Experimental Study On Acid Gas Removal Using Absorption-Adsorption Unit
Experimental Study On Acid Gas Removal Using Absorption-Adsorption Unit
Experimental Study On Acid Gas Removal Using Absorption-Adsorption Unit
ABSORPTION-ADSORPTION UNIT
iv
APRIL 2009
ABSTRACT
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
1.3
unit
1.4
Problem Statement
10
1.5
Objectives
10
1.6
10
viii
1.7
10
LITERATURE REVIEW
11
2.1
Methyldiethanolamine (MDEA)
11
2.2
Monoethanolamine (MEA)
13
2.3
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
26
26
27
Experiment Procedures
27
3.4
30
4.1
Introduction
30
4.2
30
31
4.4
33
ix
5
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
1.2
12
2.2
14
2.3
17
2.4
19
2.5
22
3.1
24
Unit
4.1
31
the flowrate
4.2
32
34
ix
LIST OF FIGURES
FIGURE NO.
1.1
TITLE
Schematic Diagram of Acid Gas Removal Using
PAGE
5
Chemical Absorption
1.2
2.1
Gas analyzer
20
3.1
25
3.2
Summary of methodology
29
4.1
33
aqueous MDEA
4.2
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
H2 S
Hydrogen sulfide
HCO3-
Bicarbonate ion
PTFE
Polytetrafluoroethylene
PFA
xi
LIST OF APPENDICES
APPENDIX
TITLE
PAGE
41
Project 1
B
42
Project 2
C
43
48
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
3
1.2
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
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
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].
7
1.3.3 A Combination of Absorption-Adsorption Technique
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
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.
Disadvantages
10
1.4
Problem Statement
1.5
Objective
1.6
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
11
CHAPTER 2
LITERATURE REVIEW
2.1
Methyldiethanolamine (MDEA)
MDEA
which
stands
for
methyldiethanolamine
is
psychedelic
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
Density
1.040
Melting point
-21oC
Boiling point
247oC @ 760mmHg
Solubility in water
complete
Solubility
Benzene, alcohol
1.4694
Viscosity
101cP @ 20C
Flash point
135oC pmcc
Autoignition
temperature
265oC
Explosive limits
13
2.2
Monoethanolamine (MEA)