Accepted Manuscript

Recent advances on membrane-based gas separation processes for

CO2 separation

Jiayou Xu, Hongyu Wu, Zhi Wang, Zhihua Qiao, Song Zhao,
Jixiao Wang

PII: S1004-9541(18)30459-2
DOI: doi:10.1016/j.cjche.2018.08.020
Reference: CJCHE 1246
To appear in: Chinese Journal of Chemical Engineering
Received date: 8 June 2018
Revised date: 19 August 2018
Accepted date: 27 August 2018

Please cite this article as: Jiayou Xu, Hongyu Wu, Zhi Wang, Zhihua Qiao, Song Zhao,
Jixiao Wang , Recent advances on membrane-based gas separation processes for CO2
separation. Cjche (2018), doi:10.1016/j.cjche.2018.08.020

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 ACCEPTED MANUSCRIPT

Review

Recent advances on membrane-based gas separation

processes for CO2 separation☆

Jiayou Xu , Hongyu Wu , Zhi Wang, Zhihua Qiao, Song Zhao and Jixiao Wang
# #

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Chemical Engineering Research Center, School of Chemical Engineering and Technology, Tianjin

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University, Yaguan Road, Jinnan District, Tianjin 300350, PR China

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Tianjin Key Laboratory of Membrane Science and Desalination Technology, State Key
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Laboratory of Chemical Engineering, Collaborative Innovation Center of Chemical Science and

Engineering, Tianjin University, Yaguan Road, Jinnan District, Tianjin 300350, PR China
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Abstract
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Membrane separation technology has popularized rapidly and attracts much

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interest in gas industry as a promising sort of newly chemical separation unit

operation. In this paper, recent advances on membrane-based gas separation processes
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for CO2 separation are reviewed. The researches indicate that the optimization of
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☆ Supported by the National Key R&D Program of China (No.2017YFB0603400),

Natural Science Foundation of China (No.21436009), and Tianjin Research Program
of Basic Research and Frontier Technology (No. 15JCQNJC43400).

Corresponding author at: Chemical Engineering Research Center, School of Chemical

Engineering and Technology, Tianjin University, Yaguan Road, Jinnan District, Tianjin 300350,

China.

E-mail address: wangzhi@tju.edu.cn (Z. Wang).

#Author Contributions: These authors contributed equally.

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operating process designs could improve the separation performance, reduce the
energy consumption and decrease the cost of membrane separation systems. With the
improvement of membrane materials recently, membrane processes are beginning to
be competitive enough for CO2 separation, especially for post-combustion CO2
capture, biogas upgrading and natural gas carbon dioxide removal, compared with the
traditional separation methods. We summarize the needs and most promising research

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directions for membrane-based gas separation processes for CO2 separation in current
and future membrane applications. As the time goes by, novel membrane materials

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developed according to the requirement proposed by process optimization with
increased selectivity and/or permeance will accelerate the industrialization of

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membrane process in the near future. Based on the data collected in pilot scale test,
more effort could be made on the optimization of membrane separation processes.
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This work would open up a new horizon for CO2 separation/Capture on Carbon
Capture Utilization and Storage (CCUS).
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Keywords: membrane-based process systems; separation; flue gas; CO2 capture;

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biogas upgrading; natural gas

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1. Introduction
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In recent years, membrane separation technology has received more and more
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attentions, since membrane process is energy efficient, environmentally friendly and

easy to scale up. With the improvement of membrane selectivity and permeance [1, 2],
the feasibility of membrane process development for CO2 separation is increasing.
The advantages and disadvantages of different CO2-separation processes were
summarized in Table 1. This work mainly reviews the membrane processes for CO2
separation, including post-combustion CO2 capture, biogas upgrading and natural gas
carbon dioxide removal.

