist
companies that offer this service and normally use a proprietary charging method. Whichever
method is used it is important that a uniform loading of the tubes is achieved and the same
weight of catalyst is charged to each tube. A significant variation in the weight of the catalyst
charged to one tube, compared with others, indicates that there may be voids in the catalyst
due to bridging. The weight of the catalyst in each tube should not vary by more than five
percent, although with careful charging a variation of less than this can be achieved.

The preferred method used by Hydro-Chem when charging the reformer catalyst is the pre-
charged sock technique and this method along with an alternative loading method is
described below.
Pre-charged Sock Technique
This method utilizes polyethylene tubes, open at the bottom, filled with a measured amount
of catalyst. The length of each polyethylene tube is approximately 1.5 m, the inside diameter
being less than the inside diameter of the Reformer tube. At the bottom of the polyethylene
tube the polyethylene is doubled back approximately 150 mm to prevent the catalyst
emptying prematurely. A rope is tied on the top part of the polyethylene tube and the catalyst
filled polyethylene tube is lowered to the bottom of the Reformer tube. A sharp tug will cause
the loose bottom end to slip and allow catalyst to empty as the polyethylene tube is lifted.
Bucket Technique
This method utilizes a cylindrical bucket made of a light material such as sheet metal and
with a hinged bottom. Bucket diameter must be less than the Reformer tube inside diameter
and the bucket height should be no more than one meter. The bucket is then filled with
catalyst which is lowered into the Reformer tube. The bottom of the bucket is held shut with
a separate line or rope. When the bucket reaches the Reformer tube bottom or catalyst level,
it is slowly lifted while allowing the bottom to open.
Charging Method
1. Ensure that the inlet trombones are disconnected from the Reformer tubes

2. Inspect the Reformer tubes for debris. The easiest method of doing this is to remove the
lid from the top of each tube and look up from the bottom of the tube.

3. Number each tube so that the quantity of catalyst charged to each tube can be recorded.

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4. Measure the height from the Reformer catalyst support, located at the bottom of the tube,
to the tube top flange face and ensure this is in accordance with the design documents.
This can be done by attaching a weight to a tape and lowering the tape into the tube until
it contacts the support.

5. Load each tube with 1-3 bags / buckets of catalyst. Record the weight of catalyst loaded
to each tube. Note that the catalyst must not undergo a free fall as this will cause the
catalyst to break.

6. Vibrate each tube by either striking the top support of the tube with a hammer or shaking
the tube from the base of the Reformer, noting that metal impacts on the Reformer tube
itself should be avoided.

7. Measure the height of the catalyst bed in each tube. This can be done using the tape plus
weight and measuring the distance to the tube top flange face.

8. Using the lowest bed as a reference, reduce the heights of the beds in all other tubes to
this value by further vibration of these tubes. Ensuring that the catalyst is charged evenly
as the tubes are filled in this manner should prevent large variations in charged weights
occurring once the tubes are filled.

9. Repeat steps 5 to 8 until the tubes are full.

10. The catalyst tube should be filled to a point 25mm to 50mm below the pigtail outlet take
off pipe, (approximately 530mm from the face of the flange to the top of the catalyst
bed). Ensure that no catalyst becomes lodged in the pigtail outlet connection.

NOTE: When charging catalyst, refer to the design drawing to determine the volume of
catalyst required to be charged and the finished elevation of catalyst in the Reformer tube.
Ensure no foreign materials are left behind in the Reformer tubes.

A representative sample of the Reformer catalyst should be taken during loading and stored
on site. This sample can be used for analysis if problems occur in operation at a later date.

Reformer Catalyst Tube Pressure Drop

Once the catalyst tubes have been filled a pressure drop across each tube should be done to
confirm even loading of each tube. The pressure drop equipment consists of either an orifice
plate or a needle value, which can be used as a variable orifice, and pressure gauges
connected both upstream and downstream of the orifice / needle valve. The following
procedure can be used:

1. Make sure that all flanges are completely removed from the top of the catalyst tubes.

2. Connect the pressure drop equipment to the bottom inlet flange of the catalyst tube.

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3. Connect nitrogen or clean dry air (approximately 5.0 – 7.0 Barg) to the inlet of the
pressure drop equipment. Note that a large flow is required to create a back pressure
across the catalyst, so a 3/4" supply line should be used if possible.

4. Ensure that the pressure upstream of the orifice plate can be accurately set to a constant
value. The actual value is not important (between 5.0 – 7.0 Barg) but it is important that
it is set to exactly the same value as each tube is tested.

5. If a needle valve is used as a variable orifice, adjust the needle valve to get a reading on
the downstream pressure gauge. If an orifice is used past experience would suggest an
orifice bore of 6.5 mm to 8.0mm should impose a sufficient back pressure to get a
reading.

NOTE: The downstream gauge needs to accurately measure small differences in back
pressure. If a needle valve is used the needle valve should be adjusted to give a
downstream pressure reading in the region of 0.25 Barg.

6. If a needle valve is used, once the downstream pressure is set for the 1st tube then the
needle valve must be locked in this position. The valve is then considered a fixed orifice.

NOTE: Care must be taken to ensure that the valve position is not adjusted after the first
tube has been checked and the reading of the downstream and upstream gauges recorded,
otherwise all testing will need to be repeated.

7. Check all tubes in this way ensuring that the inlet pressure and needle valve opening (if a
needle valve is used) are kept the same for all tubes. Record the reading of the
downstream pressure gauge each time.

8. If the reading from any tube varies by more than +/- 5 % from the average tube reading,
then the pressure drop across that tube must be changed until the pressure drop is within
the 5 % differential. The best way to achieve this is to increase the lower pressure drop
readings by vibrating these tubes so that the catalyst level drops and then adding more
catalyst back to the design level.

NOTE: The pressure drop from all the tubes is averaged and then this average
multiplied and divided by 1.05 to obtain the upper and lower acceptable limits. The
pressure drop on each tube should be within this range.

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B. HIGH TEMPERATURE SHIFT CONVERTER CATALYST

The shift converter catalyst is loaded through the top manway of the vessel. Before loading,
the catalyst should be screened to remove fines and debris. Although the catalyst tablets are
rugged, rough treatment should be avoided. The catalyst should not undergo a free fall of
more than 2m. Care should be taken to keep the shift converter catalyst from getting wet.

It is important that the catalyst loading be even throughout the bed so that any pressure drop
variations or uneven gas flows are minimized. This is not achieved if the catalyst is poured
into a pile that is subsequently raked level. Catalyst should be loaded through a canvas sock
or flexible chute that is moved around so as to direct the catalyst evenly throughout the
vessel. Care should be taken to ensure that catalyst does not enter the outlet pipe (which is
located inside the vessel) during charging.

NOTE: Ensure that any laydown screens shown on the design drawings are installed. Also
ensure that the lower manway heat insulating plug is installed prior to charging.

A representative sample of the shift converter catalyst should be taken during loading and
stored on site. This sample can be used for analysis if problems occur in operation at a later
date.

C. HYDROTREATER AND DESULFURIZER CATALYST

The Co/Mo hydrotreating catalyst and zinc oxide desulfurization catalyst are both charged
through the top manway of the vessel. The catalysts should be loaded in the same manner as
the Shift Converter catalyst. Each bed depth should be set to match the design drawings.

NOTE: Ensure that any laydown screens shown on the design drawings are installed. Also
ensure that both the lower and upper manway heat insulating plugs are installed prior to
charging.

A representative sample of the hydrotreater and desulfurizer catalyst should be taken during
loading and stored on site. This sample can be used for analysis if problems occur in
operation at a later date.

D. PSA ADSORBENTS

The PSA adsorbents are charged through the top manway on each PSA vessel. This requires
a secure working platform to be erected for charging. A crane is also necessary during
charging to lift the adsorbents to the manway. Hydro-Chem uses a dense loading system for
charging and strongly recommends that all PSA charging is done under the supervision of
Hydro-Chem personnel.

To ensure the PSA can operate at its design efficiency when loaded, the following must be
considered before, during and after charging:

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1. The containers holding the adsorbent must be left unopened and in a dry location until
immediately before loading.

2. The adsorbent must not come into contact with water. Adsorbents have a strong
affinity for water and adsorbed water will adversely affect purification system
efficiency.

3. Exposure to air must be kept to an absolute minimum during handling and loading.
This minimizes moisture pickup. For this reason adsorbents should not be loaded in
adverse weather conditions or until immediately before startup, after all checkout
operations are completed.

4. Each adsorber vessel, (711-D-3, 711-D-4, 711-D-5, 711-D-6 and 711-D-7) must be
packed in the same manner. Alumina is loaded in the bottom of each vessel, then
activated carbon and finally the molecular sieve is loaded at the top. The bed heights
must be in accordance with the design drawings.

