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Experimental Study On Acid Gas Removal Using Absorption-Adsorption Unit

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EXPERIMENTAL STUDY ON ACID GAS REMOVAL USING

ABSORPTION-ADSORPTION UNIT

MUHAMMAD ASYRAQ BIN ARIFIN

UNIVERSITI MALAYSIA PAHANG

iv

EXPERIMENTAL STUDY ON ACID GAS REMOVAL USING


ABSORPTION-ADSORPTION UNIT

MUHAMMAD ASYRAQ BIN ARIFIN

Submitted to the Faculty of Chemical & Natural Resources


Engineering in partial fulfillment of the requirements for the degree of
Bachelor of Chemical Engineering (Gas Technology)

Faculty of Chemical & Natural Resources Engineering


University Malaysia Pahang

APRIL 2009

ABSTRACT

Acid gas removal is an important gas treatment in natural gas process. It is


because carbon dioxide (CO2) can cause global warming beside, if more than 3% of
CO2 composition in natural gas, it is unmarketable. CO2 also cause corrosion to the
pipeline because it can react with water vapor to form a carbonic acid. Nowadays,
among the most effective and economic acid gas removal is by using package blended
amine, for example MEA and MDEA in aqueous solution. This research focused on the
percentage removal efficiency of CO2 based on parameters such as MEA/MDEA
mixture composition and amine concentration in an absorption-adsorption unit. The
experiments began by combining methane and CO2 flowrate to represent actual sour
gas. The sour gas will flow through the absorption-adsorption column and at the same
time, amine solvent flow through that column countercurrently with the gas. Amine
solvent flows using the circulation pump at the flowrate 120 L/hr. For parameter
MEA/MDEA mixture composition, five different ratios of amine solvents were used in
every 10 minutes of experiment. The second parameter used is MDEA various
concentrations by using the best amine mixture of the first parameter. As a result,
increasing the composition of MDEA in MEA/MDEA mixture and increasing the
MDEA concentration tend to increase the removal of acid gas. Thus, in analyzing the
acid gas removal process efficiency in absorption-adsorption unit, parameters such as
MEA/MDEA blending composition and MDEA concentration are among to be
considered for reliability and economic benefits.

vi

ABSTRAK

Process pengasingan bendasing didalam gas asli adalah satu proses yang sangat
penting didalam industri. Ia adalah kerana carbon dioxide (CO2) boleh menyebabkn
pemanasan global dan pada masa yang sama jika kandungan CO2 dalam gas asli
melebihi 3% ia tidak dapat dijual. Gas CO2 juga bole menyebabkn pengaratan kepada
saluran paip gas kerana CO2 bole bertindakbalas dengan wap air untuk menghasilkan
asid karbonik. Dalam satu kajian menyeluruh pada proses ini, kaedah yang paling tepat
dan menjimatkan ialah dengan mencampurkan MEA dengan MDEA mengunakan
teknik penyerapan dan penjeraban. Penyelidikan ini tertumpu pada peratusan bagi
penyingkiran gas CO2 menggunakan parameter seperti nisbah kandungan MEA/MDEA
dan juga kepekatan cecair MDEA yang digunakan. Experimen ini bermula dengan
menggabungkan gas metana dengan gas CO2 untuk menghasilkan kandungan gas asli
yang sebenar sebelum proses pengasingan bendasing dibuat. Gas asli akan di alirkan
melalui lajur yang padat dengan pengaktifan karbon dan pada masa yang sama, cecair
amina dengan aliran penukar arus balikan. Cecair amina akan dialirkan menggunakan
pam pemutaran dengan kadar aliran sebanyak 120 liter per jam. Parameter pertama
ialan nisbah kandungan MEA/MDEA, dimana ada lima bacaan dibuat dan setiap satu
selama 10 minit. Experimen kedua menggunakan kepekatan cecair amina sebagai
parameter dengan menggunakan nilai optimum nisbah kandungan MEA/MDEA. Di
dalam keputusan itu, didapati bahawa kenaikan jumlah MDEA dalam campuran
MEA/MDEA dan kepekatan MDEA boleh meningkatkan proses pengasingan CO2.
Oleh itu, untuk menganalisis proses pengasingan CO2 dengan lebih tepat dalam teknik
penyerapan dan penjeraban, parameter seperti nisbah kandungan MEA/MDEA dan juga
kepekatan cecair MDEA mestilah diambil kira untuk kepentingan ekonomi dan
sebagainya.

