CATACARB PROCESS FOR CO2 REMOVAL

FOLLOWED BY METHANATION IN AMMONIA

PLANT

SESSION: 2011 2015

SUPERVISED BY:
Maam Sana Zahid
Maam Kanwal Shabbir
SUBMITTED BY:
2011 CH 05

Abdul Mannan Khan

2011 CH 43

Yusra Batool

2010 CH 53

Saad Naseer

2010 CH 127

Affan Shahid

2010 CH 133

Usama Shakil

DEPARTMENT OF CHEMICAL ENGINEERING

UNIVERSITY OF ENGINEERING & TECHNOLOGY, LAHORE, PAKISTAN

CATACARB PROCESS FOR CO2 REMOVAL

FOLLOWED BY METHANATION IN AMMONIA
PLANT
This project is submitted to Department of Chemical Engineering,
University of Engineering & Technology Lahore.

for the partial fulfillment of the requirements for the

BACHELORS DEGREE

in

CHEMICAL ENGINEERING

INTERNAL EXAMINER:

EXTERNAL EXAMINER:

___________________

____________________

Maam Sana Zahid

Name: ________________

___________________
Maam Kawal Shabbir
(Project Supervisors)

DEPARTMENT OF CHEMICAL ENGINEERING

UNIVERSITY OF ENGINEERING & TECHNOLOGY, LAHORE, PAKISTAN

In the name of Allah,

the most beneficial & the most merciful

ACKNOWLEDGEMENT | 7

ACKNOWLEDGEMENT
All praise to ALMIGHTY ALLAH, who provided us with the strength to
complete this final year Plant Design project. All respects are for the Holy
Prophet (PBUH), whose teachings are true source of knowledge & guidance
for whole of the mankind.
Before anybody else we thank our parents who have always been a source of
moral support and driving force behind whatever we do.
The preparation and writing of this report faced many challenges, as we have
tried to cover CO2 removal and methanation section of ammonia plant in this
project. The project could not have been researched, compiled and written in
these circumstances without the support of our Project Advisors.
We are highly indebted to our project advisors Maam Sana Zahid (Lecturer,
UET Lahore) and Maam Kanwal Shabbir (Lecturer, UET Lahore) for their
encouragement, technical discussions, inspiring guidance, remarkable
suggestions, keen interest, constructive criticism and discussions which enabled
us to complete this report. They spared a lot of precious time in advising &
helping us in writing this report.
We are thankful to our respected Chairman Dr. Hassan Javaid & honorable
teachers. We are also thankful to librarians of National Library of Engineering
Sciences, & Chemical Engineering Departmental Library for their cooperation
in search of design material.
We assure the reader that this may be our first project of its own kind, but at
least for a while, we have put a bit of "heart and soul" into it! Therefore, we
hope that you will find this report immensely educative & informative.
Authors

PROJECT MOTIVATION | 8

PROJECT MOTIVATION
As students of Chemical Engineering we have always been interested in
Fertilizer industry and Oil Refineries. There is no doubted the fact that every
chemical engineer is fascinated by the Fertilizer and Petroleum industry.
As Fertilizer is one of the two attractive fields, the other being petroleum
industry, every Chemical Engineer is interested in making his/her career in, the
decision of taking this project and working on it was both challenging and
interesting.
This project for the first time gave us the opportunity to explore the ammonia
plant which is the most complex plant and immensely worthy in terms of
gaining experience. We did project on CO 2 removal section (Natural Gas
Sweeting Process) and Methanation Section in detail. Our knowledge of this
process at the start of the project was casual. We knew generally about ammonia
plant and its CO2 removal and methanation section, knowing nothing specific
about the process flow circuit and design of a chemical plant, also it would not
be an oversimplification of the facts, if we assert that we knew nothing about a
chemical plant before this project.
The learning curve embarked on was considerably steeper than previous work
we have ever undertaken. Hence, the report constitutes our first ever attempt of
understanding a whole chemical process combined with the process flow
conditions and process selection. Our previous knowledge did not cater for this
scale of work but if we can dream it we can do it was the core motivation
behind this project.

Authors

PREFACE | 9

PREFACE

Ammonia is a source of nitrogen for growing plants. Every fertilizer contains

nitrogen either in the form of ammonia or compounds derived from ammonia.
Removal of CO2 from reformed natural gas and conversion of unconverted
oxides is necessary otherwise liquefaction process in ammonia production will
be affected.
As the art and science of design is a matter of handful experience, supported by
sound theoretical background. So due to the lack of experience, certain aspects
might have been incomplete in this work. But overall design procedures,
significant modification and assumptions strongly justified by logical and
theoretical ground give this work a status of a valuable concise report on
CATACARB process for CO2 removal followed by methanation in ammonia
plant.
To remove CO2 from reformed natural gas and to convert the remaining carbon
oxides to methane, first of all, mass and energy balance was carried out over the
whole system along with simulation including equipment like knock out drum,
absorber, stripper, methanator and heat exchangers etc. This forms the basis for
our design, where the design specs are set in order to meet the ranges specified
by the rules of thumb or in accordance with the International Design Standards
like TEMA etc. Simulation of absorber and methanation section was also
conducted and results were compared with our calculations.
For the stability, optimization, and reduction of the effect of external forces,
instrumentation of the absorber and stripper section is a necessary action
performed after equipment design completion. After that, HAZOP study gives
an accurate idea about the effect of changing variables on equipment strength
and on how far we can push the process variables. HAZOP Study of methanator
was conducted. Owing to the global environmental consensus and the growing
need to preserve our planet, Environmental Impact Assessment or EIA is
considered an integral part of any industrial scale project. Cost analysis of the
major equipment were conducted.
I hope this report will be helpful in understanding the CATACARB process for
CO2 removal followed by methanation in ammonia plant.

PREFACE | 10

Authors

CONTENTS |

TABLES OF CONTENTS
ACKNOWLEDGEMENT......................................................................................I
PROJECT MOTIVATION....................................................................................II
PREFACE...................................................................................................... III
1.