NOTE: Ensure that all laydown screens shown on the design drawings are installed.

5. A uniform, maximum loading density must be achieved.

6. The migration and settling of the adsorbent after loading must be minimized.

7. Once loading is complete the adsorber vessels must be closed immediately and the
vessels blanketed with inert gas to minimize the adsorbents exposure to air and
moisture. From thereon the vessel should be maintained with a positive pressure of
inert gas.

A representative sample of each adsorbent should be taken during loading and stored on site.
These samples can be used for analysis if problems occur in operation at a later date.

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VII. PREPARATION FOR PLANT START-UP


Once all pre-commissioning activities are completed and the catalyst and adsorbents charged
the plant is ready to be started. The following sections detail the steps to be undertaken.
A. PURGING THE EQUIPMENT

Prior to flammables being introduced into the plant, it must be leak tight and the oxygen in
the pipe work must be removed to ensure there is no possibility of forming an explosive
mixture in the pipe work. The oxygen is removed from the pipe work by purging with
nitrogen. In addition, whenever the pipe work pressure decreases to below 0.2 Barg,
consideration should be given to re-purging the system with nitrogen to prevent air ingress.
After purging, the oxygen content of the pipe work at various locations must be tested. If
oxygen is detected then the plant must be re-purged.

The Oxygen content must be less than 1% before introducing flammables

Once purging is complete, keep the plant under nitrogen pressure of at least 1.0 Barg to
prevent the possibility of air ingress.

1. PLANT FRONT END PURGE

The following procedure can be used to purge the process pipework up to the PSA system:

NOTE: During a normal plant start-up from cold, nitrogen is passed through the plant and
discharged upstream of the PSA whilst the plant is bought up to temperature and this process
will inherently purge the front end of the plant. However, the following procedure also
includes the purging of other systems, such as the fuel gas system to the burner, which will
not inherently be purged during this start-up phase.

NG Pipe Work Purging

If the plant is to be operated on NG the NG pipe work outside the plant battery limit and up
to the injection point upstream of the Feed Heater 711-E-2 must be purged. In addition the
NG fuel gas system must also be purged. This can be done using the following procedure:

a. Connect a nitrogen supply to a suitable location at the origin of the NG feed pipe work
(outside the plant battery limit).

b. Close manual isolation valve 16-104 upstream of Feed Heater 711-E-2 and open vent
valve downstream of FV-200A.

c. From the control screen open FV-200A to purge the NG feed pipe work.

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d. Connect a nitrogen supply to a suitable location at the original of the NG fuel pipe work
(outside the plant battery limit).

e. Open a vent connection at the fuel gas skid and from the control screen open PV-612 to
purge the NG fuel pipe work.

LPG Pipe Work Purging

If the plant is to be operated on LPG the LPG pipe work outside the plant battery limit and up
to the injection point upstream of the Feed Heater 711-E-2 must be purged. In addition the
LPG fuel gas system must also be purged. This can be done using the following procedure:

a. Connect a nitrogen supply to a suitable location at the origin of the LPG pipe work
(outside the plant battery limit).

b. Close manual isolation valve 18-104 upstream of Feed Heater 711-E-2 and open vent
valve downstream of FV-200B.

c. From the control screen open FV-200B to purge the LPG feed pipe work.

d. Open a vent connection at the fuel gas skid to purge the LPG fuel pipe work.

Common System Purging

The following procedure can be used to purge the remainder of the common pipe work in the
front end of the plant.

a. Connect the nitrogen supply to upstream of the Feed Heater 711-E-2 via the quick
disconnect hose.

b. Connect a nitrogen supply to a suitable location at the origin of the hydrogen injection
pipe work (outside the plant battery limit) and ensure manual isolation valve downstream
of FV-202 is open.

c. Ensure the manual isolation valve downstream of HV-804 is closed and ensure any
process vent and drain valves on the system are closed.

d. From the control screen open HV-804 and pressurize the system with nitrogen to 4.0
Barg. Ensure nitrogen flows from both the quick disconnect fitting upstream of Feed
Heater 711-E-2 and via the hydrogen injection line by opening FV-202.

e. Once the system is pressurized to 4.0 Barg isolate both nitrogen supplies.

f. Open the 1” vent valve located downstream of HV-804 and allow the system to
depressurize to approximately 0.2 Barg.

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g. Repeat this purging sequence three times or until a gas sample is tested to be less than
1% of oxygen at the 1" vent valve. Also open all other high and low point vent and drain
valves on the feed gas and hydrogen injection systems to this point and test for an oxygen
content of less than 1%. This will purge the Hydro-desulfurizer (711-D-1).

h. Once this part of the system is purged, proceed to purge up to the PSA.

i. Ensure that the manual isolation valve on the steam system at SP-1600, the manual
isolation valve upstream of PV-606C and the manual isolation valve at the PSA inlet are
all closed.

j. Ensure that LV-403 and PV-602 are closed and the manual isolation valves up and
downstream of PV-602 are open.

k. Open the manual isolation valve downstream of HV-804.

l. Introduce nitrogen into the front end of the plant from the quick disconnect hose
upstream of Feed Heater 711-E-2 and allow the system to pressurize to approximately 4.0
Barg. Then close the nitrogen supply and open PV-602 and depressurize the system to
approximately 0.2 Barg.

m. Repeat this purging sequence three times or until a gas sample is tested to be less than
1% at the PSA inlet. Also open all other high and low point vent and drain valves on the
system to this point and test for an oxygen content of less than 1%.

2. PSA SYSTEM PURGE

The PSA purification system can be purged by running it on nitrogen using the following
procedure.

a. Ensure that the manual isolation valve downstream of PV-603A is closed.

b. Ensure PV-603A and PV-603B are closed.

c. Connect a nitrogen supply to the PSA inlet header downstream of PSA manual isolation
valve 01-111. Alternatively the front end of the plant may be used to supply nitrogen to
the PSA if it has been nitrogen purged and contains nitrogen only.

d. From the control screens select the PSA to NITROGEN MODE and START-UP MODE
and cycle the PSA to step 1 using the PAUSE and MANUAL STEP buttons.

e. Open the nitrogen supply to the PSA inlet header or open the PSA manual isolation valve
01-111 to supply nitrogen to the PSA.

NOTE: Only open the PSA manual isolation valve 01-111 to supply nitrogen to the PSA if it
can be guaranteed that the front end of the plant contains nitrogen only.

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f. From the control screen open the PSA repressurization valve FV-204 and put PIC-606A
into AUTO mode with a set point of 0.2 Barg.

g. From the control screen press the START button to start the PSA cycling. The PSA will
automatically cycle and blow down nitrogen to the Tail Gas Drum (711-F-1). The
nitrogen collected in the Tail Gas Drum (711-F-1) will automatically vent through PV-
606. This will purge out all the PSA vessels and the Tail Gas Drum (711-F-1).

h. Whilst cycling the PSA on nitrogen and with nitrogen pressure on the front end of the
plant open PV-606C to purge this line to the Tail Gas Drum (711-F-1).

i. Allow the PSA to cycle with nitrogen until tests show that all the adsorber vessels and
the Tail Gas Drum (711-F-1) have an oxygen content of less than 1%. The oxygen
content at the Tail Gas Drum (711-F-1) should be confirmed to be below 1% at both the
connection at the top of the vessel and the drain at the bottom of the vessel.

NOTE: It is also desirable when purging out the PSA to run for a time with the Tail Gas
Drum (711-F-1) manway open to allow dust fines from the PSA to be blown from the
system. The asphyxiation hazard associated with nitrogen must be considered when doing
this.

B. STEAM GENERATOR BOIL OUT (PRIOR TO INITIAL START-UP)

Prior to operation of the steam system for the first time, it is important to remove any traces
of oil, grease, and dirt that may be present in the steam system. This is achieved by adding
chemicals to the water in the Steam Generators and gently heating for 24 / 48 hours.

The following instructions are based on Section VIII of the ASME Boiler and Pressure
Vessel Code entitled, “Suggested Rules and Care of Steam Boilers”.

1. Remove any instrumentation that may become damaged by the boil out chemicals from
the Steam Generators and fit temporary blanks in their place.

