A Plant Design Project on Production of

Gasoline by Sulphuric Acid Alkylation of Olefins

Session: 2010-2014
Project Advisors
Prof. Dr. Syed Nadir Hussain
Project Members
Zain Ul Abidin

CE-M10-02

Ahmed Javed

PG-M10-03

Umar Draz

CE-M10-24

Ali Hasnain

CE-M10-47

Institute of Chemical Engineering and Technology

UNIVERISITY OF THE PUNJAB
LAHORE-PAKISTAN

STATEMENT BY THE AUTHORS

We hereby declare that this submission is our own work and to the best of our
knowledge, it contains no material previously published or written by another
person, no material which to a substantial extent has been accepted for the
award of our other degree or diploma at any educational institution, except
where due acknowledgement is made in the thesis.

Signatures

Date

Approved by: Supervisor:

Prof. Engr. Dr. Syed Nadir Hussain,
Institute of Chemical Engineering & Technology, Faculty of Engineering &
Technology, University of the Punjab.

Signature

Date

Director:
Prof. Dr. Amir Ijaz,
Institute of Chemical Engineering & Technology, Faculty of Engineering &
Technology, University of the Punjab.

Signature

Date

DEDICATION
To Almighty Allah; for His daily blessings, make all
our work possible.
To our Parents; who are full of sympathy and
everlasting love.
To Prof. Engr. Dr. Syed Nadir Hussain ; for his
fatherly behavior and inspiring guidance.
To our dearest homeland, Pakistan.

ABSTRACT
Light Ends are the valuable products of a Petroleum refinery, their utilization as
a refinery fuel is not an effective solution; considering economic, product slate
and environmental factors. Alkylated Gasoline is one of the most promising
additions to refinery's Gasoline pool, with its High Octane number and added
advantages of Lower sulfur, Lower RVP, Lower Drivability Index, No Aromatic
Contents.
The new environmental regulations are forcing refineries to adapt new
technologies to reduce the sulfur, aromatics contents while increasing the
products quality and reducing emissions for Gasoline. There are number of
ways by which these requirements can be met, and Alkylation is one of the
best method that a refinery can adopt, not only to meet new environmental
regulations, but also to increase the quality of Gasoline Pool by positively
affecting the Refinery economic end because of the utilization of the light ends,
that are converted to a more valuable Gasoline product.
The installation of Alkylation unit is quite feasible, as considerable amount of
Light ends can be obtained from petroleum refinery's number of processes, like
FCCU, Plat-forming Unit, Coker, Thermal Cracking, Gasoline Stabilization Unit
etc
The Alkylated Gasoline can be produced using different patented processes
available, depending on the type of catalyst or the technology offered by a
specific company. The properties of the Gasoline produced using these
processes depends on the type of feed available for the process, the relevant
processes taking place in refineries from which light ends are obtained, the
catalyst type used, the operating temperature & pressure conditions & several
other factors.
The H2SO4 Alkylation Process of Exxon Mobil with Auto-refrigeration
technology is used; all the calculations of Material & Energy are performed
with the designing of some important equipment as well. Consideration is
given to related factors for the safety of the environment and people working
and
residing
near
the
plant
area.

ACKNOWLEDGMENTS
I have only the pearls of my eyes to admire the blessings of the Compassionate
and Omnipotent because the words are bound, knowledge is limited and the
time is short to express HIS dignity. We are immeasurably grateful to Almighty
Allah, the Propitious, the Benevolent and Sovereign, who has endowed our
brain and instable instinct contraction of knowledge and body to accomplish
our work in the form of this dissertation, whose blessing and glory flourished
our thoughts, thrived our ambitions, granted us talented teachers, affectionate
parents, sweet sisters, loving brothers and exceptional friends.
Trembling lips and wet eyes praise for The Last Prophet Hazrat Muhammad
(PBUH) for enlightening our conscience with the essence of faith in ALMIGHT
ALLAH, enabling us to recognize the Oneness of our creator, and showed us
the right path for the success. Faithfulness in the performance of small duties
gives us strength to adhere to difficult determinations that life will someday
force us to make.
"The ink of the scholar is more holy than the blood of the martyr."
The work presented in this thesis was accomplished under the sympathetic
attitude, fatherly behavior, animate direction, observant pursuit, scholarly
criticism, sheering perspective and enlightened supervision of Prof. Dr. Engr.
Syed Nadir Hussain, Institute of chemical Engineering and Technology,
University of the Punjab for his thorough analysis and rigorous critique
improved not only the quality of this thesis, but also our overall understanding.
We are also very grateful to his ever inspiring guidance, keen interest, scholarly
comments and constructive suggestions during the course of our studies.
We appreciate his valuable comments and suggestions to make this work
complete. We deem it our utmost pleasure in expressing our cordial gratitude
with the strategic command at every step. His valuable suggestion will always
serve as beacon of light throughout the course of our studies.
We owe a great debt of gratitude to our worthy Director Prof. Dr. Amir Ijaz, for
his kind, loving positive thoughtful criticism, keen personal interest, sincere

advice, vital instructions throughout the course of our studies besides his very
busy schedule. We fervently extent my zealous thanks to him, also for creating
a healthy & beautiful environment.

NOMENCLATURE
SYMBOL
V
V

DESCRIPTION

UNIT
m3
m3
Cp
W/m2.oC
W/m2.oC
W/m2.oC
kg/m3
kJ/kmol.K
Bar
C
M
Mm
Mm
Mm
um
m/s
kg/s.m2
kg/h
Watt
m3.Pa/mol.C
m/s2

S
E
H
Ad
Ah
An
AT

volume of the reactor

volume of catalyst
Viscosity
inside heat transfer coefficient
shell side heat transfer coefficient
overall heat transfer coefficient
Density
specific heat
pressure drop
Temperature
Length
outer diameter of tube
inner dia ot tube
dia of the particle
dia of the dispersed phase
terminal falling velocity
mass velocity
mass flow rate
Heat
gas constant
number of tubes
Reynolds number
acceleration due to gravity
Voidage
total entrainment
Enthalpy
down comer area
hole area
net area
total area

Ada

area under down comer apron

(m2)

Df

flow width normal to liquid flow

(m)

diameter of tower

(m)

reflux ratio

Rm

minimum reflux ratio

relative volatility

UOP

Universal Oil Products

HF

Hydrofluoric Acid

hi
hs
U
P
CP

AP
T
L
Do
Di
Dp
Dd
Ut
G
M
q

R
Nt
Re
g

(kg/sec)
(kJ/kgmol C)
(m2)
(m2)
(m2)
(m2)

Table of Contents
1.1 WHAT IS GASOLINE? ................................................................................. 24
1.2 BACKGROUND & USES .............................................................................. 24
1.3 OCTANE RATING ....................................................................................... 25
1.4 PHYSICAL PROPERTIES OF GASOLINE ........................................................ 26
1.5 WHAT IS ALKYLATION? ............................................................................. 26
1.6 HISTORY OF ALKYLATION .......................................................................... 27
1.7 ALKYLATION FEEDSTOCKS ......................................................................... 28
1.8 TYPES OF ALKYLATION PROCESSES ........................................................... 29
1.8.1

THERMAL ALKYLATION ........................................................................ 29

1.9 CATALYTIC ALKYLATION ............................................................................ 30

1.10 TYPES OF ACID CATALYSTS USED IN ALKYLATION ..................................... 30
1.10.1

SULPHURIC ACID ALKYLATION PROCESS .............................................. 30

1.10.2

HF ALKYLATION ................................................................................... 32

1.11 COMPARISON OF H2SO4 & HF ................................................................... 33

1.11.1

FEED AVAILABILITY AND PRODUCT REQUIREMENTS ........................... 34

1.11.2

SAFETY & ENVIRONMENTAL CONSIDERATIONS ................................... 34

1.11.3

OPERATING COSTS .............................................................................. 36

1.11.4

UTILITY COSTS ..................................................................................... 36

1.11.5

CATALYST AND CHEMICAL COSTS ........................................................ 37

1.11.6

CAPITAL INVESTMENT ......................................................................... 37

1.11.7

MAINTENANCE .................................................................................... 38

1.12 H2SO4 VS. HF SUMMARY ........................................................................... 38

2 CHAPTER # 2: ..................................................................................... 40
2.1 METHODS OF H2SO4 ALKYLATION MANUFACTURE ................................... 40
2.2 EFFLUENT REFRIGERATION ....................................................................... 40
2.2.1

CASCADE AUTOREFRIGERATION.......................................................... 41

2.3 PROCESS VARIABLES ................................................................................. 42

8

2.3.1

REACTION TEMPERATURE ................................................................... 42

2.3.2

ACID STRENGTH .................................................................................. 42

2.3.3

ISOBUTANE CONCENTRATION ............................................................. 43

2.3.4

OLEFINS SPACE VELOCITY .................................................................... 43

2.4 ALKYLATION CHEMISTRY .......................................................................... 43

2.4.1

REACTION MECHANISM ...................................................................... 43

3 CHAPTER # 3: ..................................................................................... 46
3.1 CAPACITY & BASIS .................................................................................... 46
3.2 EQUATION OF MATERIAL BALANCE .......................................................... 46
3.3 REACTOR (R-101) ...................................................................................... 47
3.3.1

MATERIAL IN ....................................................................................... 47

3.3.2

REACTIONS .......................................................................................... 48

3.3.3

MATERIAL OUT .................................................................................... 49

3.4 PHASE SEPARATOR (PS-101) ..................................................................... 50

3.4.2

MATERIAL IN ....................................................................................... 50

3.4.3

MATERIAL OUT: ................................................................................... 51

3.5 DISTILLATION COLUMN (DC-101) ............................................................. 52

3.5.2

MATERIAL IN ....................................................................................... 52

3.5.3

MATERIAL OUT .................................................................................... 52

3.6 DISTILLATION COLUMN (DC-102) ............................................................. 54

3.6.2

MATERIAL IN ....................................................................................... 54

3.6.3

MATERIAL OUT .................................................................................... 55

3.7 BALANCE TO MIXING POINT ..................................................................... 55

4 CHAPTER # 4: ..................................................................................... 57
4.1 ENERGY BALANCE EQUATION ................................................................... 57
4.2 HEAT OF REACTIONS................................................................................. 57
4.2.1

At 298K ............................................................................................... 57

4.2.2

REACTION 1 ......................................................................................... 57

4.2.3

REACTION 2 ......................................................................................... 57

4.2.4

REACTION 3 ......................................................................................... 58

4.2.5

Heats of Formation Data: Hf (kJ/gmol): Vol. 6 .................................... 58

4.3 REACTOR (R-101) ...................................................................................... 59

4.3.1

Table 16: Stream 3+13: ....................................................................... 59

4.3.1.1

Table 17: Stream 4+14: ....................................................................... 60

4.3.2

Heat of Reaction Added At 298 K ........................................................ 60

4.3.3

Total Heat of Reaction: ........................................................................ 60

4.3.4

Latent Heat Required To Vaporize the Mixture ................................... 60

4.4 PHASE SEPARATOR (PS-101) ..................................................................... 61

4.5 ACROSS COMPRESSOR ............................................................................. 62
4.5.2

Balance ............................................................................................... 63

4.5.3

63

4.5.4

kJ ......................................................................................................... 63

4.6 ACROSS HEAT EXCHANGER HX-102 (CONDENSER) ................................... 63

4.6.2

Vapor Stream After Compression enters in cooler condenser: ............ 63

4.6.3

Balance: .............................................................................................. 63

4.7 ACROSS DE-PROPANIZER DC-102.............................................................. 64

4.8 ACROSS PUMP (STREAM 6)....................................................................... 65
Stream 6 in:............................................................................................................ 65
4.8.2

Table 25: Stream 6 out: ....................................................................... 65

4.9 ACROSS HEAT EXCHANGER HX-108 .......................................................... 66

Stream 6 in:............................................................................................................ 66
4.9.1.1

Table 27: Stream 6 out: ....................................................................... 66

4.10 ACROSS DE-ISOBUTANIZER DC-101 .......................................................... 67

4.10.1.1

Table 29: Stream 11: ........................................................................... 67

4.10.1.2

Table 30: Stream 7: ............................................................................. 67

4.11 AT MIXING POINT ..................................................................................... 68

4.11.1.1

Table 32: Stream 1: ............................................................................. 68

4.11.2

Table 33: Stream 2: ............................................................................. 69

4.11.2.1

Table 34: Stream 12: ........................................................................... 69

10

4.11.3

Balance: .............................................................................................. 69

5 CHAPTER # 5: ..................................................................................... 70
5.1 HEAT EXCHANGER .................................................................................... 70
5.2 TYPES OF HEAT EXCHANGERS ................................................................... 70
5.3 HEAT-TRANSFER FLUIDS ........................................................................... 70
5.4 HEAT-EXCHANGER EVALUATION AND SELECTION .................................... 71
5.5 SHELL AND TUBE HEAT EXCHANGER ......................................................... 74
5.5.1

Tube diameter:.................................................................................... 74

5.5.2

Tube thickness: ................................................................................... 74

5.5.3

Tube length: ........................................................................................ 74

5.5.4

Tube pitch: .......................................................................................... 75

5.6 CONSTRUCTION OF 1-2 SHELL AND TUBE HEAT

EXCHANGER 75
5.6.1

Shell .................................................................................................... 75

5.6.2

Tubes .................................................................................................. 76

5.6.3

Tube sheets ......................................................................................... 76

5.7 TUBE TO TUBE-SHEET ATTACHMENT ........................................................ 77

5.8 NOZZLES 77
5.8.2

IMPINGEMENT PLATE.......................................................................... 78

5.8.3

TUBE-SIDE CHANNELS ......................................................................... 78

5.8.4

CHANNEL COVERS ............................................................................... 78

5.8.5

PASS DIVIDER ...................................................................................... 78

5.9 BAFFLES 78
5.9.1

CLASSIFICATION OF BAFFLES: .............................................................. 79

5.9.2

Transverse Baffles: .............................................................................. 79

5.9.3

Segmental Baffles:............................................................................... 79

5.9.4

BAFFLE SPACING ................................................................................. 80

5.9.5

Disk and doughnut baffle .................................................................... 80

5.9.6

Orifice baffle ....................................................................................... 81

5.9.7

Longitudinal baffles ............................................................................. 81

11

5.9.8

Flanged joints ...................................................................................... 82

5.9.9

Flanged Joint Types ............................................................................. 82

5.9.10

TUBE PITCH ......................................................................................... 82

5.10 THERMO HYDRAULIC DESIGN PROCEDURE............................................... 83

5.10.1

Shell and Tube Heat Exchanger ........................................................... 83

5.10.2

SHELL SIDE CALCULATION ................................................................... 83

5.10.3

TUBE SIDE CALCULATION .................................................................... 83

5.11 DESIGN DATA............................................................................................ 86

5.11.1

Fluid 1: Process stream ....................................................................... 86

5.11.2

Fluid 2 : Cooling Utility (25 % Brine Soln.) ............................................ 86

5.11.3

Unknowns: .......................................................................................... 86

5.11.4

Heat Duty ............................................................................................ 86

5.11.5

Flowrate .............................................................................................. 86

5.11.6

Flowrate Of Utility ............................................................................... 87

5.12 PHYSICAL PROPERTIES .............................................................................. 87

5.12.1

Process Stream : .................................................................................. 87

5.12.2

Brine Solution : .................................................................................... 87

5.13 ASSUME OVERALL COEFFICIENT, U0.......................................................... 87

5.14 MEAN TEMPERATURE DIFFERENCE .......................................................... 87
5.15 HEAT TRANSFER AREA .............................................................................. 88
5.16 DECIDE THE EXCHANGER LAYOUT ............................................................ 88
5.17 INDIVIDUAL H.T.C ..................................................................................... 89
5.17.1

TUBE SIDE CALCULATION .................................................................... 89

5.17.2

Mass Vel: ............................................................................................. 90

5.17.3

Linear Vel: ........................................................................................... 90

5.17.4

Renould's # :........................................................................................ 90

5.17.5

Prandle # : ........................................................................................... 90

5.18 SHELL SIDE CALCULATION ......................................................................... 90

5.18.1

Mass Velocity ...................................................................................... 91

5.18.2

Linear Velocity..................................................................................... 91
12

5.18.3

Equivalent Diameter............................................................................ 91

5.18.4

Reynold Number: ................................................................................ 91

5.18.5

Prandle Number: ................................................................................. 91

5.19 OVERALL CO-EFFICIENT UO ....................................................................... 91

5.20 PRESSURE DROP P .................................................................................. 92
5.20.1

TUBE SIDE ........................................................................................... 92

5.20.2

SHELL SIDE .......................................................................................... 93

6 CHAPTER # 6: ..................................................................................... 96
6.1 CHEMICAL REACTORS ............................................................................... 96
6.2 TYPES OF REACTORS ................................................................................. 96
6.3 SELECTION OF REACTOR ........................................................................... 96
6.4 WHY WE SELECTED CSTR? ........................................................................ 97
6.5 SOME IMPORTANT ASPECTS OF THE CSTR................................................ 97
6.6 PFR (PLUG FLOW REACTOR) ..................................................................... 98
6.7 CSTR (CONTINUOUS STIRRED-TANK REACTOR) ........................................ 98
6.8 SELECTION OF IMPELLER .......................................................................... 100
6.8.1

Based on: ............................................................................................ 100

6.9 DESIGN OF CASCADE AUTOREFRIGERATED REACTOR ............................... 101

6.10 VOLUME OF REACTOR .............................................................................. 101
6.11 VOLUME OF REACTION ZONE ................................................................... 101
6.12 VOLUME OF SETTLING ZONE .................................................................... 102
6.13 LENGTH AND DIAMETER ........................................................................... 103
6.14 BAFFLES 103
6.15 IMPELLER DESIGN ..................................................................................... 103
6.15.1

Conditions ........................................................................................... 103

6.16 REYNOLDS NUMBER ................................................................................. 104

6.17 POWER CONSUMPTION............................................................................ 104
6.18 TYPES OF HEAD COVERS ........................................................................... 104
6.19 MECHANICAL DESIGN ............................................................................... 105
13

6.19.1

SHELL THICKNESS ................................................................................ 105

6.19.2

ELLIPSOIDAL HEAD THICKNESS ............................................................ 105

6.20 MATERIAL OF CONSTRUCTION ................................................................. 106

6.20.1

FOR REACTOR...................................................................................... 106

6.20.2

FOR IMPELLER BLADES ........................................................................ 106

6.20.3

FOR BAFFLES ....................................................................................... 106

6.21 SPECIFICATION SHEET ............................................................................... 107

7 CHAPTER 7:........................................................................................ 108

7.1 CHOICE BETWEEN PLATE AND PACKED COLUMN ..................................... 108
7.2 CHOICE OF PLATE TYPE ............................................................................. 109
7.3 NATURE OF FEED ...................................................................................... 113
7.4 PINCH TEMPERATURE............................................................................... 113
7.4.1

Pinch temperature: ............................................................................. 113

7.5 MINIMUM REFLUX RATIO ......................................................................... 114

7.5.2

Colburns Method: .............................................................................. 114

7.6 NUMBER OF PLATES ................................................................................. 114

7.6.1

Gilliland Method: ................................................................................ 115

7.7 EFFICIENCY OF THE COLUMN ................................................................... 115

7.8 FEED PLATE ............................................................................................... 116
7.8.1

Kirkbride Method: ............................................................................... 116

