Demonstration of Amine Gas Treating

(Acid gas removal through Alkanolamine solvent)

Group No.08 Batch: 2011-12

Name Seat No.

Shehroz Javed CH-11005

Aaisha Yasmeen CH-11017

Saman Zehra Bilgrami CH-11026

Syed Muhammad Azfar Zaidi CH-11050

Internal Advisor: Miss Aliya Arhar

DEPARTMENT OF CHEMICAL ENGINEERING

NED UNIVERSITY OF ENGINEERING AND TECHNOLOGY

 CERTIFICATE

This is to certify that the work in this project report on Demonstration of Amine Gas
Treating (Acid gas removal through Alkanol amine solvent) is entirely written by the
following students under the supervision of Miss Aliya Arhar. This project is submitted to
Department of Chemical Engineering for the fulfillment of the Bachelor Degree in
Chemical Engineering.

Group No. 08 Batch: 2011-2012

Name Seat No.

Shehroz Javed CH-005

Aaisha Yasmeen CH-017

Saman Zehra Bilgrami CH-026

Syed Muhammad Azfar Zaidi CH-050

____________________
Internal Advisor

____________________ ____________________
Examiner – I Examiner - II

DEPARTMENT OF CHEMICAL ENGINEERING

NED UNIVERSITY OF ENGINEERING AND TECHNOLOGY

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ii
 ABSTRACT

The world is facing a serious problem of global warming which is due to the presence of
greenhouse gases containing mainly CO2 gas .Industries exhausting acid gases in the
environment leads to the life threatening conditions. In order to control such conditions
absorption of these harmful gases can minimize these problems. Amine gas treating is an
suitable technique to carry out this work .A packed column is designed of 6 inch in
diameter and 5 feet in height. Alkanolamine solvents MEA and DEA are used to absorb
the acid gases. Different results are observed on different conditions. Pressure, solvent
circulation rates, wt. % of solvents varied and results observed. Practical experiments are
compared with ASPEN HYSYS results. HAZOP is performed on the overall system.

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ACKNOWLEDGEMENT

iv
 CONTENTS

ABSTRACT ..................................................................................................III

ACKNOWLEDGEMENT ............................................................................ IV

CONTENTS ................................................................................................... V

LIST OF FIGURES ..................................................................................... VII

LIST OF TABLES ......................................................................................VIII

NOMENCLATURE ........................................................................................1

1. CHAPTER 01: INTRODUCTION ...........................................................3

1.1 BACKGROUND OF STUDY ........................................................................3

1.2 PROBLEM STATEMENT ............................................................................3
1.3 OBJECTIVES ............................................................................................3

2. CHAPTER 02: LITERATURE REVIEW ................................................5

3. CHAPTER 03: PRODUCTION DESCRIPTION ....................................8

3.1 AVAILABLE PROCESSES .................................................................8

3.1.1 BATCH PROCESS..........................................................................9
3.1.2 PHYSICAL SOLVENTS ................................................................11
3.1.3 DIRECT CONVERSION PROCESS.............................................15
3.1.4 CHEMICAL SOLVENTS ..............................................................18
3.1.5 MEMBRANE PROCESS...............................................................20
3.2 PROCESS SELECTION .....................................................................21
3.3 DETAILED PROCESS DESCRIPTION OF SELECTED PROCESS
27
3.3.1 SELECTION OF SOLVENT .........................................................27

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 3.3.2 SELECTION OF COLUMN .........................................................28
3.3.3 SELECTION OF PACKINGS.......................................................29
3.3.4 PROCESS DESCRIPTION ...........................................................30

4. CHAPTER 04: EQUIPMENT DESIGN ................................................35

5. CHAPTER 05: HAZOP ..........................................................................39

6. CHAPTER NO.06: EXPERIMENTS.....................................................40

6.1 OBSERVATIONS...............................................................................40

7. CHAPTER 07: COSTING ......................................................................44

8. CHAPTER NO.08: RESULTS AND DISCUSSION ...........................45

9. CHAPTER NO.09: CONCLUSION ......................................................47

REFERENCES ..............................................................................................48

APPENDICES ...............................................................................................50

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 LIST OF FIGURES

FIGURE 3-1: GENERAL BLOCK FLOW DIAGRAM ...............................................9

FIGURE 3-2: TYPICAL IRON OXIDE PROCESS FLOWSHEET ...............................10
FIGURE 3-3: SWEETENING OF NATURAL GAS BY MOLECULAR SIEVES ...........11
FIGURE 3-4: FLOUR PROCESS ..........................................................................12
FIGURE 3-5: PURISOL PROCESS .......................................................................13
FIGURE 3-6: SELEXOL PROCESS.......................................................................14
FIGURE 3-7: SULFINOL PROCESS .....................................................................15
FIGURE 3-8: STRETFORD PROCESS ..................................................................16
FIGURE 3-9: SULFEROX PROCESS ....................................................................17
FIGURE 3-10: LOCAT PROCESS......................................................................18
FIGURE 3-11: AMINE PROCESS FLOW DIAGRAM .............................................19
FIGURE 3-12: HOT POTASSIUM CARBONATE PROCESS....................................20
FIGURE 3-13: SPIRAL-WOUND AND ELEMENTS ASSEMBLY ..............................21
FIGURE 3-14:HOLLOW-FIBRE SEPARATOR ASSEMBLY .....................................21
FIGURE 3-15: PROCESS FLOW DIAGRAM .........................................................31
FIGURE 3-16: PIPING & INSTRUMENTATION DIAGRAM ...................................32
FIGURE 3-17: ..................................................................................................31
FIGURE 3-18: ..................................................................................................31
FIGURE 3-19: ..................................................................................................31
FIGURE 6-1: SOLVENT CIRCULATION RATE VS % CO2 ABSORBED.................41
FIGURE 6-2: WT. % AMINE VS % CO2 RECOVERY .........................................44