vii

TABLE OF CONTENTS

CHAPTER

TITLE

PAGE

DECLARATION

ii

DEDICATION

iii

ACKNOWLEDGEMENTS

iv

ABSTRACT

ABSTRAK

vi

TABLE OF CONTENT

vii

LIST OF TABLES

LIST OF FIGURES

xi

LIST OF ABBREVIATIONS

xii

LIST OF APPENDIXES

xiii

INTRODUCTION

1.1

Natural Gas

1.2

Acid Gas in Natural Gas flow

1.3

Method in Removing Acid Gas

1.3.1 Chemical Absorption Technique

1.3.2 Adsorption Technique

1.3.3 A Combination of absorption-adsorption

unit
1.4

Problem Statement

10

1.5

Objectives

10

1.6

Scope of Research Work

10

viii
1.7

Significance and Rationale of Research Work

10

LITERATURE REVIEW

11

2.1

Methyldiethanolamine (MDEA)

11

2.2

Monoethanolamine (MEA)

13

2.3

Blending MDEA with MEA

15

2.4

Methane

16

2.5

Carbon Dioxide

18

2.6

Gas Analyzer

19

2.7

Previous Work

21

METHODOLOGY

23

3.1

Introduction

23

3.2

Analysis Method

25

3.3

Operating Procedure

26

3.3.1 General Start-up Procedures

26

3.3.2 Safety Consideration

26

3.3.3 General Shut Down Procedures

27

Experiment Procedures

27

3.4

(Batch Absorption-Adsorption process)

RESULTS AND DISCUSSIONS

30

4.1

Introduction

30

4.2

Representing Sour Natural Gas by Mixing

30

Methane and Carbon Dioxide


4.3

Ratio of MEA and MDEA mixture composition

31

4.4

Concentration of Amine Solvent

33

ix
5

CONCLUSIONS AND RECOMMENDATIONS

36

5.1

Conclusions

36

5.2

Recommendations

37

REFERENCES
Appendices A E

38
38-49

viii

LIST OF TABLES

TABLE NO.

TITLE

PAGE

1.1

Physical properties of natural gas

1.2

Advantages and Disadvantages of combination

Adsorption and Absorption


2.1

Physical properties of MDEA

12

2.2

Physical properties of MEA

14

2.3

Physical properties of Methane

17

2.4

Physical properties of Carbon dioxide

19

2.5

Previous Work of the research

22

3.1

General description absorption and adsorption

24

Unit
4.1

Result of percentage natural gas by adjusting

31

the flowrate
4.2

Result of MEA and MDEA ratio mixture in

32

removing acid gas


4.3

Result of amine concentration in removing


acid gas

34

ix

LIST OF FIGURES

FIGURE NO.
1.1

TITLE
Schematic Diagram of Acid Gas Removal Using

PAGE
5

Chemical Absorption
1.2

Combinations of Absorption and Adsorption

2.1

Gas analyzer

20

3.1

Analyze Acid Gas Content Using Gas Analyzer

25

3.2

Summary of methodology

29

4.1

Graph percentage removals of CO2 vs Liter of

33

aqueous MDEA
4.2

Graph percentage removals of CO2 vs Molar


concentration of aqueous MDEA

35

LIST OF ABBREVIATION

CH4

Methane

C 2 H6

Ethane

C 3 H8

Propane

C4H10

Butane

C5H12

Pentane

CO2

Carbon Dioxide

MDEA

Methyldiethanolamine

MEA

Monoethanolamine

DEA

Diethanolamine

AMP

2-amino-2-methyl-1-propanol

Toe

Table of Organization and Equipment

H2 S

Hydrogen sulfide

HCO3-

Bicarbonate ion

PTFE

Polytetrafluoroethylene

PFA

Perfluoroalkoxy or plastic or polymer resin

xi

LIST OF APPENDICES

APPENDIX

TITLE

Gantt chart for Undergraduate Research

PAGE

41

Project 1
B

Gantt chart for Undergraduate Research

42

Project 2
C

Calculation of Dilution Process

43

Table result of MEA and MDEA ratio mixture

48

in removing acid gas


E

Table result of amine concentration in removing


acid gas

49

CHAPTER 1

INTRODUCTION

1.1

Natural Gas

Natural gas is a gaseous fossil fuel consisting primarily of methane and also
has significant quantities of ethane, propane, butane, pentane, carbon dioxide,
nitrogen, helium and hydrogen sulfide. In 1950s, the story about natural gas has
begun to arouse worldwide interest but it cannot compete with oil because it was
difficult to exploit due to the size of investment and transport costs to the end user.
Later in 1960s, the discoveries of gas and the proliferation of gas projects caused a
steep climb in world production. After ten years of growth, in both production and
proved reserves, natural gas was no longer a second-rate energy resource. In 1970s,
its production approached the milestone figure of one billion tons oil equivalent
(1.109 toe) and its serves rose to about half of proved reserves [1].