7.9 COLUMN DIAMETER: DC CALCULATION .................................................... 116

7.10 FLOODING VELOCITY ................................................................................ 117
7.10.1

Maximum volumetric flow rate of vapors: .......................................... 117

7.10.2

Net area required: ............................................................................... 117

7.10.3

Column Cross sectional Area: .............................................................. 118

7.10.4

Diameter Of Column: .......................................................................... 118

7.11 PROVISIONAL PLATE DESIGN .................................................................... 118

7.11.1

Column Area ....................................................................................... 118

7.11.2

Downcomer Area ................................................................................ 118

14

7.11.3

Net area .............................................................................................. 118

7.11.4

Active area .......................................................................................... 118

7.11.5

Hole area............................................................................................. 118

7.11.6

Assumptions: ...................................................................................... 118

7.12 WEEP POINT ............................................................................................. 119

7.12.1

WEIR LENGTH ...................................................................................... 119

7.12.2

WEIR LIQUID CREST ............................................................................. 119

7.12.3

WEEP POINT ........................................................................................ 119

7.13 PLATE PRESSURE DROP ............................................................................. 120

7.13.1

DRY PLATE PRESSURE DROP ................................................................ 120

7.13.2

orifice co-efficient ............................................................................... 120

7.13.3

Dry Head ............................................................................................. 120

7.13.4

Residual Head ..................................................................................... 120

7.13.5

Total Head loss .................................................................................... 120

7.13.6

Total Dry Pressure Drop ...................................................................... 120

7.14 DOWNCOMER LIQUID BACKUP ................................................................ 121

7.14.1

Area Of Apron ..................................................................................... 121

7.14.2

Head loss in Down Comer: .................................................................. 121

7.14.3

DownComer Backup ............................................................................ 121

7.15 RESIDENCE TIME ....................................................................................... 121

7.16 ENTRAINMENT ......................................................................................... 121
7.17 NUMBER OF HOLES PER PLATE ................................................................. 122
7.18 HEIGHT OF THE COLUMN ......................................................................... 122
7.19 SPECIFICATION SHEET ............................................................................... 123

8 CHAPTER 8......................................................................................... 124

8.1 INTRODUCTION ........................................................................................ 124
8.2 ENVIRONMENTAL EFFECTS ....................................................................... 125
8.2.1

EFFECTS OF SULPHURIC ACID ON HEALTH ........................................... 125

8.2.2

EFFECTS OF SULPHURIC ACID ON ENVIRONMENT ............................... 125

15

8.2.3

ACID RAIN ........................................................................................... 125

8.2.4

MSDS OF H2SO4 .................................................................................. 125

8.2.5

Product Identification ......................................................................... 125

8.3 Chemical Formula: H2SO4 in H2O Product Codes: .................................. 126

8.3.1

Composition/Information on Ingredients ............................................ 126

8.4 Hazards Identification ............................................................................... 126

8.5 Risk of cancer depends on duration and level of
exposure. SAFETY DATA(tm): ........................................................................... 127
8.6 Potential Health Effects: ........................................................................... 127
Inhalation: 127
Ingestion: 127
8.6.1

Skin Contact: ....................................................................................... 127

8.6.2

Eye Contact: ........................................................................................ 128

8.6.3

Chronic Exposure: ............................................................................... 128

8.6.4

Aggravation of Pre-existing Conditions:............................................... 128

8.7 FIRST AID MEASURES ................................................................................ 128

Inhalation: 128
Ingestion: 128
8.7.1

Skin Contact: ....................................................................................... 128

8.7.2

Eye Contact: ........................................................................................ 128

8.8 FIRE FIGHTING MEASURES ........................................................................ 129

Fire:

129

Explosion: 129
8.8.1

Fire Extinguishing Media: .................................................................... 129

8.8.2

Special Information: ............................................................................ 129

8.9 ACCIDENTAL RELEASE MEASURES ............................................................ 129

8.10 HANDLING AND STORAGE ........................................................................ 129
8.11 PHYSICAL AND CHEMICAL PROPERTIES .................................................... 130
Stability:

130

8.11.1

Hazardous Decomposition Products: ................................................... 130

16

8.11.2

Hazardous Polymerization: .................................................................. 130

Incompatibilities: ................................................................................................... 130

8.11.3

Conditions to Avoid: ............................................................................ 131

8.12 ECOLOGICAL INFORMATION ..................................................................... 131

8.12.1

Environmental Fate: ............................................................................ 131

8.12.2

Environmental Toxicity: ....................................................................... 131

8.13 MSDS OF GASOLINE .................................................................................. 131

8.14 HAZARDS IDENTIFICATION ........................................................................ 131
8.14.1

Eyes ..................................................................................................... 131

8.14.2

Skin ..................................................................................................... 131

8.14.3

Ingestion ............................................................................................. 132

8.14.4

Inhalation ............................................................................................ 132

8.15 WARNING: ................................................................................................ 132

8.15.1

Chronic Effects and Carcinogenicity .................................................... 132

8.15.2

Medical Conditions Aggravated By Exposure ....................................... 133

8.16 FIRST AID MEASURES ................................................................................ 133

8.16.1

Eyes ..................................................................................................... 133

8.16.2

Skin ..................................................................................................... 133

8.16.3

Ingestion ............................................................................................. 133

8.16.4

Inhalation ............................................................................................ 133

8.17 FIRE FIGHTING MEASURES ........................................................................ 133

8.17.1

Flammable Properties: ........................................................................ 133

8.17.2

Fire and Explosion Hazards .................................................................. 134

8.17.3

Extinguishing Media ............................................................................ 134

8.17.4

Fire Fighting Instructions ..................................................................... 134

8.18 ACCIDENTAL RELEASE MEASURES ............................................................ 135

8.18.1

Activate facility spill contingency or emergency plan. ......................... 135

8.19 HANDLING AND STORAGE ........................................................................ 135

8.19.1

Handling Precautions .......................................................................... 135

8.19.2

Storage Precautions ............................................................................ 136

17

8.19.3

Work/Hygienic Practices ..................................................................... 136

8.20 PHYSICAL AND CHEMICAL PROPERTIES .................................................... 137

8.20.1

Appearance ......................................................................................... 137

8.20.2

Odour .................................................................................................. 137

8.20.3

Odour Threshold ................................................................................. 137

8.20.4

Basic Physical Properties ..................................................................... 137

8.21 STABILITY AND REACTIVITY ....................................................................... 138

8.21.1

Stability: .............................................................................................. 138

8.21.2

Conditions to Avoid ............................................................................. 138

8.21.3

Incompatible Materials ....................................................................... 138

8.21.4

Hazardous Decomposition Products .................................................... 138

9 CHAPTER # 9: ..................................................................................... 138

9.1 INSTRUMENTATION AND PROCESS CONTROL .......................................... 138
9.2 TEMPERATURE MEASUREMENT AND CONTROL ....................................... 139
9.3 PRESSURE MEASUREMENT AND CONTROL............................................... 139
9.4 FLOW MEASUREMENT AND CONTROL ..................................................... 139
9.5 CONTROL SCHEME OF DISTIALLATION COLUMN ...................................... 140
9.5.1

Objectives: .......................................................................................... 140

9.5.2

Manipulated variables: ........................................................................ 140

9.5.3

Loads or disturbances: ........................................................................ 140

9.5.4

Control scheme ................................................................................... 141

9.5.5

Advantage ........................................................................................... 141

9.5.6

Disadvantage ...................................................................................... 141

10 141
11 CHAPTER # 10 .................................................................................... 142
11.2 Fixed Cost: ................................................................................................ 145
11.3 Annual Production Cost: ........................................................................... 146
11.4 Processing Cost / Liter: ............................................................................. 146
11.5 Profit per annum: ..................................................................................... 146

18

11.6 Economic Evaluation: ............................................................................... Error! Bookma

11.6.1

Cash Flow diagram: ............................................................................. Error! Bookmar

11.7 Pay Back Period: ....................................................................................... Error! Bookma

11.8 Discounted Pay Back Period: .................................................................... Error! Bookma

11.9 Net present value: .................................................................................... Error! Bookma

11.10

Profitability index: ..................................................................... Error! Bookma

12 APPENDIX .......................................................................................... 148

12.1 APPENDIX A-1 ........................................................................................... 148
12.2 149
12.3 APPENDIX A-2 ........................................................................................... 149
12.4 APPENDIX A-3 ........................................................................................... 150
12.5 150
12.6 APPENDIX A-4 ........................................................................................... 151
12.7 APPENDIX A-5 ........................................................................................... 152
12.8 APPENDIX A-6 ........................................................................................... 153
12.9 APPENDIX A-7 ........................................................................................... 154
12.10

APPENDIX B-1 ............................................................................ 155

12.11

APPENDIX B-2 ............................................................................ 156

12.12

APPENDIX B-3 ............................................................................ 157

12.13

APPENDIX B-4 ............................................................................ 158

12.14

APPENDIX B-5 ............................................................................ 159

12.15

Appendix B-6 ............................................................................. 160

12.16

APPENDIX C-1 ............................................................................ 161

19

20

CHAPTER # 01:
INTRODUCTION
1.1 WHAT IS GASOLINE?
A volatile mixture of flammable liquid hydrocarbons
derived chiefly from crude petroleum and used principally as a fuel for
internal-combustion engines. Gasoline is a complex mixture of over 500
hydrocarbons that may have between 5 to 12 carbons. Smaller amounts of
alkane cyclic and aromatic compounds are present. Gasoline has a typical
boiling range from 100 to 400F (38 to 205C) as determined by the ASTM
method.
Alkylate gasoline is the product of the reaction of
isobutane with propylene, butylene, or pentylene to produce branched-chain
hydrocarbons in the gasoline boiling range. Alkylation of a given quantity of
olefins produces twice the volume of high octane motor fuel as can be
produced by polymerization. In addition, the blending octane (PON) of alkylate
is higher and the sensitivity (RON _ MON) is significantly lower than that of
polymer gasoline.

1.2 BACKGROUND & USES

Before internal-combustion engines were invented in the mid 19th century,
gasoline was sold in small bottles as a treatment against lice and their eggs. At
that time, the word Petrol was a trade name. This treatment method is no
longer common, because of the inherent fire hazard and the risk of dermatitis.
Gasoline was also sold as a cleaning fluid to remove grease stains from
clothing. Gasoline was also used in kitchen ranges and for lighting, and is still
available in a highly purified form, known as camping fuel or white gas, for use
in lanterns and portable stoves.
The invention and development of the automobile as primary mode of
personal transportation required a parallel development of the fuels that

would power the automobiles. Hydrocarbon fuels were an integral component

of society in the 19th century as a source of light. Automobile engines
demanded unprecedented amounts of petroleum. The early refiners could
convert only a small proportion of their crude oil to gasoline - the rest was
wasted or spilled to the environment.

1.3 OCTANE RATING

The octane number or rating of gasoline is a measure of its resistance to knock.
The octane number is determined by comparing the characteristics of a
gasoline to isooctane (2,2,4-trimethylpentane) and n-heptane. Isooctane is
assigned an octane number of 100. It is a highly branched compound that
burns smoothly, with little knock. On the other hand, n-heptane, a straight
chain, un-branched molecule is given an octane rating of zero because of its
bad knocking properties.
Straight-run gasoline (directly from the refinery distillation column) has an
octane number of about 70. In other words, straight-run gasoline has the same
knocking properties as a mixture of 70% isooctane and 30% heptanes. Many of
these compounds are straight chain alkanes. Cracking, Isomerization, and other
refining processes can be used to increase the octane rating of gasoline to
about 90. Anti-knock agents may be added to further increase the octane
rating.
The octane rating became important as the military sought higher output
for aircraft engines in the late 1930s and the 1940s. A higher octane rating
allows a higher compression ratio or supercharger boost, and thus higher
temperatures and pressures, which translate to higher power output. Some
scientists even predicted that a nation with a good supply of high octane
gasoline would have the advantage in air power. These requirements lead to
the production of high octane gasoline by alkylation of olefins.

1.4 PHYSICAL PROPERTIES OF GASOLINE

Property

Gasoline

Chemical Formula

C4 to C12

Molecular Weight

100-105

Specific gravity, 60 F/60 F

0.720.78

Density, lb/gal @ 60 F

6-6.5

Boiling temperature, F

80-437

Heating values
>Lower (Btu/lb)

18,676

>Higher (Btu/lb)

20,004

Freezing point, F

-40

Viscosity, mm2/s
>@104 F

0.5-0.6

>@68 F

0.8-1.0

Auto ignition temperature, F

-45

Specific heat, Btu/lb F

0.4

1.5 WHAT IS ALKYLATION?

The addition of an alkyl group to any compound is an alkylation reaction but in
petroleum refining terminology the term alkylation is used for the reaction of
low molecular weight olefins with an iso-paraffins to form higher molecular
weight iso-paraffins (collectively called alkylate).

Alkylation is an important refining process for the production of alkylates a

high-octane gasoline blending component. Alkylate product is a mixture of
branched hydrocarbons of gasoline boiling range. Alkylate has a motor octane
(MON) of 90-95 and a research octane (RON) of 93-98. Because of its high
octane number and low vapor pressure, alkylate is considered an excellent
blending component for gasoline.

1.6 HISTORY OF ALKYLATION

Alkylation is a twentieth century refinery innovation. Developments in
petroleum processing in the late 1930s and during World War II were directed
toward production of high-octane liquids for aviation gasoline. The sulfuric acid
process was introduced in 1938, and hydrogen fluoride alkylation was
introduced in 1942.
Humble Oil built the first commercial H2SO4 alkylation unit in 1938 at Baytown,
Texas. Alkylation for aviation gasoline grew rapidly with the Allies war effort.
In 1939, six petroleum companies formed a consortium to pool their alkylation
technology and develop both sulfuric acid and HF acid processes for 100
octane aviation fuel. The first commercial HF alkylation unit started up in 1942.
During the war 60 alkylation units were built. Half were built with sulfuric acid
as the catalyst and half with HF.
Following World War II, most alkylation operations were discontinued
although a few refiners continued to use the process for aviation and premium
automobile gasoline.
In the mid-1950s, use of higher performance automotive engines required the
refining industry to both increase gasoline production and quality. The
development of catalytic reforming, such as UOP Plat forming, provided
refiners with an important refining tool for production of high octane gasoline.
However, the motor fuel produced in such operations, called reformate, is
highly aromatic with a higher sensitivity (the spread between research and
motor octane) and a lower lead response than alkylate.
Many refiners expanded their alkylation operations and began to broaden the
range of olefin feeds to both existing and new alkylation units to include
propylene and occasionally even some pentenes along with the butenes.

With the phase-out of leaded gasoline and the advent of environmental

gasoline the lead response of alkylate is no longer valued, but the importance
of alkylate and its production have both grown because of its other properties.
Its high unleaded motor octane, low volatility, low-sulfur, and nearly zero
olefins and aromatics make alkylate critical to the production of quality
environmental gasoline.
Licensors of motor fuel HF Alkylation processes are UOP LLC and Phillips.
Licensors of H2SO4 alkylation processes are Exxon Mobil and Stratco
Engineering.

1.7 ALKYLATION FEEDSTOCKS

Olefins and isobutane are used as alkylation unit feedstock. The chief
sources of olefins are catalytic cracking and coking operations. Butenes and
propene are the most common olefins used, but pentenes (amylenes) are
included in some Olefins can be produced by dehydrogenation of paraffins,
and isobutane is cracked commercially to provide alkylation unit feed.
Hydrocrackers and catalytic crackers produce a great deal of the
isobutene used in alkylation but it is also obtained from catalytic reformers,
crude distillation, and natural gas processing. In some cases, normal butane is
isomerized to produce additional isobutane for alkylation unit feed. Olefins and
iso-butane obtained usually in Refinery are given in table.

1.7.1.1
Table 1: Olefins and isobutane production from
different units
LV %
Iso-Butane

Olefins

Hydro-cracker

FCC

15

Coker

15

Hydrotreater

Reformer

Isomerization

Crude Unit

0.5

1.8 TYPES OF ALKYLATION PROCESSES

There are two main types of alkylation processes,
Thermal alkylation
Catalytic alkylation
1.8.1 THERMAL ALKYLATION
Alkylation can be done without the use of catalysts. But a very high
temperature and pressure conditions are required i.e.
T = 950 OF
P = 3000-5000psi
In this process iso-butane along with ethylene is used as raw materials. This is a
vapor phase process and no catalysts are used, but it is commercially not
favorable.

1.9 CATALYTIC ALKYLATION

Catalytic alkylation of iso-paraffin involves addition of tertiary hydrogen to an
olefin. This process occurs at low temperature (30-100oC) and pressure.

1.9.1.1
Table 2: COMPARISON BETWEEN THERMAL
AND CATALYTIC ALKYLATION
THERMAL ALKYLATION
CATALYTIC ALKYLATION
It takes place at high temperature It takes place at much lower temperature
and pressure without the aid of pressure with the aid of catalyst.
catalyst.
It occurs with both normal and iso- It occurs with paraffins containing tertiary
paraffins.
carbon atom.
In this process, ethylene reacts more In this process, the higher molecular
readily than higher molecular weight weight olefins react more readily than
olefins.
ethylene.
Thermal alkylation is of little Catalytic process has economic advantage
importance in refinery operation.
with better selectivity and milder operating
conditions that make them preferred for
commercial processing.

1.10 TYPES OF ACID CATALYSTS USED IN ALKYLATION

Sulphuric acid
Hydrofluoric acid
1.10.1 SULPHURIC ACID ALKYLATION PROCESS
Two sulphuric acid alkylation processes are commonly available. These are the
auto-refrigeration process licensed by Exxon and the effluent refrigeration
process licensed by Stratford Engineering Corporation. The major difference
between the two processes is in the reactor design. In the auto-refrigeration
process, the evaporation of iC4 and Propane induces cooling of the emulsion in
the reactor. In the effluent refrigeration process, a refrigeration unit provides
cooling to the reactor. The auto-refrigeration unit is shown in Figure 1.

1.10.1.1.1 Figure 1: Auto refrigeration unit:

The olefin is fed to the first reactor in the cascades, together with the recycled
acid and refrigerant. Recycled and make-up isobutanes are distributed to each
reactor. Evaporated gases are compressed and fed back to the reactor along
with the fresh olefin feed which is also cooled by this stream. The reactor
operates at a pressure of 90 kPa (10 psig) and at a temperature of 5 oC (40 oF)
for up to 40 min.
In the Stratco process, the reactor is operated at a higher pressure of 420 kPa
(60 psig), to prevent evaporation of hydrocarbon, and at a temperature of 10
o
C (50 oF). The effluent refrigeration process uses a single Stratco reactor
design as shown in Figure 2. An impeller emulsifies the hydrocarbonacid
mixture for about 2035 min.