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 LIST OF TABLES

TABLE 3-1: COMPARISON BETWEEN CHEMICAL & PHYSICAL PROCESS ..........22

TABLE 3-2: COMPARISON BETWEEN AMINE & CARBONATE PROCESS ............23
TABLE 3-3: COMPARISON BETWEEN DIFFERENT ALKANOLAMINE SOLVENTS.24
TABLE 3-4: SELECTION OF SOLVENT...............................................................27
TABLE 3-5: SELECTION OF SOLVENT...............................................................28
TABLE 3-6: COMPARISON BETWEEN RANDOM & STRUCTURED PACKINGS .....29
TABLE 4-1: LEAN SOLVENT IN .......................................................................35
TABLE 4-2: ACID GAS IN ...............................................................................35
TABLE 4-3: CALCULATIONS ...........................................................................36
TABLE 5-1: HAZOP CHART ...........................................................................39
TABLE 6-1: INLET CONDITIONS .......................................................................40
TABLE 6-2: OBSERVED RESULT ......................................................................40
TABLE 6-3: INLET CONDITIONS .......................................................................42
TABLE 6-4: OBSERVED RESULT ......................................................................42
TABLE 7-1: COSTING CHART ..........................................................................44

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 NOMENCLATURE
ρL Density of solution

TL Temperature of solution

PL Pressure of Gas

VL Volumetric flow rate

µG Viscosity of Gaseous mixture

ρG Density of Gaseous mixture

TG Temperature of Gas

PG Pressure of Gas

mG Molar flow rate

ν Kinematic viscosity

VG Flooding Velocity

GG Gas mass velocity

GG60% Actual velocity

A Area

r Radius

d Diameter

1
Gm Mass flowrate of gas

Lm Mass flowrate of solvent

y1 Mole fraction of acid gas

y2 Mole fraction of acid gas removed

m Slope

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 1. CHAPTER 01: INTRODUCTION
1.1 Background of study

According to the Pakistan Environment Protection Act 1997, No person may import hazardous
substances of which chemical activity is toxic, explosive, flammable, corrosive, radioactive, cause
directly or in combination with other matters, an adverse environmental effect.

The industrial gases which are exhausted out or sour natural gas contain appreciable amount of toxic
gases like CO2, H2S etc. which are a big reason of the poor air quality data at oil and gas field.

CO2 itself is a major cause of increasing global warming which might be controlled by proper capturing
of CO2 and disposing off in a suitable way.

1.2 Problem Statement

An industrial gas stream containing CO2 (acid gas) as an impurity is introduced in the packed column
along with the alkanol amine (MEA/DEA) solution flowing counter currently. After the absorption takes
place the pure gas is collected from the top and the rich solvent is flowed out from the bottom.

1.3 Objectives

Since absorption is dependent on many parameters such as pressure, temperature, solvent circulation rate,
concentration of reactants etc. By altering such parameters the process can lead to the optimized results.

i. Two types of solvents i.e. MEA and DEA are used to observe which one gives more efficiency
and on which conditions. There circulation rates and composition may be varied.

ii. Pressure is one of the most powerful tools to maximize the absorption. A pressure from 2 to 8
bars is varied in order to observe the trend of absorption w.r.t pressure.

iii. A comparison is made on experimental and HYSYS results, evaluating the accuracy of the
designed absorption column by CO2 recovery analysis.

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The project leads to the domestic use ease of natural gas. The capturing of greenhouse gas may lead to the
protection of ozone layer, making environment friendly.

Industrial gases that are released in atmosphere contain contaminants which may condense producing
corrosion causing acids which might be harmful for human and equipment life.

Socially, such innovations when carried out in industry they may increase the employment rate because
these projects contain large scale constructive work and technical minds.

2.

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 CHAPTER 02: LITERATURE REVIEW

L. S. Tan, K. K. Lau, M. A. Bustam, A. M. Shariff (1)studied Removal of high concentration CO2

from natural gas at elevated pressure via absorption process in packed column and concluded that
CO2 absorption took place faster at lower temperature than higher temperature but 100% removal of CO2
was achieved at both temperatures. It was observed that lower the temperature more will be the absorption
rate which was due to the exothermic reaction of solvent while absorbing CO2. At first, temperature
remained constant then it raised gradually when the reaction started. Highest temperature was achieved at
middle of the packing then it was decreased due to the decreased concentration of CO2 in feed gas stream.

P.J.G. Huttenhuis , N.J. Agrawal , J.A. Hogendoorn , G.F. Versteeg (2) studied Gas solubility of H2S
and CO2 in aqueous solutions of N-methyldiethanolamine and concluded that acid gases (CO2 and
H2S) are necessary to remove from natural gas and industrial gas streams in order to meet operational,
economic and environmental conditions which is done through absorption. Total system pressure is an
important parameter in process of removing acid gases from both natural gas and industrial gas streams
through alkanol amines and also explained that partial pressure of acid gases increases on increasing
temperature while keeping liquid loading, amine concentration and pressure constant.