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Table 1 The advantages and disadvantages of different CO2-separation processes [14, 47]

CO2-separation
advantages disadvantages
processes

1.strong capacity of CO2 adsorption 1.high energy penalty

Adsorption 2.endurable in high pressure 2.two-step process governed by

3.high selectivity thermodynamic equilibrium

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1.ease of installation by skid-mounting 1.moderate product purity

2.small footprint and operational 2.not mature enough

Membrane

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simplicity
technology
3.low capital cost

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4.low energy consumption NU
1.successfully industrialized for 1.high energy consumption

decades to treat gas streams. 2.corrosion caused by the

2.able to treat feed gas with low CO2

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degradation of amines
Absorption
concentration 3.emissions of the corrosive

3.complete separation of CO2 solvent to the environment

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4.high product purity

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As known, membrane performance is mainly characterized by two parameters [1]

permeance and selectivity. Although membranes with extremely high permselectivity
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are available for different processes, the feasibility of membrane process depends on
not only the membrane selectivity and permeance, but also the operating conditions
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(including operating pressure and number of stages). Therefore, membrane-based CO2

separation processes discussed in this work are intending to illustrate the membrane
process for specific application based on process simulation and economic cost
estimation. The trade-off between membrane permeance and selectivity always exists,
and it could be described by the empirical Robeson upper bound [3, 4] for CO2 versus
different gases. Therefore, a good design of membrane separation processes have to
take the trade-off between permeance and selectivity into consideration.

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Mathematical modeling and experiment testing are two main aspects for the
investigation of membrane-based gas separation processes. There have been many
researchers [5-10] developing and improving the mathematical model, since Weller
and Steiner [5] developed the mathematical model for binary components gas
separation membrane process. Solutions for multicomponent membrane process were
presented by Shindo et al. [8] who investigated membrane process operated with three

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commonly reported flow patterns (including cross flow, counter-current flow and
co-current flow). The differences among these three flow patterns can be negligible

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when the stage cut (the ratio of the permeate flow rate to the feed flow rate) is
relatively low (around 0.2). The product purity calculated by cross flow is between

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counter-current flow and co-current flow [11]. Therefore, cross flow pattern is
recommended for the calculation of membrane processes, especially for the
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simulation of spiral wound membrane. When simulating the separation performance
of hollow fiber membrane, the counter-current flow pattern is often applied due to the
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high driving force along the membrane module [9]. Recently, further improvement on
membrane process simulation has been proposed. For instance, Alshehri et al. [10]
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have improved Shindo’s model by adding minor revisions to take pressure drop, gas
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non-ideal behavior, pressure and temperature dependence of membrane permeance

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and concentration polarization into consideration. Coker et al. [9] introduced a

stage-wise mathematical model by dividing the length of hollow fiber into many
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sections and solved the mass balances in each section. The developed model could be
applied for co-current flow, counter-current flow, and cross flow. The effect of
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permeate sweep, pressure-dependent permeance and pressure drop also could be taken
into consideration. The boundary layer on either side of the membrane was found to
result in the decrease of concentration gradients across the membrane (i.e.
concentration polarization) and thus the reduction of driving force. Scholz et al. [12]
highlighted that when operated with high pressure, the Joule-Thomson effect, pressure
drop and real gas behavior should be considered in the membrane process. Since the
mathematical modeling validated experimentally is accurate enough, it offers the
advantage of cost effectiveness, safety and flexibility to extensive parametric studies
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compared to experiment testing, and most of the researches with regard to membrane
separation processes could be conducted by the modeling.
In this paper, according to the significant differences of the specific separation
system on feed pressure, feed gas CO2 concentration and membrane permselectivity,
we review three frequently reported and promising membrane-based gas separation
processes for CO2 separation, including the post-combustion CO2 capture, biogas

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upgrading and natural gas carbon dioxide removal, and discuss some complementary
developments of membrane process design. As for the other membrane processes for

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CO2 separation, which behave relatively less reported and not systematic enough, they
are not within the scope of this review. We guess that there might be a great

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bottleneck to be tackled before the prevailing studies of these specific membrane
processes, that is, the membrane permselectivity of their materials waits for further
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enhancing and immune tolerance of the membrane should be investigated
systematically for the complicated separating conditions. Besides, the
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membrane-based gas separation technology for CO2 separation has not shown its
enough maturity to extend to various industrial processes. Therefore, the reported
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researches mainly focus on several typical membrane-based gas separation processes,

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i.e. post-combustion CO2 capture, biogas upgrading and natural gas carbon dioxide
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removal, which would be discussed in detail below.

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2. Membrane-based gas separation processes

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2.1 Post-combustion CO2 capture from flue gas

The increased CO2 concentration in environment leads to global warming.