1.10.1.2

Figure 2: Effluent refrigeration unit:

1.10.2 HF ALKYLATION
This is highly successful process for combining iso-butane and iso-butane
involves the recirculation of about 6 parts of iso-butane to 1 part of iso-butane.
A temp of 75-105 oF and a Pressure of 100-150psig is maintained on the
reaction contractor. The acid is currently dried, about 6% of heavy oils are
removed, and acid consumption is 0.20lb per barrel of alkylates produced.
Plain carbon steel is used throughout except that some rundown lines are
constructed of Monel metal. The cycle time efficiency is said to be 96%.The
basic advantage of HF Alkylation process over H 2SO4 alkylation process is that
acid recovery is easy.
Two hydrofluoric acid (HF) alkylation processes are commonly available. These
are the Phillip process and the UOP process. The HF processes have no
mechanical stirring as in the sulphuric acid processes. The low viscosity of HF
and the high solubility of isobutane in the acid allow for a simpler design. The
emulsion is obtained by injecting the hydrocarbon feed into the continuous HF
phase through nozzles at the bottom of a tubular reactor. Reaction
temperature is about 30 oC (86 oF), allowing for the use of water as a coolant to
the reactor. The two processes are quite similar. The flow diagram of the
Phillips process is shown in Figure 3. The residence time in the reactor is 2040
s. The hydrocarbon phase is sent to the main fractionation column to obtain

stabilized alkylate. H2SO4 alkylation processes are favored over the HF

processes because of the recent concern about the mitigation of HF vapors. HF
is a very hazardous material for humans because it can penetrate and damage
tissue and bone.

1.10.2.1

Figure 3: HF Alkylation unit:

1.11 COMPARISON OF H2SO4 & HF

A process comparison of H2SO4 and HF alkylation processes shows that neither
has an absolute advantage over the other. From a safety an environmental
standpoint, H2SO4 has a clear advantage over HF. Economics of the processes
are sensitive to base conditions for feed stocks and operating conditions, as
well as refined product pricing. Thus, the actual choice for a particular location
is governed by a number of site-specific factors that require a detailed analysis.
Commercial alkylation catalyst options for refiners today consist of
hydrofluoric (HF) and sulfuric (H 2SO4) acids. In some areas of the world, HF is
no longer considered an acceptable option for a new unit due to concerns over
safety; however, this is not the case everywhere. Due to site-specific
differences in utility economics, feed and product values, proximity to acid
regeneration facilities, etc, both H2SO4 and HF alkylation technologies should
be evaluated. The evaluation criteria can be divided into the following
categories:

Feed Availability and Product Requirements.

Safety and Environmental Considerations.
Operating Costs.
Utilities.
Catalyst and Chemical Costs. And Capital Investment
Maintenance.

1.11.1 FEED AVAILABILITY AND PRODUCT REQUIREMENTS

Historically, butylenes from the FCC were the traditional olefins fed to the
alkylation unit. Today, alkylation units are using a broader range of light olefins
including propylene, butylenes and amylenes. Alkylate composition and
octanes from pure olefins are quite different for each catalyst as shown in
Table for light olefin alkylate octanes.

1.11.1.1

Table 3: Types of olefins

Types of Olefin

RON

MON

HF

H2SO4

HF

H2SO4

Propylene

91-93

91-92

89-91

90-92

1-Butene

90-91

97-98

88-89

93-94

2-Butene

96-97

97-98

92-93

93-94

Iso-Butene

94-95

94-95

91-92

92-93

Amylenes

90-92

89-92

88-89

88-90

1.11.2 SAFETY & ENVIRONMENTAL CONSIDERATIONS

Safety and environmental concerns are extremely important when choosing an
alkylation technology. A huge concern is the large volume of LPG present
within the unit. Refineries must protect against conditions that could lead to
LPG releases and potential fire hazards. All of the alkylation technologies being
evaluated have similar volumes of hydrocarbon within the unit. In addition,
neither acid catalyst impacts the flammability of LPG; therefore, no one
technology has an advantage over another in this regard.

Another major safety concern is the acid catalyst used to promote the
reaction. Both HF and H2SO4 acids are hazardous materials, however, HF is
considerably more dangerous. In the United States, HF has been identified as a
hazardous air pollutant in current federal and state legislation. Sulfuric acid has
not. HF and H2SO4 represent an ever-present danger to personnel working on
alkylation units. Contact with either HF or H 2SO4 can result in chemical burns.
However, HF burns tend to be more severe, since the fluoride ion penetrates
the skin and destroys deeper layers of tissue. If not treated, it may even cause
dissolution of the bone. In addition, inhalation of HF vapors may cause
pulmonary edema and, in severe cases, may result in death. The volatility of
the acid at ambient conditions is a chief concern. HF is a toxic, volatile gas at
these conditions, while H2SO4 is a toxic liquid. Therefore, H2SO4 is much easier
to contain in the event of an accidental release. The hazardous nature of both
materials has been known and respected for years. In more densely populated
areas of the world, safety and environmental concerns of HF usage have given
H2SO4 alkylation a notable advantage.
In 1986, tests were conducted in the Nevada desert to determine the dangers
of a possible HF liquid release. Under conditions similar to those that exist in
an alkylation unit, lethal concentrations of an HF aerosol were present up to 8
km (5 miles) from the release points. It was during these tests that HF releases
were observed to be much more dangerous than anticipated. Due to the risk,
many refiners are implementing water mitigation and detection devices in an
effort to remove any HF that would vaporize in the event of a release. With
water/HF ratios of 40:1, nearly 90% of the HF can be removed. However, these
systems are expensive and there is the concern that the water sprays could
become inoperative as a result of an accident. In addition, details have not yet
been obtained, or at least reported, on the fate of the HF that is not removed
by the water sprays. For a major leak (200 lb/s 100 kg/s) that might result from
a 4 inch (10 cm) hole at process conditions, water systems are thought to be
less effective. Major HF leaks have been rare in the industry, and when they
have occurred, there has usually been a major fire event that has dissipated
the HF cloud as it formed. However, the impact of a major HF release should
always be considered.

Following a number of HF incidents in the 1980s, and in view of the impact

that the Bhopal and Valdez calamities had on the companies concerned, many
refiners have carried out Quantified Risk Assessment studies to identify the risk
associated with specific HF units. In terms of offsite impact, an unmitigated HF
unit will usually generate by far and away the largest element of the risk
associated with the site. Tests conducted in 1991 by Quest Consultants, Inc.
showed that the potential for a H2SO4 aerosol formation from an alkylation
unit release is highly unlikely. Several tests were performed under a variety of
conditions resembling those observed in an alkylation unit. The tests provided
conditions favorable to the formation of airborne particles. However, the
released acid did not remain airborne, and an aerosol was not formed
1.11.3 OPERATING COSTS
Operating costs for H2SO4 technologies tend to be spread equally amongst
steam, electric power and acid costs. With the HF process, most operating
costs are associated with high pressure steam or fuel requirements for the
isostripper reboiler. This reboiler provides thermal de-fluorination of the
alkylate product, in addition to providing the required reboiler duty.
1.11.4 UTILITY COSTS
Utility costs tend to favor the H2SO4 systems. Many HF units require isobuteneto-olefin ratios on the order of 13 - 15/1 to produce an acceptable octane
product. Other HF units and many H2SO4 units develop conditions of mixing
and recycle optimization such that they produce similar octane products with
isobutane to olefin ratios on the order of 7 - 9/1. Clearly the latter, betterdesigned units operate with significantly lower fractionation costs. Today,
many HF units are operating below the design isobutene-to olefin ratio, but to
obtain the required octane, due to increasingly tight gasoline specifications,
these ratios will need to be increased back to design ratios. The H 2SO4 process
employs either electric or turbine drives for the reactors and compressor to
optimize refinery utilities. Horsepower input to the HF reaction zone is lower
than to the H2SO4 reaction zone. In addition, the HF process does not require
refrigeration.

1.11.5 CATALYST AND CHEMICAL COSTS

Catalyst and chemical costs favor HF units, with the main difference being acid
cost. Although HF is more expensive, much less is used, and, can be
regenerated on site. The operating cost of H2SO4 alkylation depends heavily on
reactor design, feed pretreatment, residual contaminants, and the cost and
availability of H2SO4 regeneration. Presently, refiners can either regenerate the
catalyst on site or send it to an outside regenerator. The latter choice is very
common in the United States, where most refiners are not too distant from
H2SO4 manufacturers who can regenerate spent acid at a reasonable cost. Onsite acid regeneration is much more common outside the U.S, due to the lack
of regional commercial acid regeneration facilities. Over 25% of the new
alkylation units built outside the United States in the last five years have
elected to build on-site regeneration facilities. Some regenerators have greatly
reduced acid regeneration cost by providing total sulfur handling facilities for
refiners.
1.11.6 CAPITAL INVESTMENT
It has been over ten years since a comparative cost analysis was conducted
between HF and H2SO4 alkylation technologies. Changes in peripheral
equipment to both technologies have changed dramatically in the past ten
years, and the impact of these on capital investment will be discussed later in
this section. When the above referenced cost estimate was performed there
was objectively no real difference in installed costs between the two
technologies. Since that time, there have been no improvements in either
technology that would warrant a significant change in the cost advantage of
one technology over the other. The separate studies performed by
independent consulting firms (Pace Engineering and Chem Systems) found that
the cost for H2SO4 and HF alkylation units were comparable.

Installed Capital Cost ($MM)

Alkylate Production (BPD)

H2SO4

HF

5000

14.9

14.5

7000

18.8

18.2

It is not surprising that the two processes are competitive on a capital cost
basis, when one considers the basic process differences. The H 2SO4 process has
a more expensive reactor section and requires refrigeration. However, equal
costs are realized in the HF unit by the need for feed driers, product treating,
regeneration equipment and more exotic metallurgy. In addition, most refiners
will require a dedicated cooling system for an HF unit, to remove the risk of
site-wide corrosion in the case of an HF leak.
It should be noted that these capital cost estimates do not account for the
additional safety and mitigation equipment now required in HF units. Due to
the possible hazardous aerosol formation when the HF catalyst is released as a
superheated liquid, expensive mitigation systems are now required in many
locations throughout the world where HF is used as an alkylation catalyst.
Consequently, capital costs for a grassroots HF unit are greater by $2-5 million
(U.S.) depending upon the degree of sophistication of the mitigation design.
1.11.7 MAINTENANCE
Maintenance costs and data are difficult to obtain on a comparable basis. HF
units have much more peripheral equipment (feed driers, product treaters,
acid regeneration column and an acid-soluble oil neutralizer); thus, more
pieces of equipment to operate and maintain. H 2SO4 units have larger pieces of
equipment, such as the compressor and reactor, but maintenance costs are
generally lower. Unit downtime to prepare for a full unit turnaround can take
longer for HF units, since the reactor-settler system and all the fractionators
must be neutralized before maintenance work can proceed. In H 2SO4 units,
only the reactor-settler system requires neutralization. In addition, extensive
safety equipment (breathing apparatus, etc.) is required whenever
maintenance is performed with a potential of HF release.

1.12 H2SO4 VS. HF SUMMARY

A process comparison of the alkylation processes shows that neither has an
absolute advantage over the other. From a safety and environmental
standpoint, H2SO4 has a clear advantage over HF. Economics of the processes

are sensitive to base conditions for feed stocks and operating conditions, as
well as refined product pricing. Thus, the actual choice for a particular refinery
is governed by a number of site-specific factors, which require a detailed
analysis.
As a result of these factors, nearly 90% of new units licensed since 1990 have
selected H2SO4 alkylation technology over HF.

2 CHAPTER # 2:
PROCESS DESCRIPTION
On the basis of the above discussion we select ultimately H 2SO4 alkylation
process.

2.1 METHODS OF H2SO4 ALKYLATION MANUFACTURE

Methods for H2SO4 production is classified on the basis of reactors types
EFFLUENT REFRIGERATION
CASCADE AUTOREFRIGERATION

2.2 EFFLUENT REFRIGERATION

The effluent refrigeration process is licensed by Stratford Engineering
Corporation. The effluent refrigeration process (Stratco) uses a single-stage
reactor in which the temperature is maintained by cooling coils. The reactor
contains an impeller that emulsifies the acidhydrocarbon mixture and recirculates it in the reactor. Average residence time in the reactor is on the
order of 20 to 25 minutes. Emulsion removed from the reactor is sent to a
settler for phase separation. The acid is re-circulated and the pressure of the
hydrocarbon phase is lowered to flash vaporize a portion of the stream and
reduce the liquid temperature to about 30F (1C). The cold liquid is used as
coolant in the reactor tube bundle. The flashed gases are compressed and
liquefied then sent to the depropanizer where LPG grade propane and recycle
isobutane are separated. The hydrocarbon liquid from the reactor tube bundle
is separated into isobutane, n-butane, and alkylate streams in the
deisobutanizer column. The isobutane is recycled and n-butane and alkylate
are product streams. A separate distillation column can be used to separate
the n-butane from the mixture or it can be removed as a side stream from the
deisobutanizing column. The choice is a matter of economics because including
a separate column to remove the n-butane increases the capital and operating
costs. Separating n-butane as a side stream from the deisobutanizing can be
restricted because the pentane content is usually too high to meet butane

sales specifications. The side stream n-butane can be used for gasoline
blending. In this type of reactor there are chances of
Degradation of alkylate
Polymerization may occur at a high level
Compressor demands for the effluent refrigeration process are larger
2.2.1 CASCADE AUTOREFRIGERATION
The major alkylation processes using sulfuric acid as a catalyst are the autorefrigeration process, licensed by Exxon Research and Engineering (similar to a
process previously licensed by the M. W. Kellogg Company), The major
differences between the auto-refrigeration and effluent refrigeration
processes are in the reactor designs and the point in the process at which
propane and isobutane are evaporated to induce cooling and provide the
process refrigeration required. The auto-refrigeration process uses a
multistage cascade reactor with mixers in each stage to emulsify the
hydrocarbonacid mixture. Olefin feed or a mixture of olefin feed and
isobutane feed is introduced into the mixing compartments and enough mixing
energy is introduced to obtain sufficient contacting of the acid catalyst with the
hydrocarbon reactants to obtain good reaction selectivity. The reaction is held
at a pressure of approximately 10 psig (69 kPag) in order to maintain the
temperature at about 40F (5C). In the Stratco, or similar type of reactor
system, pressure is kept high enough [4560 psig (310420 kPag)] to prevent
vaporization of the hydrocarbons. In the Exxon process, acid and isobutane
enter the first stage of the reactor and pass in series through the remaining
stages. The olefin hydrocarbon feed is split and injected into each of the
stages. Exxon mixes the olefin feed with the recycle isobutane and introduces
the mixture into the individual reactor sections to be contacted with the
catalyst. The gases vaporized to remove the heats of reaction and mixing
energy are compressed and liquefied, the liquefied hydrocarbon is sent to a
depropanizer column for removal of the excess propane which accumulates in
the system. The liquid isobutane from the bottom of the depropanizer is
pumped to the first stage of the reactor. The acidhydrocarbon emulsion from
the last reactor stage is separated into acid and hydrocarbon phases. The acid
is removed from the system for reclamation, and the hydrocarbon phase is
then sent to a deisobutanizer. The deisobutanizer separates the hydrocarbon

feed stream into isobutane (which is returned to the reactor), n-butane, and
alkylate product. Although high amount of iso-butane is required to maximize
the conversion and high power input is also needed to achieve better mixing
but acid consumption values are lesser and high quality Alkylate is produced.

2.3 PROCESS VARIABLES

The most important process variables are.
Reaction temperature
Acid strength
Isobutane concentration
Olefin space velocity.
Changes in these variables affect both product quality and yield.
2.3.1 REACTION TEMPERATURE
Reaction temperature has a greater effect in sulfuric acid processes than in
those using hydrofluoric acid. Low temperatures mean higher quality and the
effect of changing sulfuric acid reactor temperature from (4 to 23C) is to
decrease product octane from one to three numbers depending upon the
efficiency of mixing in the reactor. In hydrofluoric acid alkylation, increasing
the reactor temperature from 60 to 125F (16 to 52C) degrades the alkylate
quality about three octane numbers. In sulfuric acid alkylation, low
temperatures cause the acid viscosity to become so great that good mixing of the
reactants and subsequent separation of the emulsion is difficult. At temperatures
above 70F (21C), polymerization of the olefins becomes significant and yields
are decreased. For these reasons the normal sulfuric acid reactor temperature is
from 40 to 50F (5 to 10C) with a maximum of 70F (21C) and a minimum of
30F (1C). For hydrofluoric acid alkylation, temperature is less significant and
reactor temperatures are usually in the range of 70 to 100F (21 to 38C).
2.3.2 ACID STRENGTH
It has varying effects on alkylate quality depending on the effectiveness of
reactor mixing and the water content of the acid. In sulfuric acid alkylation, the
best quality and highest yields are obtained with acid strengths of 93 to 98% by
weight of acid, 1 to 2% water. The water concentration in the acid lowers its
catalytic activity about 3 to 5 times as much as hydrocarbon diluents.

2.3.3 ISOBUTANE CONCENTRATION

Higher ratios of isobutane to olefins in the feed streams to the reactor
minimize the undesired polymerization reactions. The quality of alkylates
hence increases as the ratios increases. Alkylation plants employing H2SO4 as
the catalyst often operate in the range of 5:1 to 8:1.
2.3.4 OLEFINS SPACE VELOCITY
It is defined as gallon per hour of olefin feed divided by the gallons of acid
catalyst instantaneously resident in the true reaction zone. As the space
velocity decreases octane no of alkylate goes to maximum value.

2.4 ALKYLATION CHEMISTRY

The alkylation reaction combines light C 3-C5 olefins with isobutane in the
presence of a strong acid catalyst. Although alkylation can take place at high
temperature without catalyst, the only processes of commercial importance
involve low to moderate temperatures using either sulfuric or hydrofluoric
acid.
2.4.1 REACTION MECHANISM
It is accepted that alkylation of isobutane with C 3 C5 olefins involves a series of
consecutive and simultaneous reactions occurring through carbocation
intermediates. A generalized reaction scheme for butene alkylation can be
summarized as follows.
The first step is the addition of a proton to the olefin to form a
t-butyl cation.

This reaction with sulfuric acid results in the production of alkyl sulfates.
Occasionally alkyl sulfates are called esters. Propylene tends to form much
more stable alkyl sulfates than either C4 or C5 olefins. With either 1-butene or 2butene, the sec-butyl cation formed may isomerize via methyl shift to give a
more stable t-butyl cation.