Abolghasem Kazemi , Mojtaba Malayeri , Abolfazl Gharibi kharaji , Ahmad Shariati (3) studied
feasibility study, simulation and economical evaluation of natural gas sweetening processes and
concluded that the maximum allowable concentrations for acid gases like H2S and CO2 in natural gas are

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restricted to 4 ppm and 2 mol% respectively. Low temperatures and high pressures are favorable for
absorption and vice versa for regeneration. Higher reaction rates are accomplished through primary
amines. Tertiary amines are more reactive towards H2S while primary and secondary amines are more
reactive towards CO2. Solvent circulation rate affects the size of absorber and piping. Higher the
circulation rate, higher the required size of the equipment and lower will be the acid gas concentration in
rich alkanol amine solution. Moreover, higher the loading of acid gas, lower will be the circulation rate of
solvent. Results of this research paper suggested that alkanol amine process is best suited for the removal
of acid gases economically.

Young Eun Kim, Jin Ah Lim, Soon Kwan Jeong, Yeo Il Yoon, Shin Tae Bae, and Sung Chan Nam
(4) studied Comparison of Carbon Dioxide Absorption in Aqueous MEA, DEA, TEA and AMP
Solutions and concluded that acid base neutralization forming ionic intermediates is occurred by the direct
reaction of acid gases (CO2) with basic alkanol amine solution in which increased mass transfer of CO2
is achieved. Two important factors for CO2 removal processes are solubility of CO2 in solvent and its
heat of absorption. The heat released during the exothermic reaction between CO2 and alkanol amine
solvent is the same as the energy required for desorption of CO2 from the solvent in the stripper. Heat of
absorption is dependent on CO2 loading and structure of amines used and is not mostly effected by
reaction temperature and pressure. MEA showed highest heat of absorption among all the four solvents
and gave rapid reaction rate.

Seok Kim, Hyung-Taek Kim (5) studied ASPEN Simulation of CO2 absorption system with various
amine solutions. ELECNRTL method in Aspen plus was used for the simulation. Pressure was varied
from 1 to 10 atm. Concentration of MEA solution was fixed at 30 wt. % for the initial simulation study.

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Flue gas flow rate was set as 35 l/min and the composition of flue gas is CO2=13.89%, N2=82.56% and
O2=3.55%. The results concluded by them were on increasing pressure the absorption rate increased up
to 3 atm and after that it became almost constant also the increase in flue gas flowrate and decrease in
MEA flowrate decreased the absorption rate while concentration of MEA remained constant at 30 wt. %.
The capacity of the absorber used 5 Nm3/hr. Optimum results were obtained when flow rates of feed gas
of 9 kg/h and MEA solution of 65 kg/h with over 97% CO2 absorption.

Udara S. P. R. Arachchige (6)studied Selection of Packing Material for Gas Absorption and
concluded that both random and structured packings are used in absorption column. The height of packing
(packing section) provides contact time to gas and liquid for mass transfer. Main purpose of packings is
to maximize the contact area. Factors to be considered are to maximize the efficiency in the given capacity
within reasonable cost. The simulation study conducted for this research was to understand the effect of
random and structured packing on CO2 capture process. Five different random packings and six different
structured packings were selected for study. Higher the surface area higher will be the CO2 loading and
lower will be the amount of solvent used. Pall-16 for random packings gave the most efficient results as
it has the highest surface area.

Cheng-Hsiu Yu, Chih-Hung Huang, Chung-Sung Tan (7) studied A Review of CO2 Capture by
Absorption and Adsorption and concluded that different technologies are suggested for CO2 removal
like physical absorption, chemisorption, adsorption and membrane technique but the best among them is
chemisorption using alkanol amine solvents. The absorption experiment conducted for this research had
total pressure of 1 bar and the temperature ranged from 40-60˚C for absorption and 120-140˚C for
stripping and the comparison of all four techniques showed that chemisorption is the best suited technique
for CO2 capture but it requires large amount of energy for regeneration.

Amornvadee Veawab, Adisorn Aroonwilas, and Paitoon Tontiwachwuthikul (8) studied CO2
Absorption performance of aqueous Alkanolamines in Packed columns and concluded that MEA and
DEA were able to perform complete removal of CO2 and their results can be compared on the basis of

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height required by them for complete removal. MEA required only 0.8m while DEA required 1.8m of
column height. It showed that MEA performed well as compared to DEA.

Impact of high pressure on high concentration carbon dioxide capture from natural gas by
monoethanolamine/N-methyl-2-pyrrolidonesolvent in absorption packed column

L.S. Tan, A.M. Shariff∗, K.K. Lau, M.A. Bustam (9) studied Impact of high pressure on high
concentration carbon dioxide capture from natural gas by mono ethanol amine/N-methyl-2-
pyrrolidonesolvent in absorption packed column and concluded that high pressure could accelerate the
reaction between MEA aqueous solution with CO2. In the study conducted, a back pressure regulator was
used to maintain the desired pressure of the column. At 0.1 MPa, 76% of CO2 was removed while at 1
MPa 95% removal was achieved. CO2 was removed completely at increased pressure of 5 MPa. The
greatest height of column and therefore the greater removal of CO2 was achieved by increased pressure.

L.S. Tan, A.M. Shariff *, K.K. Lau, M.A. Bustam (10) studied factors affecting CO2 absorption
efficiency in packed column and concluded that:

 Higher the solvent flowrate, higher will be the absorption efficiency because of increase in wetted
surface of packing for gas-liquid contact.
 Increase in solvent concentration in specific range would increase the absorption efficiency
because excessive increase would lead to higher heat of reaction.
 The greater the surface area provided by packings the greater will be the absorption efficiency.
 Higher the void fraction of packing lower will be the pressure drop in the column.