2. Fill the Steam Drum (711-F-3) with cold clean water to a level of approximately 10%
using LIC-400.

3. Dissolve sufficient chemicals in cold water to give the following concentrations when
added to the Steam Generators:

 1.35 Kg of Sodium Nitrate per 454 Kg of water

 0.3 Kg of Caustic Soda per 454 Kg of water

 0.1 Kg of Wetting Agent per 454 Kg of water (A good household or


commercial detergent can be used)

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If sodium nitrate is not available the following alternative mixture can be used:

 1.35 Kg of Soda Ash per 454 Kg of water

 1.35 Kg of Caustic Soda per 454 Kg of water

 0.1 Kg of Wetting Agent per 454 Kg of water (A good household or


commercial detergent)

NOTE: Other boil-out solutions as recommended by a water treatment consultant may also
be used.

4. Add the dissolved chemicals through a nozzle on the top of the Steam Drum (711-F-3).

CAUTION: Boil out chemicals are highly caustic. Caustic soda will produce a violent flash
if introduced too fast into water. Wear goggles, face shield, rubber apron, and rubber gloves
at all times while mixing and handling chemicals. Warn all personnel to exercise due care.
Refer to appropriate MSDS sheets for proper safety and first aid treatments.

5. Top up the Steam Drum level to approximately 30% using LIC-400. As the Steam
Generators are heated the water will expand. The aim is to maintain the water level at
50% during the boil out. Do not over fill the Steam Drum during the initial fill when the
system is cold otherwise it will be necessary to blow down the system as it is heated and
boil out chemicals will be lost from the system.

6. Close the manual isolation valve on the Steam Drum outlet and open the 2" manual vent
valve on the Steam Drum.

7. Start the Reformer burner (see NORMAL OPERATING PROCEDURES section). As the
Reformer temperature (TIC-306) increases steam will appear at the manual vent on the
Steam Drum. At this point close in the manual vent and increase the Steam Drum
pressure to 5.0 Barg. Maintain the steam drum pressure (PIC-600) between 5.0 – 12.0
Barg by adjusting the manual vent valve. Maintain the Reformer temperature (TIC-306)
between 250°C – 350°C. These conditions will give a gentle boil up.

NOTE: This procedure will take a few hours to start producing steam.

8. During the boil-out, blow down the Steam Generators hard every 6-8 hours. The blow
down will gradually become clear and void of solids, this can take between 24 to 48
hours. Refill the water level back to 50% whenever the level drops below 40%.

NOTE: The Steam Generator blow down will contain boil out chemicals and so the same
precautions used to handle the chemicals should be followed. In addition, provisions need to
be made to safely dispose of the blow down effluent.

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9. When blow downs are clean the boil out is complete. Allow the Steam Generators to cool
and completely drain the system. Flush the entire system with clean water until all
cleaning agent has been removed. The Steam Drum can then be opened for inspection, if
required.

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VIII. NORMAL OPERATING PROCEDURES


Plant normal start up and shutdown procedures are contained within a separate Appendix of
this manual as it is expected that the site will develop these procedures further to take into
account specific operating practices used on site. In addition, Hydro-Chem start-up personnel
may alter these procedures during the initial start-up due to unforeseen circumstances that
may arise during commissioning.

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IX. OPERATING SCENARIOS – OTHER THAN NORMAL


The following sections provide some general guidance on operating scenarios (other than
normal operation) that may be encountered during the life time of the plant. The list is not
exhaustive and there may be other scenarios that are not covered.

A. FLAME OUT SHUTDOWN (FOSD)

Refer to the Cause and Effects matrix to see what conditions cause a FOSD.

When an FOSD is activated the following actions occur automatically:

 The PSA stops cycling and all the PSA switching valve and the hydrogen product
valves PV-603A/B close.

 The hydrogen injection valve FV-202 closes.

 The PSA Tail Gas burner and Make-up Gas burner (and pilot if operating) shut down.

 The feed gas to the Reformer (FIC-200A/B) stops.

 Steam flow to the Reformer (FIC-201) is set to 50% of the design flow.

 PIC-602 ramps to a set point of 4.14 Barg to maintain the steam flow through the
Reformer tubes.

 When the Reformer tube outlet temperature (TIC-310) reaches 540C or the Steam
Drum (711-F-3) pressure PIC-600 drops below 6.9 Barg then the steam flow to the
Reformer (FIC-201) stops.

The re-start procedure from a FOSD is determined by the length of time it takes to rectify the
cause of the trip and how much the plant cools. If the burner can be re-lit quickly and there is
still steam flow (FIC-201) in the Reformer tubes then the Reformer can quickly be bought
back to operating temperature and the feed gas reintroduced, as detailed in APPENDIX A -
section I D.

If on the other hand the plant cools to a point where the steam flow through the tubes stops,
nitrogen will need to be reintroduced to the Reformer tubes and the start up procedure will be
the same as for a normal plant start up (See APPENDIX A - section I).

NOTE: Ensure that any condensate that collects in the pipe work as the plant cools
(particularly at the Reformer inlet ring header and the Shift Converter outlet) is drained prior
to the plant being re-started. Failure to do this may result in the catalysts being damaged.

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NOTE: Ensure the plant is maintained at a positive pressure at all times to prevent air
ingress. If air ingress is suspected confirm the oxygen content of the system is less than 1%
before attempting to re-start the plant.

NOTE: If nitrogen is to be reintroduced to the Reformer tubes do not purge residual


hydrocarbon feed through the Reformer tubes.

B. LOW FIRE SHUTDOWN (LFSD)

Refer to the Cause and Effects matrix to see what conditions cause a LFSD.

When a LFSD is activated the following actions occur automatically:

 The PSA stops cycling and all the PSA switching valve and the hydrogen product
valves PV-603A/B close.

 The hydrogen injection valve FV-202 closes.

 The PSA Tail Gas burner shuts down.

 The Make-up Gas burner is set to low fire, with fuel gas flow through PCV-664 only.

 The feed gas to the Reformer (FIC-200A/B) stops.

 Steam flow to the Reformer (FIC-201) is set to 50% of the design flow.

 PIC-602 ramps to a set point of 4.14 Barg to maintain the steam flow through the
Reformer tubes.

 When the Reformer tube outlet temperature (TIC-310) reaches 540C or the Steam
Drum (711-F-3) pressure PIC-600 drops below 6.9 Barg then the steam flow to the
Reformer (FIC-201) stops.

To re-start after a LFSD, first determine and rectify the cause of the LFSD and then
reintroduce feed gas as detailed in the normal plant start up procedure (APPENDIX A -
section I D) and bring the plant back on line.

NOTE: Ensure that any condensate that collects in the pipe work as the plant cools
(particularly at the Reformer inlet ring header and the Shift Converter outlet) is drained prior
to the plant being re-started. Failure to do this may result in the catalysts being damaged.

NOTE: Ensure the plant is maintained at a positive pressure at all times to prevent air
ingress. If air ingress is suspected confirm the oxygen content of the system is less than 1%
before attempting to re-start the plant.

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NOTE: If nitrogen is to be reintroduced to the Reformer tubes do not purge residual


hydrocarbon feed through the Reformer tubes.

C. PSA TRIP

Refer to the Cause and Effects matrix to see what conditions cause the PSA to trip.

When the PSA trips tail gas burning is also stopped unless process gas burning is enabled. If
process gas burning is enabled the PSA bypass controller PIC-606C will automatically open
PV-606C to maintain the gas pressure in the Tail Gas Drum (711-F-1) and thereby maintain a
gas flow to the PSA Tail Gas burner. The only action required by the Operator in this
scenario is to reduce the set point of PIC-602 to 17.93 Barg.

NOTE: The calorific value of the process gas is higher than that of the PSA waste gas and so
if the flow on FIC-205 were left unchanged the Reformer firebox temperature (TIC-306)
would increase significantly. To avoid this and provided FIC-205 is in CASCADE mode
when the PSA trips, the set point of FIC-205 is automatically reduced when process gas
burning commences.

Once the PSA trip has been rectified the PSA can be re-started using the normal plant start up
procedure (See APPENDIX A - section I E). As PSA waste gas is re-introduced to the Tail
Gas Drum (711-F-1) the PSA bypass controller PIC-606C will close the bypass control valve
PV-606C. The set point on FIC-205 will need to be increased as process gas is replaced by
PSA waste gas in 711-F-1 to maintain the Reformer firebox temperature (TIC-306).

NOTE: The bypass valve PV-606C will automatically be locked closed 30 minutes after the
PSA has started.

If process gas burning is not enabled when the PSA trips the PSA Tail Gas Burner will
automatically shut down and the heat input into the Reformer will drop significantly. If the
plant is operating at greater than 30% capacity at the time of the trip it is unlikely that the
Make-up Gas burner will be able to supply sufficient heat to the Reformer to maintain the
Reformer tube outlet temperature (TIC-310) at the required value. Under these circumstances
the Operator will need to take the following actions:

Reducing feed gas flow

1. Increase the firing on the Make-up Gas burner (FIC-203) and at the same time reduce
the feed gas flow (FIC-200A/B). The intention is to reduce the feed gas flow to a point
where the Make-up Gas burner can supply sufficient heat to the Reformer to maintain
the Reformer tube outlet temperature (TIC-310). Adjust the combustion air to maintain
excess oxygen in the flue gas (AIC-721).