These initiation reactions are required to generate a high level of ions but
become less important at steady state. Typically, this can be observed as a
higher rate of acid consumption initially when using fresh acid. The t-butyl
cation is then added to an olefin to give the corresponding C 8 carbocation:

2.4.1.1.1 Figure 4: PROCESS FLOW DIAGRAM

3 CHAPTER # 3:
MATERIAL BALANCE
3.1 CAPACITY & BASIS
10000 BPSD of Alkylate Produced
Since 1m3 = 6.29bbls & Density of Alkylate = 720 kg/m3
Avg. Molecular Mass of Alkylate = 113.85 kg/kmol
Alkylate

= 47694.75 kg/hr

= 418.92 kmol/hr
Basis: 1 hr Operation

3.2 EQUATION OF MATERIAL BALANCE

At steady State,
Overall Material Balance can be given by equation,

3.3 REACTOR (R-101)

3.3.1 MATERIAL IN

3.3.1.1

Table 4: Stream 3 = 383658.1 kg

Component

kmol

Kg

Butane

412.67

23109.52

Isobutane

5105.61

296128.2

n-butane

1033.82

59961.67

Propene

6.20

260.48

Propane

95.42

4198.26

Sum

6653.76

383658.1

3.3.1.1.1 Figure 5: Reactors single step:

3.3.1.2

Table 5: Stream 13 = 4769.4 kg

Substance

kmol

Kg

H2SO4

47.69

4674.01

Water

5.23

95.38

Sum

52.99

4769.4

3.3.2 REACTIONS
REACTION 1
C4H8 (l) + iC4H10 (l)C8H18 (l)

H298= -90.572 kJ/gmol

REACTION 2
C3H6 (l) + iC4H10 (l) C7H16 (l)

H298 = -83.81 kJ/gmol

REACTION 3
C3H6 (l) + 2iC4H10 (l) C3H8 (l) + C8H18 (l)

H298 = -79.16 kJ/gmol

From Patent
At 12 oC & 25 Psig, Conversion to Alkylate according is:
Reaction 1 98.51%
Reaction 2 0.341%
Reaction 3 1.149%

3.3.3 MATERIAL OUT

3.3.3.1

Table 6: Stream 4 = 383659.3 kg

Component

kmol

kg

Isobutane

4682.54

271588

nbutane

1033.94

59968.54

propane

100.19

4408.68

alkylate

418.92

47694.04

Sum

6235.61

383659.3

3.3.3.2

Table 7: Stream 14 = 4769.4 kg

Component

kg

Spent Acid

4769.4

Balance:
Stream 3 = 383658.1 kg

Stream 13 = 4769.4

Total Material In = 383658.1 + 4769.4 = 388427.5 kg

kg

Stream 4 = 383659.3 kg
Stream 14 = 4769.4 kg
Total Material Out = 383659.3 + 4769.4 = 388428.7 kg

3.4 PHASE SEPARATOR (PS-101)

3.4.1.1.1 Figure 6: phase separators single step:

3.4.2 MATERIAL IN

3.4.2.1

Table 8: Stream 4 = 383659.3 kg

Component kmol

kg

Isobutane

4682.54 271588

nbutane

1033.94 59968.54

propane

100.19

4408.68

alkylate

418.92

47694.04

Sum

6235.61 383659.3

3.4.3 MATERIAL OUT:

3.4.3.1

Table 8: Stream 5 = 122417.2 kg

Component kmol

kg

Isobutane

1791.62

103914.1

nbutane

271.96

15773.91

propane

62.02

2729.183

Sum

2125.61

122417.2

3.4.3.2

Table 9: Stream 6 = 261242.1 kg

Component kmol

kg

Isobutane

2890.93

167673.9

nbutane

761.97

44194.63

propane

38.17

1679.49

alkylate

418.92

47694.04

Sum

4109.99

261242.1

Balance: Stream 4 = 5+6

Stream 4

= 383659.3 kg

Stream 5+6 = 122417.2 + 261242.1= 383659.1 k

3.5 DISTILLATION COLUMN (DC-101)

3.5.1.1.1 Figure 7: De-isobutanizer:

3.5.2 MATERIAL IN

3.5.2.1

Table 10: Stream 6 = 261242.1 kg

Component kmol

kg

Isobutane

2890.93

167673.9

nbutane

761.97

44194.63

propane

38.17

1679.49

alkylate

418.92

47694.04

Sum

4109.99

261242.1

3.5.3 MATERIAL OUT

3.5.3.1

Table 11: Stream 11 = 203308.9 kg

Component

kmol

kg

Isobutane

2886.16

167397.2

n-butane

590.20

34232.16

propane

38.17

1679.49

Sum

3514.53

203308.9

3.5.3.2

Table 12: Stream 7 = 57933.24 kg

Component

kmol

kg

n-butane

171.75

9962.46

Isobutane

4.77

276.73

Alkylate

418.92

47694.04

Sum

595.44

57933.23

Balance:
Stream 6 = 7 + 11
Stream 6

=261242.1 kg

Stream 7+8+11

= 57933.24 + 203308.9= 261242.14 kg

3.6 DISTILLATION COLUMN (DC-102)

3.6.1.1.1
3.6.1.1.2 Figure 8: De-propanizer:

3.6.2 MATERIAL IN

3.6.2.1

Table 13: Stream 5 = 122417.2 kg

Component kmol

kg

Isobutane

1791.62

103914.1

nbutane

271.96

15773.91

propane

62.02

2729.183

Sum

2125.61

122417.2

3.6.3 MATERIAL OUT

3.6.3.1

Table 14: Stream 10 = 1259.62 kg

Component

kmol

kg

Propane

28.62

1259.62

3.6.3.2

Table 15: Stream 9 = 121157.6 kg

Component

kmol

kg

Isobutane

1791.62

103914.1

nbutane

271.96

15773.92

propane

33.39

1469.56

Sum

2096.98

121157.6

Balance:

Stream 5 = 9 + 10

Stream 5

= 122417.2 kg

Stream 9 + 10

= 1259.62 + 121157.6= 122417.22 kg

3.7 BALANCE TO MIXING POINT

Stream 1 + Stream 2 + Stream 12 = Stream 3
Total Amount = Stream 1 + 2 + 12
= 28560.58 + 30631.06 + 324466.5 = 383658.14 kg

3.7.1.1

Table 15: Flow rates of different streams

Stream 1

Stream 2

Component

kmol

kg

Butene

412.67

23109.52

nbutane

85.87

4980.665 85.77

propene

6.20

260.483

propane

4.77

209.9131 19.07

Iso Butane

Sum

509.51

kmol

Stream 12

kg

kmol

kg

4974.926 862.17

50006.08

839.2908 71.57

3149.057

427.87

24816.84 4677.78 271311.3

28560.58 532.71

30631.06 5611.52 324466.5

4 CHAPTER # 4:
ENERGY BALANCE
4.1 ENERGY BALANCE EQUATION

At steady State,
Overall Energy Balance can be given by equation,

4.2 HEAT OF REACTIONS

4.2.1 At 298K
4.2.2 REACTION 1
C4H8 (g) + iC4H10 (l) C8H18 (l)

H298 = -90.572 kJ/gmol

H298 = -223.9 - (-134.5 + 1.172) = -90.572 kJ/gmol

4.2.3 REACTION 2
C3H6 (g) + iC4H10 (l) C7H16 (l)

H298 = -83.81 kJ/gmol

H298 = -197.9-(-134.5 + 20.41) = -83.81 kJ/gmol

4.2.4 REACTION 3
C3H6 (g) + 2iC4H10 (l) C3H8 (l) + C8H18 (l) H298 = -79.16 kJ/gmol
H298 = -223.9 103.85 (20.41 2(134.5)) = -79.16 kJ/gmol
4.2.5 Heats of Formation Data: Hf (kJ/gmol): Vol. 6
C3H6 (g) = 20.41

C3H8 (l) = -103.85

C4H8 (g) = 1.172

C8H18 (l) = -223.9

iC4H10 (l) = -134.5

C7H16 (l) = -197.9

4.2.5.1.1 Figure 9: Graphical Representation of Hess Law

4.3 REACTOR (R-101)

4.3.1 Table 16: Stream 3+13:
T= 12oC & let Tref. = 25oC
Component

Cp (kJ/kmol K)

kmol

H (kJ)

Propene

66.92

6.20

5395.504

propane

76.96

95.41

95461.71

butene

93.51

412.67

501665.9

butane

105.82

1033.82

1422218

isobutane

106.52

5105.65

7070434

H2SO4

140.97

47.69

87405.2

Water

24.65

5.29

1698.173

H1: 9.18E+06 kJ

4.3.1.1

Table 17: Stream 4+14:

T= 12 C & let Tref. = 25oC

Component

Cp (kJ/kmol K)

kmol

H(kJ)

propane

76.96

100.19

-100246.29

butane

105.822

1033.94

-1422380.91

isobutane

106.52

4682.55

-6484507.20

2,2,4,Tmpentane

196.47

417.24

-1065710.48

2,3,Dmpentane

183.49

1.67

-3995.63

H2SO4

140.97

47.69

-87405.19

Water

24.65

5.29

-1698.17

H2: -9.17E+06 kJ
4.3.2 Heat of Reaction Added At 298 K
H298 = (-90572*412.67) + (-79160*4.57) + (-83810*1.675)
= -3.8E+07 kJ
4.3.3 Total Heat of Reaction:
Hr

= H1 + H298 + H2
= 9.18E+06 - 3.8E+07 - 9.17E+06
= -3.79E+07 kJ

4.3.4 Latent Heat Required To Vaporize the Mixture

Hl

= 4.28E+07 kJ

Balance:
H3

= 9.10E+06 kJ

H4

= 3.37E+07 kJ

Hi

= Hr + Hl = 4.89E+06 kJ (Heat added by impellers)

4.4 PHASE SEPARATOR (PS-101)

4.4.1.1

Table 18: Stream 4:

Component

Cp (kJ/kmol K)

kmol

H(kJ)

propane

75.80

100.19

75956.22

butane

102.62

1033.94

1061079

isobutane

102.36

4682.55

4793516

Alkylate

196.01

418.92

821137.7

H4: 4.95E+07 kJ (Including Latent Heat)

4.4.1.2

Table 19: Stream 5:

Component

Cp (kJ/kmol K)

kmol

H(kJ)

Isobutane

102.37

1791.62

1834084

nbutane

102.62

271.96

279089.47

propane

72.37

62.02

44888.853

H5: 4.49E+07 kJ (Including Latent Heat)

4.4.1.3

Table 20: Stream 6:

Component

kmol

Cp (kJ/kmol K)

H(kJ)

Isobutane

2890.92

102.37

2959444.7

nbutane

761.97

102.62

781940.14

propane

38.17

72.37

27623.909

alkylate

418.92

196.013

821137.66

H6 = 4.59E+06 kJ

4.5 ACROSS COMPRESSOR

Inlet P1 = 14.2 psig, Target P2 = 175 Psig
Average Cp at inlet T1 15oC = 101.52 kJ/kmol K
From Stream:

Tr = 0.704

From Graphs 3.8, 3.9, 3.10 [3]: X= 0.22

Pr = 0.053

Y= 1.06

Efficiency Ep = 0.67

4.5.1.1.1 Figure 10: Air Compressor:

m = 0.133
n = 1.114
Wp = 2270.63 kj/kmol
Actual Work = W
W = Wp/Ep = 3389.01 kj/kmol
Power = W x No. of moles/ 3600

Z= 0.95

P = 2MW
Final Temp = 370 K = 97oC
4.5.2 Balance

kJ

H into system via compressor

7203732.5

H out of compressor

5.21E+07

4.6 ACROSS HEAT EXCHANGER HX-102 (CONDENSER)

4.6.1.1.1 Figure 11: Condenser:

4.6.2 Vapor Stream After Compression enters in cooler condenser:

4.6.2.1

Table 21: T in = 97oC, T out = 75oC

Component kmol

Cp (kJ/kmol K)

H ( KJ)

= kJ/kmol H (kJ)= N *

Isobutane 1791.62 145.48

5734237.5

20001.02

35834289.66

nbutane

271.96 144.84

866609.95

21799.22

5928604.833

propane

62.026 103.13

140733.06

15920.62

987506.5037

Sum

2125.61

6.74E+6

4.27E+7

Total Heat Removed / cooling utility= 6.74E+6 + 4.27E+7 = 4.95E+07 kJ

4.6.3 Balance:
Total H in =

5.21E+07 kJ

Total H out =

2.62E+06 kJ

4.7 ACROSS DE-PROPANIZER DC-102

Heat In=H5= 2.62E+06 kJ

4.7.1.1

Table 22: Stream 10:

Component

kmol

Cp (kJ/kmol K)

Delta T

H (kJ)

Propane

28.62

103.13

15

44286.493

Hd = 4.428E+4 KJ

4.7.1.2

Table 23: Stream 9:

Component

kmol

Cp (kJ/kmol K)

Delta T

H (kJ)

Isobutane

1791.62

145.48

55

14335597

nbutane

271.96

144.84

55

2166525.4

propane

33.39

103.13

55

189448.4

Hb = 1.67E+7 kJ

4.7.1.3

Table 24: Let: R= 0.85

Component kmol

Cp (kJ/kmol K)

Latent Heat Delta T kJ

H (kJ)

Ln

22.90

103.13

15

Vn

51.53

103.13

15

Duty Of condenser = Hv- Hl- Hd = 4.88E+05 kJ

From Column Balance:

Hl=3.54E+4
4.56E+5

Hv=5.68E+5

HF+Duty of reboiler = Hd+ Hb+duty of condenser

Duty of reboiler

= 4.428E+4 + 1.67E+7 + 4.88E+05 - 2.62E+06 =1.46E+07 kJ

4.8 ACROSS PUMP (STREAM 6)

4.8.1.1.1 Figure 12: Pump:

Stream 6 in:
P= 14.2 Psig
Hin = 4.59E+06 kJ

4.8.2 Table 25: Stream 6 out:

P= 100 Psig
Component

kmol

Cp (kJ/kmol K)

H (kJ)

Isobutane

2890.92

139.74

4039785.2

nbutane

761.97

140.36

1069510

propane

38.17

101.62

38788.748

alkylate

418.92

284.02

1189816.6

Hout = 6.34E+6 kJ

4.8.2.1

Table 26: Balance:

kJ

Energy Added to Stream 1.75E+06

H in

4.59E+06

H out

6.34E+06

4.9 ACROSS HEAT EXCHANGER HX-108

Stream 6 in:
T= 15oC
Hin = 6.34E+6 kJ

4.9.1.1

Table 27: Stream 6 out:

T = 67 C
Component

kmol

Cp (kJ/kmol K)

H (kJ)

Isobutane

2890.92

139.74

16967098

nbutane

761.97

140.36

4491942.1

propane

38.17

101.62

162912.74

alkylate

418.92

284.02

4997229.7

Hout = 2.66E+07 kJ

4.9.1.2

Table 28: Balance:

kJ

Energy Added to Stream

2.03E+07

H in

6.34E+06

H out

2.66E+07

4.10 ACROSS DE-ISOBUTANIZER DC-101

Heat In=H6= 2.66E+07 KJ

4.10.1.1

Table 29: Stream 11:

o

Top T = 50 C
Component

kmol

Cp (kJ/kmol K)

H (kJ)

Isobutane

2886.15

126.48107

9126110.5

n-butane

590.21

127.84035

1886315.2

propane

38.17

94.132021

89826.398

Hd = 1.11E+07 kJ

4.10.1.2

Table 30: Stream 7:

T = 160oC
Component

kmol

Cp (kJ/kmol K)

H (kJ)

n-butane

172

140.0362

3.25E+06

Isobutane

4.77

137.254

8.84E+04

Alkylate

419

284.124

1.61E+07

Hb = 1.94E+07 kJ

4.10.1.3

Table 31: Let: R= 0.45

kmol

Cp (kJ/kmol K)

Delta T Latent Heat (kJ) H (kJ)

Ln

1581.54

126.35

25

Vn

5096.08

126.35

25

Hl=3.54E+4
7.12E+07

Hv =8.73E+7

Duty Of condenser = Hv- Hl- Hd = 7.13E+07 kJ

From Column Balance:
Hf+Duty of reboiler = Hd+ Hb + Hs +duty of condenser
Duty of reboiler

= 1.11E+07 + 1.94E+07 + 7.13E+07 - 2.66E+07 = 7.52E+07 kJ

4.11 AT MIXING POINT

Stream 1 + Stream 2 + Stream 12 = Stream 3

4.11.1.1

Table 32: Stream 1:

T = 22oC
Substance

kmol

Cp (kJ/kmol K)

H (kJ)

Butene

412.67

91.41

113178.54

nbutane

85.87

106.95

27554.564

propene

6.20

68.26

1270.0411

propane

4.77

78.87

1128.9069

H1 = 1.43E+05 kJ

4.11.2 Table 33: Stream 2:

T =19 oC
Substance

kmol

Cp (kJ/kmol K)

H (kJ)

propane

19.07

78.87

9027.36

nbutane

85.77

106.95

55045.62

isobutane

427.87

105.27

270256.63

H2 = 3.34E+05 kJ

4.11.2.1

Table 34: Stream 12:

T = 50 oC
Substance

kmol

Cp (kJ/kmol K)

H (kJ)

Isobutane

4677.78

105.27047

12310807

nbutane

862.17

106.95793

2305408

propane

71.56

78.876949

141129.57

H12 = 1.48E+07 kJ
4.11.3 Balance:
H3 = H1 + H2 + H12
1.52E+07 kJ

=> H3 = 1.43E+05 + 3.34E+05 + 1.48E+07=

5 CHAPTER # 5:
HEAT EXCHANGER DESIGN
5.1 HEAT EXCHANGER
A heat exchanger is a device built for efficient heat transfer from one medium
to another, whether the media are separated by a solid wall so that they never
mix, or the media are in direct contact. They are widely used in space heating,
refrigeration, air conditioning, power plants, chemical plants, petrochemical
plants, petroleum refineries, and natural gas processing. One common
example of a heat exchanger is the radiator in a car, in which a hot enginecooling fluid, like antifreeze, transfers heat to air flowing through the radiator.

5.2 TYPES OF HEAT EXCHANGERS

Shell and Tube heat exchanger
Plate heat exchanger
Regenerative heat exchanger
Adiabatic Wheel heat exchanger
Fluid heat exchangers
Dynamic Scraped surface heat exchanger

5.3 HEAT-TRANSFER FLUIDS

Before selecting a heat-transfer fluid, examine the process for any possibility of
interchanging heat between process streams to conserve energy. Frequently,
one process stream needs to be heated and another process stream cooled.
After this possibility has been exhausted, select a heat-transfer fluid to cool or
heat the process Stream. The factors that must be considered in evaluating
and selecting a heat transfer fluid are:
Operating temperature range
Environmental effects
Toxicity
Flammability
Thermal stability

Corrosivity
Viscosity

5.4 HEAT-EXCHANGER EVALUATION AND SELECTION

The process engineer must be familiar with the types of equipment that are
available for the various process units. Because the evaluation and selection of
equipment occur frequently, we will first establish general criteria that applies
to most equipment. These criteria are to determine:
Operating principles
Equipment type
Sealing
Thermal expansion
Maintenance
Materials of construction - shell, tubes, and seals
Temperature-pressure rating
Economics
The most commonly used heat exchangers are the coil and double pipe for
small heat-exchange areas and the shell-and-tube design for large areas. it is
recommend that if:
A < 2m2 (21.5 ft2) select a coiled heat exchanger
2 m2 < A < 50 m2 (538 ft2) select a double-pipe heat exchanger
A > 50 m2 select a shell-and-tube heat exchanger.

5.4.1.1
Table 35: Different types of tube sheets and their
properties:

Type

Significant
feature

Applications best
Limitations
suited

Approximat
e
relative
cost
in
carbon steel
constructio
n

Condensers;
liquid-liquid; gasgas;
gas-liquid;
Fixed tube Both tube sheets
cooling
and
sheet
fixed to shell.
heating,
horizontal
or
vertical, reboiling.

Temperature
difference
at
extremes
of
1.0
o
about 200 F Due
to
differential
expansion.

One tubesheet
floats in shell
Floating
or with shell,
head
or tube bundle may
tubesheet
or may not be
(removable removable from
and
shell, but back
nonremova cover can be
ble bundles) removed
to
expose
tube
ends.

High temperature
differentials,
above about 200
o
F extremes; dirty
fluids
requiring
cleaning of inside
as well as outside
of
shell,
horizontal
or
vertical.

Internal gaskets
offer danger of
leaking.
Corrosiveness of
fluids on shell- 1.28
side
floating
parts.
Usually
confined
to
horizontal units.

Only one tube

sheet required.
Tubes bent in Ushape. Bundle is
removable.