The greatest height of column and therefore the greater removal of CO2 was achieved by increased
pressure.

3. CHAPTER 03: PRODUCTION DESCRIPTION

3.1 AVAILABLE PROCESSES

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 Figure 3-1: General Block Flow Diagram

3.1.1 BATCH PROCESS

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As it is mentioned above that these processes are particularly for low concentration of H2S feed the
detailed processes are discussed.

3.1.1.1 Iron Sponge

One of the most common and widely used processes in batch processing is Iron sponge fixed bed chemical
absorption which is particularly applied for low concentration of H2S in sour gas around 300 ppm. In this
treatment the fixed bed reactor is completely packed with hydrated iron oxide and wood chips and gas is
fed from the top of it .Moderate pressure around 50-500 psig is used for operation and CO2 is not removed
through this process.

The main reaction is the production of ferric sulfide when iron oxide combines with H2S.

2Fe2O3 + 6H2S ------- 2Fe2S + 6H2O

Another reaction is considered as by this reaction the bed is regenerated through controlled oxidation

2Fe2S3 + 3O2 ----- 2Fe2O3 + 6S (11)

Figure 3-2: Typical Iron oxide Process Flowsheet

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3.1.1.2 Zinc-Oxide

Another compound zinc oxide can be used as a replacement of iron oxide as this can remove CS2,H2S,
COS and mercaptans.This can minimize the H2S upto 1 ppm at about a temperature of 300 deg C and has
proved to be a better sorbent .When zinc oxide reacts with H2S it produces water and zinc sulphide as
shown in the below reactions

ZnO .+ H2S ----- ZnS + H2O (11)

3.1.1.3 Molecular Sieves

Molecular sieves are available with large surface areas and have very low range of pore sizes. They are
crystalline sodium alumino silicates.

Molecular sieves (MSs) are crystalline sodium alumino silicates and have very large surface areas and a
very narrow range of pore sizes. They have the tendency to remove H2S efficiently that the processes
natural gas is left with 4 ppm of H2S ,as it contains polar charges on their surface which can act as active
sites and adsorption occurs. (11)

Figure 3-3: Sweetening of Natural gas by Molecular Sieves

3.1.2 PHYSICAL SOLVENTS

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Physical solvents are basically the organic solvents which are operated at low temperature and high
pressure and H2S is removed favorably over CO2 gas.

3.1.2.1 Fluor Process

It is an one step process in which CO2,C,COS,H2S are removed from sour natural gas by using propylene
carbonate. (11)

Figure 3-4: Flour process

3.1.2.2 Purisol Process

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N-methyl-2-pyrrolidone commonly known as NMP is used as a solvent which removes H2S ,CO2.
RSH,H2O , elastomers and hydrocarbons but this solvent is highly favorable for H2S removal .

It has a boiling point of 396 deg F which is quite low so they are not compatible with amine mixed solvents.
(11)

Figure 3-5: Purisol process

3.1.2.3 Selexol Process

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A blend of dimethyl ether of propylene glycols is used as a solvent in selexol process.

It also has not enough boiling point like NMP so that it could not be used in mixed amine preparation.This
process is restricted to high partial pressure of acid gas and absence of heavy hydrocarbons. DIPA can be
added to this formulation in order to remove CO2 down to pipeline conditions. (11)

Figure 3-6: Selexol process

3.1.2.4 Sulfinol Process

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A mixture of 40% sulfolane (tetrahydrothiophene1-1 dioxide), 40% DIPA (di-isopropanolamine), and
20% water is used as solvent is this process which is and appreciable example of improving the amine
selectivity by the addition of the physical solvent like sulfolane. (11)

Figure 3-7: Sulfinol process

3.1.3 DIRECT CONVERSION PROCESS

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Direct conversion process is the vast topic but here the discussion is restricted to the natural gas
sweetening. Usually the absorption takes place between alkaline solution which contains oxidizing agent
and H2S thus converting H2S into Sulphur.

3.1.3.1 Stretford Process

This process utilizes the captivating solution i.e diluted Na2CO3, NaVO3, and anthraquinone disulfonic
acid (ADA). The process involves four step reaction:

H2S + Na2CO3 ==== NaHS + NaHCO3

4NaVO3 + 2NaHS + H2O === Na2V4O9 + 4NaOH + 2S + Na2V4O9 + 2NaOH + H2O +

2ADA(quinone)==== 4NaVO3 + 2ADA(hydroquinone)

ADA(hydroquinone) + ½ O2 ====== ADA(quinone) (11)

Figure 3-8: Stretford process

3.1.3.2 Sulferox Process

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Sulferox process is based on chelating iron compounds which is a redox technology.H2S is oxidized
with the help of concentrated iron to produce elemental Sulphur. Such chelating agents are helpful in
increasing the solubilty of iron during the operation of the solution.Due to high concentration of iron in
the solution the circulation rate of the liquid is kept low. (11)

Figure 3-9: Sulferox process

3.1.3.3 LOCAT Process

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LOCAT process involves the phenomenon of chelating agent in which iron used as chelates.In absorber
this chelating agent contacts with the sour gas resulting in the formation of elemental Sulphur as this
chelating agent is used as a watery solution.However, iron chelates in a small amount are lost with the
solid Sulphur due to side reactions. The main reactions involve,