Excessive increase of atmosphere temperature is responsible for severe environmental
problems including the rise of water-level in sea, the higher number of storms and
floods, etc. [13] Coal-fired power plant is one of the main sources of CO2 emission
from fossil fuel. In order to mitigate the climate change due to CO2 emission, CO2
capture from flue gas has been received considerable attentions. As a result, a great

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number of separation processes have been investigated intensively through laboratory

test, simulation studies and even pilot scale test.
Membrane separation technology is one of the most promising technology for
CO2 capture from flue gas, when taking into account the benefits of membrane
processes, including simplicity of operation, modular construction, small footprint, no
hazardous by-product emissions. However, CO2 capture from flue gas based on

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membrane process is still not fully explored, since the separation targets proposed by
U.S. Department of Energy (DOE) with product purity higher than 95% and recovery

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higher than 90% are too difficult to achieve with low energy consumption and capture
cost. The low CO2 concentration and low pressure in flue gas are responsible for the

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difficulty of separation process, high energy consumption and capture cost. Many
researchers [14-30] are optimizing membrane-based CO2 capture processes from flue
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gas and intend to find the optimal materials and operating conditions with lowest
energy consumption and capture cost.
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The low CO2 concentration [28] in power plant flue gas (13%~15% for typical
coal fired power plant) is one of the most important obstacle for post-combustion CO2
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capture. Favre et al. [14] mentioned that with feed gas CO2 concentration of 10%, the
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energy consumption required for membrane system was too high to be accepted, even
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with selectivity above 120. When the CO2 concentration in feed gas exceeded 20%,
the energy consumption for membrane system decreased, which would make
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membrane process more competitive than traditional absorption process. For a typical
case, with a selectivity of 60 and a downstream pressure of 30 mbar, single stage
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membrane system would generate an energy requirement of 0.7 MJ/kg, for a feed gas
with 20% CO2. Therefore, the low CO2 concentration in flue gas is the main
bottleneck to realize a capture cost as low as 20 $/ton CO2.

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Fig. 1. Single-stage membrane processes for flue gas CO2 capture.

For single-stage membrane process shown in Fig. 1, in order to realize the

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separation target of 95% purity and 90% recovery of CO2, high selectivity is needed.

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As reported by Favre et al. [14], selectivity above 200 is required to realize the targets
stated above. Further studies conducted by Yang et al. [24] point out that the minimal
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selectivity is a function of permeate/feed pressure ratio. The decrease of
permeate/feed pressure ratio will lead to a decrease in selectivity required to realize
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the targets proposed by DOE. For instance, when pressure ratio approaches 0,
selectivity of 300 is needed for the fulfillment of 95% CO2 purity and 90% CO2
recovery. While with permeate/feed pressure ratio of 0.02, selectivity above 600 is
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required to realize the same product purity and recovery. Therefore, it is not practical
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for single-stage membrane process to realize the targets proposed by DOE, mainly
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because the product purity is restricted by the low feed gas CO2 concentration and the
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trade-off between product purity and recovery.

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Fig. 2. Two-stage membrane processes for flue gas CO2 capture.

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Relatively speaking, it is easier for two-stage membrane process to realize the
targets proposed by DOE, since the cycle gas significantly improves the CO2 recovery.
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Fig. 2 illustrates a typical two-stage membrane system with cycle gas. The first stage
provides concentrated gas which is directed to the second stage to further improve its
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purity. In this case, the second stage residue stream is recirculated to the first stage to
ensure the high CO2 recovery. As reported by Yang et al. [24], with membrane
selectivity of 52, CO2 permeance of 3.12  10-3 m3 (STP) m-2 s-1 MPa-1 and pressure
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ratio of 0.081, the separation target proposed by DOE could be satisfied by two-stage
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membrane system with a capture cost of 48.7 $/ton CO2. If the permeate/feed pressure
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ratio decreased to 0.05, the two-stage membrane system could realize the separation
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target with membrane selectivity as low as 40. The membrane is operated at the
temperature of 313 K.
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As shown in Figs. 2, compared with single-stage membrane process [28],

two-stage membrane process requires a larger number of compressors or vacuum
pumps which consume more power, and the cycle gas brings about higher membrane
area requirement. Therefore, for two-stage membrane process, the reduction of energy
consumption and membrane area is the main target of flue gas CO2 capture process
optimization.
Zhao et al. [27] found that the energy consumption effectively decreased with the
improvement of membrane CO2/N2 selectivity. With the pressure ratio of 10 in the