High temperature
differentials,
which
might
require provision
for expansion in
fixed tube units.
Easily
cleaned

Bends must be
carefully made, or
mechanical
damage
and 0.9-1.1
danger of rupture
can result. Tube
side velocities can

U-tube;
U-Bundle

conditions
both tube
shell side.

Each tube has

own
shell
forming annular
Double pipe space for shell
side fluid. Usually
use
externally
finned tube.

Pipe coil

Plate
frame

Spiral

on cause erosion of
and inside of bends.
Fluid should be
free of suspended
particles.

Relatively small
transfer
area
service, or in
banks for larger
applications.
Especially suited
for high pressures
in tube (greater
than 400 psig).

Services suitable
for finned tube.
Piping-up a large
0.8-1.4
number
often
requires cost and
space.

Pipe coil for

submersion
in
coil-box of water
or sprayed with
water is simplest
type
of
exchanger.

Transfer
Condensing,
or
coefficient is low,
relatively
low
requires relatively 0.5-0.7
heat loads on
large space if heat
sensible transfer.
load is high.

Composed
of
metal-formed
thin
plates
and
separated
by
gaskets.
Compact, easy to
clean.

Not well suited

for boiling or
Viscous
fluids,
condensing; limit
corrosive fluids,
350-500 oF by 0.8-1.5
slurries, high heat
gaskets. Used for
transfer.
liquid-liquid only;
not gas-gas.

Compact,
Cross-flow,
concentric plates;
condensing,
no
bypassing,
heating.
high turbulence.

Process corrosion,
suspended
0.8-1.5
materials.

5.5 SHELL AND TUBE HEAT EXCHANGER

Shell and tube heat exchangers consist of a series of tubes. One set of these
tubes contains the fluid that must be either heated or cooled. The second fluid
runs over the tubes that are being heated or cooled so that it can either
provide the heat or absorb the heat required. A set of tubes is called the tube
bundle and can be made up of several types of tubes: plain, longitudinally
finned etc. Shell and Tube heat exchangers are typically used for high pressure
applications (with pressures greater than 30 bar and temperatures greater
than 260C). This is because the shell and tube heat exchangers are robust due
to their shape.
There are several thermal design features that are to be taken into account
when designing the tubes in the shell and tube heat exchangers. These include:
5.5.1 Tube diameter:
Using a small tube diameter makes the heat exchanger both economical and
compact. However, it is more likely for the heat exchanger to foul up faster
and the small size makes mechanical cleaning of the fouling difficult. To prevail
over the fouling and cleaning problems, larger tube diameters can be used.
Thus to determine the tube diameter, the available space, cost and the fouling
nature of the fluids must be considered.
5.5.2 Tube thickness:
The thickness of the wall of the tubes is usually determined to ensure:
There is enough room for corrosion
That flow-induced vibration has resistance
Axial strength
Ability to easily stock spare parts cost
Sometimes the wall thickness is determined by the maximum pressure
differential across the wall.
5.5.3 Tube length:
Heat exchangers are usually cheaper when they have a smaller shell diameter
and a long tube length. Thus, typically there is an aim to make the heat
exchanger as long as possible. However, there are many limitations for this,
including the space available at the site where it is going to be used and the

need to ensure that there are tubes available in lengths that are twice the
required length (so that the tubes can be withdrawn and replaced). Also, it has
to be remembered that long, thin tubes are difficult to take out and replace.
5.5.4 Tube pitch:
When designing the tubes, it is practical to ensure that the tube pitch (i.e. the
centre-centre distance of adjoining tubes) is not less than 1.25 times the tubes'
outside diameter

5.5.4.1.1 Figure 13: Shell and tube Heat Exchanger:

5.6 CONSTRUCTION OF 1-2 SHELL AND TUBE HEAT

EXCHANGER
5.6.1 Shell
The shell is simply the container for the shell-side fluid. The shell normally has
a circular cross section and is commonly made by rolling a metal plate of the
appropriate dimensions into a cylinder and welding the longitudinal joint large
diameter, near-atmospheric pressure shells have been designed with a partial

ball-joint in the shell designed to allow the shell to partially "rotate" to

accommodate stresses.
5.6.2 Tubes
The tubes are the basic component of the shell and tube exchanger, providing
the heat transfer surface between one fluid flowing inside the tube and the
other fluid flowing across the outside of the tubes. The tubes may be seamless
or welded and most commonly made of copper or steel alloys. Other alloys of
nickel, titanium, or aluminum may also be required for specific applications.
5.6.3 Tube sheets
A tube sheet is an important component of a heat exchanger. It is the principal
barrier between the shell-side and tube-side fluids. Proper design of a tube
sheet is important for safety and reliability of the heat exchanger. Tube sheets
are mostly circular with uniform pattern of drilled holes. Tube sheets of surface
condensers are rectangular shape. Tube sheets are connected to the shell and
the channels either by welds (integral) or with bolts (gasketed joints) or with a
combination of both. Tube-sheet connection with the shell and channel for
fixed tube-sheet exchanger can be categorized into two types:
Both sides integral construction
Shell-side integral and tube-side gasketed construction
Tube-sheet connection with the shell and channel for floating heat
exchanger and U-tube heat exchangers can be categorized into three
types:
Both sides integral construction
One side integral and the other side gasketed construction
Both sides gasketed construction

5.6.3.1.1 Figure 14: Tube Sheet lay out:

5.7 TUBE TO TUBE-SHEET ATTACHMENT

Tubes are attached to the tube sheet by:
Rolling
Welding
Rolling and Welding
Explosive Welding
Brazing
Schematic sketch of tube to tube-sheet attachment are given in fig. Expansion
of the tubes into the tube sheet is most widely used and is satisfactory for
many services. However, when stresses are higher, or where pressures are
such that significant leakage could occur, or where contamination between
fluids is not permitted, the tubes are welded to the tube sheet. Explosion
welding can be used instead of conventional welding where there is
incompatibility between tube and tube-sheet materials and for tube plugging
under hazardous conditions.

5.8 NOZZLES
The nozzles are the inlet and exit ports which allow the entrance and
departure of two fluid streams separately in the shell and tube heat exchanger.

5.8.1.1.1 Figure 15: Nozzles lay out:

5.8.2 IMPINGEMENT PLATE

The inlet nozzle often has an impingement plate set just below to divert the
incoming fluid jet from impacting directly at high velocity on the top row of
tubes.
5.8.3 TUBE-SIDE CHANNELS
Tube-side channels and nozzles simply control the flow of the tube-side fluid
into and out of the tubes of the exchanger. Since the tube-side fluid is
generally the more corrosive, these channels and nozzles will often be made
out of alloy materials (compatible with the tubes and tube sheets, of course).
They may be clad instead of solid alloy.
5.8.4 CHANNEL COVERS
The channel covers are round plates that bolt to the channel flanges and can
be removed for tube inspection without disturbing the tube-side piping. In
smaller heat exchangers, bonnets with flanged nozzles or threaded
connections for the tube-side piping are often used instead of channels and
channel covers.
5.8.5 PASS DIVIDER
A pass divider is needed in one channel or bonnet for an exchanger having two
tube-side passes, and they are needed in either channels or bonnets for an
exchanger having more than two passes. If the channels or bonnets are cast,
the dividers are integrally cast and then faced to give a smooth bearing surface
on the gasket between the divider and the tube sheet. If the channels are
rolled from plate or built up from pipe, the dividers are welded in place.

5.9 BAFFLES
Baffles serve two functions:
They support the tubes in the proper position during assembly and operation
and prevent vibration of the tubes caused by flow-induced eddies
They guide the shell-side flow back and forth across the tube field, increasing
the velocity and the heat transfer coefficient.

5.9.1 CLASSIFICATION OF BAFFLES:

Baffles are either normal or parallel to the tubes. Accordingly, baffles may be
classified as transverse or longitudinal.
5.9.2 Transverse Baffles:
The transverse baffles direct the shell-side fluid into the tube bundle at
approximately right angles to the tubes, and increase the turbulence of the
shell fluid.
Transverse baffles are of two types:
Plate baffles
Rod baffles
Three types of plate baffles are
Segmental baffles
Disk and doughnut baffles
Orifice baffles
5.9.3 Segmental Baffles:
The segmental baffle is a circular disk (with baffle holes) having a segment
removed. Predominantly, a large number of shell and tube exchangers employ
segmental baffles. This cutting is denoted as the baffle cut and it is commonly
expressed as a percentage of the shell inside diameter. The segmental baffle is
also referred to as a single segmental baffle. The heat transfer and pressure
drop of cross flow bundles are greatly affected by the baffle cut. The baffle
cuts vary from 20 to 49% with the most common being 20-25%, and the
optimum baffle cut is generally

5.9.3.1.1 Figure 16: Segmental Baffles lay out:

20%, as it affords the highest heat transfer for a given pressure drop. Baffle
cuts smaller than 20% can result in high pressure drop. As the baffle cut
increases beyond 20%, the flow pattern

5.9.3.1.2 Figure 17: Flow patterns:

deviates more and more from cross flow and can result in stagnant regions or
areas with lower flow velocities; both of these reduce the thermal
effectiveness of the bundle.
5.9.4 BAFFLE SPACING
The practical range of single-segmental baffle spacing is to 1 shell diameter,
though optimum could be 40-50%. TEMA provides maximum baffle spacing for
various tube outer diameters, tube materials, and the corresponding maximum allowable temperature limit. The baffles are generally spaced between
the nozzles. The inlet and outlet baffle spacings are in general larger than the
central baffle spacing to accommodate the nozzles, since the nozzle
dimensions frequently require that the nozzle should be located far enough
from the tube sheets.
5.9.5 Disk and doughnut baffle
The disk and doughnut baffle is made up of alternate disks and doughnut
baffles as shown in Fig. Disk and doughnut baffle heat exchangers are primarily
used in nuclear heat exchangers.

5.9.5.1.1 Figure 18: Disk and doughnut baffles:

This baffle design provides a lower pressure drop compared to a single

segmental baffle for the same unsupported tube span, and eliminates the tube
bundle to shell bypass stream.

5.9.5.1.2 Figure 19: Baffle orifice:

5.9.6 Orifice baffle

In an orifice baffle, the tube-to-baffle hole Clearance is large so
that it acts as an orifice for the shell-side flow. These baffles do not provide
support to tubes, and, due to fouling, the annular orifices plug easily and
cannot be cleaned. This baffle design is rarely used.
5.9.7 Longitudinal baffles
Longitudinal baffles divide the shell into two or more sections, providing
multipass on the shell side. The longitudinal baffles are used to control the
direction of the shell side flow. But this type should not be used unless the
baffle is welded to the shell and tube sheet. Nevertheless, several sealing
devices have been tried to seal the baffle and the shell, but none has been very
effective.
They are:

Sealing strips or multiflex arrangement

Packing arrangement
Slide-in or tongue-and-groove arrangement
5.9.8 Flanged joints
Flanges are often employed to connect two sections by bolting them together
so that the sections can be assembled and disassembled easily. In heat
exchangers, the flange joints are used to connect together the following
components:
Channel and channel cover
Heads or channels with the shell/tube sheets
Inlet and outlet nozzles with the pipes carrying the fluids
The flanged joints play an important role from the standpoint of integrity and
reliability of heat exchangers. Improper design of flanges causes leakage of
heat exchanger fluids. Therefore, preventing the liquid or gas leaks is one of
the most important considerations while designing flanged joints.
5.9.9 Flanged Joint Types
From a conceptual standpoint, flanged joints may be subdivided into two
major categories:
Bolted joints
Pressure-actuated or self-energizing joints
5.9.10 TUBE PITCH
The shortest center-to-center distance between the adjacent tubes is termed
as tube pitch. Although The square pitch has the advantage of easier external
cleaning, the triangular pitch is sometimes preferred because it permits the
use of more tubes in a given shell diameter.

5.9.10.1.1 Figure 20: Tube Pitch:

5.10 THERMO HYDRAULIC DESIGN PROCEDURE

5.10.1 Shell and Tube Heat Exchanger
Thermo hydraulic design steps for shell and tube heat exchanger are,
Calculation of heat duty
Calculation of log mean temperature difference
Finding out correction factor for LMTD
Correction of LMTD
Assuming overall heat transfer coefficient(Uo)
Area calculation
Calculation of number of tubes
Corrected area
5.10.2 SHELL SIDE CALCULATION
Selection of shell inside diameter
Baffle spacing
Pitch calculation
Tube clearance
Shell area
Mass velocity
Equivalent diameter
Reynolds number across shell side
Factor for heat transfer calculation
Prandtls number
Individual overall heat transfer coefficient
5.10.3 TUBE SIDE CALCULATION
Flow area per tube
Number of tubes calculation
Tube area calculation
Mass velocity calculation
Reynolds number across tube side
Velocity calculation
Prandtls number

Calculation of factor for heat transfer coefficient

Calculation of individual heat transfer coefficient

5.10.3.1.1 Figure 21: Steps involved in designing Heat Exchanger:

5.11 DESIGN DATA

5.11.1 Fluid 1: Process stream
Flowrate = m1 = 1.848 kmol/sec
T1 in = 25 oC
T1 out = 12 oC
T1 = 13
Cp1 Avg = 135.6 kJ/kmol K (At mean temperature)
5.11.2 Fluid 2 : Cooling Utility (25 % Brine Soln.)
Flowrate = m2 = ?
T2 in = -5 oC
T2 out = 10 oC
T2 =15
Cp2 Avg = 80.02 kJ/ kmol K (At mean temperature)
5.11.3 Unknowns:
Duty (heat transfer rate).
Flowrate of Utility.

Calculating the unknowns

5.11.4 Heat Duty
H = m1 x Cp1 Avg x T1
5.11.5 Flowrate
m1 = 1.848 kgmol/sec
T1 = 13
Cp1 Avg = 135.6 kJ/kmol K
H = 3257.654 kW

5.11.6 Flowrate Of Utility

m2 = H / Cp2 Avg x T2
H = 3257.654 kJ/sec
T2 =15
Cp2 Avg = 80.02 kJ/ kmol K
m2 = 2.714 kmol/sec

5.12 PHYSICAL PROPERTIES

5.12.1 Process Stream :
Viscosity = = 0.163508 cp
Thermal Conductivity = k = 8.74E-05 kW/m K
Specific heat capacity = Cp1 = 2.416689 kJ/kg K
5.12.2 Brine Solution :
Viscosity = = 3.3 cp
Thermal Conductivity = k = 5.50E-04 kW/m K
Specific heat capacity = Cp2= 2.845 kJ/kg K

5.13 ASSUME OVERALL COEFFICIENT, U0

Assume Uo , From Appendix A1 ,get value of overall coefficient as light
organics
Uo= 600 W/ 0C .m2

5.14 MEAN TEMPERATURE DIFFERENCE

LMTD = T2 T1 / ln T2 / T1
T1 = T1 in - T2 out = 25 10 = 15 oC
T2 = T1 out - T2 in = 12 (-5) = 17 oC
LMTD = 16 oC

Corrected LMTD = TLM

R = 0.866
P = 0.5
Now, from the value of R and S, we find out that F for 1-2 heat exchanger Fig,
(A-2)
F = 0.86
Corrected LMTD = TLM = LMTD x F = 13.76 oC

5.15 HEAT TRANSFER AREA

Heat transfer area is evaluated using:
Heat duty = H = 3257.654 kW
LM = = 13.76 oC
Heat transfer coefficient = U = 600 W/m2 C
A = H / TLM x U
A = 394.6 m2

5.16 DECIDE THE EXCHANGER LAYOUT

Fixed tube exchanger is used because:
Simplest & Cheapest.
T is less than 80oC and Shell Pressure less than 8bars
Square pitch is selected for low pressure drop.
The process stream has greater pressure than cooling utility therefore
Process Stream through the tubes.
Cooling utility in the shell.
Let, ODt = 1 & BWG= 16
Inner Dia = ID = 0.022 m
Outer dia = OD = 0.025 m

Tube thickness 0.002 m

Area of 1 tube 0.379 m2
Length Of tube =16 ft = 4.83 m (Standard)
Square Pitch = 0.03125 m pitch (pitch/dia. = 1.25)

5.16.1.1.1 Figure 22: Tube Pitch and Clearance:

5.17 INDIVIDUAL H.T.C

5.17.1 TUBE SIDE CALCULATION
Number of Tubes = N:
Number of tubes = Area of exchanger / Area of one tube
N = 394.6376 /0.379 = 1041 say 1040
For 2 tube passes,
tubes / pass = 1040 / 2 = 520
Tube Cross-sectional area = Di2 / 4
= x (0.022)2 / 4
= 0.00038 m2
Total Flow Area At = Number of tubes * tube cross-sectional area
= 520 x 0.00038 = 0.197808 m2

5.17.2 Mass Vel:

Gt=m1/At
= 538.7628 Kg/m2. sec
5.17.3 Linear Vel:
Vt= Gt / Density
= 0.979569 m/s [normal range (1-2 m/sec)]
5.17.4 Renould's # :
NRe = Vt Di /
= 7.25E+04

5.17.5 Prandle # :
Pr = Cp / k
= 4.52 & (Pr)1/3 = 1.653
From Appendix A-3
Jh= 3.00E-03 (Graph)
hi = jh.(k/Di)( Pr)1/3.( /w)0.14. NRe
hi = 1429.15 W/m2.C
Neglecting viscosity factor ( /w)0.14 , as the temperature difference is not too
high.

5.18 SHELL SIDE CALCULATION

Bundle Dia= Do x (Nt / K1)(1/n1) Eq 12.3b - vol6
Bundle Dia = Db= 1.1675m
Shell Dia = Ds = Db + Tube clearance
Tube Clearance = 13 mm

Ds = 1.1675 + 0.013 => Ds = 1.18 m (Appendix A-4)

Baffle Spacing = Ib = 0.5 times Ds => Ib= 0.59 m
Cross-sectional area of Shell (As)
= (tube pitch Do)/ pitch *Ib*Ds
As = 0.14 m2
5.18.1 Mass Velocity
Gs= 547. 8 Kg/m2. sec

5.18.2 Linear Velocity

Vs= 0.52 m/s (0.3-1 m/s)
5.18.3 Equivalent Diameter
= 1.27 /Do (Pt2 0.785 x Do2)
De= 0.0177m
5.18.4 Reynold Number:
NRe = 2.95E+03
5.18.5 Prandle Number:
Pr = 17.07
(Pr)1/3=2.57
Assuming Baffle Cut=25 percent
Jh =1.00E-02 (Appendix A-5)
ho= 2348.558 W/m2 .oC

5.19 OVERALL CO-EFFICIENT UO

Fouling(dirt) factor = 1/h = m2 oC/W

For light Organics 0.0002
Refrigerated Brine 0.00025
Cupro Nickel alloy k = 50 W/m2.oC
1/Uo = 0.001022 + 3.20E-05 + 6.76E-04
1/Uo = 1.73E-03
Uo = 580 W/m2 oC (Assumed = 600 W/m2 oC)

5.20 PRESSURE DROP P

5.20.1 TUBE SIDE

1040 Tubes
Number of passes = Np = 2 passes
Tube Di = 0.022 m
Neglecting Viscosity term
Linear Velocity: Vt = 0.979569 m/s
Reynolds Number : NRe= 7.25E+04
From Figure for jf = 3.80E-02( Appendix A-6 )
Pt= 36542.73 Pa
Pt= 5.30 PSI

5.20.2 SHELL SIDE

Shell Dia = Ds =1.18 m

Length = L = 4.83 m
Baffle Spacing = IB = 0.031 m
Velocity at shell side = us = 0.52 m/s
friction factor jf = 8.00E-02 (Appendix A-7)
Ps = 4.96E+04 Pa
Ps = 7.2 PSI

5.20.2.1

Table 36: SPECIFICATION SHEET

Identification:

HX101

Function:

Cooling

Operation:

Continuous

Type

1-2 Shell and Tube heat Exchanger

Heat Duty

H = 3257.654 kW

Tube Side
Process Stream

Tubes Side

Components

Molar Fraction

Outer Dia

0.025 m

Butene

0.062

Inner Dia

0.022 m

Isobutane

0.76

BWG

16

n-butane

0.155

Length

4.8 m

Propene

0.00093

No. of tubes

1040

Propane

0.0143

No. of Passes

Square pitch

0.03125 m

Flowrate

1.848 kmol/sec Material

Pressure Drop

Cupro Nickel Alloy

5.3 PSI

Shell Side

Shell

Utility Stream:

Shell Dia

1.18 m

Component

Mol fraction

No. of passes

NaCl

25

Baflle Spacing

0.59 m

Water

Flowrate

75

Velocity

0.52 m/s

Material

Steel 303

2.714 kmol/sec Pressure Drop

7.2 PSI

6 CHAPTER # 6:
REACTOR DESIGN
6.1 CHEMICAL REACTORS
Chemical reactor is the heart of the chemical reaction process. Chemical
reactors are containers that are designed for a chemical reaction to occur
inside of them. The design of a chemical reactor deals with multiple aspects of
chemical engineering.