H2S + 2Fe3+ === 2H + S + 2Fe2+

The reduced iron ion can be regenerated as :

½ O2 + H2O +2Fe2+ === 2(OH)- + 2Fe3+ (11)

Figure 3-10: LOCAT process

3.1.4 CHEMICAL SOLVENTS

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3.1.4.1 Amine Processes

Alkanolamines are highly appreciable when H2S and CO2 has to be removed simultaneously from acid
gas. A typical process includes an absorption column in which acid gas is fed from the bottom and the
lean amine solvent from the top.The sweet gas is collected at the top and the rich solvent from the
bottom.The absorption column can be either packed or tray.In order to regenerate the solvent the rich
solvent before sending to the stripper is flashed and filtered.It is then fed to the top of the stripper and
also the CO2 and H2S are exit from the top .The regenerated solvent is sent back to the absorption
column and the refluxed water help in steam regeneration of rich amine solvent. (11)

Figure 3-11: Amine Process Flow Diagram

3.1.4.2 Hot Potassium Carbonate Process

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Hot Potassium carbonate process is the process in which CO2 and H2S both can be treated.Since the
reaction involve is reversible ,so in the reversible reaction it also removes COS and CS.The process
optimum operating condition is the partial pressure of CO2 which might be in the range of 30-90 psi.

K2CO3 + CO2 + H2O === 2KHCO3

K2CO3 + H2S === KHS + KHCO3

The reactions shows that at only high partial pressure of Co2 ,H2S can be removed, and for this purpose
this process could not be able to produce acid gases of less concentration and to achieve better results
molecular sieves could be use.This process is accomplished in absorber in which the sour gas reacts with
countercurrently flowing liquid carbonate. The operating conditions of absorber are 230 deg F and 90
psia .As the asbortion occurs, the rich liquid flows out from the bottom which can further circulated to
the stripper for the regeneration of carbonate solution operating at 245 deg F and 14.7 psia.

The concentration of K2CO3 should be in the range of 20-35 wt %. (11)

Figure 3-12: Hot Potassium Carbonate Process

3.1.5 MEMBRANE PROCESS

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In membrane process, membranes made up of polymers are selected in which the gas is being separated
by the selective permeation of gas species. The phenomenon is described as the gas liquefies at the
contact surface permeating through the membrane wall under the influence of the partial pressure across
it. This can be further explained as that the gas to be treated (acid gas) when passes through the
membrane only the acid gas components are diffused across the membrane and the remaining gas exits,
which can be called as sweet gas. (11)

Two types of membranes are used including spiral wound and hollow-fibre modules.

Figure 3-13: Spiral-wound and elements assembly

Figure 3-14:Hollow-fibre separator assembly

3.2 PROCESS SELECTION

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There are a number of processes available for the purification of acid gas which all are suitable
depending upon the available conditions.

As the objective discussed above is about the treating of CO2 and H2S both at the same time for which
Liquid phase processes (Chemical and physical solvent) and membrane process are compatible.

Table 3-1: Comparison between Chemical & Physical Process

Properties Chemical Process Physical Process

Capacity Less sensitive to the partial More sensitive to the partial

pressure of the gas to be pressure of the gas to be
treated treated

Heat of absorption High Low

Extent of acid gas removal High Low

Selectivity H2S & CO2 H2S

Utility Cost High Low/Medium

Since chemical absorption leads to chemical reactions which may results in efficient absorption rate,
increasing the absorption capacity of the respective solvent being used in the process. Furthermore, it
may have the capability that when a solvent absorbs any hazardous gas it may convert it to any harmless
compound and even reacts selectively to the targeted components.

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After selecting chemical process, further is made on amine process and carbonate process

Table 3-2: Comparison between Amine & Carbonate Process

Properties Amine Process Carbonate process

Utility cost High Medium

Efficiency More efficient Less efficient

Operating temperature(deg F) 100-400 200-250

Selectivity H2S & CO2 May be selective for both

Chemical process is sub divided into two processes that are amine and hot potassium carbonate process,
on point of selection the most strong reason to select amine process is that the hot potassium carbonate
process does not give high quality acid gas removal as it works on high partial pressure of CO2 and for
better results molecular sieves are used to further treat the exit gas. Amine process on the other hand has
a greater compatibility when H2S and CO2 both have to be removed at the same time. This process
doesn’t restrict to treat one acid gas component at a single time, also has the capability to remove the
impurities according to the desired amount.

Conclusively, the process which has been chosen for the acid gas treatment is the amine gas treating in
which alkanol amines is used as solvent.

Alkanol amines due to their high reactivity with H2S and CO2 simultaneously are the main reason to
choose this process.

And when amine process is selected, a comparison is made on the different types of Alkanolamine
solvents.

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Table 3-3: Comparison between Different Alkanolamine Solvents (11)

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 i. Monoethanolamine (MEA)

Primary amine MEA is the most reactive amine among all and reacts with H2S and CO2 for which the
reactions are given below

2(RNH2) + H2S ==== (RNH3 )2S

(RNH3)2S + H2S === 2(RNH3) HS

2(RNH2) + CO2 ===== RNHCOONH3R

The reactions are carried in a forward direction (for absorber) and are reversible. MEA cannot be used in
a pure form only 15-20 wt. % is MEA while the other proportion is of water which gives a loading of
about 0.3-0.3 moles of acid gas per moles of MEA.