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NOTE: The automatic control system will not respond quickly enough to re-adjust the fuel
gas flow to the burner and feed gas flow to the Reformer tubes to maintain the Reformer tube
outlet temperature. The Operator must remove the system from cascade control and make the
adjustments quickly.

2. Reset PIC-602 set point to 17.93 Barg.

3. Reduce the steam flow (FIC-201), if required, to a minimum setting of 50% of the
design steam flow whilst maintaining the steam to carbon ratio at or above the design
value for the feedstock. Ensure that the steam flow does not depressurize the Steam
Drum (PIC-600).

4. Once the Reformer temperatures have stabilized rectify any issues with the PSA or
PSA Tail Gas burner.

5. Re-start the PSA using the normal plant start up procedure (See APPENDIX A -
section I E).

6. Re-start the PSA Tail Gas burner using the normal plant start up procedure (See
APPENDIX A - section I G).

7. Return the plant to MASTER RATE control.

D. EMERGENCY SHUTDOWN PROCEDURE

In an emergency the following procedure can be used to shut the plant down quickly:

At the Control Screen:

1. Stop the PSA Tail Gas burner, which will cause FV-205, BV-707 and BV-708 to close
and BV-709 to open.

2. Stop the PSA, which will cause PV-603A, PV-603B and all the PSA switching valves
to close.

3. Stop hydrogen injection and ensure valve FV-202 closes.

4. Put FIC-200A/B to manual mode with an output of 0%.

5. Stop the Make-up Gas burner firing, which will cause FV-203, BV-701 and BV-702 to
close and BV-703 to open.

6. If it is safe to do so allow steam to continue flowing through the Reformer tubes. If not,
place FIC-201 into manual mode with an output of 0%.

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7. If it is safe to do so allow the ID Fan (711-G-3) and FD Fan (711-G-4) to continue to


run to cool the Reformer firebox. If not, stop the fans.

8. Stop chemical injection into the steam system.

9. Reduce the plant pressure to a safe level using PIC-602.

At the Skids:

10. If possible close the following manual valves:


 Manual isolation valves downstream of FV-200A/B.
 Manual isolation valve downstream of FV-201.
 Manual isolation valves on the fuel gas line to the burner.
 Manual isolation valves on the hydrogen product line.
 Manual isolation valves on the hydrogen injection line.
 Manual isolation valve on the PSA inlet.
NOTE: If possible ensure a positive pressure is maintained on all parts of the plant using
nitrogen

E. GENERAL POWER FAILURE

In the event of a general power failure, the plant will automatically shut down. All control
valves will go to their fail position and all motors will stop. The following steps should be
taken:

1. If pressure is lost on the plant purge the plant with nitrogen before attempting any re-
start.

NOTE: Do not purge residual hydrocarbon feed in the Hydro-desulfurizer through the
Reformer tubes.

2. As the plant cools drain any condensate from the manual drain on the Reformer inlet
ring header and the drain downstream of the Shift Converter.

3. Close the manual isolation valves detailed in section D point 10 above.

F. INSTRUMENT AIR FAILURE

In the event of a general instrument air failure, all control valves will go to their fail position
and the plant will automatically shut down. The steps shown above in the General Power
Failure section should be followed.

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G. STEAM FAILURE

In the event of a steam failure to the process, the plant will trip to LFSD due to steam to
carbon ratio shut down FFSLL-800 activating. If possible nitrogen should be passed through
the Reformer tubes whilst they cool down.

NOTE: Shutdown FFSLL-800 is bypassed at start up and until the plant is set to NORMAL
mode.

NOTE: Do not purge residual hydrocarbon feed in the Hydro-desulfurizer through the
Reformer tubes.

H. FEED GAS FAILURE

In the event of a feed gas failure, a steam flow (FIC-201) of 50% of design should be
maintained in the Reformer tubes. The PSA should be stopped along with the PSA Tail Gas
burner and hydrogen injection. The Make-up Gas firing (FIC-203) should then be adjusted to
maintain the Reformer tube outlet temperature at approximately 760C. Follow the relevant
steps from the normal shutdown procedure for further details (See APPENDIX A - section
II).

NOTE: It is not recommended to steam the Reformer catalyst for extended periods of time as
this can cause the catalyst to be re-oxidized and also lead to changes in the catalyst structure.
If feed gas can not be re-established within 8 hours it is recommend that the Reformer tube
outlet temperature (TIC-310) is reduced to below 550C. If the feed gas can not be restored
within 24 hours it is recommended that the plant either be shut down or the Reformer tube
outlet temperature (TIC-310) be reduced to 400C, steam removed from the Reformer tubes
and a nitrogen flow established instead.

NOTE: If nitrogen is to be reintroduced to the Reformer tubes do not purge residual


hydrocarbon feed through the Reformer tubes.

I. FIRE, EXPLOSION OR RUPTURE

The following advice is provided as a general guide only as the nature of any fire, explosion
or rupture needs to be carefully assessed before taking appropriate action.

1. Shut off the source of gas to the circuit that has the failure.

2. Vent the circuit at some point remote from the fire or rupture until there is a small
positive pressure left in the circuit.

3. Introduce nitrogen or steam to the circuit. Do not introduce nitrogen or steam at a high
flow rate since this could increase the intensity of any fire by forcing fuel to the point
of the fire or rupture at a high flow rate.

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4. In the case of a fire, protect equipment adjacent to the fire by either moving the
equipment or by spraying it with water to keep it cool.

J. REFORMER TUBE RUPTURE


Reformer tubes are designed for an operating life of 100,000 hours at the maximum expected
tube wall temperature. Operating the tubes at higher temperatures, poor catalyst packing
(which can lead to hotspots in the tubes) and excessive thermal cycling all reduce the useful
working life of the Reformer tubes.
To help prevent and detect tube ruptures the tubes should be inspected through the Reformer
peep doors, during plant operation, on a regular basis. A normal tube appearance is indicated
if the tube is black in color for the majority of the tube length with a small red portion at the
very top of the tube as it exits the reformer. If a tube is ruptured the appearance is likely to be
black below the rupture site and red above that point due to the loss of gas from the rupture
site.

Other indications that a tube rupture may have occurred include:

a) Decrease in hydrogen production.

b) Unusual noise coming from the Reformer.

c) Reformer combustion problems.

Continued operation with a ruptured tube can cause damage to the Reformer insulation or
other Reformer tubes and / or lead to damage of equipment in the waste heat section of the
plant due to excessive flue gas temperatures or combustion occurring in the flue gas duct.

If a tube rupture is detected the plant should be shut down. The shutdown procedure is
essentially the same as the normal plant shutdown procedure (See APPENDIX A - section II)
and is summarized below for quick reference.

1. Stop the PSA, PSA Tail Gas burner and hydrogen injection.

2. Put FIC-200A/B (Feed gas) flow controller into manual mode with an output of 0% to
immediately stop gas flow to the Reformer tubes.

3. Maintain steam flow to the Reformer tubes at 50% of design.

4. Flow nitrogen through the Reformer tubes, if possible.

NOTE: Do not purge residual hydrocarbon feed in the Hydro-desulfurizer through the
Reformer tubes.

5. Stop the Make-up Gas burner.

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6. If required, increase the Reformer draft (PDIC-601) to remove excess heat from the
Reformer firebox as quickly as possible.

7. When the Reformer tube outlet temperature (TIC-310) decreases to less than 540C or
the Steam Drum pressure (PIC-600) reduces to less than 6.9 Barg FIC-201 will go to
MANUAL mode with an output of 0%.

K. TEMPORARY SULFUR POISONING OF REFORMER CATALYST

Sulfur leakage from the Hydro-desulfurizer (711-D-1) can cause sulfur poisoning of the
Reformer catalyst. The immediate effect of sulfur poisoning is a pronounced loss of catalyst
activity, which in turn leads to a sudden rise in methane leakage from the Reformer and
results in a lower hydrogen production rate for the same hydrocarbon feed.

