1
Removal of CO2 from Natural Gas using
Membrane Process: Design, Fabrication and
Parametric study
Faizan Ahmad, Lau Lok Keong, Azmi Shariff, Department of Chemical Engineering, Universiti
Teknologi PETRONAS, Malaysia
Abstract— Natural Gas (NG) processing is one of the largest
markets for the industrial separation processes. Membrane
process, relatively new technology among other available
techniques, can be used for the removal of contaminants like
carbon dioxide from NG. In this work, an experimental pilot
test rig would be designed and fabricated for the removal of
Carbon dioxide (CO2) from NG. The parametric study would
be planned and designed using Design of Experiment (DOE)
approach. Different gas specifications and operating conditions
would be investigated for optimal cleaning of NG. In addition,
the study on pretreatment conditions, multistage system and
energy recovery would also be carried out. Moreover,
mathematical models would be developed for membrane,
pretreatment system and process flow. Based on the
mathematical modeling of individual unit operations, process
simulation would help for scale up purposes. Finally, an
optimum model would be proposed based on the correlations
suggested by DOE and the proposed optimal model would be
validated by experimental results.
Index Terms—Gas separation, Membrane process, Natural
gas processing, Process design
I. INTRODUCTION
The composition of natural gas varies from source to
source. Methane is the major component (75%-90%), but
natural gas also contains significant amounts of ethane,
propane, butane and 1%-3% of other higher hydrocarbons
[1]. In some deposits, it may contain complex contaminants
such as CO2, H2S, CO which constitutes environmental
hazards and also hindered natural gas processes. The
upgrading of low quality crude natural gas is an attracting
interest due to the high demand for pipeline-grade gas in
recent years. CO2 needs to be removed in order to; increase
the heating value of the gas, prevent corrosion of pipeline
and process equipments and crystallization during
liquefaction process. [2, 3]
CO2 contents in the NG can vary from 4 to 50%
depending upon the source gas or oil well. Before the
transportation of NG, It must be pre-processed so as to meet
the typical pipeline specification of 2-5% CO2 [4]. Most of
the natural gas, produced in the lower 48 states of USA,
contains more than 5% CO2. Currently, many natural gas
wells are shut due to their low production rate and low
quality (i.e., high CO2 and/or H2S content) [5]. In Malaysia,
NG from Tangga Barat Cluster fields of PETONAS contains
relatively high level of CO2 [6]. Therefore, it has become
necessary to develop efficient processes for the removal of
CO2 from NG [5, 6]
CO2 can be removed by the number of processes
considering the factors of; capital and operating costs, gas
specifications and environmental concerns. The major
processes can be grouped as
• Absorption Processes (Chemical and Physical absorption)
• Adsorption Process (Solid Surface)
• Hybrid Solution (Mixed Physical and Chemical Solvent)
• Physical Separation (Membrane, Cryogenic Separation) [7,
8, 9]
Membranes processes are commercially proven
technology for natural gas processing application.
Separation of CO2 with common polymeric or inorganic
(e.g. zeolite, sol–gel silica or carbon molecular sieve)
membranes is achieved by differences in terms of diffusion
rates and/or adsorption strengths of mixture components in
the polymer matrix or the inorganic membrane pores. For a
gas to permeate through a membrane surface, the gas must
first dissolve in the high-pressure side of the membrane,
diffuse across the membrane wall, and evaporate from the
low-pressure side. Gas separation therefore works on the
principle that some gases are more soluble in, and pass more
readily through polymeric membrane than other gases [7, 10,
11].
In membrane process, feed gas is pretreated before
entering the membrane system to ensure efficient operation.
The conditioning of feed stream controls the fouling,
plasticization and condensation of hydrocarbons on the
membranes [1, 12]. The pre-treatment equipment depends
on the conditions and composition of feed gas. Usually in
the case for natural gas, the feed gas is filtered, as a first
step, for removal of entrained particulates or aerosols
including sand, pipe scale. The feed gas is then cooled in a
cooler. Any condensed liquids are removed in the gas/liquid
separator. After liquid removal, the feed gas enters the feed
preheater. The temperature control system is provided to
maintain the gas at the desired operating temperature of the
membrane fibers. Finally, the heated gas enters the
membrane gas separators where it is separated into two
streams; the permeate, a low pressure CO2-rich stream and
the non-permeate or residue, a high pressure hydrocarbon
rich stream [7, 12].
The design of CO2 removal system depends on the
following factors:
i) Selectivity and Permeability of the membrane
ii) Concentration of CO2 and the separation required
iii) The value of the gas
 2

iv) The location of the plant [1] scale study, a membrane separation system that can cater
high flow rates and pressures is required for CO2 separation.
II. BACKGROUND
Gas separation by membrane technology has become a IV. SCIENTIFIC OBJECTIVE
major industrial application only during the last few decades
A. Main Objective
but the study of gas separation has a long history [10]
Graham measured the permeation rates of all the gases The main focus of the work would be on the development
then known through different diaphragms [10, 13]. In 1940s of a process for CO2 removal from NG using membrane
to 1950s, Barer, Amerongen and Stern played an important technology.
role in the development of solution diffusion model for the B. Measurable Objectives
explanation of gas permeation [14, 15, 16]. The first
Listed below are the proposed measurable objectives:
company to establish a Prism membrane was Monsanto for
1. To design and fabricate pilot experimental test rig
hydrogen separation. The success of Monsanto encouraged
2. To apply Design of Experiment (DOE) approach
other companies like Cynara, Separex and Grace Membrane
for experiment planning and design.