Due to corrosive nature of MEA it is used in small proportion. It can react non-selectively with CO2 and
H2S; moreover they can even react irreversibly with carbonyl sulphide and carbon disulphide resulting
in the loss of the solution as it can form solid products in the processing solution (11)

ii. Diethanolamine (DEA)

Another amine solvent which can even work better than MEA due to its lower reactivity and less
corrosivity.It can be used to about 35 wt. % along with water which gives the loading of 0.6 moles of
acid gas per moles of DEA. DEA has a lower vapor pressure means it has lower losses and has lower
heat of reaction than MEA.

The reactions are more or less same as MEA

2R2NH + H2S === (R2NH2)2s

(R2NH2)2S + H2S === 2R2NH2SH

2R2NH + CO2 === R2NCOONH2R2 (11)

25
 iii. Methyldiethanolamine (MDEA)

This solvent can be used up to 20-50 wt. % as it has low corrosion factor than MEA and DEA. It gives
the loading up to 0.7-0.8 moles of acid gas/moles of MDEA which are practically applicable on carbon
steel equipment. Low weight percent solutions are used when low pressure process is used. (11)

iv. Di-isopropanol amine (DIPA)

Di-isopropanol amine (DIPA) is mostly used in ADIP process licensed by Shell .It is a secondary amine,
which removes H2S selectively at low pressures and at high pressures remove CO2 and H2S both. It is
non corrosive unlike MEA/DEA and requires low heat for the regeneration of the rich amine solvent.
(11)

v. Mixed Amines

Amines are also used in a mixture form, using MEA or DEA along with MDEA in order to enhance the
CO2 removal. At the lower concentrations of MEA and DEA, the overall concentration of the amine can
be taken up to 55 wt. % in which corrosion problems are not raised. (11)

26
3.3 DETAILED PROCESS DESCRIPTION OF SELECTED PROCESS

3.3.1 SELECTION OF SOLVENT

Availability of solvents

According to the market survey, MEA and DEA are available in long and short terms.

Economics:

Economically, MEA and DEA are suitable to buy due to their affordable price

Table 3-4: Selection of Solvent

Solvents Availability Cost Concentration CO2 loading/

Efficiency
Monoethanolamine Easily available cheap About 10 to 25 % 0.25 to 0.45 moles
(MEA) for removing CO2 acid/mole MEA
only

Diethanolamine Easily available Expensive About 20 to 25 % 0.5 to 0.6 moles acid

(DEA) than MEA for removing CO2 gas/mole DEA
only

Methyldiethanolamine Not easily Very About 30 to 55 % 0.6 to 0.65 moles

(MDEA) available expensive for removing CO2 acid gas/ mole
only MDEA

27
3.3.2 SELECTION OF COLUMN

Table 3-5: Selection of Solvent

Acrylic Pyrex Stainless Steel

It is a hard plastic It is a type of glass It is steel alloy

It is light in weight and easy Difficult handling It is heavy but easy

to fabricate fabrication

Strong, impact resistant Heat resistant Excellent impact resistance,

heat & corrosion resistant

Cost effective Expensive Cost effective

Pressure limit: up to 12 bar Pressure limit: up to 20 bar Pressure limit: more than 20
bar

Since the process selected to achieve the maximum acid gas removal is the amine gas treating using
MEA and DEA solvents. In order to run this process an absorption column is needed.

The absorption column is the packed column (acrylic) of 6 inch in diameter and 6 feet in height .The
column can bear the pressure up to 12 bars.

28
3.3.3 SELECTION OF PACKINGS

Table 3-6: Comparison between Random & Structured Packings

Random Structured

Mass transfer is less than structured More mass transfer due to large contacting
packings area

Cheaper than structured packing Provides better performance and are costly

Easy for storage and transportation Transportation is difficult without damaging

The packings which are used in the column are pall rings (plastic) which is 2cm in diameter and 1.3 cm
in length dumped into the column randomly (random packing).

29
 3.3.4 PROCESS DESCRIPTION

At the bottom of the column there is the inlet for gas where CO2 analyzer is installed .The acid gas
containing 20% CO2 is introduced from the bottom of the absorption column at 40 deg C ,4 bar and 0.5
kgmol/h which contacts with MEA 20 wt. % / DEA 35 wt.% flowing counter currently. The pump used
to provide pressure head to solvent in order to send it to top of the column is of 0.5 HP which can
provide maximum flowrate up to 40 L/min. A regulating flowmeter is linked with the pumping line in
order to control the flow. Two 65 liters tank are placed on both side of the column at the bottom, one for
the fresh feed and another for collecting the rich amine solvent. For rich amine solvent line another
flowmeter is installed. The outlet of the exit gas is at the top where pressure gauge is installed along with
the CO2 analyzer. With the help of the digital CO2 analyzer the rate of absorption can be analyzed by
calculating the percentage of acid gas removed.