6.2 TYPES OF REACTORS

There are two main types of reactors
Batch reactors
Flow reactors
Flow reactors are further classified into two main categories
Continuous Stirred Tank Reactors (CSTR)
Plug Flow Reactor

6.3 SELECTION OF REACTOR

The factors considered in reactor design are:

Conversion
Selectivity
Productivity
Yield
Heat exchange
Mixing
Catalyst Distribution
Hold-up Time
Availability
Energy utilization
Safety
Economics

6.4 WHY WE SELECTED CSTR?

Following are the reasons due to which CSTR is preferred for this process
First of all the process we selected is a continuous process for
the manufacture of Gasoline in which reaction mixture is of
very large capacity with 10 times excess reactant.
In this process intense mixing is required.
We need a reactor in which the contents are well stirred and
uniformly mixed throughout.
In plug flow reactors there is no back mixing.
In CSTR the contents are completely mixed and there is also
back mixing. It is also known as back mix flow reactor.
Mixing of Reactants
Good Temperature Control
High heat and mass transfer efficiencies
Useful for slow reactions requiring large hold up time
Uniform
Distribution of Catalyst
For Liquid-Gas system Control
Less Man power requirements

6.5 SOME IMPORTANT ASPECTS OF THE CSTR

In At steady-state, the flow rate in must equal the mass flow rate out,
otherwise the tank will overflow or go empty (transient state). While the
reactor is in a transient state the model equation must be derived from the
differential mass and energy balances.
All calculations performed with CSTRs assume perfect mixing.
The reaction proceeds at the reaction rate associated with the final
(output) concentration.
Often, it is economically beneficial to operate several CSTRs in series or
in parallel. This allows, for example, the first CSTR to operate at a higher
reagent concentration and therefore a higher reaction rate in these
cases, the sizes of the reactors may be varied in order to minimize the
total capital investment required to implement the process.

It can be seen that an infinite number of infinitely small CSTRs

6.6 PFR (PLUG FLOW REACTOR)

In a PFR, one or more fluid reagents are pumped through a pipe or
tube. The chemical reaction proceeds as the reagents travel through the PFR.
In this type of reactor, the reaction rate is a gradient; at the inlet to the PFR the
rate is very high, but as the concentrations of the reagents decrease and the
concentration of the product(s) increases the reaction rate slows. Some
important aspects of the PFR:
All calculations performed with PFRs assume no upstream or downstream
mixing, as implied by the term "plug flow".
Reagents may be introduced into the PFR at locations in the reactor other than
the inlet. In this way, a higher efficiency may be obtained, or the size and cost
of the PFR may be reduced.
A PFR typically has an higher efficiency than a CSTR of the same volume. That
is, given the same space-time, a reaction will proceed to a higher percentage
completion in a PFR than in a CSTR.

6.7 CSTR (CONTINUOUS STIRRED-TANK REACTOR)

In a CSTR, one or more fluid reagents are introduced into a tank reactor
equipped with an impeller while the reactor effluent is removed continuously.
The impeller stirs the reagents to ensure proper mixing. The contents of the
reactors are completely mixed so that the complete contents of the reactors
are at the same concentration and temperature as the product stream. Since
the reactor is designed for steady state, the flow rates of the inlet and outlet
streams, as well as the reactors conditions ,remain unchanged with time.
Simply dividing the volume of the tank by the average volumetric flow rate
through the tank gives the residence time, or the average amount of time a
discrete quantity of reagent spends inside the tank.

6.7.1.1.1 Figure 23: DESIGN STEPS

10

Residence Time

Total volumetric flow rate

Volume of the reactor

Length and Diameter of the reactor

Impeller specifications

Baffles Dimensions

Shell thickness

Reactor head

Power calculations

Material of construction

6.7.1.2

Table 37: Types of Impellers

Factors/Types

Propellers

Paddles

Turbine

Viscosity

For Low to
ModerateVisco
us Liquids

For Low to High

Viscous Liquids

Flow Pattern

For Axial Flow

For
Moderate
Viscous
Liquids
For
Radial
flow

Types

No. of Blades

RPM Ranges

Square Pitched
Marine
Propellers
3-blade,
4Blade Toothed
400-800, 1150

6.8 SELECTION OF IMPELLER

6.8.1 Based on:
Viscosity of Liquid
Density of liquids
Degree of Mixing
Flow Pattern
Rpm
Power Requirement
Economics
Selected: propller

Flat Paddle,
Anchor
Agitator
2
and
4
bladed
Paddles
20-150

For Radial and

Tangential Flow.
Vertical
Flat
Curved,
and
Pitched Blade
2-8 Blades

50-250

6.9 DESIGN OF CASCADE AUTOREFRIGERATED

REACTOR
As the reaction vessel is divided into two zones.
Reaction zone
Settling zone.

6.9.1.1.1 Figure 24: The Kellogg Cascade Auto refrigeration

unit:

6.10 VOLUME OF REACTOR

So, we will find out the volume of 2 compartments first.

6.11 VOLUME OF REACTION ZONE

Residence time=27 min

6.11.1.1 Table 38: Balance across

Reactor T= 12C n 25 PSIg
IN

Stream 3
Substance

Butane
Isobutane
n-butane
Propene
Propane
Sum
Stream 4
H2SO4
Water
Sum

Mass

Density

Kgs
23109.52
296128.2
59961.67
260.483
4198.261
383658.1

Kg/m3
601.9
566.6
588.1
528.01
512.1

4674.016
95.38808
4769.404

1853
1017

Volume
Flow
m3/hr
38.39428
522.6406
101.9583
0.49333
8.198128
671.6846

2.522405
0.093794
2.616198

Total mass flow rate of inlet streams = 388427.5 Kg/hr

Average density of the entering mixture = 576.3 Kg/m3
Volumetric flow rate of entering mixture into the reactor = V o = 674 m3/hr
Residence Time (known) = = 27 min = 0.45 hr.

So Volume of the reactor is given as

V = Vo
Vr = 303.3 m3

6.12 VOLUME OF SETTLING ZONE

Here, settling time =2 min = 0.0333 hr
So,

Vol. of settling zone=0.0333*674

Vs=22.4m3
TOTAL VOLUME=Vr+Vs
= 303.3+22.4
= 325.7 m3

6.13 LENGTH AND DIAMETER

Vr is divided into five compartments:
For 1 compartment:
V = Vr/5 = 60.68 m3
Since
V = ( / 4) *L * D2
L = 1.5 D
D = 3.72 m
L = 1.5 * D
L = 5.57 m

6.14 BAFFLES
Baffles are used to prevent vortexing and rotation of the liquid mass as a
whole. Four radial baffles at equal spacing are mostly used.
Baffles width Of one compartment = D/12 = 0.31 m

6.15 IMPELLER DESIGN

6.15.1 Conditions
Viscosity of feed+acid= 0.1975 mN.s/m2
Density of liquid in the tank= 576.34 kg/m3
Our desired applications for impeller are

For pumping liquids,

for high speed applications
Side entry feed.
If Da/Dt if ranges from 1/2-1/3 then Reynolds no. > 300
Propeller type impellers are employed.

6.16 REYNOLDS NUMBER

N Re

Nd 2

N= Rotation/Sec=5 (300 RPM)

d = Diameter of Impeller = D/3 = 1.24 m
= Density = 577.589 kg/m3
= Viscosity = 0.1977 cp
NRe = 2.24E+07

6.17 POWER CONSUMPTION

Calculation of Power

For turbulent flow for NRe >10,000

Np = Power Number = 3.7
n = RPM = 5
d = Dia of impeller = 1.238 m
= Density = 577.59 kg/m3
Power Consumption = 77.88 KW or 104.4 Hp

6.18 TYPES OF HEAD COVERS

Flanged Only
Dished Ends:

Hemispherical
Ellipsoidal
Torispherical
Selected: Ellipsoidal
Moderate Pressures
Moderately Economical
Less thickness for a particular Pressure as compared to Flanged only and
torispherical heads.

6.19 MECHANICAL DESIGN

6.19.1 SHELL THICKNESS

P * Di
C
2* J * f P

e=thickness of shell
P=internal pressure=273.64 KPa
f=permissible stress=1.65*105 KPa
J=joint efficiency=0.9 (Table 13.3 Coluson & Richadson - Chemical
engineering design Vol 6)
Type of joint: Single welded joint with bonding strips
Degree of radiography: 100%
C=corrosion allowance=3mm (Optimum)
e = 8.5 mm
6.19.2 ELLIPSOIDAL HEAD THICKNESS

e
e=thickness of head
P=internal pressure=273.64 KPa

Pi * Di
2 * J * f 0.2 * Pi

f=permissible stress=1.65*105 KPa

J=joint efficiency=0.9
e = 5.49 mm

6.20 MATERIAL OF CONSTRUCTION

6.20.1 FOR REACTOR
Stainless Steel : Type 304
Cr=17 %, Ni=8 % C (max) =0.15 %
Characteristics:
Have good corrosion resistance
Excellent mechanical properties
Easy to fabricate
6.20.2 FOR IMPELLER BLADES
Stainless steel: Type 316
18% Cr, 8%Ni, 2.5%Mo, 0.08%C
Characteristics:
Corrosion and pitting resistance.
Thermal strength
Shows good mechanical properties over large flow rates.
6.20.3 FOR BAFFLES
Stainless steel: Type 405
11.50% Cr , 0.08%C
Characteristics:
Good weld ability properties.
Mostly used for Baffles, Tower lining and heat Exchanger Tubing.

6.21 SPECIFICATION SHEET

Identification
Item

Cascade Auto Refrigeration Reactor

Item Number

R-101

Required No.

Function

Formation of gasoline via sulphuric acid alkylation of olefins

Operation

Continous

Type

Cascade Agitated Cylindrical Vessels

6.21.1.1

Table 39: Types of Vessels:

Design Data
Overall

Compartment

Reaction Volume

303.43 m3

Impeller type

Propeller

Settling Volume

22.16 m3

Diameter of impeller

1.24 m

Total Volume

374.43 m3

RPM

300

Residence time

27 min

Mixing Time

21.2 sec

Settling time

2 min

Pumpimg Rate

4.56 m3/sec

Shell thickness

8.5 mm

Power Consumed

67.36 kW

Cover Head

Ellipsoidal

Material

SS-316

Head thickness

5.5 mm

No. of baffles

Material

SS-304

Baffle Width

0.31 m

7 CHAPTER 7:
DE-ISOBUTANIZER COLUMN DESIGN
7.1 CHOICE BETWEEN PLATE AND PACKED COLUMN
Vapour liquid mass transfer operation may be carried either in plate column or
packed column. These two types of operations are quite different. A selection
scheme considering the factors under four headings.
Factors that depend on the system i.e. scale, foaming, fouling factors,
corrosive systems, heat evolution, pressure drop, liquid holdup.
Factors that depend on the fluid flow moment.
Factors that depends upon the physical characteristics of the column
and its internals i.e. maintenance, weight, side stream, size and cost.
Factors that depend upon mode of operation i.e. batch distillation,
continuous distillation, turndown, and intermittent distillation.
The relative merits of plate over packed column are as follows:
Plate column are designed to handle wide range of liquid flow rates
without flooding.
If a system contains solid contents, it will be handled in plate column,
because solid will accumulate in the voids, coating the packing materials
and making it ineffective.
Dispersion difficulties are handled in plate column when flow rate of
liquid are low as compared to gases.
For large column heights, weight of the packed column is more than
plate column.
If periodic cleaning is required, man holes will be provided for cleaning.
In packed columns packing must be removed before cleaning.
For non-foaming systems the plate column is preferred.
Design information for plate column are more readily available and more
reliable than that for packed column.
Inter stage cooling can be provide to remove heat of reaction or solution
in plate column.

When large temperature changes are involved as in the distillation

operations tray column are often preferred because thermal expansion
or contraction of the equipment components may crush the packing.
Random-Packed Column generally not designed with the diameter larger
than 1.5 m and diameters of commercial tray column is seldom less than
0.67m.
For this particular process, TDI, Residues and ODCB, I have selected plate
column because:
System is non-foaming.
Temperature is very high i.e. about 250C
Diameter is greater than 0.67 meter.
Height of the Column is very large.

7.2 CHOICE OF PLATE TYPE

There are four main tray types, the bubble cap, sieve tray, ballast or valve trays
and the counter flow trays. I have selected sieve tray because:
They are lighter in weight and less expensive. It is easier and cheaper to
install.
Pressure drop is low as compared to bubble cap trays.
Peak efficiency is generally high.
Maintenance cost is reduced due to the ease of cleaning.
Good flexibility in operation(Turndown ratio).

7.2.1.1.1 Figure 25: DESIGN STEPS OF DISTILLATION

COLUMN

Calculation of Minimum Reflux Ratio Rm

Calculation of optimum reflux ratio

Calculation of theoretical number of stages

Calculation of actual number of stages.

Calculation of diameter of the column

Calculation of weeping point.

Plate Design

Calculation of pressure drop.

Calculation of thickness of the shell and head.

10

Calculation of the height of the column.

7.2.1.1.2 Figure 26: De-Isobutanizers Lay out:

7.2.1.2
Table 40: FEED, DISTILLATE AND BOTTOM
SPECIFICATION
Feed: T = 64oC

Kmoles

Mol.Frac X

propane

38.17

0.01

Isobutane

2890.93

0.70

nbutane

761.98

0.19

alkylate

418.92

0.10

Top: T = 58oC

Kmoles

Mol.Frac X

propane

38.17

0.01

Isobutane

2886.16

0.82

n-butane

590.21

0.17

Bottom: T = 130oC

Kmoles

Mol.Frac X

isobutane

4.77

0.01

nbutane

171.76

0.29

Alkylate

418.92

0.70

7.3 NATURE OF FEED

Temperature

=64 0C

Pressure

=100 psig

7.3.1.1

Table 41: Nature of Feed

Feed
propane

Kmol

Fraction

K Value

Alpha

38.17

0.01

2.29

2.54

2890.93

0.70

1.14

1.27

761.98

0.19

0.90

1.0

418.92

0.10

0.07

0.078

Isobutane(LK)

N-butane(HK)

alkylate

7.4 PINCH TEMPERATURE

Top Temperature (Tp)

=58 oC

Bottom temperature (Tb) = 130 oC

7.4.1 Pinch temperature:
Upper pinch Tn= Tp+0.33(Tb-Tp)
=

81.76 oC

Lower pinch Tm= Tp+0.67(Tb-Tp)

=

106.24 oC

7.5 MINIMUM REFLUX RATIO

7.5.1.1

Table 42: minimum reflux ratio

Component

At Tn=81.76

C3
iC4
nC4
C8

2.541
1.2
1
0.0754

At Tm=106.24 Xf
o
C

2.61
3.211
1
0.07581
0.10

Since:
xnA

rf

=XfL / XfH =3.8

XnA

= 0.785

X nB

= 0.215

rf
(1 rf )(1 x fh )

xnB

xnA
rf

7.5.2 Colburns Method:

Relative Volatility (LK/HK) AB= 1.27
Mole fraction of LK in distilate = xdA=0.82
Mole fraction of HK in distilate = xdB=0.17
xnA= 0.785

xnB= 0.215

Then the relation finds the minimum reflux ratio:

Rm = 0.361

7.6 NUMBER OF PLATES

FENSKES Equation for minimum number of plates at total reflux:

*Xf
Xfh

0.0077

N min

x x
log LK HK
xHK d xLK b

log LK

Number of plate (min) = Nmin = 5.5

=6 plates
7.6.1 Gilliland Method:
Shows the relationship between the minimum number of plates and minimum
reflux ratio to the actual number of plates and actual reflux ratio. Appendix B6

7.6.1.1
Table 43: relation between reflux ratio and number of
plates
(R-Rm)/(R+1)
R
0.397
0.433
0.469
0.5
0.54

0.026
0.05
0.07
0.096
0.12

((n+1)-(nm+1))
/(n+2)
0.6
0.68
0.55
0.52
0.5

n
15.5
14.67
13.55
12.58
12.

When R = 1.3 Rm = 0.47 then N = 13.55

or
Number of plates = 14
Selecting R = 1.3 Rm because its difference of change than others is large and
economical.

7.7 EFFICIENCY OF THE COLUMN

Empirical relation

Eo 51 32.5Log (a * a )
Viscosity = 0.136 cp
a= 1.27

Eo

=76.6%

Total plates= 18.7 or 19 (Sieve trays are used)

7.8 FEED PLATE

7.8.1 Kirkbride Method:

Nr / Ns = 0.163
Nr + Ns = 18
Ns = 15

7.9 COLUMN DIAMETER: DC CALCULATION

We have:

7.9.1.1

Table 44: Flow rates and densities:

Top condition
Ln=27.41 kmol /min
Vn =85.99 kmol/min
Lw= 1589.28 kg/min
Vw= 4985.01 kg/min
Vap density =20.1 kg/m3
Liq density =510.13 kg /m3

Bottom condition
Lm=95.91 kmol/min
Vm=85.99 kmol/min
Lw=9361.1 kg/min
Vw=8392.5 kg/min
Vap density =25.46 kg/m3
Liq density =560.28 kg /m3

For calculating diameter we have to calculate:

7.10 FLOODING VELOCITY

L dv
Flv w
Vw d l

FLV(top)=0.063
FLV(bottom)=0.24
When Plate spacing= 0.8m
k1(top)= 1.30E-01 (Appendix B-1)
k1(bottom)= 7.00E-02

Top

Bottom

Surface tension = 0.0067 N/m

Surface tension =0.0069 N/m

Corrected k1 =0.1046

Corrected k1 =0.057

Uf=

Uf=

0.5167 m/s

0.26 m/s

Assuming 85 % of flooding velocity

Uf top= 0.44 m/s

Ufbottom =0.221 m/s

7.10.1 Maximum volumetric flow rate of vapors:

qv
qv=4.13 m3/sec

Vw
dv
qv= 5.49 m3/sec

qv

7.10.2 Net area required:

Uc
An

An=9.42 m2

An=24.88 m2
Ac

An
0.88

7.10.3 Column Cross sectional Area:

Ac= 10.7 m2

Ac= 28.27 m2

7.10.4 Diameter Of Column:

Dc

4 * Ac

Dc= 3.71m

Dc=6m

Selecting Dc=6m. Constructing the column on the basis of this diameter and
reducing the perforations to the top in order to accommodate the desired flow
conditions.