If sulfur poisoning is suspected, the origin of the sulfur-poisoning needs to be determined and
action taken to rectify this. It may be that all that is required is for the temperature of the
Hydro-desulfurizer to be increased to enable more sulfur compounds to be absorbed on the
zinc oxide catalyst or the hydrogen injection to be increased. However, if after 12 hours this
action shows no sign that the Reformer catalyst is re-activating then the following procedure
can be used to try and desulfurize and re-activate the catalyst:

1. Reduce FIC-200A/B (Feed gas) flow controller to 10% of the design flow rate.

2. Set FIC-201 (Steam to process) flow controller to 50% of the design flow rate.

3. Adjust the burner firing (FIC-203) to give a Reformer tube outlet temperature
(TIC-310) of 820 – 830C.

4. Maintain this condition for 12-24 hours. If after this time the catalyst is not re-activated
then it is likely the sulfur poisoning is irreversible and the catalyst needs to be replaced.

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X. CATALYST REDUCTION
During the initial plant start-up or whenever the catalyst is replaced the start-up procedure
needs to be modified from the normal plant start-up procedure to enable the catalyst to be
reduced. The reduction process depends on the feedstock to be used. If LPG is to be used as
the feedstock then hydrogen is required for the reduction, however, if NG is to be used as the
feedstock then an on online catalyst reduction technique can be used. The following sections
provide details of the changes required to the normal plant start up procedures to be followed
to ensure the catalyst is reduced successfully.

A. HYDROTREATER/DESULFURIZER CATALYST (711-D-1)

The hydrotreater catalyst does not normally require any special activation procedures as
conversion to the more active sulphided form is achieved to a sufficient extent by reaction of
sulfur compounds in the feed gas.

NOTE: Operating the Hydrotreater on low sulfur feeds (< 2 ppmv) for extended periods of
time can lead to permanent partial deactivation of the catalyst.

NOTE: Prolonged exposure of the hydrotreater catalyst to hydrogen only at normal operating
temperatures may lead to over reduction of the hydrotreater catalyst, however, problems
associated with this are very rare.

The desulfurizing catalyst does not require reduction but to work effectively it needs to be
brought to the correct operating temperature. This is particularly important when LPG
feedstock is used due to the high sulfur and olefins content of the feedstock.

B. REFORMER CATALYST

For the Reformer catalyst to operate effectively it first needs to be reduced from nickel oxide
to nickel. The reduction procedure is dependent on the feedstock available.

1. REDUCTION PROCEDURE WITH NG FEEDSTOCK

If natural gas is to be used as the feedstock then an on line reduction of the catalyst should
pose no problems provided any operational adjustments during the reduction period are made
slowly and deliberately. The on line reduction procedure is detailed below:

1. Ensure the Reformer outlet temperature (TIC-310) is approximately 780C with 50% of
steam (3,006 Kg/hr) flowing through the tubes.

2. Gradually introduce feed gas into the Reformer tubes by opening FV-200A. The amount
of feed gas should be limited to give a steam to carbon ratio of 10 to 1. This steam to
carbon ratio is set to prevent the Shift Converter catalyst being reduced too rapidly and
causing damage but is also good for reducing the Reformer catalyst.

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NOTE: The Reformer catalyst will be reduced at the same time that the Shift Converter is
being reduced.

NOTE: With 3,006 Kg/hr of steam the maximum NG feed is 358 Nm3/hr.

3. The addition of feed should cause a slight drop in the Reformer outlet temperature. At
this point, hydrogen is being formed in the Reformer tubes. The hydrogen formed serves
as a reducing agent for both the Reformer catalyst and the Shift Converter catalyst. As the
Reformer catalyst reduces and becomes more active this promotes the steam/hydrocarbon
reaction, thus forming more hydrogen and thereby reducing the Reformer catalyst on line.

4. Gradually increase Reformer firing to obtain a Reformer outlet temperature (TIC-310) of


815ºC - 825ºC.

5. The Reformer effluent gas will be cooled in the Reformer Effluent Steam Generator
(711-E-1), the Feed Heater (711-E-2), the Shift Effluent Steam Generator (711-E-3), the
BFW Exchanger (711-E-4) and the Process Cooler (711-E-5). Steam will be condensed
in the Cold Condensate Separator (711-F-2) and the process gas vented via PV-602.

6. The Reformer catalyst is considered completely reduced when the methane concentration
of the vented gas is less than 5 mol% on a dry basis and is expected to take between 12 –
24 hours.

2. REDUCTION PROCEDURE WITH LPG FEEDSTOCK

If LPG is to be used as the feedstock then it is recommended that the reformer catalyst if first
reduced using hydrogen using the following procedure:

1. Ensure the Reformer outlet temperature (TIC-310) is approximately 780C with 3006
Kg/hr of steam flowing through the tubes.

2. Gradually introduce hydrogen into the Reformer tubes by opening FV-202A or


connecting a temporary hydrogen supply to the reformer inlet ring header. The amount of
hydrogen should be set to give a steam to hydrogen ratio of 10 to 1.

NOTE: With 3,006 Kg/hr of steam the hydrogen required is 371 Nm3/hr.

3. Gradually increase Reformer firing to obtain a Reformer outlet temperature (TIC-310) of


815ºC - 825ºC.

4. The Reformer effluent gas will be cooled in the Reformer Effluent Steam Generator
(711-E-1), the Feed Heater (711-E-2), the Shift Effluent Steam Generator (711-E-3), the
BFW Exchanger (711-E-4) and the Process Cooler (711-E-5). Steam will be condensed
in the Cold Condensate Separator (711-F-2) and the process gas vented via PV-602.

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5. The Reformer catalyst is considered completely reduced when the methane concentration
of the vented gas is less than 5 mol% on a dry basis and is expected to take between 12 –
24 hours.

C. REDUCTION OF SHIFT CONVERSION CATALYST (711-D-2)

For the initial plant start-up when all the catalyst is new the reduction of the Shift Converter
catalyst should be initiated in conjunction with the reduction of the Reformer Catalyst.

The Shift Converter catalyst is supplied in the form of Fe2O3 and contains traces of sulfur in
the form of sulfates. During reduction, the Fe2O3 is converted to Fe3O4 and the sulfur is
liberated in the form of H2S. The reduction reaction is highly exothermic. The temperature
will increase 7.5C for each one percent of carbon monoxide present in the gas processed by
the Shift Converter.

1. Set the Reformer conditions as described in the section above.

2. Set the Shift Converter inlet temperature controller (TIC-307) to automatic with a set
point of 300C. Observe the inlet and outlet temperature of the Shift Converter. Initially
the outlet temperature (TI-311) will be less than the inlet temperature (TIC-307). Once
the reduction process begins the outlet temperature will start increasing and will
eventually increase to above the inlet temperature. At the end of the reduction process,
which should take between 30 and 60 minutes, the outlet temperature will spike high and
then start to decrease to the normal temperature difference between inlet and outlet. Once
this is complete increase the inlet temperature on TIC-307 to 330C whilst watching the
outlet temperature to ensure the reduction is complete. Once the reduction process is
complete reduce the inlet temperature on TIC-307 to the normal operating temperature
for new catalyst.

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XI. OPERATIONAL ROUTINES AND MAINTENANCE SCHEDULE


Hydro-Chem recommends that all operating personnel become intimately familiar with all
details of plant and equipment operation in order to ensure the plant is operated in a safe and
efficient manner.

It is expected that the Client will develop their own operational routines and maintenance
schedules to suit the on site requirements. The following details are provided here to provide
some guidance to the Client on what is typically required.

NOTE: Any specific requirements contained in the vendor manuals will also need to be
undertaken.

ACTIVITIES TO BE COMPLETED EACH SHIFT

1. Monitor the plant process parameters and react to any alarm or unusual conditions.

2. Record all process parameters on a log sheet (typically every 4 hours when the plant is
operating in steady state condition).

3. Conduct a general walk round of the site to determine if there are any leaks, unusual
noises or abnormal conditions evident and log local instrument readings.

ACTIVITIES TO BE COMPLETED ON A DAILY BASIS

The following activities are recommended to be completed on a daily basis:

1. Inspect the Reformer tubes and burner from the peep doors on the Reformer base.

2. Check the Flare KO Drum (711-F-5) for accumulation of liquid and drain as required.

3. Check Steam Generator dosing chemical charge, complete a water analysis of the
Steam Generator system and adjust dosing and / or continuous blow down as required..

ACTIVITIES TO BE COMPLETED ON A WEEKLY BASIS

The following additional activities are recommended to be undertaken on a weekly basis:

1. Calibrate the flue gas and CO analyzers.

2. Drain any accumulated water from the Tail Gas Drum (711-F-1).

3. Check plant mass balance for consistency.

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ACTIVITIES TO BE COMPLETED ON A MONTHLY BASIS

The following additional activities are recommended to be undertaken on a monthly basis:

1. Grease fan bearings, if required (see fan manufacturer recommendations).

2. Check all motors and grease, if required (see motor manufacturer recommendations).

3. Check Induced Draft Fan (711-G-3) and Forced Draft Fan (711-G-4) bearings for
excessive heat, vibration, etc. and correct any problems found.