PROCESS FLOW DIAGRAM

Solvent In: 30
Temperature: 104 deg F
Pressure: 1.013 bars
Gas In:
Temperature: 104 deg F
Pressure: 8 bar
Flowrate: 23 lit/min

Figure 3-15: Process Flow Diagram

PIPING & INSTRUMENTATION DIAGRAM

31
Figure 3-0-16: Piping & Instrumentation Diagram

32
AMINE GAS TREATING UNIT MODEL

Figure 3-17

33
Figure 3-18

Figure 3-19

34
 CHAPTER 04: EQUIPMENT DESIGN
Data:

Table 0-1: Lean Solvent In

Mono ethanol Mine (MEA) 20 wt%

Water (H2O) 80 wt%

Density of solution (ρL) 62.491 lbm/ft3

Temperature (TL) 104˚F

Pressure (PG) 1.013 bar

Volumetric flow rate (VL) 7 lit/min

Table 0-2: Acid Gas In

Natural Gas 80 mol%

Carbon dioxide (CO2) 20 mol%

Average Molecular weight 24 lb/lbmol

Viscosity of Gaseous mixture (µ) 0.0125 centipoise

Density of Gaseous mixture (ρG) 0.149 lbm/ft3

Temperature (TG) 104˚F

Pressure (PG) 8 bar

Flow rate (mG) 23 lit/min

35
Ratio of Liquid to Gas flow (GL/GG) = 2

Packing Factor for Pall rings 20mm dia (FP) = 77.134 ft-1

Since FP is greater than 60 ft-1, therefore, pressure drop (∆P) = 2 in of H2O/ft

80% flooding

Table 0-3: Calculations

Name Formula Value

Flow parameter [ (GL/GG)( ρG/ ρL)0.5] 0.171723

Capacity parameter [VG*((ρG / ρL -ρG)0.5)*(FP0.5)*(ν0.05)] 1.4

(from pressure drop graph)

Kinematic viscosity (ν) ν = µ/ ρG 1.69645 cst

Superficial Velocity (VG) 1.6/[((ρG / ρL -ρG)0.5)*(FP0.5)*(ν0.05)] 1.801547 ft/sec

Gas mass velocity (GG) GG = VG * ρG 0.829976

lbm/ft2.sec

Actual velocity (GG60%) 0.8*GG 0.663981

lbm/ft2.sec

Area (A) A = mG / GG60% 0.009386 ft2

Radius (r) 𝐴 = 𝜋𝑟 2 0.054655 ft

Diameter (d) D = r*2 0.10931 ft

Pressure Drop ∆P @ 80% flooding from graph 0.24 in H2O/m

Residence time T = V / mG 36.26087 sec

MEA circulation rate 41*Qy/x 1.2498 lit/min

36
Other Instruments/Accessories

Centrifugal Pump

Centrifugal pump of 0.5 HP is used to deliver the solvent at the top of the column with a maximum
capacity of 40 lit/min.

Flow meters

Four flowmeters are mounted on the equipment one at the entrance of the gas line whose range is 1- 25
lit/min, one on the CO2 cylinder, one is at the inlet of the solvent which is of the range 1-5 GPM and the
last one at the outlet of the solvent which is also of the range 1-5 GPM.

Pressure gauges

Since there are two lines of the gas therefore two pressure gauges are installed at the inlet and outlet, both
are of the range 0-140 psia.

Piping

The material used for piping is PVC and is of Schedule 40.The pipes connected to the inlet and outlet of
the gas are of 1 inch where as those that are connected to the solvent in and out lines are of ½ inch.
Moreover, 5 elbows at the gas line in and 1 at the gas line out , all of 1 inch are used to support the turning
of the pipes. For solvent lines 10 elbows are installed at the inlet and 7 on the outlet all of ½ inch.

Globe Valves

Globe valves of ½ inch are mounted for the purpose of drain or any overflow controlling at the inlet and
outlet of the solvent pipelines.

CO2 Analyzers

37
Two CO2 analyzers are installed at the inlet and outlet of the gas line for the automatic analysis of CO2
percentage.

Liquid Distributor

In order to distribute the solvent equally to the column, liquid distributor is fixed at the top of the column
which is shower type (sprayer) and 3 inch in diameter. The material used in its construction is stainless
steel for its protection from corrosion.

Molecular Sieve

Molecular sieve is fixed at the bottom of the column. It is made up of acrylic and is 5.8 inch in diameter.
It distributes the gas by atomizing it.

38
 4. CHAPTER 05: HAZOP
Table 4-1: HAZOP Chart

Guide Word Deviation Causes Consequences

Stream: Solvent In

More Increase in flow Failure of valve V-1 Less absorption

Less Decrease in Failure of valve V-1 Inefficient absorption

flow

No No flow Solvent pump trips No absorption

Stream: Solvent Out

No No flow Failure of valve V-2 Flooding

Stream: Gas In

Less Low pressure Leakage of gas High pressure drop in

the packed bed

Stream: Gas Out

More High pressure High pressurized No absorption
cylinder

Column

39
 Other Blockage of Improper Channeling
flow distribution of
solvent at the top

6. CHAPTER .06: EXPERIMENTS

6.1 OBSERVATIONS

Experiment No.01

Increasing the solvent circulation rate from 1-5 lit/min and observing the trend of CO2 absorption in
percentage.

Table 6-1: Inlet Conditions

Gas In Solvent In

Pressure: 1.5 bar Pressure: 1.013 bar

Temperature: 104 deg F Temperature: 104 deg F

Molar Flow: 0.1036 lbmol/hr

Vol. flowrate: 18.5 lit/min

Table 6-2: Observed Result

S.NO % CO2 Absorbed

40
 Solvent Circulation Rate
(lit/min)
1. 1 21.7

2. 2 31.5

3. 3 49.8

4. 4 62.4

5. 5 73.4

Graphical Representation:

Figure 6-1: Solvent Circulation Rate vs % CO2 Absorbed

Conclusion:

Interpreting the graphic trend, a conclusion is drawn that,

On increasing the flowrate of solvent (MEA) the absorption of CO2 is increased as well.

41
Experiment No.02

Different experiments were performed by changing the wt.% of MEA solvent keeping all the operating
parameters constant.