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first stage and pressure ratio of 4 in the second stage, by increasing membrane CO2/N2
selectivity from 20 to 40, the energy consumption decreased more than halved.
However, when the selectivity increased to higher value, the decreasing tendency
became slower. Therefore, for two-stage membrane process, CO2/N2 selectivity of 40
might bring about enough energetic advantage. The required membrane area
decreased with the increase of CO2 permeance, thus the capture cost also decreased

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accordingly. In sum, the improvement of membrane selectivity and permeance is
contributive to the reduction of energy consumption and membrane area, respectively.

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When the Robeson upper bound [3, 4] was imposed on membrane process design, a
medium selectivity combined with relative high permeance was found to be more

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advantageous in improving post-combustion carbon capture membrane performance,
than simply using a membrane with high selectivity. Similar conclusion was also
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summarized by Zhang and coworkers [26]. They found that with the increase of
CO2/N2 selectivity, energy consumption decreased but a larger membrane area was
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required for two-stage membrane process. Thus, a trade-off between energy

consumption and membrane area was encountered. The optimal selectivity was found
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to range from 70 to 90 for two-stage membrane process.

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In order to obtain the driving force for membrane process, vacuum pump in the
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permeate side or compressor in the feed side should be installed. Through the analysis
conducted by Yang and coworkers [24], it was found that the vacuum process
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consumed less energy than pressurized process, but required higher membrane area. A
higher pressure difference greatly would reduce the membrane area of the process,
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however, with a higher energy consumption. Actually, the success of membrane

processes for CO2 capture from flue gas depends not only on excellent membrane
permselectivity but also on process operating conditions. The appropriate pressure on
either permeate side or feed side is crucial for the optimization of membrane process.
Huang et al. [18] emphasized the importance of pressure ratio on membrane
separation performance. Pressure ratio not only limited the product purity but also led
to the change of compressor capital cost and energy consumption. The balance
between pressure ratio and selectivity should be highlighted by researchers afterwards.
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For a two-stage membrane process shown in Fig. 2(b), by pulling a vacuum on the
permeate side, a pressure ratio of 10 provided the minimal energy consumption. With
this pressure ratio, membranes with high permeance are always preferred, but the
optimal membrane process configuration might not need membrane of the highest
selectivity. The optimal selectivity of the process is decided by both the pressure ratio
and the other operating conditions.

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Fig. 3. The two-stage membrane separation for CO2 capture from the coal-fired flue gas
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designed by Shao and coworkers [22].

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Recently, more concerns have been focused on multi-stage processes, with

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respect to energy consumption and CO2 capture cost. For instance, Shao et al. [22]
investigated a two-stage membrane system for CO2 capture from flue gas with 13%
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CO2. As shown in Fig. 3, the first stage (A1) was responsible for improving CO2
concentration to 85%. The second stage (A3) was able to provide a permeate gas with
CO2 concentration above 99%. While A2 was meant to improve CO2 recovery by
capturing the CO2 in residue gas and recycling it back to first stage. The capture cost
could be reduced with further improvement of membrane selectivity. With CO2/N2
selectivity of 200, membrane permeance of 100 GPU (1GPU= 10-6 cm3 cm-2 s-1
cmHg-1 =3.346×10-10 mol m-2 s-1 Pa-1), feed pressure of 2.4 bar and permeate side
pressure of 0.14 bar, capture cost as low as 17.9 $/ton CO2 could be achieved with

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24.4% output power consumption, which is more competitive than traditional amine
absorption process for CO2 capture from coal fired flue gas.
Different from the traditional studies on single-stage and two-stage membrane
processes performance, advanced algorithms take its place among the research
methods, which could take more factors into consideration during the optimization of
membrane separation process. For instance, Yuan et al. [25] used genetic algorithm to

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simultaneously optimize energy consumption and membrane area requirement for
single-stage and two-stage membrane processes. The decision variables included the

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operating pressures, temperature and intermediate composition. The lowest energy
consumption was found to be 1.1 GJ/ ton CO2 for a hybrid two-stage process with