4. Check the zinc oxide catalyst bed for sulfur break through.

5. Check the gas analysis at the inlet and outlet of the Shift Converter (711-D-2). This can
be used to determine whether the catalysts are operating satisfactorily, whether
operating changes need to be made or the catalyst needs to be scheduled for
replacement.

ACTIVITIES TO BE COMPLETED ON A YEARLY BASIS

The following additional activities are typically scheduled during a maintenance turnaround,
which is typically performed annually. However, statutory and / or client operational
requirements may enable some of these requirements to be completed on a less frequent
basis. In this case the period between maintenance turnarounds may be extended.

1. Inspect the Steam Generators.

2. Conduct a thermographic analysis of the Reformer.

3. Clean the heat exchangers, in particular those that use cooling water.

4. Re-test the pressure relief valves.

5. Re-calibrate the instrumentation.

6. Perform a proof test of the safety instrumented system.

7. Check valves (PSA switching valves in particular) for leakage and replace seats and
seals, as required.

8. Perform Reformer flue gas analysis.

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XII. INSPECTION AND REMOVAL OF PLANT CATALYSTS


If problems are encountered during plant operation it may become necessary to open vessels
and inspect the catalyst. When doing this precautions need to be taken to prevent hazardous
and / or explosive conditions from occurring.

All the catalysts (except the PSA adsorbents) are in the reduced state during plant operation
and exposure to uncontrolled amounts of air can cause damage to the catalyst by rapid
oxidation.

The following sections provide some details on how each catalyst bed can be opened up for
inspection. No details of vessel entry procedures are included as each Client has their own
procedures, which must be strictly adhered to. In addition the catalyst MSDS should be
consulted for further details and disposal requirements.

NOTE: Suitable PPE must be worn at all times by personnel involved in these activities.

A. HYDROTREATER AND DESULFURIZER CATALYST

Prior to opening the vessel the catalyst beds should be cooled to 40C or less and flammable
material purged from the vessel using nitrogen. Then while maintaining a slight positive
bleed of nitrogen the vessel manway can be opened for inspection.

If it is necessary to remove the hydrotreater (Co/Mo) catalyst the desulfurizer (ZnO) catalyst
must also be removed. The catalyst can either be dumped through the bottom manway on the
side of the vessel or vacuumed out through the top manway.

The desulfurizer (ZnO) can be removed without removing the hydrotreater (Co/Mo) catalyst.
This is achieved either by dumping it through the upper manway on the side of the vessel at
the base of the ZnO catalyst bed or vacuuming it from the top manway.

NOTE: Used catalyst should be assumed to be potentially combustible because of the


adsorbed hydrogen and hydrocarbons or finely-divided carbon that can be present.

B. REFORMER CATALYST

Should uncontrolled quantities of air come into contact with the reforming catalyst at
temperatures above 146C, the nickel in the catalyst will become oxidized. This reaction
causes heat to be released at a rate sufficient to cause fusion of the catalyst. To prevent this
from happening, the catalyst must be cooled to less than 146C before it is contacted with air.
Since it is often difficult to make certain that all portions of the catalyst bed have been cooled
to below 146C, it is advisable to oxidize the nickel under controlled conditions before
contacting the catalyst with air.

The following procedure can be used to oxidize the catalyst:

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1. Stop the Reformer feed gas flow (FIC-200A/B).

2. Increase the steam flow to the 100% design (6,013 Kg/hr).

3. Adjust the burner firing to maintain a Reformer tube outlet temperature (TIC-310) of
780C and maintain these conditions for six to eight hours.

At temperatures above 774C, the steam oxidizes much of the metallic nickel in the
Reformer catalyst to nickel oxide with formation of hydrogen.

Cool the Reformer to a temperature less than 146 C and purge the Reformer tubes with a
flow of dry nitrogen. Check the discharge gas to confirm all the hydrogen and hydrocarbons
have been expelled.

The catalyst is removed from the Reformer tubes by vacuuming from the top flange of the
tube.

C. SHIFT CONVERTER CATALYST

In general the Shift Converter catalyst is non pyrophoric, however, any iron sulphide present
in the catalyst is pyrophoric, so rapid oxidization from the reduced state can cause very high
temperatures, which may ignite the catalyst and damage the vessel. Therefore after the Shift
Converter catalyst has been reduced it must not be exposed to oxygen or air except under
controlled conditions.

It is normal practice to maintain the catalyst in the reduced state during plant shut downs by
keeping it in contact with an inert or reducing atmosphere. It is recommended that the
catalyst is only oxidized when absolutely necessary, as even careful re-oxidation can cause
some damage to the catalyst.

To inspect the Shift Converter catalyst from the top manway the catalyst bed should first be
cooled to 40C or less and flammable material purged from the vessel using nitrogen. Then
while maintaining a slight positive bleed of nitrogen the vessel manway can be opened for
inspection.

It is recommended that a specialist company be engaged to remove the Shift Converter


catalyst.

D. PSA ADSORBENTS

The PSA adsorbents are expected to last for the life of the plant and therefore inspection or
replacement should not be necessary.

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XIII. S A F E T Y
The following sections are provided as a general guide only to the safe operation and
maintenance of a hydrogen plant. Not all items will be applicable to all plants and some
plants may require additional measures. Specific site and / or national occupational health
and safety requirements must be adhered to at all times and take precedence over any
information contained in these sections, when a conflict is identified.

A. GENERAL

A large part of safety on these plants revolves around the experience, training and knowledge
of the Operating personnel together with having detailed and accurate operating procedures
to follow. It is therefore incumbent on the Owner / Operator of the plant to develop these
detailed procedures to meet their particular needs and to provide adequate training to
Operating and Maintenance personnel.

Whilst these plants are designed to operate efficiently and reliably there is always a
possibility of an emergency occurring on the plant. It is therefore also incumbent on the
Owner / Operator of the plant to develop suitable Emergency Response Plans to any
foreseeable incident.

B. SUMMARY OF POTENTIAL HAZARDS

Despite the plant being designed to minimize the exposure of Operating and Maintenance
personnel to hazards, the following hazards are typically present:

(1). Fire and / or explosion.

(2). Asphyxiation from exposure to atmospheres that are low in oxygen content.

(3). Electrical shock.

(4). Falls from ladders or platforms.

(5). Chemical Handling.

(6). Equipment noise.

(7). Heat Stress.

Recommended practices for ensuring safety in each of these areas are provided in the
following sections.

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1. FIRE AND EXPLOSION

Carbon monoxide, methane and hydrogen gas are all continuously present on the plant when
in operation and each of these gases is flammable when mixed with oxygen. In addition,
when the plant is operated with LPG feedstock butane, butene, propane and propene may
also be present and these gases are also flammable when mixed with oxygen.

The following table indicates the flammable limits of each of these gases with air:

Component Lower Explosive Limit Upper Explosive Limit


(LFL) [Vol%] (UFL) [Vol%]

Hydrogen 4.0 77.0

Carbon Monoxide 10.9 74.0

Methane 4.4 17.0

Butane 1.4 9.3

Butene 1.6 10.0

Propane 1.7 10.9

Propene 2.0 11.0

If a fire occurs with any of these gases and the flames are extinguished without stopping the
gas flow, the gases can re-ignite explosively.

To reduce the possibility of fire and / or explosion the following precautions should be
adopted:

1. Do not permit smoking on site at any time.

2. Do not permit mobile phones to be used on site in any areas where potentially
explosive atmospheres may exist.

3. Do not permit any hot works on site unless the area where the work is to be
performed is tested for the presence of a flammable atmosphere and work is strictly
controlled using a hot work permit system.

4. Provide adequate signage on the site to inform personnel when they are entering an
area where potentially explosive atmospheres are likely to occur.

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5. Ensure all electrical equipment used on the site is suitable for use in a potentially
explosive atmosphere. Any portable electrical equipment that is bought onto the site
which is not suitable for a potentially explosive atmosphere must only be operated
under the hot work permit system.

6. Aluminum alloys when impacted on steel structures can produce an incendive spark
which is capable of igniting an explosive atmosphere. Therefore normal maintenance
equipment used on site, such as aluminum ladders and scaffolding, are potential
ignition sources. Care should be taken if items such as these are used on site and it is
recommended that they are used under the hot work permit system.

7. Due to the very low ignition energy of hydrogen a static discharge could ignite a
potentially explosive atmosphere. Take measures to prevent static discharges by
wearing antistatic clothing, using antistatic tools and providing adequate equi-
potential bonding on equipment.