Systems to produce membrane plants to remove CO2 in
3. To conduct parametric study under different
natural gas [10, 17].
operating conditions.
Datta and Sen optimized gas processing cost of the
4. To develop mathematical models for unit
membrane unit. It was shown that there is no unique
operations involved and simulate the process.
configuration that will be always optimum irrespective of the
5. To Optimize/validate the proposed model by
values of carbon dioxide concentration and cost of natural
experimental results.
gas. However, within certain ranges of the carbon dioxide
concentration and the cost of natural gas, the optimum
V. METHODOLOGY
configuration may be unique and the minimum gas
processing cost can be achieved by adjusting only the A. Conceptual Design
number of modules in each stage and the compressor power
[4]. Feed gas is prepared by mixing methane, carbon dioxide,
Wang enhanced operational flexibility and adaptability of ethane and propane using mass flow meters with each gas
membrane process, using one optimal method in which auto- cylinder. The flow rate of 2-5 million standard cubic foot per
controlling of the permeate gas flux was applied for the first day (MSCF) is maintained and sent to compressor for
time. Moreover, it was shown that the permeate gas flux increasing pressure up to almost 80-100 bars.
could be auto-controlled through a control valve installed on The compressed gas is then sent into preheater where
the residue gas line [18] temperature is raised to approximately 60-800C.
Qi and Hensen developed the optimal design strategy for
spiral membrane networks for gas separations [19] whereas T, F, C, P
Lababidi developed the mathematical model to optimize
three configurations including single stage, the two stage, T, F, C, P
and the continuous membrane column (CMC) [20]. The
simple models for the permeability and selectivity variations
of the CO2 /CH4 system have been derived by Safari, Mixer
Ghanizadeh and Rehmat that included both temperature and
pressure effects simultaneously [21]. F
J. Hau worked on upgrading low quality natural gas with C Membrane
H2S and CO2 selective membranes and studied process C T, F, C, P
design, economics, and sensitivity of membrane stage with M
recycle streams [22].
Lee, Feldkirchner, and others made field tests of
membrane modules for the separation of carbon dioxide
from low-quality natural gas. In their study, they investigated
the effects of the operating variables of pressure, feed flow
rate, and the carbon dioxide concentration in the feed. In
addition, computer models were applied for the separation of Compressor Preheater
gases under perfect mixing and cross flow conditions to the
analysis of the field data [5]
Fresh feed
III. PROBLEM STATEMENT
Figure 1: Flow sheet for the removal of CO2 from natural gas using
The above cited works for CO2 separation using membrane
membrane process
technology are mostly limited to laboratory scale. It is found
that laboratory scale experimental data is non-reliable for
commercial scale design especially in the case of high feed
Finally, the gas is introduced into membrane test skid where
flow rates and pressures [5, 23]. Hence, there is a lot of
potential in the field of CO2 separation from NG by gases will be separated. The permeate stream would contain
membrane process on commercial scale. Under the pilot carbon dioxide rich stream whereas retentate side will

contain hydrocarbon rich stream. The analysis for flow rate,
pressures, temperatures and concentration will be done
before and after the separation through the membrane. Both
streams will be mixed together in order to recycle back for
the next cycle.
B. Design of Experiment (DOE)
Design of Experiment (DOE) approach would be applied
to plan and design the number of experiments to be carried
out in order to determine the correlations for scale up and
modeling purposes. These correlations include
Flux = ƒ (T, P, C, pretreatment conditions)
Recovery = ƒ (T, P, C, pretreatment conditions)
Methane loss = ƒ (T, P, C, pretreatment conditions)
Moreover statistical analysis and ANOVA study would be
conducted using different DOE methods such as Taguchi
and response methods.
C. Experimental Parametric Study
Based on DOE, experimental investigation would be
conducted on the process to find the suitable operating
conditions such as pressure, temperature and concentration.
Different pretreatment conditions would also be studied.
Moreover energy recovery system and multistage study can
also be done in order to get the optimal and economical
configuration. The fouling/concentration study can lead to
find the ways to prolong the lifespan of the membrane.
D. Mathematical Modeling and Process Simulation
The mathematical modeling would be done for membrane,
pretreatment system and process flow. Based on the
modeling of these unit operations, process would be
simulated using MATLAB that would serve for scale up
purposes. Finally, optimal model would be proposed based
on DOE and validated by experimental results.
VI. CONCLUSION
Even though the conventional technologies are still in
operation for the removal of the CO2 from the natural gas,
the membrane process has certain advantages over others
available technologies. Membrane has good weight and
space efficiency, which make it more applicable for off
shore environment. Moreover its high adaptability to
variation of CO2 content in the feed gas makes it a suitable
process. Finally, periodical removal and handling of spent
solvent or adsorbent used by conventional system make this
system more environmental friendly.