Table 6-3: Inlet Conditions

Gas In Solvent In

Pressure: 2.5 bar Pressure: 1.013 bar

Temperature: 104 deg F Temperature: 104 deg F

Molar Flow: 0.396 lbmol/hr Vol. flowrate: 2 lit/min

Table 6-4: Observed Results

S.NO Wt. % MEA % CO2 Recovery

1. 5 7.52

2. 6 21.23

3. 7 94.12

42
 4. 8 94.98

5. 9 95.36

6. 10 95.85

Graphical Representation:

43
 Figure 0-1: Wt. % Amine vs % CO2 Recovery

Conclusion:

A different trend is observed that on 7 wt. % of MEA the %CO2 recovered was 94.12 %.
On increasing the wt. % of MEA there is no considerable increase in the recovery of CO2.

A conclusion is drawn that this experiment can lead to good economic factor

7. CHAPTER 07: COSTING

Table 7-1: Costing Chart

S.No Equipment/Instrument Quantity Price/Piece Total Price

(PKR) (PKR)
1. Column 1 32,000 32,000

2. Centrifugal Pump 1 5,000 5,000

3. Packing 20,000 20,000

4. Liquid Flowmeters 2 2,600 5,200

5. Gas flowmeter 1 3,400 3,400

6. Liquid distributor 1 1,500 1,500

44
 7. Valves 5 800 4,000

8. Back pressure controller 1 2200 2.200

9. Pressure regulator CO2 1 4,800 4,800

10. Molecular sieve 1 2000 2,000

11. CO2 cylinder 1 3,500 3,500

12. Liquid storage tanks 2 1,500 3,000

13. Pipes 4,000

14. Elbows 23 87 2,000

15. Nozzles 4 125 500

16. Tees 2 250 500

17. Back pressure controller 1 2200 2200

18. MEA solvent 12 liter 800 per liter 9600

Total=105,600

Labor cost= 25000 PKR

Overhead cost= 5000 PKR

Total Cost=Equipment/Instrument cost + labour cost + overhead cost

= 105,600 + 25000 + 5000

Total Cost= 135,600 PKR

45
CHAPTER .08: RESULTS AND DISCUSSION

46
 CHAPTER .09: CONCLUSION

Amine gas treating proved to be a good absorbing technique. Different trends observed after
experimentation. On increasing the solvent circulation rate keeping all other operating parameters
constant, absorption rate is increased.

On 7 wt. % of MEA the absorption rate enhances drastically when experiments performed on different
wt. % MEA keeping all other operating parameters constant.

47
 REFERENCES
1. Removal of high concentration CO2 from natural gas at elevated pressure via absorption process in
packed column. L.S.Tan, K.K.Lau,M.A.Bustam,A.M.Shariff. Perak : s.n., 2011.

2. Gas Solubility of H2S and CO2 in aqueous solutions of N-methyldiethanolamine. P.J.G.Huttenhuis,

N.J.Agrawal ,J.A.Hogendoom ,G.F.Versteeg. Enschede : s.n., 2006.

3. Feasibility study,simulation and economical evaluation of natural gas sweetening processes e Part 1 :
A case study on a low capacity plant in iran. Abolghasem Kazemi, Mojtaba Malayeri,Abolfazl Gharibi
kharaji,Ahmad Shariati. Isfahan,Ahwaz : s.n.

4. Comparison of Carbon Dioxide Absorption in Aqueous MEA,DEA,TEA and AMP Solutions. Young
Eum Kim, JIn Ah Lim, Soon Kwan Jeong,Yeo ll Yoon,Shin Tae Bae and Sung Chan Nam. Korea :
s.n., 2012.

5. Aspen Simulation of CO2 Absorption System With Various Amine Solution. Seok Kim, Hyung-Taek
Kim. Suwon : s.n.

6. Selection of Packing Material for Gas Absorption. Arachchige, Udara S.P.R. Porsgrum : s.n., 2012,
Vol. 87.

7. A Review of CO2 Capture by Absorption and Adsorption. Cheng-Hsiu Yu, Chih-Hung Huang,
Chung-Sung Tan*. Taiwan : s.n., 2012.

8. CO2 Absorption Performance of Aqueous Alkanolamines in Packed Columns. Amornvadee Veawab,

Adisorn Aroonwilas, and PaitoonTontiwachwuthikul. Saskatchewan,Canada : s.n.

9. Impact of high pressure on high concentration carbon dioxide captrue from natural gas by
monoethanolamine/N-methyl1-2-pyrrolidonesolvent in absorption packed column. L.S. Tan, A.M.
Shariff∗, K.K. Lau, M.A. Bustam. Perak,Malaysia : s.n.

10. Factors effecting CO2 absorption efficiency in packed column: A review. L.S. Tan, A.M. Shariff *,
K.K. Lau, M.A. Bustam. Perak,Malaysia : s.n.

11. Aggour, H. K. Abdel-Aal and Mohamed. Petroleum and gas field processing. Dharan,Safat : Marcel
Dekker,Inc., 2003.

48
12. Dutta, Binay K. Principles of Mass Transfer and Separation Processes. 2nd. New Dehli : Prentice
Hall, 2007. pp. 507-513. pp. 501-513.

13. Richardson, Coulson. Chemical Engineering Design Vol 6. s.l. : Elsevier Butterworth-Heinemann.
ISBN 0 7506 6538 6.

49
APPENDICES

50
APPENDIX - A

(12)

51
(12)

52
 APPENDIX – B

(12)

53