INTRODUCTION.......................................................................................2
1.1.
FERTILIZER............................................................................................................. 2
1.2.
FERTILIZER HISTORY: THE HABER-BOSCH PROCESS........................................................2
1.3.
FEED FOR AMMONIA PRODUCTION..............................................................................3
1.3.1. Impurities in Natural Gas................................................................................5
1.4.
WHY CO2 REMOVAL IS NECESSARY IN AMMONIA PRODUCTION?..........................................5
1.5.
CO2 USES.............................................................................................................. 5
1.5.1. Urea manufacturing........................................................................................5
1.5.2. Healthcare...................................................................................................... 5
1.5.3. Pulp & Paper................................................................................................... 5
1.5.4. Water & Wastewater Treatment......................................................................5

2.

PROCESS SELECTION...............................................................................7
2.1 PHYSICAL ABSORPTION................................................................................................... 7
2.2 PHYSICAL ADSORPTION.................................................................................................. 7
2.3 CRYOGENIC FRACTIONATION............................................................................................ 7
2.4 PERMEATION (MEMBRANE)..............................................................................................7
2.5 CHEMICAL ABSORPTION.................................................................................................. 7
2.6 FACTORS AFFECTING SELECTION OF PROCESS....................................................................7
2.7 PROCESSES USED IN CHEMICAL INDUSTRIES.......................................................................8
2.7.1 CATACARB Process............................................................................................ 8
2.7.2 MDEA................................................................................................................ 9

3.

PROCESS DESCRIPTION..........................................................................11
3.1.
CARBON DIOXIDE REMOVAL SECTION........................................................................11
3.2.
ABSORBENT REGENERATION SECTION........................................................................11
3.2.1. Stripper (T-02)............................................................................................... 11
3.2.2. Stripper (T-01)............................................................................................... 12
3.3.
METHANATION SECTION.......................................................................................... 13

4.

MATERIAL BALANCE...............................................................................16
4.1
4.2
4.3
4.4

5.

MATERIAL
MATERIAL
MATERIAL
MATERIAL

BALANCE
BALANCE
BALANCE
BALANCE

ACROSS
ACROSS
ACROSS
ACROSS

KNOCK-OUT DRUM (D-01)....................................................16

ABSORBER (T-03)................................................................17
METHANATOR (R-01)............................................................19
STRIPPERS (T-01 & T-02).....................................................20

ENERGY BALANCE..................................................................................23
5.1
5.2
5.3
5.4
5.5
5.6

KNOCK OUT DRUM (D-01)........................................................................................... 23

HEAT EXCHANGER (E-05)............................................................................................ 24
HEAT EXCHANGER (E-01)............................................................................................ 25
HEAT EXCHANGER (E-02)............................................................................................ 26
HEAT EXCHANGER (E-03)............................................................................................ 27
METHANATOR (R-01).................................................................................................. 27

6. EQUIPMENT DESIGN.................................................................................31

CONTENTS |
6.1 SHELL & TUBE HEAT EXCHANGER DESIGN (E-05)............................................................31
6.1.1 Heat Exchanger?.............................................................................................31
6.1.2 Shell and Tube Heat Exchanger.......................................................................32
6.1.3 Tube side and shell fluid allocation..................................................................34
6.1.4 Thermo-Hydraulics Calculations......................................................................34
6.1.5 Design Calculations......................................................................................... 35
6.1.6 Tube Side Specification...................................................................................36
6.1.7 Shell Side Specification...................................................................................37
6.1.8 Number of tubes.............................................................................................37
6.1.9 Flow Area........................................................................................................ 37
6.1.10 Mass velocity................................................................................................. 38
6.1.11 Reynolds Number......................................................................................... 38
6.1.12 Individual heat transfer coefficient................................................................38
6.1.13 Overall heat transfer coefficient....................................................................39
6.1.14 Pressure drop Calculations............................................................................39
6.2 ABSORPTION & STRIPPING COLUMN................................................................................40
6.2.1 Selection of Column........................................................................................40
6.2.2 Selection of Packing........................................................................................41
6.2.3 Selection Of Packing And Material...................................................................41
6.3 DESIGN OF STRIPPER (LEAN SOLUTION REGENERATOR).......................................................42
6.3.1 K4 Calculation.................................................................................................. 43
6.3.2 Check For Channeling.....................................................................................44
6.3.3 Height of Column............................................................................................45
6.3.4 Pressure drop Calculations..............................................................................48
6.4 DESIGN OF ABSORBER (T-03).......................................................................................50
6.4.1 Semi-Lean Lower Section Diameter Calculations..........................................51
6.4.2 Semi-Lean Lower Section Height Calculations..............................................53
6.4.3 Lean Upper Section......................................................................................... 56
6.4.4 Pressure Drop Calculations..............................................................................56
6.5 METHANATOR DESIGN.................................................................................................. 58
6.5.1 Chemical Reactions.........................................................................................58
6.5.2 Reaction Kinetics............................................................................................. 58
6.5.3 Rate Constants................................................................................................ 59
6.5.4 Equilibrium Constants.....................................................................................59
6.5.5 Description Of The Process In Reactor.............................................................60
6.5.6 Reactor Selection............................................................................................60
6.5.7 Reactor Design Steps......................................................................................61
6.5.8 Calculation Of Weight Of Catalyst...................................................................61
6.5.9 Estimation Of Volume Of Catalyst...................................................................64
6.5.10 Determination of Volume of Reactor.............................................................64
6.5.11 L/D Ratio:...................................................................................................... 64
6.5.12 Calculation Of Length & Diameter.................................................................65
6.5.13 Pressure Drop Calculations............................................................................65
6.6 KNOCK-OUT VESSEL DESIGN........................................................................................66
6.6.1 Selection Criteria............................................................................................. 66
6.6.2 General Design Steps......................................................................................66
6.6.3 Vapor Velocity Calculation...............................................................................66
6.6.4 Diameter Calculation.......................................................................................67
6.6.5 Length Calculation..........................................................................................68
7.