8. Always purge the plant with nitrogen if air ingress into the process system is
suspected, before introducing any flammable material.

FIRE FIGHTING

If a fire is detected, immediately alert the fire department and evacuate all non essential
personnel from the area. If appropriate shut down the plant.

If possible, shut off the flow of fuel to the fire but DO NOT PUT YOURSELF IN
DANGER.

Use water cannons and / or hoses to cool equipment adjacent to the fire but do not extinguish
the fire until the fuel source is removed, as this can lead to re-ignition of the fuel causing an
explosion.

If the fire is large, only the Fire Department is equipped to fight the fire.

If the fire is small, local fire extinguishers may be used to control the fire but ensure the
correct extinguisher is used to fight the fire. For instance, an electrical fire should only be
fought with an extinguisher containing carbon dioxide or dry chemical and never with water.

2. ASPHYXIATION HAZARDS

Asphyxiation can occur when the oxygen content in the atmosphere is reduced to below
normal levels. Safe oxygen levels for human occupation are considered to be between 19.5%
and 23%. When the concentration of oxygen in the atmosphere falls below 16%, symptoms
of anoxia begin to appear in humans. If the concentration of oxygen falls below 6%,
respiration stops and in a few minutes heart action may cease. Sudden entry into areas
containing little or no oxygen will result in almost immediate loss of consciousness with no
warning.

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If it is suspected that the oxygen content falls outside what is considered the safe range then
special precautions are required. These special precautions may include providing adequate
ventilation in the area or using breathing apparatus to enter the area.

Typical areas on the plant where it may be possible to have an atmosphere with a reduced
oxygen concentration are inside closed buildings or near an opening to a tank, vessel, duct,
vent or container, particularly when nitrogen purging operations are in progress.

As nitrogen, hydrogen and carbon monoxide are colorless, odorless, and tasteless gases they
can not be detected by human senses. Atmospheric monitors are the only method to ensure a
suitable atmosphere for human occupation is present. Ensure that atmospheric monitors are
maintained and calibrated in accordance with the manufacturers instructions at all times.

Entry into vessels poses a very unique hazard due largely to the possibility than the
atmosphere inside the vessel will be oxygen deficient. Vessel entry should only be
considered when absolutely necessary and strictly controlled via a vessel entry permit system.

3. ELECTRICAL SHOCK

Improper use and / or setting of electrical devices or attempting to service equipment without
first disconnecting the electric power source can lead to electrical shock. The following list
provides general precautions that should be observed when operating and / or maintaining
electrical equipment:

1. Only qualified electrical personnel should maintain electrical equipment.

2. Maintenance on any electrical equipment (and the equipment driven by the electrical
equipment) should only be carried out under an electrical permit system which has
provisions for positive electrical isolations.

3. Safety interlocks on electrical equipment should never be bypassed.

4. Before commencing work on any electrical equipment, become thoroughly familiar


with the manufacturer's instructions and follow them explicitly.

5. Before removing any covers or opening any doors which permit access to the primary
circuits, it is essential that the circuit is de-energized and locked out.

6. All electrical connections should be considered live until proven otherwise.

7. Switches that have been opened to de-energize a circuit to permit work to be


undertaken should be padlocked or blocked open and clearly labeled.

8. Ensure any arc chutes and barriers are in place before operating circuit breakers,
contacts, and switches under load. Arc chutes are essential to confine and extinguish
arcs. Without the chutes the arcs may do serious damage.

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9. Do not close a breaker or contact with the compartment door open. Always keep all
doors closed and latched when equipment is operating.

10. Breaker tripping capacitors retain their charge for some time after disconnecting
power. Discharge capacitors before touching any wiring or connections.

11. The insulating surfaces of high voltage equipment should never be touched when the
equipment is energized. A voltage stress exists across the entire surface from
terminals to grounded parts, and serious injury or death can result from coming in
contact with this material.

12. Transformer tap changers are not usually designed to interrupt current. For this
reason, the tap changer must not be operated while the transformer is energized and
the transformer must not be energized unless the tap changer handle is locked in an
operating position.

13. If a motor trips due to an overload, do not increase the overload trip device setting to
keep the motor running without investigating and correcting the cause of the
overload.

14. Never work on energized electrical equipment alone. Always have someone else in
the immediate vicinity in case of accident or other emergency.

15. Plant safety is dependant upon proper operation and maintenance of the electrical
equipment. Keep this equipment in good working condition by routinely inspecting
and maintaining the equipment, as required.

4. FALLS FROM LADDERS OR PLATFORMS

The following general advice is provided when work from a ladder or platform is required:

1. Ensure any portable ladders or scaffolding complies with the site standard and is
covered under the permit to work system.

2. Do not climb ladders or work at elevated heights if you feel dizzy or sick.

3. Wear appropriate footwear to maximize grip; if possible avoid work on ladders and
platforms when wet, but in any event use special care under such conditions to avoid
slipping.

4. Use a safety harness whenever working at elevated heights over 1.6m (or other
maximum height limit set by the site requirements or national occupational health
and safety requirements).

5. Use both hands when climbing ladders; hoist up tools after you have reached your
work position.

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6. If possible, do not work alone.

5. CHEMICAL HANDLING

The following general advice is provided on chemical handling and suggested first aid
procedures given. However, the MSDS for any chemicals handled must always be consulted
before handling and all recommendations and procedures contained therein strictly adhered
to.

a) INHALATION OF CHEMICALS

Chemicals that vaporize may be inhaled by personnel in the vicinity. This may lead to a local
irritation of the upper respiratory tract (nose, mouth, and throat), irritation of the lower
respiratory tract (bronchi and lungs), or may even lead to the chemical being absorbed into
the body causing general illness or clouding of consciousness.

Some chemicals exert effects on the central nervous system that may produce dizziness,
faintness, stupor and eventual coma. This action is known as anesthesia or narcosis. Other
chemicals may interfere with proper oxygenation of the blood, thereby producing asphyxia.
An anesthetized or asphyxiated worker constitutes a real emergency.

Any personnel complaining of illness, acting strangely, or appearing ill in the area of the
chemicals should be taken immediately to obtain medical assistance.

Suggested first aid procedures for personnel incapacitated by the inhalation of chemical
vapors are a follows:

1. Shout for assistance.

2. Protect yourself. Use suitable respiratory protection.

3. Move victim to non-contaminated area.

4. Remove, tear off, or cut off contaminated garments.

5. If victim stops breathing, immediately begin artificial respiration and continue until
medical assistance arrives.

6. If victim is vomiting, place victim in the recovery position to prevent the victim
choking on the vomit.

NEVER GIVE AN UNCONSCIOUS PERSON ANYTHING BY MOUTH!

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b) CHEMICALS IN THE EYES

Many chemicals are capable of injuring the eyes. Any vapor, solid, or liquid chemical
contamination of the eyes should be treated rapidly. Rinse, flood, flush, or irrigate eyes with
copious amounts of WATER ONLY.

NEVER use any neutralizing agent or solution in eyes.

Suggested first aid procedures for personnel with chemicals in their eyes are a follows:

1. Use fingers to spread eyelids widely and wash eyes with water continuously for at
least fifteen minutes.

2. Move or roll eyes in all directions up, down, right, left, and roll in a circle so that the
irrigating water can wash out all crevices and corners of the eyes.

3. Seek medical assistance.

c) CHEMICALS ON THE SKIN

Many chemicals are capable of injuring the skin; some injure immediately and some have a
delayed action. Some chemicals may also penetrate the skin in amounts sufficient to cause
systemic illness. Any chemical on the skin should be removed as soon as possible.

The severity of chemical injury to the skin is usually determined by the concentration and
length of contact. In most cases, the more concentrated the chemical and the longer the
exposure, the more severe the skin injury.

The irritant action of any chemical is greatly increased when the chemical is held in contact
with the skin, for instance from clothing impregnated with the chemical. Do not overlook
contaminated shoes.

Suggested first aid procedures for personnel with chemicals on their skin are a follows:

1. Small chemical exposures to the skin should be promptly flooded with water followed
by thorough, gentle scrubbing with soap and water.

2. Contaminated clothing should be removed and the underlying skin washed with
running water followed by soap and water.

3. If large skin or clothing contact occurs, the person should hurry to the nearest safety
shower and remove clothing while standing in the shower. The skin should be
thoroughly washed with water in the shower followed by gentle scrubbing with soap
and water.

4. Seek medical assistance.

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d) SWALLOWED CHEMICALS

It is unlikely that personnel would intentionally swallow any chemical, but in an accident a
forceful stream or spray may strike a person’s face resulting in nose or mouth contamination
which may subsequently be swallowed.