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N2-selective membrane in the first stage and CO2-selective membrane in the second
stage. Arias et al. [30] constructed a superstructure which included several candidate
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configurations as a nonlinear programming (NLP) model to figure out the optimal
number of stages, with lower membrane area and total cost, and their results showed
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that the objective product CO2 concentration determined the optimal number of stages.
With product CO2 concentration ranging from 90% to 93%, two-stage membrane
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system with a recycle stream was found to be the optimal configuration. With CO2
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concentration ranging from 94% to 96%, two-stage membrane system and three-stage
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membrane system were found to remain a minimum of the total cost. More recently,
this conclusion also has been confirmed by researchers afterwards. Gabrielli et al. [16]
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utilized genetic algorithm to find the appropriate process configuration with minimum
energy consumption and membrane area. With product purity fixed as 95%, the
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differences between two-stage and three-stage membrane processes of membrane area

and energy consumption were found to be negligible. As such, the two-stage
membrane system was proven to be the most practical design for the realization of
separation targets proposed by DOE while the three-stage membrane system did not
notably reduce the capture cost but remarkably increased the process complexity. For
the CO2 capture from flue gas, more focus should be put on the optimization of
two-stage membrane system in the future.

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Fig. 4. Simplified flow diagram of a two-step vacuum membrane process to capture CO2 in flue gas

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from a coal-fired power plant designed by Merkel and coworkers [20]. The membrane with a CO2

permeance of 1000 GPU and a CO2/N2 selectivity of 50 was used in the calculations.
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Another way to reduce the energy consumption of CO2 capture from flue gas is
the utilization of air as sweep gas. Merkel et al. [20] proposed a two-step membrane
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process by employing air as sweep gas to capture CO2 from flue gas and recycling the
sweep air back to the boiler. In the two-step membrane process, the residue gas
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leaving the first step is sent to the second step to improve the CO2 recovery. While for
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the two-stage membrane process, the permeate gas of the first stage is sent to the
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second stage to improve the CO2 concentration. Sweep operation was found to
consume less energy than that with compressor or vacuum pump, since the sweep gas
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could increase the driving force for CO2 permeation without improving pressure. As
shown in Fig. 4, in the first step, a vacuum pump was used to provide the driving
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force for CO2 separation. Since the CO2 enriched permeate gas passing through the
vacuum pump was only a fraction of the volume of the flue gas, the energy
consumption caused by the vacuum pump was much lower than that consumed by
compressing the flue gas. The CO2 concentration in the first step residue gas was
around 7%. In the second step, a counter-flow/sweep configuration was applied to
further reduce the residue gas CO2 concentration to 1.8% by utilizing air as sweep gas
on the permeate side. The CO2 in the sweep air was returned back to the boiler to
improve the flue gas CO2 concentration to 20%. As a result of high feed gas CO2
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concentration and high residue gas CO2 concentration, the first step permeate gas CO2
concentration could be as high as 83%, which still required further treatment to
improve the CO2 concentration to 95%. Overall, with product purity of 95% and CO2
recovery of 90%, a capture cost of about 23 $/ton CO2 could be realized.
The cost-sensitivity analysis conducted by Ramasubramanian et al. [21] also
proved that membrane-based air sweep process could realize the DOE capture targets.

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To further reduce the cost of the membrane process, the membrane with CO2/N2
selectivity above 140 and CO2 permeance of 3000 GPU was recommended to realize

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a capture cost of 24 $/ton CO2. Higher CO2/N2 selectivity significantly reduced
energy requirement due to the higher CO2 concentration in the first step. Increasing

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CO2 permeance was definitely beneficial due to ensuing decrease in membrane area.
Therefore, further improvement in membrane permselectivity was crucial to reduce
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the capture cost of membrane-based air sweep process.
Franz et al. [15] carried out an energetic and economic analysis to compare the
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process with sweep gas and the process merely with compressor. The result also
showed that using sweep gas in a two-stage membrane system led to lower energy
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consumption than using compressor. However, due to the large membrane area
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accompanied, the cost of membrane process using air sweep was nearly the same as
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that without sweep gas. Using sweep gas also resulted in the variation of feed gas O2
concentration and the change of combustion temperature in the boiler. Therefore,
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further investigation was needed to prove the feasibility of this method.