SIMULATION OF ABSORBER & METHANATOR...........................................70

7.1 PHYSICAL PROPERTY METHOD - SRK..............................................................................70

CONTENTS |
7.2 COMPONENTS............................................................................................................. 70
7.3 STREAM INPUTS.......................................................................................................... 71
7.3.1 Feed Reformed Natural Gas..........................................................................71
7.3.2 Lean Solution.................................................................................................. 71
7.3.3 Semi-Lean Solution.........................................................................................72
7.4 STREAM RESULTS........................................................................................................ 74
7.4.1 Methanator...................................................................................................... 74
7.4.2 Absorber Upper Section...................................................................................75
7.4.2 Absorber Lower Section...................................................................................76
8. INSTRUMENTATION & CONTROL................................................................78
8.1 INTRODUCTION........................................................................................................... 78
8.1.1 Instrument...................................................................................................... 78
8.1.2 Control............................................................................................................ 78
8.1.3 Incentives Of Control.......................................................................................78
8.2 OBJECTIVES............................................................................................................... 79
8.2.1 Safe Plant Operation.......................................................................................79
8.2.2 Production Rate...............................................................................................79
8.2.3 Production Quality........................................................................................... 79
8.2.4 Cost................................................................................................................. 79
8.3 COMPONENTS OF THE CONTROL SYSTEM........................................................................79
8.3.1 Process............................................................................................................ 79
8.3.2 Measuring Means............................................................................................79
8.3.3 Main Process Variables & Their Control...........................................................79
8.3.4 Controller........................................................................................................ 80
8.3.5 Final Control Element......................................................................................80
8.4 CLASSIFICATION OF CONTROLLER...................................................................................80
8.4.1 Modes Of Control.............................................................................................81
8.5 TYPES OF CONTROL.................................................................................................. 81
8.5.1 Feedback Control Loop.................................................................................81
8.5.2 Feed Forward Control Loop...........................................................................81
8.6 LEAN SOLUTION FLOW CONTROL LOOP OF CO2 ABSORBER.................................................82
8.7 SEMI FLOW CONTROL OF CO2 ABSORBER T-03B:.............................................................83
9. HAZARD OPERABILITY..............................................................................85
9.1 HISTORY AND INTRODUCTION........................................................................................85
9.2 INTRODUCTION........................................................................................................... 85
9.2.1 Hazard............................................................................................................. 85
9.2.2 Operability...................................................................................................... 85
9.2.3 Types Of Hazop...............................................................................................86
9.2.4 The Reasons For Such Widespread Use Of Hazop...........................................86
9.2.5 When To Perform A Hazop?.............................................................................86
9.2.6 Success Or Failure Of The Hazop.....................................................................87
9.3 OBJECTIVES OF HAZOP STUDY.......................................................................................87
9.4 FEATURES OF HAZOP STUDY......................................................................................... 88
9.5 HAZOP STUDY METHODOLOGY.......................................................................................88
9.5.1 Specify The Purpose, Objective, And Scope Of The Study...............................88
9.5.2 Select The Hazop Study Team.........................................................................89
9.5.3 Collect Data..................................................................................................... 89
9.5.4 Conduct The Study.......................................................................................... 90
9.5.5 Write The Report............................................................................................. 91
9.5.6 Hazop method Flow Diagram..........................................................................93

CONTENTS |
9.6 CONCLUSIONS............................................................................................................ 94
9.7 ADVANTAGES............................................................................................................. 95
9.8 LIMITATION OF THE HAZOP TECHNIQUE...........................................................................95
9.8.1 Requires A Well-Defined System Or Activity....................................................95
9.8.2 Time Consuming.............................................................................................95
9.8.3 Focuses On One-Event Causes Of Deviations..................................................95
9.9 HAZOP STUDY OF METHANATOR (R-01).........................................................................96
10. ENVIRONMENTAL IMPACT ASSESSMENT (EIA)...........................................98
10.1 WHAT IS EIA?.......................................................................................................... 98
10.2 PURPOSE OF EIA...................................................................................................... 98
10.3 ORIGINS AND HISTORY OF EIA....................................................................................98
10.5 THE EIA PROCESS..................................................................................................... 99
10.6 STEPS INVOLVED IN EIA.............................................................................................. 99
10.6.1 Preliminary Activities And Decision Of Terms Of Reference (TOR).................99
10.6.2 Scoping......................................................................................................... 99
10.6.3 Base Line Studies........................................................................................100
10.6.4 Environment Impact Evaluation..................................................................100
10.6.5 Mitigation Measures....................................................................................101
10.6.6 Assessment Of Alternative Measures..........................................................101
10.6.7 Preparation Of The Final Document.............................................................101
10.6.8 Decision Making.......................................................................................... 102
10.6.10 Monitoring................................................................................................. 102
10.7 IMPACTS STUDIED UNDER EIA DEVELOPMENT...............................................................102
10.7.1 Air Quality Impacts......................................................................................102
10.7.2 Water Quality Impacts.................................................................................102
10.7.3 Heritage And Construction Impact..............................................................103
10.7.4 Geology And Soils Impact............................................................................103
10.8 EIA ASSESSMENT OF THE PROJECT.............................................................................103
10.8.1 Air/ Climatology...........................................................................................103
10.8.2 Noise........................................................................................................... 104
10.8.3 Plant Life..................................................................................................... 104
10.8.4 Transportation And Traffic Circulation.........................................................105
10.8.5 Land Form................................................................................................... 106
10.8.6 Water.......................................................................................................... 107
10.8.7 Utilities........................................................................................................ 108
11. COST ESTIMATION................................................................................110
11.1 PLANT COST ESTIMATION......................................................................................... 110
11.2 CAPITAL INVESTMENT............................................................................................... 110
11.2.1 FIXED-CAPITAL INVESTMENT...................................................................................110
11.2.2 WORKING CAPITAL............................................................................................... 111
11.3 METHODS FOR ESTIMATING CAPITAL INVESTMENT..........................................................111
11.4 PERCENTAGE OF DELIVERED - EQUIPMENT COST...........................................................111
11.5 COST OF EQUIPMENTS............................................................................................. 112
11.5.1 Cost Of Packed Absorber.............................................................................112
11.5.2 Cost Of Stripper (Lean Regenerator)...........................................................114
11.5.3 Cost Of Fixed Bed Reactor...........................................................................115
11.5.4 COST OF HEAT EXCHANGER........................................................................115
11.5.5 Cost Of Knock Out Drum.............................................................................116
11.5.6 Cost Of Pump.............................................................................................. 116
11.6 TOTAL COST OF EQUIPMENTS....................................................................................116