No suggested first aid is given for this scenario as the actions dependent very much on the
chemicals ingested. Any garments contaminated with the chemicals should be removed and
medical assistance sought immediately.

6. EQUIPMENT NOISE

Equipment is designed for a maximum noise level of 85 dBA when measured 1m from the
device. Any areas of high noise (if any) should be identified during plant operation and
suitable precautions taken in these areas.

7. HEAT STRESS

The hydrogen plant operates at elevated temperatures and therefore there may be areas on the
plant where personnel are exposed to high heat concentrations. Typically one such area is on
top of the Reformer and personnel working here for any period of time should be monitored
for heat stress.

Other areas (if any) that may be subject to high heat concentrations should be identified
during plant operation and suitable precautions taken to prevent personnel succumbing to
heat stress in these area. As the plant is located outside high ambient temperature should also
be considered as a potential cause of heat stress.

If it is suspected that a person is suffering from heat stress remove them to a cool
environment and seek medical assistance.

C. HAZARDOUS AREA CLASSIFICATION

The process areas of the plant (including the PSA) have generally been classified as a Class 1
Division 2 Group B hazardous area in accordance with the NEC requirements. Reference
should be made to the hazardous area classification drawing for full details.

D. GENERAL PROPERTIES OF GASES AND CATALYSTS USED ON SITE

The following sections provide some background information on gases and catalyst materials
found on site. Reference should also be made to the relevant MSDS and any local regulations
for handling these gases and materials.

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1. CARBON MONOXIDE

Carbon monoxide is an insidious gas because it is colorless, odorless, and possesses no


properties that might warn of its presence. It is neutrally buoyant in air and can form an
explosive mixture with air. CO has an affinity for hemoglobin at least 200 times greater than
that of oxygen. Thus, by combining with hemoglobin, it renders the blood incapable of
carrying oxygen to tissues in humans and is therefore an asphyxiant. The OSHA standard for
personnel exposure to CO is 50 ppm by volume in air. No person should work in an area that
contains more than 75 ppm of CO without adequate breathing protection.

CO is a poison when inhaled and inhalation is the only way it can enter the body. At high CO
concentrations, a person may become unconscious in seconds and without warning.
Symptoms of CO poisoning are headache, nausea, dizziness, impairment of vision and
hearing, mental confusion, collapse, and unconsciousness. Sometimes muscular weakness
develops so rapidly that escape by physical means becomes impossible.

Preventing CO poisoning is best accomplished by providing good ventilation where


contamination may be a problem. If good ventilation is not possible in the work areas, then
CO poisoning can be prevented by use of suitable respiratory protective equipment. Because
a person will normally be unaware of any accidental buildup of CO while wearing respiratory
equipment, they can be quickly overcome if the respiratory equipment suddenly fails.
Warning devices and detection equipment to determine concentrations of CO in the plant
work areas should be provided.

The following table provides an indication of the effect of CO at varying concentrations.

CO CONCENTRATION
EFFECT
(%) (ppm)

0.005 50 Permissible for 8 hours exposure

0.02 200 Possible mild headache in 2 to 3 hours

0.04 400 Headache and nausea after 1 to 2 hours

0.08 800 Headache, dizziness, and nausea in 3/4 hour, collapse


possibly unconsciousness in 2 hours

0.16 1,600 Headache, dizziness, and nausea in 20 minutes, collapse,


unconsciousness, and possibly death in 2 hours

0.32 3,200 Headache and dizziness in 5 to 10 minutes; unconsciousness


and danger of death in 30 minutes

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CO CONCENTRATION
EFFECT
(%) (ppm)

0.64 6,400 Headache and dizziness in 1 to 2 minutes; unconsciousness


and danger of death in 10 to 15 minutes

1.28 12,800 Immediate headache and dizziness; unconsciousness and


danger of death in 1 to 3 minutes

Typical first aid for a person exposed to CO poisoning would be:

1. Remove the person to an uncontaminated area, however, do not enter an area where
high CO concentrations are suspected without suitable breathing apparatus, otherwise
one victim many become two.

2. If breathing has stopped, perform artificial respiration until natural breathing is


restored.

3. Administer oxygen, if available, as soon as possible even during application of


artificial respiration. Continue until medical assistance becomes available.

4. Keep exposed individual warm and quiet.

5. Seek medical assistance.

2. HYDROGEN GAS

Hydrogen is colorless, odorless, and possesses no properties that might warn of its presence.
It is much lighter than air and will migrate quickly upwards if released in air. Hydrogen can
form a highly explosive mixture with air. A hydrogen atmosphere will cause asphyxia.

Less that 20μJ of energy are required to ignite hydrogen. Hydrogen burns with a colorless,
odorless flame that makes it invisible to the naked eye. Whilst a hydrogen flame burns
intensely the low radiant heat generated by the flame can enable a person to come into close
contact with the flame without realizing the flame is present.

3. NATURAL GAS

Natural gas (main component is typically methane) is colorless and odorless in its raw state,
however, it is usually odorized to enable the gas to be detected by smell. It is lighter than air
and will migrate upwards if released in air. Natural gas can form an explosive mixture with
air. A natural gas atmosphere will cause asphyxia.

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4. LPG GAS

LPG gas is colorless and is usually odorized to enable the gas to be detected by smell. It is
heavier than air and will migrate downwards if released in air. LPG gas can form an
explosive mixture with air.

5. NITROGEN

Nitrogen is colorless, odorless, and possesses no properties that might warn of its presence. It
is neutrally buoyant in air and is non toxic. Nitrogen does not form an explosive mixture with
air. A nitrogen atmosphere will cause asphyxia.

6. ZINC OXIDE

Zinc oxide comes in the form of a white or yellowish powder. Zinc is not inherently a toxic
element, however, when heated it evolves fumes of zinc oxide, which when inhaled can
cause a disease known as “brass founders' ague” or “brass chills.” It is possible for people to
become immune; however, this immunity can be lost by cessation of exposure in only a few
days. There are no known cumulative effects to the inhalation of zinc oxide fumes. It has
been stated that zinc oxide dust can block the ducts of the skin secretion glands and give rise
to a papular, pustular eczema in men engaged in packing this compound into barrels.
Sensitivity to zinc oxide in man is extremely rare. Wearing of respiratory protective
equipment to prevent inhalation of fresh fumes is recommended in known high concentration
areas.

A limit of 5 mg/m3 is recommended by the American Conference of Governmental Industrial


Hygienists for zinc oxide fume. It is believed that if concentrations are kept below this level,
the incidence of “brass chills” will be low and any attacks that do occur will be mild. The
symptoms of zinc oxide fume inhalation include fever, chills, muscular pain, nausea, and
vomiting, but complete recovery normally occurs within 24 to 48 hours. Medical attention
should be sought in case of accidental ingestion.

7. MOLECULAR SIEVES

Molecular sieves are synthetically produced crystalline metal aluminosilicates that have been
activated for adsorption by removing their water of hydration. No information regarding
toxicity has been found on molecular sieves.

8. ACTIVATED CARBON

Inhalation of activated carbon is considered only slightly toxic. No Threshold Limit Value
(TLV8) for an 8 hour time weighted exposure or OSHA standard have been established. The
activated carbon used in this unit may liberate iron/nickel carbonyls upon regeneration which
may be toxic. Activated carbon should be considered as a nuisance particulate.

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9. NICKEL CARBONYL HAZARD

Catalysts containing metallic nickel (such as the Reformer catalyst) must not be exposed to
gases containing carbon monoxide at temperatures below 200C otherwise it is possible to
form nickel carbonyl (NiCO4) which is highly toxic. Nickel carbonyl is a colorless liquid at
ambient temperature and is reported to have a musty smell and has a very low boiling point
of 42.5C at 1 atm. During normal operation the Reformer catalyst is well above this
temperature and during plant shutdown the catalyst is normally steamed to remove the
hazard, however, if conditions are present where nickel carbonyl may form then stringent
precautions must be observed to avoid any risk to personnel.

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APPENDIX A. NORMAL OPERATING PROCEDURES


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APPENDIX B. PLANT READINGS AT 100% CAPACITY


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APPENDIX C. INITIAL ALARM SETTINGS


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APPENDIX D. PROCESS FLOW DIAGRAMS/HEAT AND MATERIAL


BALANCE
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APPENDIX E. MECHANICAL FLOW DIAGRAMS


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APPENDIX F. CAUSE AND EFFECT MATRIX


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APPENDIX G. PSA STEPPING LOGIC


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APPENDIX H. HAZARDOUS AREA CLASSIFICATION DRAWING