Although the membrane-based separation processes has been proved to be a
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competitive solution to separate CO2 from the mathematic point of view, more effort
still should be put on the realization of membrane process in pilot scale or even in
industrial scale.

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Fig. 5. Performance data for 1 TPD carbon capture membrane system reported by White and

coworkers [23].

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During 2012–2014, a membrane-based CO2 capture process from coal-fired

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power plant flue gas using full-scale Polaris™ module had been installed and
investigated at the National Carbon Capture Center in Wilsonville, Alabama, USA
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[23]. Both cross-flow and counter-current sweep spiral-wound modules were
employed to construct a two-step membrane process, which ran up to 1800 h and
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effectively provided an enriched permeate gas with CO2 concentration of 62.6% and
CO2 recovery around 90%. As shown in Fig. 5, the sweep gas could reduce the first
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step residue gas CO2 concentration to 2.78%, which effectively improved the CO2
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recovery. These results were in good agreement with the process design proposed by
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Merkel and coworkers [20]. Hence the experiment gathered from this pilot plant could
be potentially applied to the design and construction of a larger demonstration plant.
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Fig. 6. Membrane system tested at 23°C and a feed pressure of 2 bara with a feed flow controller set to

40 Nm3/h flue gas, reported by He and coworkers [17].

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Recently, He et al. [17] reported a pilot scale test using polyvinylamine (PVAm)
based fixed-site-carrier (FSC) hollow fiber membranes at the Tiller plant (Trondheim,
Norway). As shown in Fig. 6, a membrane system with two modules in parallel was
constructed for this pilot scale test. With a feed flue gas CO2 concentration of 9.5%, a
product CO2 purity of 55% could be obtained by a single-stage process. The water
permeation through the membrane was tested by the condenser in Fig. 6. The water

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permeance was found to be much higher than the CO2 permeance, so it was necessary
to maintain high water concentration in the feed gas in the industrial application. The

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results in this single-stage process could provide the necessary information for the
design and optimization of two stage process for CO2 capture from flue gas. The

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authors indicated that pressure should be optimized, for the pressure significantly
could affect the membrane permeance of facilitated transport membrane. As a result,
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techno-economic analysis should be conducted to balance the required membrane area
and the energy consumption.
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Thus far, membrane separation process is becoming an important option for CO2
capture from coal-fired power plant flue gas according to the recent researches. The
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choice of membrane materials and process configuration have been explored by many
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researchers. However, the methods reported are not systematic enough to provide the
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optimal solution to the process designer. Several important aspects still should be
stressed deeply in the development of membrane process listed below.
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1. The separation targets proposed by DOE could be realized by two-stage

membrane process. Two-stage membrane process should be investigated
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systematically enough to explore its potential in reducing energy consumption and

membrane area, before a new process with much lower energy consumption or
capture cost was developed.
2. Membrane materials development of lab scale should be tailored according to
the requirement of optimal conditions in process design, considering the pressure ratio,
membrane selectivity, membrane permeance, feed gas temperature and feed gas CO2
concentration.
3. Compared to traditional chemical absorption technology, membrane-based
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separation process is still underdeveloped. Therefore, the process design is important

for the capture system optimization, and pilot scale and full scale test are the ultimate
measurement for the success of membrane-based CO2 capture technology from flue
gas.
4. The improvement of membrane selectivity and permeance contributes to a
lower energy consumption and lower capture cost. For the improvement of membrane

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selectivity, for example, the polyethersulfone (PESU) membrane [55] with the CO2/N2
selectivity of 34 would be potentially suitable, and the PEOT/PBT/ZIF-71 membrane

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[56] with the CO2/N2 selectivity of 52.6 is also recommended for the post-combustion
CO2 capture. For the improvement of membrane permeance, the optimal

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PIM-CD/PDMS/PAN composite membrane [57] enjoys a CO2 permeance of 483
GPU, and the PDMS/PAN composite hollow fiber membrane [58] with a CO2
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permeance of >5000 GPU is reported.
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2.2 Biogas upgrading

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Biogas is playing a more and more important role in the renewable energy
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market in recent decades. Produced from a variety of aspects, such as municipal