CONTENTS |
11.7 DIRECT COST......................................................................................................... 117
11.8 INDIRECT COST...................................................................................................... 117
11.9 FIXED CAPITAL INVESTMENT......................................................................................118
APPENDIX.................................................................................................. 119
SPECIFICATION SHEETS.................................................................................................... 119
GRAPHS FOR COST ESTIMATION......................................................................................124
REFERENCES.............................................................................................. 126

CHAPTER # 1

INTRODUCTION

1. INTRODUCTION
1.1.

FERTILIZER

Looking back at 5,000 years of recorded world history reveals two important facts about
human nature. First, human beings possess limitless potential for compassion, innovation and
achievement. Secondly, these qualities are brought to full bloom where and when people have
access to healthy food.
Experts estimate that there will be more than nine billion people on our planet by 2050.
Thats nearly three billion more people than are alive today. People from all walks of life with
all kinds of ideas, but who share one common challenge: each will experience hunger,
requiring food to survive. Fertilizer has playedand will continue to playa key role in
meeting this eternal challenge.
Fertilizer and plant food are terms used to describe additives that increase soils fertility
its capability of producing abundant crops. Nutrients are substances providing nourishment
essential for growth and the maintenance of life. Nutrients are whats provided, through the
application of fertilizer, to enhance the fertility of the soil.
Nitrogen is the single most important plant nutrient in todays commercial fertilizers. Its
essential for making sure plants are healthy as they grow and nutritious to eat after theyre
harvested. But today in agriculture, we take for granted Ns ready availability.

1.2.

FERTILIZER HISTORY: THE HABER-BOSCH PROCESS

More than 175 years ago, a scientific debate was raging in Europe over the importance of N
for the growth of plants. British scientists Bennet Lawes and Joseph Henry Gilbert settled the
debate when they published research showing that the addition of N fertilizers increased
wheat yields in England. Fifty years later, industrialized nations were challenged with how to
feed their growing populations and Great Britain was importing the majority of its wheat. In
1898, William Crooks, president for the British Association for the Advancement of Science,
called for chemistry researchers to find solutions to aid in the manufacture of N fertilizers to
help solve the coming food crisis.
Throughout the nineteenth century the demand for nitrates and ammonia for use as fertilizers
and industrial feed stocks had been steadily increasing, however the main source remained
the mining of niter deposits. By the start of the twentieth century it was being predicted that
these reserves would be unable to satisfy future demand and research into new potential
sources of ammonia became ever-more important. The most obvious source was atmospheric
nitrogen (N2), which makes up nearly 80% of the air, however N 2 is exceptionally stable and
will not readily react with other chemicals. Converting N 2 into ammonia is therefore
exceedingly difficult and posed a chemical challenge which occupied the efforts of chemists
across the world.

The solution soon came from German scientist Fritz Haber, who discovered in 1909 that the
chemical reaction of N and hydrogen-produced ammoniathe main component in nitrogenbased fertilizers. In July of that same year, Germanys largest chemical company, BASF,
funded German chemist and engineer, Carl Bosch, to develop commercial scale production of
ammonia.
The process wasnt easy, however. Ammonia production depended on high temperatures and
pressures, as discovered by Haber. Much of the necessary machinery had to be invented to
handle the extreme production conditions. Boschs machine, unveiled in 1914, stood 26 feet
tall and could produce 198 pounds of ammonia per hour.
Soon after the plant was built, World War I began, and the new plant was used to manufacture
material for explosives. Following the wars end, Germany attempted to keep the HaberBosch process a secret. During negotiations at Versailles, however, Bosch, who was a
member of the German negotiating team, offered the French government the technical details
they would need to build their own Haber-Bosch plant. The French began producing
ammonia in the early 1920s, followed soon by the British and Americans.
Habers and Boschs contributions to ammonia production were honored with two Nobel
Prizes. Haber was presented with the Nobel Prize in 1920 for his research that unlocked the
ammonia production process. In 1932, Bosch and Frederick Bergius received the Nobel Prize
for their contributions to the invention and development of chemical high pressure methods.
Today, a modern ammonia production facility produces approximately 1,000 tons of
ammonia per day. These advances in ammonia production have significantly increased yields
of food and feed grain crops. In just 70 years, theres been a six-fold increase in U.S. corn
yields, thanks to the abundance of available nitrogen.
The world simply cannot do without N fertilizer, and the contributions made by Fritz Haber
and Carl Bosch. Through fertilizer, we have the means to ensure that each growing seasons
crops have the nutrients necessary to yield nutritious, bountiful foods for an increasing global
population.

1.3.