The oil crises from 1973 till 1979 caused world demand for crude oil to
shrink drastically, while natural gas demand continued to grow, but at a slower pace.
Gas has steadily gained on oil, as in term of energy equivalence, world gas
production grew from 37% to 58% compared to oil production between 1970 and
1994 [2]. Consequently, the costs of the gas production and transport systems from
producing well to the end user has increased and making it more difficult for natural
gas to compete with other primary energy such as crude oil. In this condition,
research and development on more efficient process and technologies has been

2
designed to reduce the costs of production, processing, and transport for natural gas.
Table 1.1 below shows the properties of natural gas at the room temperature.

Table 1.1 Physical properties of natural gas [Except where noted otherwise, data are
given for materials in their standard state (at 25 C, 100 kPa)]
Natural Gas

Molecular formula

CH4, C2H6

Molar mass

16 g/mol, 30 g/mol

Appearance

Colourless gas

Density

0.747 kg/Sm3

Boiling point

-162oC

Flash point

-187C

Autoignition
temperature

573C

Flammable Limit

UEL = 15.4% vol


LEL = 4.5% vol

3
1.2

Acid Gas in Natural Gas flow

Natural gas processing plants are used to purify the raw natural gas extracted
from underground gas fields and brought up to the surface by gas wells. The
processed natural gas, used as fuel by residential, commercial and industrial
consumers, is almost pure methane and is very much different from the raw natural
gas. The raw natural gas must be purified to meet the quality standards specified by
the major pipeline transmission and distribution companies. Those quality standards
vary from pipeline to pipeline and are usually a function of a pipeline systems
design and the markets that it serves.

One of the contaminants in natural gas flow is carbon dioxide (CO2). Known as
acid gas, CO2 has to be removed from natural gas to avoid problems such as
corrosion, equipment plugging due to the formation of CO2 solid in the low
temperature system and also to maintain the heating value of natural gas. In this
context, acid gas removal also can be known as gas treating or gas sweetening. The
group of process uses the aqueous solution of various amines to remove CO2 from
natural gas. Removal of acid gas is a common unit process used in refineries,
petrochemical plants, and other industries to remove the contaminant in natural gas.

1.3

Method in Removing Acid Gas

CO2 is widely recognized as a major greenhouse gas contributing to global


warming. This greenhouse gas is produced in large quantity worldwide by many
important industries, including fossil-fuel electric power generation, steel production,
chemical and petrochemical manufacturing, and cement production. In the past
several decades, continuous and rapid development of these industries has caused
considerable concern in this regard.
To mitigate the global warming problem, removal of CO2 from the industrial
flue gas is necessary. Various technologies had been developed for CO2 removal by

4
various investigators in the past. These include absorption by chemical solvents,
physical absorption, cryogenic separation, and membrane separation [3, 4]. Among
those methods, CO2 absorption by chemical solvents appears to offer an interesting
and practical alternative. In fact, CO2 absorption by alkanolamines has been the most
effective one and extensive research has been performed by many investigators in the
past several decades [5, 6].

The removal of acid gas impurities such as CO2 from industrial gas stream is
a significant operation in natural gas processing. The industrial gas streams
containing acid gases impurities that must be purified in order to meet the
requirement of acid gas mixtures sequential processing or environmental regulation.
Since in the middle of 1980s, in order to further improve absorption performance of
methyldiethanolamine (MDEA) solvent, blended alkanolamine solvents have been
developed by adding another alkanolamine into MDEA. These blended solvents
include MDEA blended with monoethanolamine (MEA), diethanolamine (DEA), and
2-amino-2-methyl-1-propanol (AMP) [7, 8]. The blended solvents have the
compatibility of advantages of singles solvent in blended solvent [9].

5
1.3.1 Chemical Absorption Technique

Chemical absorption by a solvent is the technique most commonly used to


remove acid gas in natural gas flow. The basic principle of this process is illustrated
in Figure 1.1.

Figure 1.1 Schematic Diagram of Acid Gas Removal Using


Chemical Absorption [10]

The gas to be processed is contacted in countercurrent flow with solvent in a


plate or packed column. If the solvent introduced at the top of the column is pure, the
solvent circulation rate and the number of plate can be set to obtain gas purity at the
exit that corresponds to the specification. The solvent leaving the absorption column
is sent to a distillation column for regeneration at lower pressure operating.