7.11 PROVISIONAL PLATE DESIGN

7.11.1 Column Area
Ac = 3.14*r2
Ac= 28.28 m2
7.11.2 Downcomer Area
= Ad = 0.12*Ac
Ad =3.4 m2
7.11.3 Net area
A n= A c A
An = 24.9m2
7.11.4 Active area
Aa = Ac-2Ad
Aa = 21.5m2
7.11.5 Hole area
= 0.05 *Aa
Ah =1.1 m2
7.11.6 Assumptions:
plate thickness =Hole dia =5mm

weir height =50 mm

7.12 WEEP POINT

7.12.1 WEIR LENGTH
hl =
Factor

Dc

(Ad / Ac)*100 = 12

At (Ad / Ac) * 100 = 12

From Graph b/w (Ad/Ac)*100 vs. lw / Dc (Appendix B-2)

lw / Dc = 0.77
lw = 4.62 m
7.12.2 WEIR LIQUID CREST
Max. Liq. flowrate =156.01 kg/sec
Min. Liq. flowrate= 109.21 kg/sec
As Turn Down Ratio= 0.7
Q =qmin/density of vapor
=4.3 m3/sec

how(max)

Lw
750
d w lw

2/3

how = 91.1 mm
hw +how =141.1mm
From
At:

Appendix
hw + how = 141.1 mm K2 = 31

7.12.3 WEEP POINT

U h (min)

K 2 0.9(25.4 d h )

U min =2.50 m/sec

dv

o.5

B-4

Actual Uh (min) based on active hole area is given as:

Vw
U ( actual) 0.7
d A
h
v

U actual = 3.6 m/sec

7.13 PLATE PRESSURE DROP

7.13.1 DRY PLATE PRESSURE DROP
Max Vapor Vel. = Uh = 5.11 m/s
Ah*100/Ap=12
Plate thickness/ hole dia : Ratio = 1
From Appendix B-5 ,At (Ah/Aa)*100=10, When Plate thickness to plate dia ratio
is 1.
7.13.2 orifice co-efficient
= Co= 0.86
7.13.3 Dry Head
U
hd 51 h
Co

= hd = 92.2 mm liq

dv

dl

7.13.4 Residual Head

hr

= hr= 22.31mm liq

12.5 103
dl

7.13.5 Total Head loss

= ht = = 267.8 mm liq

ht hd hr (ho how )

7.13.6 Total Dry Pressure Drop

3

= P

Pt 9.8110 ht dl

P = 1471.92 Pa

7.14 DOWNCOMER LIQUID BACKUP

Height of Bottom edge of apron above the plate
7.14.1 Area Of Apron
Aap = hap * lw
=0.185 m2
As Aap is less than Ad
7.14.2 Head loss in Down Comer:

hdc= 1.12 mm

Lw

hdc 166
d l Aap

7.14.3 DownComer Backup

= Hd= 409.97mm

H D H t H dc (ho how )

HD < 0.5*(Tray spacing +Weir height)

410<425

(So, tray spacing is acceptable.)

7.15 RESIDENCE TIME

tr

Ad hbc d l
Lw

Ad = 3.4 m2
hbc= 1.12 mm
tr= 5 sec
Greater than 3 sec, so satisfactory

7.16 ENTRAINMENT
Where
Un

Vm
d v Ah

hap =(hw -10) = 40 mm

Un = 0.221 m/s
Since: Uf (bottom) = 0.3 m/s
% flooding = Un*100/uf =85%
Flv = 0.237
From Appendix B-3
Fractional entrainment= = 0.011
As, entrainment is less than 0.1, process is satisfactory.

7.17 NUMBER OF HOLES PER PLATE

Area of one hole = = 1.96E-05 m2

ah

Number of Holes n= 3917.12 or =3918

7.18 HEIGHT OF THE COLUMN

No. of plates = 19
Tray spacing = 0.8 m
Distance between plates = 19* 0.8 = 15.2m
Top clearance = 0.5m
Bottom clearance = 0.5m
Tray thickness = 5E-3 m /plate
Total thickness of trays =19 * 5E-3 = 7E-2 m
Total height of column = 16.27m

dh

Ah
ah

7.19 SPECIFICATION SHEET

7.19.1.1

Table 45: Identification:

Item No.

D-101

No. required

Tray type

Sieve tray

Function:

Separation of ALKYLATE from BUTANES

Operation:

Continuous

7.19.1.2

Table 46: Design data:

Design Data
No. of trays =19

Active holes = 3918

Pressure = 100 Psig

Weir height = 50 mm

Height of column = 16.27 m

Weir length = 4.62 m

Diameter of column = 6 m

Reflux ratio = 0.47

Hole size = 5 mm

Tray spacing = 0.8 m

Active area =21.5m2

Tray thickness = 5 mm

8 CHAPTER 8
HAZOP STUDY
8.1 INTRODUCTION
A HAZOP survey is one of the most common and widely accepted methods of
systematic qualitative hazard analysis. It is used for both new or existing
facilities and can be applied to a whole plant, a production unit, or a piece of
equipment It uses as its database the usual sort of plant and process
information and relies on the judgment of engineering and safety experts in
the areas with which they are most familiar. The end result is, therefore
reliable in terms of engineering and operational expectations, but it is not
quantitative and may not consider the consequences of complex sequences of
human errors.
The objectives of a HAZOP study can be summarized as follows:
To identify (areas of the design that may possess a significant hazard
potential.
To identify and study features of the design that influence the
probability of a hazardous incident occurring.
To familiarize the study team with the design information available.
To ensure that a systematic study is made of the areas of significant
hazard potential.
To identify pertinent design information not currently available to the
team.
To provide a mechanism for feedback to the client of the study team's
detailed comments.

8.2 ENVIRONMENTAL EFFECTS

8.2.1 EFFECTS OF SULPHURIC ACID ON HEALTH
Sulfuric acid is a corrosive chemical and can severely burn the skin and eyes. It
may cause third degree burns and blindness on contact. Exposure to sulfuric
acid mist can irritate the eyes, nose, throat and lungs, and at higher levels can
cause a buildup of fluid in the lungs (pulmonary oedema). Asthmatics are
particularly sensitive to the pulmonary irritation. Repeated exposures may
cause permanent damage to the lungs and teeth. The International Agency for
Research on Cancer has classified 'occupational exposures to strong-inorganicacid mists containing sulfuric acid' as carcinogenic to humans.
8.2.2 EFFECTS OF SULPHURIC ACID ON ENVIRONMENT
Sulfuric acid will exist as particles or droplets in the air if released to the
atmosphere. It dissolves when mixed with water. It has moderate acute (shortterm) toxicity on aquatic life. Sulfuric acid is very corrosive and would badly
burn any plants, birds or land animals exposed to it. It has moderate chronic
(long-term) toxicity to aquatic life. Chronic effects on plants, birds or land
animals have not been determined. Small quantities of sulfuric acid will be
neutralized by the natural alkalinity in aquatic systems. Larger quantities may
lower the pH for extended periods of time.
8.2.3 ACID RAIN
Sulfuric acid enters the air during production, use and transporting it. In the air
it will react with other chemicals present (ammonia, magnesium, calcium) to
form salts, which neutralize the acid. The acid particles dissolve in clouds, fog,
rain, or snow, resulting in very dilute acid solutions. This may impact the
environment as wet acid deposition ('acid rain').
8.2.4 MSDS OF H2SO4
8.2.5 Product Identification
Synonyms:

Oil

of

vitriol;

Babcock

acid;

sulphuric

acid

CAS No.:

7664-93-9

Molecular Weight:

98.08

8.3 Chemical Formula:

H2SO4 in H2O

Product Codes:
J.T. Baker:
5030, 5137, 5374, 5802, 5815, 5858, 5859, 5868, 5889,
5897, 5961, 5971, 5997, 6163, 6902, 9671, 9673, 9674, 9675, 9676, 9679,
9680, 9681, 9682, 9684, 9687, 9690, 9691, 9693, 9694, 9697
Mallinckrodt: 21201, 2468
8.3.1 Composition/Information on Ingredients
Ingredient
Hazardous
--------------------------------Sulfuric Acid
Yes
Water
No

CAS No

Percent

-----------7664-93-9
7732-18-5

-------

52 - 100%
0 - 48%

8.4 Hazards Identification

Emergency Overview
poison!
danger!
corrosive.
liquid and mist cause severe burns to all body tissue.
may be fatal if swallowed or contacted with skin.
harmful if inhaled. affects teeth.
water reactive.
cancer hazard.
strong inorganic acid mists containing sulfuric acid can cause cancer.

8.5 Risk of cancer depends on duration and level of exposure.

SAFETY DATA(tm):
Ratings
(Provided
here
for
your
convenience)
Health
Rating:
4
Extreme
(Poison)
Flammability
Rating:
0
None
Reactivity
Rating:
2
Moderate
Contact
Rating:
4
Extreme
(Corrosive)
Lab Protective Equip: GOGGLES & SHIELD; LAB COAT & APRON; VENT HOOD;
PROPER
GLOVES
Storage Color Code: White (Corrosive)

8.6 Potential Health Effects:

Inhalation:
Inhalation produces damaging effects on the mucous membranes and upper
respiratory tract. Symptoms may include irritation of the nose and throat, and
labored breathing. May cause lung edema, a medical emergency.
Ingestion:
Corrosive. Swallowing can cause severe burns of the mouth, throat, and
stomach, leading to death. Can cause sore throat, vomiting, diarrhea.
Circulatory collapse with clammy skin, weak and rapid pulse, shallow
respirations, and scanty urine may follow ingestion or skin contact. Circulatory
shock is often the immediate cause of death.
8.6.1 Skin Contact:
Corrosive. Symptoms of redness, pain, and severe burn can occur. Circulatory
collapse with clammy skin, weak and rapid pulse, shallow respirations, and
scanty urine may follow skin contact or ingestion. Circulatory shock is often the
immediate cause of death.

8.6.2 Eye Contact:

Corrosive. Contact can cause blurred vision, redness, pain and severe tissue
burns. Can cause blindness.
8.6.3 Chronic Exposure:
Long-term exposure to mist or vapors may cause damage to teeth. Chronic
exposure to mists containing sulfuric acid is a cancer hazard.
8.6.4 Aggravation of Pre-existing Conditions:
Persons with pre-existing skin disorders or eye problems or impaired
respiratory function may be more susceptible to the effects of the substance.

8.7 FIRST AID MEASURES

Inhalation:
Remove to fresh air. If not breathing, give artificial respiration. If breathing is
difficult, give oxygen. Call a physician immediately.
Ingestion:
DO NOT INDUCE VOMITING. Give large quantities of water. Never give
anything by mouth to an unconscious person. Call a physician immediately.
8.7.1 Skin Contact:
In case of contact, immediately flush skin with plenty of water for at least 15
minutes while removing contaminated clothing and shoes. Wash clothing
before reuse. Excess acid on skin can be neutralized with a 2% solution of
bicarbonate of soda. Call a physician immediately.
8.7.2 Eye Contact:
Immediately flush eyes with gentle but large stream of water for at least 15
minutes, lifting lower and upper eyelids occasionally. Call a physician
immediately.

8.8 FIRE FIGHTING MEASURES

Fire:
Concentrated material is a strong dehydrating agent. Reacts with organic
materials and may cause ignition of finely divided materials on contact.
Explosion:
Contact with most metals causes formation of flammable and explosive
hydrogen gas.
8.8.1 Fire Extinguishing Media:
Dry chemical, foam or carbon dioxide. Do not use water on material. However,
water spray may be used to keep fire exposed containers cool.
8.8.2 Special Information:
In the event of a fire, wear full protective clothing and NIOSH-approved selfcontained breathing apparatus with full facepiece operated in the pressure
demand or other positive pressure mode. Structural firefighter's protective
clothing is ineffective for fires involving this material. Stay away from sealed
containers.

8.9 ACCIDENTAL RELEASE MEASURES

Ventilate area of leak or spill. Wear appropriate personal protective equipment
as specified in Section 8. Isolate hazard area. Keep unnecessary and
unprotected personnel from entering. Contain and recover liquid when
possible. Neutralize with alkaline material (soda ash, lime), then absorb with
an inert material (e. g., vermiculite, dry sand, earth), and place in a chemical
waste container. Do not use combustible materials, such as saw dust. Do not
flush to sewer! US Regulations (CERCLA) require reporting spills and releases to
soil, water and air in excess of reportable quantities.

8.10 HANDLING AND STORAGE

Store in a cool, dry, ventilated storage area with acid resistant floors and good
drainage. Protect from physical damage. Keep out of direct sunlight and away
from heat, water, and incompatible materials. Do not wash out container and

use it for other purposes. When diluting, always add the acid to water; never
add water to the acid. When opening metal containers, use non-sparking tools
because of the possibility of hydrogen gas being present. Containers of this
material may be hazardous when empty since they retain product residues
(vapors, liquid); observe all warnings and precautions listed for the product.

8.11 PHYSICAL AND CHEMICAL PROPERTIES

Appearance:
:
Clear
oily
liquid.
Odor:
:
Odorless.
Solubility:
Miscible
with
water,
liberates
much
heat.
Specific
Gravity:
1.84
(98%),
1.40
(50%),
1.07
(10%)
pH: 1 N solution (ca. 5% w/w) = 0.3; 0.1 N solution (ca. 0.5% w/w) = 1.2; 0.01 N
solution
(ca.
0.05%
w/w)
=
2.1.
Boiling Point:
290C (ca. 554F) (decomposes at 340C)
Melting Point:
3C (100%), -32C (93%), -38C (78%), -64C (65%).
Vapor
Density
(Air=1):
3.4
Vapor Pressure (mm Hg): 1 @ 145.8C (295F)
Stability:
Stable under ordinary conditions of use and storage. Concentrated solutions
react violently with water, spattering and liberating heat.
8.11.1 Hazardous Decomposition Products:
Toxic fumes of oxides of sulfur when heated to decomposition.
Will react with water or steam to produce toxic and corrosive fumes.
Reacts with carbonates to generate carbon dioxide gas, and with
cyanides and sulfides to form poisonous hydrogen cyanide and hydrogen
sulfide respectively.
8.11.2 Hazardous Polymerization:
The will not occur.
Incompatibilities:
Water, potassium chlorate, potassium perchlorate, potassium permanganate,
sodium, lithium, bases, organic material, halogens, metal acetylides, oxides

and hydrides, metals (yields hydrogen gas), strong oxidizing and reducing
agents and many other reactive substances.
8.11.3 Conditions to Avoid:
Heat, moisture, incompatibles.

8.12 ECOLOGICAL INFORMATION

8.12.1 Environmental Fate:
When released into the soil, this material may leach into groundwater. When
released into the air, this material may be removed from the atmosphere to a
moderate extent by wet deposition. When released into the air, this material
may be removed from the atmosphere to a moderate extent by dry
deposition.
8.12.2 Environmental Toxicity:
LC50 Flounder 100 to 330 mg/l/48 hr aerated water/Conditions of bioassay not
specified; LC50 Shrimp 80 to 90 mg/l/48 hr aerated water /Conditions of
bioassay not specified; LC50 Prawn 42.5 ppm/48 hr salt water /Conditions of
bioassay
not
specified.
This material may be toxic to aquatic life.

8.13 MSDS OF GASOLINE

Oxygenated Conventional and Reformulated Gasoline will have oxygenates for
octane enhancement or as legally required.
MSDS No. 9950

8.14 HAZARDS IDENTIFICATION

8.14.1 Eyes
Moderate irritant.
Contact with liquid or vapor may cause irritation.
8.14.2 Skin
Practically non-toxic if absorbed following acute (single) exposure.

May cause skin irritation with prolonged or repeated contact.

Liquid may be absorbed through the skin in toxic amounts if large areas
of skin are exposed repeatedly.
8.14.3 Ingestion
The major health threat of ingestion occurs from the danger of aspiration
(breathing) of liquid drops into the lungs, particularly from vomiting. Aspiration
may result in chemical pneumonia (fluid in the lungs), severe lung damage,
respiratory failure and even death.
Ingestion may cause gastrointestinal disturbances, including irritation, nausea,
vomiting and diarrhea, and central nervous system (brain) effects similar to
alcohol intoxication. In severe cases, tremors, convulsions, loss of
consciousness, coma, respiratory arrest, and death may occur.
8.14.4 Inhalation
Excessive exposure may cause irritations to the nose, throat, lungs and
respiratory tract. Central nervous system (brain) effects may include headache,
dizziness, loss of balance and coordination, unconsciousness, coma, respiratory
failure, and death.

8.15 WARNING:
The burning of any hydrocarbon as a fuel in an area without adequate
ventilation may result in hazardous levels of combustion products, including
carbon monoxide, and inadequate oxygen levels, which may cause
unconsciousness, suffocation, and death.
8.15.1 Chronic Effects and Carcinogenicity
It Contains benzene, a regulated human carcinogen. Benzene has the potential
to cause anemia and other blood diseases, including leukemia, after repeated
and prolonged exposure. Exposure to light hydrocarbons in the same boiling
range as this product has been associated in animal studies with systemic
toxicity. See also Section 11 - Toxicological Information.

8.15.2 Medical Conditions Aggravated By Exposure

Irritation from skin exposure may aggravate existing open wounds, skin
disorders, and dermatitis (rash).Chronic respiratory disease, liver or kidney
dysfunction, or pre-existing central nervous system disorders may be
aggravated by exposure.

8.16 FIRST AID MEASURES

8.16.1 Eyes
In case of contact with eyes, immediately flush with clean, low-pressure water
for at least 15 min. hold eye lids open to ensure adequate flushing. Seek
medical attention.
8.16.2 Skin
Remove contaminated clothing. Wash contaminated areas thoroughly with
soap and water or waterless hand cleanser. Obtain medical attention if
irritation or redness develops.
8.16.3 Ingestion
DO NOT INDUCE VOMITING. Do not give liquids. Obtain immediate medical
attention. If spontaneous vomiting occurs, lean victim forward to reduce the
risk of aspiration. Small amounts of material which enter the mouth should be
rinsed out until the taste is dissipated.
8.16.4 Inhalation
Remove person to fresh air. If person is not breathing, ensure an open airway
and provide artificial respiration. If necessary, provide additional oxygen once
breathing is restored if trained to do so. Seek medical attention immediately.