FEED FOR AMMONIA PRODUCTION

Ammonia is generally manufactured from natural gas using the steam reforming process.
Natural gas mainly consists of large quantity of methane along with heavier hydrocarbons
such as higher alkanes and alkenes; moreover in the raw state it often contains a considerable
amount of non-hydrocarbons, such as nitrogen and the acid gases (carbon dioxide and
hydrogen sulfide). Natural gas is a fossil fuel. It is colorless, odorless and shapeless in its
pure form. Natural gas is lighter than air, non-toxic in its natural state and generates energy
when burned. Unlike other fossil fuels, natural gas is clean burning and emits lower levels of
potentially harmful by-products into the air, making it one of the lowest polluting fossil fuels
available. Natural gas is a combustible mixture of hydrocarbon gases. While natural gas is
formed primarily of methane, it can also include ethane, propane, butane and pentane.
Because it is odorless, mercaptan is added to the natural gas, in very small amounts to give
the gas a distinctive smell of rotten eggs. This strong smell can alert you of a potential gas
leak. The table below outlines the typical components of natural gas on the Union Gas system
and the typical ranges for these values.

Component

Typical Analysis
(mole %)

Range
(mole %)

Methane

95.0

87.0-97.0

Ethane

3.2

1.5-7.0

Propane

0.2

0.1-1.5

iso - Butane

0.03

0.01-0.3

normal - Butane

0.03

0.01-0.3

iso - Pentane

0.01

Trace-0.04

normal - Pentane

0.01

Trace-0.04

Hexanes plus

0.01

Trace-0.06

Nitrogen

1.0

0.2-5.5

Carbon Dioxide

0.5

0.1-1.0

Oxygen

0.02

0.01-0.1

Hydrogen

trace

Trace-0.02

A natural gas stream is approximately two mole percent (mole %) sour. It means for every
100 kg moles of gas 2 kg-moles of hydrogen sulfide are present in it. As a matter of fact, H 2S
and CO2 are corrosive in aqueous solution. Furthermore, they are very toxic in nature and
have very low heating value. Due to these facts, gas is required to be sweetened. The removal
of CO2 and H2S is a crucial step in the manufacture of ammonia.
Many technologies efficiently remove CO2 from the process gas. With so many choices there
is no one method fits all solution. Consequently, process designers must align technological
benefits of various techniques with the final product or downstream plant specifications.
There are many processes available for removal of acid gases from natural gas; the selection
of these processes is based on economic feasibility and cleanup ability. These processes
include chemical solvents, physical solvents, hybrid solvents, adsorption processes, and
physical separation (e.g. membrane systems). Chemical and physical solvents, or a
combination of the two, have been used extensively in many existing ammonia facilities.

1.3.1. IMPURITIES IN NATURAL GAS

1. Carbon dioxide:
Carbon dioxide forms corrosive Carbonic acid with water, if the gas is going to LNG, it will
freeze and block the cryogenic equipment.
2. Hydrogen Sulphide:
Acid, Foul smelling, Toxic gas deadly in low concentrations, forms Sulphurous acid with
water, will freeze at cryogenic temperatures. Also causes 'Hydrogen Blistering' in piping due
to reaction with iron forming FeS and Hydrogen.
3. Moisture:
It is corrosive, forms the above mentioned acids, and easily freezes.
4. Solid particles:
Solid particles of rust, scale and other debris produced from a well. Cause erosion and
blockage in equipment.
5. NORM:
Naturally occurring radioactive materials may also present in gas processing. The radioactive
gas radon can occur in wellhead gas, have extreme amounts of undesirable components.

1.4.

WHY CO2 REMOVAL IS NECESSARY IN AMMONIA PRODUCTION?

CO2 is poison to catalyst and causes fouling. Moreover, the most important reason for its
removal during in ammonia production is that its freezing point is high and if present it
freezes the lining in cryogenic purification. The removal of CO2 from natural gas before
liquefaction is done primarily to meet the ammonia product specifications, prevent corrosion
of process equipment, and meet environmental performance standards.
1.5.

CO2 USES

1.5.1. UREA MANUFACTURING

CO2 is used as a raw material for the production of Urea.

1.5.2. HEALTHCARE
Carbon dioxide USP is used for insufflation and is often combined with oxygen or air as a
respiratory stimulant to promote deep breathing.

1.5.3. PULP & PAPER

Carbon dioxide is an industrial gas used in the pulp and paper industry to control pH levels,
enhance pulp yield, and wash brown stock and bleached stock.

1.5.4. WATER & WASTEWATER TREATMENT

A safe alternative to mineral acids, carbon dioxide replaces chemicals used in pH reduction
lowering costs and improving plant safety and flexibility.

CHAPTER # 2

PROCESS SELECTION

2. PROCESS SELECTION
Following are some methods for the removal of CO2 from syngas in ammonia production:
Chemical Absorption
Physical Absorption
Physical Adsorption
Cryogenic Fractionation
Permeation

2.1 PHYSICAL ABSORPTION

Physical absorption results from a physical contact between the gas to be treated and a
solvent. The solvent is used as a pure product. As a result, there is no need for water make up
in a physical absorption process.

2.2 PHYSICAL ADSORPTION

Physical adsorption relates to the use of molecular sieves for the removal of acid gases. This
process is not suitable for the removal of high quantities of acid gases.

2.3 CRYOGENIC FRACTIONATION

The cryogenic fractionation is a process for the removal of CO 2 from Natural Gas. This
process is not recommended because it does not remove H2S from Natural Gas

2.4 PERMEATION (MEMBRANE)

Membrane is then an attractive process to remove CO 2 (bulk removal) and traces of H2S from
natural gas. H2S removal when present in high concentrations (in terms of mole %) is not
applicable due to the detrimental effect of this compound on the membrane

2.5 CHEMICAL ABSORPTION

Several chemical solvents are available for gas sweetening processes, almost all of them
being based on alkanolamine products. They are all used under form of aqueous solutions.
The main alkanolamine products used in the gas sweetening industry are as follows:
Mononethanolamine or MEA
Diethanolamine or DEA
Methyldiethanolamine or MDEA
Potassium Carbonate (Benefield process or CATACARB process)