Thus, the optimal design for the removal of carbon
dioxide from the natural gas using membrane technology can
prove itself to be key stone in the development of separation
technology.
REFERENCES
[1] Richard W. Baker and Kaaeid Lokhandwala, “Natural gas processing
with membranes: an overview,” Industrial Engineering Chemistry
Research, Vol. 4, Nov 2008, pp. 2109-2021
[2] J. Hao, P.A. Rice and S.A. Stern, “Membrane processes for the
removal of acid gases from natural gas. II. Effects of operating
conditions, economic parameters, and membrane properties”, Journal
of Membrane Science, Volume 81, Issue 3, 29 June 1993, pp. 239-
252.
3
[3] Mohammad Hosein Safari, Amin Ghanizadeh, and Mohammad
Mehdi Montazer-Rahmati, “Optimization of membrane-based CO2-
removal from natural gas using simple models considering both
pressure and temperature effects” International Journal of
Greenhouse Gas Control, 2008
[4] Datta, A.K. and Sen, P.K., “Optimization of membrane unit for
removing carbon dioxide from natural gas,” J. Membr. Sci. 283, 28
june 2006, pp. 291–298.
[5] A.L. Lee, H.L. Feldkirchner, S. A. Stern, A.Y. Houde, J.P. Gomez,
and H.S. Meyer, “Field tests of membrane modules for the separation
of carbon dioxide from low quality natural gas”, Gas sep. Purif., Vol.
9, 10 May 1994, pp 35-43.
[6] PETRONAS media releases & news 2008.
Available:http://www.petronas.com.my/internet/corp/news.nsf/2b372
bb45ff1ab3a48256b42002b19a7/d9473b4fd966e901482574eb002b3
fce?OpenDocument
[7] Salako Abiodun Ebenezer, “Removal of Carbon dioxide from natural
gas for LPG production”, Semester project work. Institute of
Petroleum Technology, Norwegian University of Science &
Technology, Trondheim, Norway. 2005
[8] Maddox, R.N. Gas and Liquid Sweetening, 2nd ed., Maddox, R.N.,
John M. Campbell (1974)
[9] W.J. Koros and R.T. Chern, “Separation of gaseous mixtures using
polymer membranes, in: R.W. Rousseau (Ed.)”, Handbook of
Separation Process Technology, Wiley, New York, 1987, pp. 863–
953
[10] R.W. Baker, Membrane Technology and Application, 2nd ed., John
Wiley & Sons, Chichester, UK, pp. 287-295
[11] George Xomeritakis, Chung-Yi Tsai and C. Jeffrey Brinker, “Anodic
alumina supported dual-layer microporous silica membranes”,
Journal of Membrane Science, Volume 287, Issue 2, 15 January
2007, pp. 157-161.
[12] Ahmad Fauzi Ismail, “Specialized workshop on membrane gas
separation technology”, Advanced Membrane Technology Research
Centre, Universiti Teknologi Malaysia, 2009.
[13] T. Graham, “On the absorption and dialytic separation of gases by
colloid septa”, Philos, Mag, 32, 1866, p 401
[14] R.M. Barrer, Diffusion in and through solids. Cambridge University
Press, London, 1951.
[15] G.J. van Amerongen, “Influence of structure of Elastomers on their
permeability to gases,” J. Appl. Poly. Sci. 5. 1950, p 307.
[16] S.A. Stern, “Industrial applications of membrane processes: The
separation of gas mixtures,” Proceedings of the symposium southern
Research Institute, Brimingham, May 1966.
[17] J. M. S. Hennis and M.K. Tripodi, “ A novel approach togas
separations using composite hallow fibre membranes,” Sep. Sci. and
Tech. 15, 1980, p 1059
[18] Wang, L., Shao, C., Wang, H., “Operation optimization of a
membrane separation process through auto-controlling the permeate
gas flux.” Sep. Purif. Technol. 55, 15 May 2007, p 30
[19] R. Qi, M.A. Hensen, “Opitmal design of spiral wound membrane
networks for gas separations”, Journal of membrane science, Vol,
148, 22 May 1998, pp. 71-89.
[20] H. Lababidi, Ghazi A., Al-Enezi and Hisham M. Ettoney,
“Optimization of module configuration in membrane gas separation,”
Journal of membrane Science, Vol 112, 1996, pp 185-197.
[21] M.H. Safari, A. Ghanizadeh. M.M. Montazer-Rahamti,
“Optimization of membrane based CO2- removal from natural gas
using simple models considering both pressure and temperature
effects,” International Journal of Green House Control, Vol. 105,
May 2008.
[22] J. Hao, P.A. Rice, S.A. Stern, “Upgrading low quality natural gas
with H2S and CO2 selective polymer membranes Part II. Process
design, economics, and sensitive study of membrane stages with
recycle streams”, Journal of Membrane Science, Vol. 320, 23 march
2008, pp. 108-122.
[23] T.E. Cooley and W.L. Detloff, “Field tests show membrane process
attractive”, Chem Eng Prog, Vol. 81, 1985, p 45.