Various types of trays and packing are used. Information on these items and
the design methods applicable in different specific cases can be found by referring to
the general works already mentioned [11, 12]. There are three types of packing
elements that are widely used such as Raschig ring, Pall ring and Beri saddle. The
use of so-called structure packing made of modular elements occupying the entire

6
cross-section of the column and helps to reconcile good efficiency with low pressure
drop [13].

1.3.2 Adsorption Technique

Adsorption is a process that occurs when a gas or liquid solute accumulates


on the surface of a solid (adsorbent), forming a film of molecules or atoms [14]. This
separation process use a solid phase with large surface area, which selectively retains
the components to be separated. The adsorbents are generally characterized by a
microporous structure which affords a very large specific surface. There are four
types of adsorbents that commonly used likes activated carbon, silica gel, molecular
sieves (zeolite), and activated carbon.

The widely used adsorbent in industry nowadays is an activated carbon.


There are many advantages offered by this adsorbent. Firstly, it is a highly porous
and amorphous solid that consisting of microcrystallites with graphite lattices and
usually prepared in small pellets or a powder. It is non-polar and cheap material that
is suitable in reduces costs of processing natural gas. The carbonization process is
completed by heating the material at 400 C to 600 C in an oxygen-deficient
atmosphere that cannot support combustion. It is also used for adsorption of organic
substances and non-polar adsorbates for waste gas treatment. Lastly, this material
usefulness derives mainly from its micropore and mesopore volumes and the
resulting high surface area.

7
1.3.3 A Combination of Absorption-Adsorption Technique

The gas absorption-adsorption unit is designed to demonstrate the basic


principles of absorption and adsorption processes. Gas absorption is a process in
which soluble components of gas mixture are dissolved in a liquid phase. The gas
and liquid normally flow counter currently among some packing which serve to
provide the contacting of interfacial surface through which mass transfer takes place.
Meanwhile, adsorptions involve the binding of molecules from their liquid or
gaseous environment onto the surface of solids. It is a separation process for the
selective removal small quantities of components from a fluid mixture or solution.

Two packed columns filled with ceramic berl saddles mixed with activated
carbon granules are provided for absorption-adsorption experiments. Each column is
to be run individually. Methane and CO2 are fed into the bottom of a packed
column. Solvent is transferred to the top of the column either from feed vessel using
centrifugal pumps, or entered directly from the laboratory supplies. Counter current
flow among the carbon bed will cause the transfer of CO2 from the gas mixture into
the solvent and subsequently onto the activated carbon. The lean air mixture will
exit at the top whereas the spent water will accumulate at the bottom of the column
and overflow out into either the feed vessel or receiving vessel as shown in Figure
1.2.

Some CO2 will present in the solvent can be stripped or desorbed in the feed
vessel. Circulation of the hot liquid around the feed vessel through pump will release
the dissolved CO2 into vent. To remove adsorbed CO2 from the activated carbon, hot
air can be passed through the column while the vacuum pump is in switched on. The
advantage using this combination unit is the efficiency in removing impurities is very
high and it also can reduce the capital cost. The disadvantage using this combination
unit is if one unit shutdown the other one also shutdown and it also very difficult for
maintenance.

AMINE

METHANE

CO2

Figure 1.2 Combinations of Absorption and Adsorption (Absorption-Adsorption unit


MODEL: BP 201)

9
The table 1.2 shows the advantages and disadvantages of combination
adsorption and absorption. The advantages of this combination are it can remove
impurities, which containing in the natural gas with the efficient. Besides of that,
combination also can reduce capital cost. Nowadays, the adsorption should be used
their adsorbent while the absorption process have their own absorbent. So, absorbent
and adsorbent should be expensive and difficult to get. Compare with the
combination, the unit also cheap compare with the absorption unit and adsorption
unit. So, it reduces the time to do investigation.

The disadvantages of the combination are if the one of the combination is


shutdown, the rest must be shut down. So it maybe difficult to manage when was
doing the different experiment in one time. Subsequently, the adsorption and
absorption have a different to perform the maintenance. Basically, the adsorption unit
is difficult to perform because of this unit can use for the solid medium.

Table 1.2 Advantages and Disadvantages of combination Adsorption and


Absorption
Advantages

Disadvantages

Remove impurities with efficient If the one of the combination is


shutdown, the rest must be shutdown

Reduce capital cost

Different to perform the maintenance

10
1.4

Problem Statement

In this research, its intention is to perform acid gas removal process in


absorption-adsorption unit. To obtain optimum acid gas removal capability, several
parameters need to be analyzed. Knowing the parameters which can mainly affect the
acid gas removal capability is a key for reliability and economics benefits. Once the
related parameters known, they must be varied in order to obtain optimum
conditions.