2.6 FACTORS AFFECTING SELECTION OF PROCESS

Each of the various processes available has advantages and disadvantages. The selection of a
process for a given situation involves weighing of many factors and in some cases a number
of processes will be found applicable with little or no technical advantage favoring one or
another. There are some broad criteria which may directionally indicate the likeliest choice.
The pressure at which the absorption is to be carried out and the inlet partial
pressure of CO2 are very important. If the CO2 pressure is above about 200 lb/in2
abs, the solvent processes will generally tend to be more economical with respect
to circulation rate than alkaline processes.
At low inlet pressure and where a very low outlet concentration of CO 2 is
required, MEA will tend to be favored.
At intermediate partial pressure and especially when the feed is available at 200 to
275 oF the catalyzed salt potassium processes have the advantages.
Any of the liquid system capable of re moving CO 2 can also remove H2S but this may not be
desirable. If the ratio of CO 2/H2S is greater than about 5 or 6 the combined CO 2 and H2S
produced from the regenerator become difficult to handle in conventional modified claus
sulphur recovery units and more expensive techniques are required to recover the sulphur
and avoid venting sulphur compounds to the atmosphere. In this situation it may be desirable
to remove the H2S selectively followed by treatment to remove a CO 2 stream with an H2S
content low enough to permit it to be vented, preferably without incineration. In this situation
the solvent or potassium salt processes might tend to be favored or the catalyzed potassium
salt processes but probably not the usual amines, since their selectivity to H2S is not great
enough.

2.7 PROCESSES USED IN CHEMICAL INDUSTRIES

CATACARB and MDEA are most commonly used processes in chemical industries because
these processes are economically favorable and have advantages over other processes. So we
shall discuss these two major processes.

2.7.1 CATACARB PROCESS

The CATACARB process uses a catalyzed aqueous solution of potassium carbonate to
remove CO2 and H2S from gas mixtures.
The solution is free of sulphur and arsenic compounds which can cause serious problems with
respect to pollution and poisoning catalyst in NH 3 and H2 Plant. The main advantages of
CATACARB process are:

Low heat and cooling requirement.

Low capital investment
Simple and reliable operation control
Low residual CO2 contact, thereby minimizing methanator hydrogen consumption and
synthesis loop purge looses
Low corrosion rate

Non- fouling, non-degradation solution.

Low cost, non-hazardous solution
Sulphur and arsenic free solution

2.7.2 MDEA
MDEA is well known for its relatively slow reaction rate for CO 2 As a result, MDEA is not
usually associated with situations where the removal of large amounts of CO 2 is desired.
However, MDEA has a number of properties which make it attractive for CO2 removal:
High solution concentration (up to 50-55 wt %)
High acid gas loading
Low corrosion even at high solution loadings
Slow degradation rates
Lower heats of reaction
Low vapor pressure and solution losses

CHAPTER # 3

PROCESS DESCRIPTION

3. PROCESS DESCRIPTION
3.1.

CARBON DIOXIDE REMOVAL SECTION

Reformed Natural Gas which is the feed (stream 1) is cooled to 123C by heat exchanging
with semi lean solution i.e stream (17) coming from pump P-05. This feed at 123 oC is fed to
the KOD D-01 where entrained liquids are removed. The gas (stream 2) is sent to absorber
T-03 consisting of 18.259 mole % CO 2. The CO2 Absorber is a two-stage split flow
CATACARB system using a promoted potassium carbonate solution that removes CO 2 from
the process gas in a two-stage absorption process. The CATACARB solution also employs a
minor rust inhibitor to decrease equipment corrosion and fouling. Inlet conditions at the CO 2
Absorber are 123C and about 29.5kg/cm2 (a). CATACARB process employs hot potassium
carbonate solution to remove CO2 via the following reversible reaction
K2CO3 + CO2+ H2O

2KHCO3

With a two-stage unit, the system has two absorption zones, the lower semi-lean or bulk
section and the top lean section. Process gas flows upwards in the bulk section through the
beds counter-current to the CATACARB solution. Most of the CO 2 is removed in this lower
semi-lean section by means of a large circulation of partially regenerated semi-lean solution
(stream 7). Gas leaving the first stage of absorption will have around 1.5 percent CO 2 by
volume. The final cleanup is done in the top lean section by counter-current flow of process
gas against a small stream of fully regenerated lean solution (stream 6). 99.58% CO 2 is
removed in gas absorption and the treated process gas with a CO 2 leakage of 1000 ppm by
volume leaves the top of the absorber (stream 8) for the downstream methanator. Whereas the
rich solution (rich in CO2) i.e. stream 3 leaves from the bottom of the absorber to a
regenerator steam boiler E-03 and sent to hydraulic turbine HT-01 for pressure let down. The
hydraulic turbine provides some of the power needed to drive the semi lean solution charge
pump P-03.

3.2.

ABSORBENT REGENERATION SECTION

The rich solution (rich in CO2) i.e stream 3 from the bottom of the absorber T-03 at a
Temperature of 129 oC is cooled in the Regenerator Steam Boiler (E-03) where it temperature
decreases to 124 oC and Pressure is 29.2 kg/cm2. After cooling it passes through the Hydraulic
Turbine (HT-01) for power recovery. The hydraulic turbine provides some of the power
needed to drive (P-03) i.e semi-lean solution charge pump. Before it enters into hydraulic

turbine the stream (3) has pressure 29.2 kg/cm2, temperature 124oC and it contains 88.613
mole % KHCO3 having all the CO2 absorbed in it.