8.17 FIRE FIGHTING MEASURES

8.17.1 Flammable Properties:
Flash Point: -45F (-43C)
Auto Ignition Temperature: highly variable; > 530F (>280C)

Osha/Nfpa Flammability Class: 1A (flammable liquid)

Lower Explosive Limit (%): 1.4%
Upper Explosive Limit (%): 7.6%
8.17.2 Fire and Explosion Hazards
Vapors may be ignited rapidly when exposed to heat, spark, open flame or
other source of ignition. Flowing product may be ignited by self-generated
static electricity. When mixed with air and exposed to an ignition source,
flammable vapors can burn in the open or explode in confined spaces. Being
heavier than air, vapors may travel long distances to an ignition source and
flash back. Runoff to sewer may cause fire or explosion hazard.
8.17.3 Extinguishing Media
SMALL FIRES: Any extinguisher suitable for Class B fires, dry chemical, CO2,
water spray, fire fighting foam, or Halon.
LARGE FIRES: Water spray, fog or fire fighting foam. Water may be ineffective
for fighting the fire, but may be used to cool fire-exposed containers. During
certain times of the year and/or in certain geographical locations, gasoline may
contain MTBE and/or TAME. Firefighting foam suitable for polar solvents is
recommended for fuel with greater than 10% oxygenate concentration - refer
to NFPA 11 Low Expansion Foam - 1994 Edition.
8.17.4 Fire Fighting Instructions
Small fires in the incipient (beginning) stage may typically be extinguished
using handheld portable fire extinguishers and other firefighting equipment.
Firefighting activities that may result in potential exposure to high heat, smoke
or toxic by-products of combustion should require NIOSH/MSHA- approved
pressure-demand self-contained breathing apparatus with full face piece and
full protective clothing. Isolate area around container involved in fire. Cool
tanks, shells, and containers exposed to fire and excessive heat with water. For
massive fires the use of unmanned hose holders or monitor nozzles may be
advantageous to further minimize personnel exposure. Major fires may require
withdrawal, allowing the tank to burn. Large storage tank fires typically require

specially trained personnel and equipment to extinguish the fire, often

including the need for properly applied fire fighting foam.

8.18 ACCIDENTAL RELEASE MEASURES

8.18.1 Activate facility spill contingency or emergency plan.
Evacuate nonessential personnel and remove or secure all ignition sources.
Consider wind direction; stay upwind and uphill, if possible. Evaluate the
direction of product travel, diking, sewers, etc. to confirm spill areas. Spills may
infiltrate subsurface soil and groundwater; professional assistance may be
necessary to determine the extent of subsurface impact. Carefully contain and
stop the source of the spill, if safe to do so. Protect bodies of water by diking,
absorbents, or absorbent boom, if possible. Do not flush down sewer or
drainage systems, unless system is designed and permitted to handle such
material. The use of fire fighting foam may be useful in certain situations to
reduce vapors. The proper use of water spray may effectively disperse product
vapors or the liquid itself, preventing contact with ignition sources or
areas/equipment that require protection. Take up with sand or other oil
absorbing materials. Carefully shovel, scoop or sweep up into a waste.
Container for reclamation or disposal - caution, flammable vapors may
accumulate in closed containers. Response and clean-up crews must be
properly trained and must utilize proper protective equipment

8.19 HANDLING AND STORAGE

8.19.1 Handling Precautions

USE ONLY AS A MOTOR FUEL

DO NOT SIPHON BY MOUTH

Handle as a flammable liquid. Keep away from heat, sparks, and open flame!
Electrical equipment should be approved for classified area. Bond and ground
containers during product transfer to reduce the possibility of static-initiated
fire or explosion.
Special slow load procedures for "switch loading" must be followed to avoid
the static ignition hazard that can exist when higher flash point material (such
as fuel oil) is loaded into tanks previously containing low flash point products
(such as this product) - see API Publication 2003, "Protection Against Ignitions
Arising Out Of Static, Lightning and Stray Currents.
8.19.2 Storage Precautions
Keep away from flame, sparks, excessive temperatures and open flame. Use
approved vented containers. Keep containers closed and clearly labeled.
Empty product containers or vessels may contain explosive vapors. Do not
pressurize, cut, heat, weld or expose such containers to sources of ignition.
Store in a well-ventilated area. This storage area should comply with NFPA 30
"Flammable and Combustible Liquid Code". Avoid storage near incompatible
materials. The cleaning of tanks previously containing this product should
follow API Recommended Practice (RP) 2013 "Cleaning Mobile Tanks In
Flammable and Combustible Liquid Service" and API RP 2015 "Cleaning
Petroleum Storage Tanks".
8.19.3 Work/Hygienic Practices
Emergency eye wash capability should be available in the near proximity to
operations presenting a potential splash exposure. Use good personal hygiene
practices. Avoid repeated and/or prolonged skin exposure. Wash hands before
eating, drinking, smoking, or using toilet facilities. Do not use as a cleaning
solvent on the skin. Do not use solvents or harsh abrasive skin cleaners for
washing this product from exposed skin areas. Waterless hand cleaners are
effective. Promptly remove contaminated clothing and launder before reuse.
Use care when laundering to prevent the formation of flammable vapors which
could ignite via washer or dryer. Consider the need to discard contaminated
leather shoes and gloves.

8.20 PHYSICAL AND CHEMICAL PROPERTIES

8.20.1 Appearance
A translucent, straw-colored or light yellow liquid
8.20.2 Odour
A strong, characteristic aromatic hydrocarbon odor, Oxygenated gasoline with
MTBE and/or TAME may have a sweet, ether-like odor and is detectable at a
lower concentration than non-oxygenated gasoline.

8.20.3 Odour Threshold

Odour Detection Odour Recognition
Non-oxygenated gasoline: 0.5 - 0.6 ppm 0.8 - 1.1 ppm
Gasoline with 15% MTBE: 0.2 - 0.3 ppm 0.4 - 0.7 ppm
Gasoline with 15% TAME: 0.1 ppm 0.2 ppm

8.20.4 Basic Physical Properties

Boiling Range: 85 to 437 F (39 to 200C)
Vapor Pressure: 6.4 - 15 RVP @ 100F (38C) (275-475 mm Hg @ 68F (20C)
Vapor Density (air = 1): AP 3 to 4
Specific Gravity (H2O = 1): 0.70 0.78
Evaporation Rate: 10-11 (n-butyl acetate = 1)
Percent Volatiles: 100 %
Solubility (H2O): Non-oxygenated gasoline - negligible (< 0.1% @ 77 F).
Gasoline with 15%

8.21 STABILITY AND REACTIVITY

8.21.1 Stability:
Stable. Hazardous polymerization will not occur.
8.21.2 Conditions to Avoid
Avoid high temperatures, open flames, sparks, welding, smoking and other
ignition sources
8.21.3 Incompatible Materials
Keep away from strong oxidizers.
8.21.4 Hazardous Decomposition Products
Carbon monoxide, carbon dioxide and non-combusted hydrocarbons (smoke).
Contact with nitric and sulfuric acids will form nitrocresols that can decompose
violently

9 CHAPTER # 9:
INSTRUMENTATION AND PROCESS
CONTROL
9.1 INSTRUMENTATION AND PROCESS CONTROL
Measurement is a fundamental requisite to process control. Either the
control can be affected automatically, semi automatically or manually. The
quality of control obtainable also bears a relationship to accuracy, re product
ability and reliability of measurement methods, which are employed.

Therefore, selection of the most affect means of measurements is an

important first step in design and formulation of any process control system.

9.2 TEMPERATURE MEASUREMENT AND CONTROL

Temperature measurement is used to control the temperature of
outlet and inlet streams in heat exchangers, reactors, etc. Most temperature
measurements in the industry are made by means of thermocouple to
facilitate bringing the measurements to centralized location. For local
measurements at the equipment bimetallic or filled system thermometers are
used to a lesser extent. Usually, for high measurement accuracy, resistance
thermometers are used all these measurements are installed with thermo
wells when used locally. This provides protection against atmosphere and
other physical elements.

9.3 PRESSURE MEASUREMENT AND CONTROL

Like temperature pressure is a value able indication of material state and
composition. In fact, these two measurements considered together are the
primary evaluating devices of industrial materials. Pumps, compressors and
other process equipment associated with pressure changes in the process
material are furnished with pressure measuring devices. Thus pressure
measurement becomes an indication of an energy decrease or increase.
Most pressure devices in industry are elastic element devices, either directly
connected for local use or transmission type to centralized location. Most
extensively used industrial pressure is the Bourderi Tube or a Diaphram or
Bellow gauges.

9.4 FLOW MEASUREMENT AND CONTROL

Flow indicators are used to control the amount of liquid. Also all manually set
streams require some flow indication or some easy means for occasional
sample measurement. For accounting purposes, feed and product streams or
metered. In addition utilities to individual and grouped equipment are also
metered. Most flow measures in the industry are/ by Variable Head devices. To

a lesser extent variable area is used as are many types available as special
metering situation arise.

9.5 CONTROL SCHEME OF DISTIALLATION COLUMN

9.5.1 Objectives:
In distillation column any of following may be the goals to achieve.
Overhead composition
bottom composition
Constant over head product rate.
Constant bottom product rate.

9.5.2 Manipulated variables:

Any one or any combination of following may be the manipulated variables.
Steam flow rate to reboiler
Reflux rate.
Overhead product with drawn rate.
Bottom product withdrawn rate.
Water flow rate to condenser.

9.5.3 Loads or disturbances:

Following are typical disturbances.
Flow rate of feed.
Composition of feed.
Temperature of feed.

Pressure drop of steam across reboiler.

Inlet temperature of water for condenser.

9.5.4 Control scheme

Overall product rate is fixed and any change in feed must be absorbed by
changing bottom product rate. The change in product rate is accomplished by
direct level control of reboiler if the stream rate is fixed feed rate increases
then vapour rate is approximately is constant and the internal reflux flow must
increase.
9.5.5 Advantage
Since an increase in feed rate increases reflux rate with vapour rate being
approximately constant, then purity of top product increases.
9.5.6 Disadvantage
The overhead change depends on dynamics of level control system that
adjusts it.

9.5.6.1.1 Figure 27: Control scheme:

10

11 CHAPTER # 10
COST ESTIMATION
11.1.1.1

Table 47: cost estimation of equipments:

Item
Reactor
De-isobutanizer
De-propanizer
Compressor
De-isobutanizer
Compressor

Quantity
Cost in Mid 2004
1
1
1
1
1

Cost($)

Total cost ($)

287391.28
99864
47857
9169.48
2689.92

287391.28
99864
47857
9169.48
2689.92

De-propanizer
Condenser
Deisobutanizer
reboiler
Deisobutanizer
reboiler
Pumps
Total cost

9760

9760

7647.12

7647.12

11700

11700

4
12

10123.5
486199.3

40494
516570

In order to find the cost escalation (INFLATION) we take purchased cost of any
one of the equipment and proceed.
A = Index in 2004 = 111
B = Index in 2000 = 100
Purchased Cost in 2004 = $ 7647.12
So,
Cost in year 2000 =
Cost in 2000 = $ 6889.30
Therefore, Escalation is 2.75 %
Following this we have,
A = Index in 2004 = 111
B = Index in 2000 = 100
Purchased Cost in 2004 = $ 7647.12
So,
Cost in year 2000
=Cost in 2000 = $ 6889.30

Therefore, Escalation is 2.75 %

Following this we have,
Total Production Cost:
Variable Cost:
Raw Materials comprises of the Olefins, Makeup Isobutane and H2SO4.
Flow rate of Olefins = 477.46 kg/min
Olefins Cost (Reference should be mentioned here) = 1 $/kg
A1 = 477.46 60 330 24
A1 = $ 22688992
Now,
Flow rate of makeup Isobutane = 1496.7 liter/min
Isobutane cost (Reference) = 0.48 $/liter
A2 = 1496.7 60 330 24
A2 = $ 341391283
And,
Flow rate of H2SO4 = 79.39 kg/min
H2SO4 Cost (Reference) = 0.24 $/kg
A3 = 79.38 60 330 24
A3 = $ 9053130
Total Cost: $ 373133405
As the cost of the miscellaneous material is 10% of the maintenance and
Utilities cost is 10% of the TCI. Whereas shipping and packing cost is taken as
negligible, therefore.

Miscellaneous material Cost = $ 35269

Utilities Cost = $ 387959
Shipping and Packing Cost = Negligible
Total Variable Cost = A = $ 373556633

11.2 Fixed Cost:

It comprises of the maintenance which is taken as 10% (as an initial estimate)
.Similarly Operating labor cost is 10% of TCI , laboratory Cost 20% of OLC ,
Supervision 20% of OLC , Plant overheads 5% of OLC , Capital Charges 10% of
FCI , Insurance and Royalties & license fee 1% of the FCI , furthermore local
taxes 2% of FCI .
Maintenance Cost = $352690.75
Operating labor Cost = $387959.82

Laboratory Cost = $77592

Supervision Cost = $77592
Plant Overheads Cost = $193980
Capital Charges Cost = $352690.75
Insurance Cost = $35269.07
Local Taxes = $ 70538.5
Royalties & licenses cost = $35269.7
Total Fixed Cost = B = $ 1583581
Direct production Cost = A + B
= $ 375140214

11.3 Annual Production Cost:

We have sales expenses which is 20 % of the DPC, whereas General overheads
and research & development cost is neglected in it .
Sales Expenses = $ 75028043
Annual Production Cost = DPC + C
$ 450168257 / year

11.4 Processing Cost / Liter:

$ 450168257

1 year

1 day

1 hour

1 bbl.

1 year

330 days

24 hour

416.66 bbl.

159 liter

Processing Cost/ liter = 0.86 $/liter

11.5 Profit per annum:

Present market Value = 1.1 $/liter
Profit per liter = 1.1 0.86 = $ 0.24/liter
$ 0.24

159 liter

10,000 bbl.

330 days

1 liter

1 bbl

day

1 year

Total Annual Profit = $ 125928000

12 APPENDIX
12.1 APPENDIX A-1
12.1.1.1.1 Fig 12.1 (Coluson & Richadson - Chemical
engineering design Vol 6)

12.2
12.3 APPENDIX A-2
12.3.1.1.1 Fig 12.19 (Coluson & Richadson - Chemical
engineering design Vol 6)

12.4 APPENDIX A-3

12.4.1.1.1 Fig 12.23 (Coluson & Richadson - Chemical
engineering design Vol 6)

12.5 APPENDIX A-4

12.5.1.1.1 Fig12.10 (Coluson & Richadson - Chemical
engineering design Vol 6)

12.6 APPENDIX A-5

12.6.1.1.1 Fig 12.29 (Coluson & Richadson - Chemical
engineering design Vol 6)

12.7 APPENDIX A-6

12.7.1.1.1 Fig-12.24 (Coluson & Richadson - Chemical
engineering design Vol 6)

12.8 APPENDIX A-7

12.8.1.1.1 Fig-12.30 (Coluson & Richadson - Chemical
engineering design Vol 6)

12.9 APPENDIX B-1

12.9.1.1.1 Fig 11.27 (Coluson & Richadson - Chemical
engineering design Vol 6)

12.10

APPENDIX B-2

12.10.1.1.1
Fig 11.28 (Coluson & Richadson - Chemical
engineering design Vol 6)

12.11

APPENDIX B-3

12.11.1.1.1
Fig 11.29 (Coluson & Richadson - Chemical
engineering design Vol 6)

12.12

APPENDIX B-4

12.12.1.1.1
Fig 11.30 (Coluson & Richadson - Chemical
engineering design Vol 6)

12.13

APPENDIX B-5

12.13.1.1.1
Fig 11.34 (Coluson & Richadson - Chemical
engineering design Vol 6)

12.14

Appendix B-6

12.14.1.1.1
Fig 11.42 Coluson & Richadson Chemical
Engineering Vol 2

12.15

APPENDIX C-1

12.15.1.1.1
Fig 10.9 Couper_ Penney_ Fair_ Walas - 2005 2nd ed. Chemical process equipment - Selection and
design

REFERENCES

1.

JONES, DAVID S. J. "STAN" and PUJAD O, PETER R. Handbook of Petroleum

Processing. Springer, Netherlands. : s.n., 2006.

2. Secretariat, OPEC. World Oil Outlook. Austria : s.n., 2013. ISBN: 978-3-9502722-6-0.
3. Parkash, Surinder. REFINING PROCESSES HANDBOOK. s.l. : Elsevier, 2003. ISBN: 0-75067721-X.
4. Gary, James H. Petroleum Refining Technology and Economics. New York : Marcel Dekker, Inc.,
2001. ISBN: 0-8247-0482-7.
5. PUJAD O, DAVID S. J. "STAN" JONES and PETER R. Handbook of Petroleum
Processing. Netherlands : Springer, 2006. ISBN-10 1-4020-2819-9.
6. Meyers, Robert A. Handbook Of Petroleum Refining Processes. s.l. : McGraw-Hill
Handbooks.
7. Alkylation. Wikipedia The free encyclopedia. [Online] [Cited: November 8, 2014.]
http://en.wikipedia.org/wiki/Alkylation.
8. SPEIGHT, JAMES G. The Chemistry and Technology of Petroleum. s.l. : CRC press,
2006.
9. M. A. Fahim, T. A. Al-Sahhaf. Fundamentals of Petroleum Refining. s.l. : Elsevier, 2010.
ISBN: 978-0-444-52785-1.
10. Daniel.Vallejo. DuPont Clean Technologies. DuPont. [Online] March 9, 2007.
http://www2.dupont.com/Clean_Technologies/pt_BR/assets/downloads/STRATCOAlkysafe
Process.pdf.
11. Vina.Lam. Comparison of H2SO4 & HF Alkylation Process Technologies. DuPont. [Online]
[Cited: November 11, 2014.] http://www.dupont.com/products-and-services/consulting-servicesprocess-technologies/articles/h2so4-vs-hf.html.

12. Ray Sinnot, Gavin Towler. Chemical Engineering Design. Burlington : Elsevier Ltd.,
2009. ISBN: 978-0-7506-8551-1.
13. Levenspiel, Octave. Chemical Reaction Engineering. s.l. : Hamilton Printing Company, 1999. ISBN
0-471-25424-X.
14. Sinnott, R. K. Chemical Engineering Design. s.l. : Elsevier Butterworth-Heinemann, 2005. ISBN 0
7506 6538 6.
15. KERN, DONALD Q. PROCESS HEAT TRANSFER. NEW YORK : McGRAW-HILL,
1950.
16. Macdonald, Dave. Practical Industrial Safety, Risk Assessment and Shutdown Systems.
s.l. : Elsevier, 2004. ISBN: 0750658045.
17. Crowl, Daniel A. Chemical Process Safety. s.l. : Prentice Hall, Inc., 2002. ISBN: 0-13018176-5.
18. Pak. J. Anal. Environ. Chem. Ghulam Yasin, Tariq Mahmood Ansari, Syed
Muhammad Sibtain Raza Naqvi. Multan : s.n., 2008, Vol. 9. ISSN-1996-918X.
19. Aslam, Faisal. ENVIRONMENTAL IMPACT ASSESSMENT IN PAKISTAN -OVERVIEW,
IMPLEMENTATION AND EFFEC TIVNESS. 2006. ISSN 1651-064X.
20. World Energy council. World Energy Resources. England and Wales : World Energy Council ,
2013. ISBN: 978 0 946121 29 8.
21. Organization of the Petroleum Exporting Countries. World Oil Outlook. Obere Donaustrasse 93A1020 Vienna, Austria : s.n., 2007. ISBN 978-3-200-00965-3.
22. US Patent 4128597, 2435029 ,420965,3162694,2320199,2429205,2666019,2829181,

3415899
23. Yaws, C.L., Handbook of Vapor Pressure Vol.1, Gulf Publishing Company .