1.5

Objective

In performing acid gas removal process on the absorption-adsorption unit,


this research has highlighted two objectives which are to study significant parameters
involved. The parameters are MDEA and MEA blending mixture composition and
the solvent concentration.

1.6

Scope of Research Work

This research focus on two main scopes that are to experimentally investigate
the absorption-adsorption unit in removing CO2 and to investigate the advantage of
MDEA blended with MEA as a chemical solvent.

1.7

Significance and Rationale of Research Work

It is very efficient to remove acid gas using absorption-adsorption unit by


emphasizing the significant parameters.

11

CHAPTER 2

LITERATURE REVIEW

2.1

Methyldiethanolamine (MDEA)

MDEA

which

stands

for

methyldiethanolamine

is

psychedelic

hallucinogenic drug and empathogen-entactogen of the phenethylamine family [15].


It is a tertiary amine and act as a solvent. It has a greater capacity to react with acid
gases because it can be used in higher concentrations. This advantage is enhanced by
the fact that it is reacting with all of the hydrogen sulfide (H2S) and only part of
carbon dioxide (CO2).

MDEA also delivers energy savings by reducing reboiler duties and lowering
overhead condenser duties. It has proved to be highly selective for absorption of
hydrogen sulfide (H2S) when compared to carbon dioxide (CO2) resulting in even
lower circulation rates and higher quality acid gases for recycle to sulfur recovery
unit. Among MEA, DEA, and MDEA, MEA has worst reputation for corrosion
related problem. It is well documented in literature that MEA and DEA form
degradation products when reacted with CO2 whereas MDEA does not.

Operating MEA, DEA, and MDEA plants have demonstrated that corrosion can
be minimized under proper operating conditions. However based on plant
experiences and laboratory data, MEA has caused higher corrosion rate compared to
DEA and MDEA [16].

12
MDEA as an absorption solvent of removing acid gases is widely used today
in natural gas processing because it possesses the characteristics such as higher
hydrogen sulfide (H2S) selectivity, bigger absorption capacity, lower regeneration
energy, smaller hot degradation and lesser corrosive. The basic properties of MDEA
are showed in Table 2.1.

Table 2.1 Physical properties of MDEA [Except where noted otherwise, data are
given for materials in their standard state (at 25 C, 100 kPa)]
Methyldiethanolamine

Molecular formula

CH3N (C2H4OH)2

Molar mass

119.2 g/mol

Appearance

Clear, colorless, 150 APHA max.

Density

1.040

Melting point

-21oC

Boiling point

247oC @ 760mmHg

Solubility in water

complete

Solubility

Benzene, alcohol

Refractive index (nD)

1.4694

Viscosity

101cP @ 20C

Flash point

135oC pmcc

Autoignition
temperature

265oC

Explosive limits

0.9-8.4 vol% in air

13

2.2

Monoethanolamine (MEA)

Ethanolamine also called 2-aminoethanol or monoethanolamine (often


abbreviated as ETA or MEA), is an organic chemical compound that is both a
primary amine and a primary alcohol. Like other amines, MEA acts as a weak base
and it is toxic, flammable, corrosive, colorless, and viscous liquid with an odor
similar to that of ammonia. MEA is one of the most studied chemicals for postcombustion capture in power plants. MEA is very reactive with a possibility of high
CO2 removal efficiency. The downside of MEA is a high energy requirement per
tonne CO2 captured, and considerable waste generation caused by amine degradation
[17]. The basic properties of MEA are showed in Table 2.2.

Aqueous solutions of MEA (solutions of MEA in water) are used as a gas


stream scrubbing liquid in amine treaters. For example, aqueous MEA is used to
remove CO2 from flue gas. Aqueous solutions can weakly dissolve certain kinds of
gases from a mixed gas stream. The MEA in such solutions acting as a weak base,
then neutralizes acidic compounds dissolved in the solution to turn the molecules
into an ionic form and making them polar and considerably more soluble in a cold
MEA solution, and thus keeping such acidic gases dissolved in this gas-scrubbing
solution. Therefore, large surface area contact with such a cold scrubbing solution in
a scrubber unit can selectively remove such acidic component as CO2 from some
mixed gas streams. Basic solutions such as aqueous MEA can neutralize CO2 into
bicarbonate ion (HCO3-).

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