3.2.1. STRIPPER (T-02)

After pressure letdown from the Hydraulic Turbine (P-03), steam and CO 2 are flashed from
the rich solution as it enters to stripper (T-02). In stripper (T-02), the rich distributor separates
the flashed vapor from the rich solution and distributes the solution over beds, where CO 2 is
stripped out by the rising steam. The temperature in the stripper (T-02) is 120 oC and a low
pressure of 0.51 kg/cm2. The reaction is the reverse of the reaction in the absorber (T-03).
Most of the CO2 is removed in this section and the stripped solution (stream 4) leaves the
bottom of stripper (T-02) as a semi-lean solution. The stripping stream (stream 17) is
provided by semi-lean solution regenerators reboiler (E-01).
At the bottom of stripper (T-02), some solution (stream 19) is drawn from a tray and sent to
semi-lean solution regenerators reboiler (E-03) to boil off the majority of the stripping
steam. From the bottom of the stripper (T-02), semi-lean solution (stream 4) enters the Semilean Booster Pump (P-02). This stream is divided and a small portion of (stream 4) stream is
sent to the top of the Lean Solution Regenerator (T-01) with (stream 5) and the rest flows
(stream 7) through the Semi-Lean Solution Charge Pumps (P-03) to the middle of absorber
(T-03) for the first stage of bulk CO2 absorption.

3.2.2. STRIPPER (T-01)

The small portion of semi-lean solution pumped to the top of stripper (T-01) is thoroughly
stripped in the lean section to remove additional CO 2. Steam (stream 21) and Air is entered
into stripper to remove CO 2. The stripper (T-01) is operating at a temperature of 119 oC and a
low pressure of 0.51 kg/cm2. Vapor (stream 12) exits the stripper, consisting of mainly steam
with a small amount of CO2 and air. It passes through the overhead line to the bottom of
stripper (T-02) and serves as the stripping medium for stripper (T-02). Stripping steam
(stream 21) for (T-01) is provided by regenerator steam boiler (E-03) i.e stream 18 and the
Regenerator Steam Boiler (E-02) i.e stream 20.
Lean solution leaves the bottom of stripper (1-T-101), exchanges heat in the Lean Solution
Water Exchanger (1-E-115) and then flows via the Lean Solution Circulation Pump (1-P-105)
to the top of absorber (1-T-103B) for the second and final stage of CO2 absorption.
Stripped CO2 and steam from the stripper (1-T-102) are cooled in Regenerator Condensers (1E-116) & (1-E-216) to 40oC where condensate separation occurs. After separation CO 2 gas is
available for urea production at 1.4 kg/cm2 and with purity above 98.5 percent.
The compositions of overhead product (stream 46) of the stripper (1-T-102) are:
Stream no: 46
H2
N2
CH4

Composition (mole %)
0.910
0.343
0.010

Ar
NH3
CO
CO2
K2CO3
KHCO3
Total Dry Molar Flow (kmol/hr)
Water molar flow (kmol/hr)
Temperature (oC)
Pressure (kg/cm2)

3.3.

0.003
0.000
0.004
98.279
0.000
0.000
2092.7
4362.3
113
1.8

METHANATION SECTION

Gas (stream 8) from the CO2 absorber (T-03) is first sent to Methanator Feed Knock-Out
Drum (D-03), where any entrained liquids are removed. The gas is then preheated to 304 oC in
the Methanator Feed/Effluent Exchanger (E-05) and the Methanator Start-up Exchanger (E05), also provides extra duty when the shift catalyst is new and the carbon oxides and the
resulting methanator temperature differential are lower than designed. The gas stream (stream
9) enters the Methanator (R-01) which contains a bed of nickel catalyst that promotes the
reaction of carbon dioxide and carbon monoxide with hydrogen to form methane and water.
In which almost all the CO and CO2 is converted into methane reducing their mole percentage
from 0.366% and 0.100% to negligible amount.
CO2+ H2
CO + 3H2

CO + H2O
CH4+ H2O

The total amount of carbon oxides (a poison to the ammonia synthesis catalyst) leaving the
methanator (steam 10) is less than 5ppm (negligible) by volume and the methane content
from increases from 2.489 mol % to 3.0 mol% (dry basis). Due to the highly exothermic
nature of the Methanation reactions, the process gas temperature increases from 304 oC to
334oC at the outlet (stream 10). After exchange with methanator feed (stream 8), the
methanator effluent (stream 10) is cooled to 40oC by further processing.

PROCESS FLOW DIAGRAM | 30

PROCESS FLOW DIAGRAM | 31

CHAPTER # 4

MATERIAL BALANCE

PROCESS FLOW DIAGRAM | 32

4. MATERIAL BALANCE
4.1 MATERIAL BALANCE ACROSS KNOCK-OUT DRUM (D-01)
Outlet Stream

Inlet Stream

Condensed Water

INLET STREAM
Composition (mole %)
Flow Rate
H2 =
40.18%
5995.552334 kmol/hr
N2 =
20.11%
3000.618092 kmol/hr
CH4 =
1.55%
230.991664 kmol/hr
Ar =
0.20%
29.442343 kmol/hr
CO =
0.23%
33.989423 kmol/hr
CO2 =
13.92%
2076.992467 kmol/hr
H20 =
23.82%
3554.4 kmol/hr
Total =
100%
14922.1 kmol/hr
Outlet STREAM Absorber Feed
Composition (mole %)
Flow Rate
H2 =
48.50%
5995.029348
N2 =
24.27%
3000.526452
CH4 =
1.87%
230.940864
Ar =
0.24%
29.435868
CO =
0.27%
33.981948
CO2 =
16.79%
2075.171868
H20 =
8.06%
996.8
Total =
100%
12362

2557.6

Condensed Water
kmol/hr
46036.8

kg/hr

kmol/hr
kmol/hr
kmol/hr
kmol/hr
kmol/hr
kmol/hr
kmol/hr
kmol/hr

PROCESS FLOW DIAGRAM | 33

4.2 MATERIAL BALANCE ACROSS ABSORBER (T-03)

Absorber Feed (2)
Composition (mole
%)
H2 =
48.50%
N2 =
24.27%
CH4 =
1.87%
Ar =
0.24%
CO =
0.27%
CO2 =
16.79%
H20 =
8.06%
Total =
100.00%