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sewage treatment waste, human or animal waste and farm agricultural waste, typical
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biogas mainly contains 55–65% CH4, 35–45% CO2 and other minor components
(such as water vapor, hydrogen sulfide, volatile organic compounds and siloxanes,
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etc.) [31]. Biogas is a common fuel for stoves, internal engines, gas turbines and fuel
cells, and also could be injected into natural gas grids after purification [32]. For the
sake of increasing the calorific value of biogas, the unwanted components, such as
CO2 and H2S, should be removed from raw biogas through the biogas upgrading
process. Besides, CO2 capture from biogas can be applied for other applications, such
as enhanced oil recovery (EOR) and algae production, which would further reduce the
cost of biogas upgrading. Therefore, the biogas upgrading technology is attracting
more and more interest in the industry processes. Depending on competitive energy

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consumption and operating costs, membrane-based technology has more and more
extensively used in biogas upgrading field.
Recently, the developments of membrane materials with high CO2/CH4
selectivity and permeance have boosted the development of membrane based biogas
upgrading process [33]. This section reviews the reported biogas upgrading process
using CO2 separation membrane. Single-stage membrane process for biogas

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upgrading has been detailedly discussed using typical polymeric membranes. The
trade-off between CH4 recovery and CH4 purity was observed, which is equivalent to

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a negative correlation between CH4 product purity and CH4 recovery [34]. Even
though the improvement of CO2/CH4 selectivity contributes to higher product purity

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for a specific CH4 recovery, single-stage gas membrane system is still unable to
provide a product with sufficiently high CH4 purity and high CH4 recovery
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simultaneously [35]. Hence, multi-stage membrane systems are developed for biogas
upgrading to tackle this drawback.
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Fig. 7. Schematic of (a) single-step membrane design and (b) two-step membrane design for biogas

upgrading.

Havas et al. [36] evaluated the potential of single-step and two-step membrane
processes for biogas upgrading, as depicted in Fig. 7. Systematic techno-economic
analysis was performed to find out the optimal membrane material that could provide
the optimal capital cost and operating cost of the membrane system. The membrane
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selectivity and permeance were determined by the Robeson’s upper bound [4] for
CO2/CH4 separation membrane. For two-step membrane process, a minimum
operating expense was detected with CH4 purity fixed as 96% and CH4 recovery fixed
as 85%. With the increase of CO2/CH4 selectivity, the operating cost firstly decreased
and then increased. Under the premise of relatively high CO2 permeance above 2000
GPU, optimal membrane with selectivity ranging from 10 to 25 could provide the
lowest operating cost of 0.037 $/Nm3, when the membrane was operated with a

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pressure ratio of 10. When the optimal membrane confirmed, the cost of biogas

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upgrading is dominated by the compressor including the capital depreciation and
utility expenses, which amounted to approximately 85% of the total cost. In addition,

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further decrease of membrane skid cost would lead to the decrease of operating cost
and the increase of CO2/CH4 selectivity with the minimum operating cost. In
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conclusion, two-step membrane process with optimal selectivity provides lower
operating cost than single-step membrane process. Membranes should have high CO2
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permeance and sufficient CO2/CH4 selectivity (10–25). As such, the polyethersulfone

(PESU) membrane [55] with CO2/CH4 selectivity of 35.5 is high enough for the
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two-step membrane processes for biogas upgrading.

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Shao et al. [37] designed a two-stage membrane process to generate pipeline

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quality methane (97% purity) with 99% recovery. The advantages of membrane
technology over pressure swing adsorption (PSA) in upgrading bio-methane from the
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biogas were demonstrated. The membrane selectivity was set as 55 and the CO2
permeance was set as 25 GPU, with the operating temperature of 303.2 K. With the
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aim of reducing the overall process cost, membrane process design was optimized by
the moderation of pressure at each side of membrane. The first stage
upstream/downstream pressure ratio was found to range from 8.5 to 8.7, and the
second stage feed pressure was set to be 5.0 bar. The separation cost of membrane
process was 0.89 $/MMBtu while the typical cost for PSA ranged from 5 $/MMBtu to
7 $/MMBtu. Moreover, when processing a 200 Nm3/h biogas stream, the energy
consumption for two-stage membrane process was 1.69 MJ/kg (equal to 1.21
MJ/Nm3), which was lower than the energy consumed in PSA process. The result
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proved that membrane process was better than traditional PSA adsorption process for
producing pipeline quality methane considering methane recovery and processing
cost.
In order to further reduce the energy consumption and operating cost, Valenti et
al. [38] elaborately investigated single-stage and two-stage membrane processes by
utilizing cellulose acetate spiral wound membrane. The results showed that for each
design, specific membrane area ranged from 1.1 to 2.4 m2h/m3, while specific energy

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varied from 0.33 to 0.47 kWh/Nm3 respectively, depending on the specific layout.