5995.03
3000.53
230.941
29.4359
33.9819
2075.17
996.8
12362

Flow Rate
kmol/hr
12086
kmol/hr
84053.7
kmol/hr
3704.98
kmol/hr
1175.9
kmol/hr
951.834
kmol/hr
91328.3
kmol/hr
17957.4
kmol/hr
211258

kg/hr
kg/hr
kg/hr
kg/hr
kg/hr
kg/hr
kg/hr
kg/hr

H2, N2, CH4, Ar and CO are not absorbed by CATACARB Solution so these gases go
directly to Absorber Overhead (8).
%age absorption of CO2 = 99.5 %
Unabsorbed CO2 will go to Absorber Overhead (8)
Amount of CO2 Absorbed =( %age Absorption ) ( CO2 Feed ) =2065.83 kmole

Extent of Reaction=E=

CO2 ( 8 )CO 2 (2 )
=2065.83
1

K2CO3 BALANCE:
K 2 CO 3 (3 )=K 2 CO3 in(6)+ K 2 CO3 in(7)-Extent
KHCO3 BALANCE:
KH CO 3 ( 3 ) =KH CO 3 in(6)+ KH CO3 in(7)+2(Extent)

PROCESS FLOW DIAGRAM | 34

WATER BALANCE:
Total Water out =Waterin(2)+Waterin(6)+ Waterin(7) -Extent

Absorber Overhead (8)

Composition (mole %)
Flow Rate
H2 =
63.50%
5995.03 kmol/hr
N2 =
31.78%
3000.53 kmol/hr
CH4 =
2.45%
230.941 kmol/hr
Ar =
0.31%
29.4359 kmol/hr
CO =
0.36%
33.9819 kmol/hr
CO2 =
0.10%
9.33827 kmol/hr
H20 =
1.49%
141.087 kmol/hr
Total =
100.00%
9440.34 kmol/hr

12086
84053.7
3704.98
1175.9
951.834
410.977
2541.69
104925

kg/hr
kg/hr
kg/hr
kg/hr
kg/hr
kg/hr
kg/hr
kg/hr

Composition (mole %)
K2CO3 =
0.98%
KHCO3 =
8.02%
H20 =
91.01%
Total =
100.00%

Rich Solution (3)

Flow Rate
1019 kmol/hr
140830.895
8370.11 kmol/hr
837973.199
95014.4 kmol/hr
1711684.9
104404 kmol/hr
2690489

kg/hr
kg/hr
kg/hr
kg/hr

Composition (mole %)
K2CO3 =
3.87%
KHCO3 =
3.41%
H20 =
92.7%
Total =
100%

Lean Solution (6)

Flow Rate
425.993 kmol/hr
58874.34
375.243 kmol/hr
37567.436
10208.8 kmol/hr
183912.224
11010.1 kmol/hr
280354

kg/hr
kg/hr
kg/hr
kg/hr

Semi-Lean Solution (7)

Composition (mole %)
Flow Rate
K2CO3 =
2.87%
2658.84 kmol/hr
367465.087 kg/hr
KHCO3 =
4.17%
3863.2 kmol/hr
386763.902 kg/hr

PROCESS FLOW DIAGRAM | 35

H20 =
Total =

93.0%
100%

86015.7 kmol/hr
92537.7 kmol/hr

1549573.01 kg/hr
2303802 kg/hr

4.3 MATERIAL BALANCE ACROSS METHANATOR (R-01)

Composition (mole %)
H2 =
63.50%
N2 =
31.78%
CH4 =
2.45%
Ar =
0.31%
CO =
0.36%
CO2 =
0.10%
H20 =
1.49%
Total =
100.00%

METHANATOR INLET
Flow Rate
5995.029 kmol/hr
3000.526 kmol/hr
230.9409 kmol/hr
29.43587 kmol/hr
33.98195 kmol/hr
9.338273 kmol/hr
141.0874 kmol/hr
9440.34 kmol/hr

12085.98
84053.75
3704.984
1175.904
951.8344
410.9774
2541.69
104925.1

kg/hr
kg/hr
kg/hr
kg/hr
kg/hr
kg/hr
kg/hr
kg/hr

Flow Rate
kmol/hr
11861.63
kmol/hr
84053.75
kmol/hr
4399.971
kmol/hr
1175.904
kmol/hr
0
kmol/hr
0
kmol/hr
2985.646
kmol/hr
104476.9

kg/hr
kg/hr
kg/hr
kg/hr
kg/hr
kg/hr
kg/hr
kg/hr

METHANATOR OUTLET
Composition (mole
%)
H2 =
62.90%
N2 =
32.08%
CH4 =
2.93%
Ar =
0.31%
CO =
0.00%
CO2 =
0.00%
H20 =
1.77%
Total =
100.00%

5883.745
3000.526
274.2611
29.43587
0
0
165.7311
9353.7

PROCESS FLOW DIAGRAM | 36

4.4 MATERIAL BALANCE ACROSS STRIPPERS (T-01 & T-02)

Composition (mole %)
K2CO3 =
3.53%
KHCO3 =
1.16%
H2O =
95.3%
Total =
100%

Lean Solution (6)

Flow Rate
425.9928 kmol/hr
337 kmol/hr
11516.07 kmol/hr
12082.08 kmol/hr

58874.34
14017.7
207462
280354

kg/hr
kg/hr
kg/hr
kg/hr

Composition (mole %)
K2CO3 =
2.87%
KHCO3 =
4.17%
H2O =
93.0%
Total =
100%

Semi-Lean Solution (7)

Flow Rate
2658.841 kmol/hr
3863.196 kmol/hr
86015.71 kmol/hr
92537.75 kmol/hr

367465.1
386763.9
1549573
2303802

kg/hr
kg/hr
kg/hr
kg/hr
30389

kg/hr

PROCESS FLOW DIAGRAM | 37

1688.278
kmol/hr
Steam (17)
60141.18
kg/hr
3341.177
kmol/hr
Rich Solution (3)
Composition (mole %)