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With the selectivity around 29 and CO2 permeance around 2.5  10-3 mol/(m2 s bar)
(74 GPU), two-stage membrane process with a cycle gas operated at 26 bar offered

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the best performance, with a specific separation energy of 0.33~0.38 kWh/Nm3 (equal
to 1.18~1.37 MJ/Nm3), which was slightly higher than 0.29~0.30 kWh/Nm3 (equal to
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1.04~1.08 MJ/Nm3) reported by Deng and coworkers [39], due to the low membrane
selectivity in Valenti’s study. The simplicity of two-stage membrane process was the
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winning factor for industrial application, and future work should be focused on
applying hollow-fiber membrane module which could effectively reduce the expense
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of biogas upgrading.
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The impact of CO2/CH4 selectivity and membrane area on separation

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performance was conducted by Makaruk and coworkers [40]. A biogas upgrading case
with feed gas flow rate of 1000 Nm3/h, feed gas methane concentration of 60% and
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product gas methane concentration of 98% was investigated. The energy consumption
for upgrading biogas to natural gas substitute was around 0.3 kWh/Nm3 (equal to 1.08
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MJ/Nm3). The result showed that the increase of membrane area contributed to
relatively higher product recovery. However, if a very high recovery close to 100%
was achieved, considerably more membrane areas should be consumed. When lower
CO2/CH4 selectivity membrane employed, more compression power would be
consumed to realize the same methane recovery. With a CO2/CH4 selectivity higher
than 50, the energy consumption could only slightly decreased. In this case, the
membrane-base gas separation processes could provide enough flexibility to keep a
high product recovery during the biogas upgrading process.
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Fig. 8. Optimal process design for a gas permeation material with Robeson upper bound characteristics

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[41].

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Scholz et al. [41] applied a structural optimization approach for membrane-based
biogas upgrading processes to minimize both required membrane area and pressure,
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and presented the most profitable membrane process. General Algebraic Modeling
System (GAMS) was implemented to optimize the selectivity and permeance in the
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membrane process with fixed product purity and recovery. Two-stage membrane
process was proven to be the optimal design, as shown in Fig. 8. The CO2 selectivity
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and permeance was determined by the Robeson upper bound [4], with CH4 recovery
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fixed as 99.5% and CH4 purity fixed as 96%. When each stage employed the same
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selectivity membrane, the optimal membrane permselectivity for two-stage membrane

process was CO2/CH4 selectivity of 123 combined with a CO2 permeance of 555 GPU.
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When each stage employed different selectivity membranes, the selectivity should be
optimized individually. For the optimal condition, membrane with high CO2/CH4
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selective of 147 and CO2 permeance of 349 GPU was applied for the first stage, while
membrane with moderate CO2/CH4 selective of 98 and CO2 permeance of 1024 GPU
was applied for the second stage. Due to the application of Robeson upper bound, the
required membrane area was significantly smaller than the commercial membranes,
which only had a permeance of 60 GPU. As such, the membrane area consumption
was only 1.95 m2 h/m3 CH4, operated at the feed pressure shown in Fig. 8. The
specific energy demand was 0.161 kWh/m3 (STP) with respect to the raw gas flow
rate (equal to 0.966 MJ/m3 CH4). In sum, the two-stage membrane process with
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membranes applied to the Robeson upper bound provided the best performance.
In conclusion, product purity requirement markedly determined the optimal
CO2/CH4 selectivity, CO2 permeance and capture cost. For the sake of competitively
high product purity, higher optimal CO2/CH4 selectivity, lower CO2 permeance and
higher capture cost were needed. This reflected that typical membrane-based gas
processes had to make strong effort in acquiring high purity product, and it is

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relatively expensive to achieve ultrahigh purity product by membrane-based
technology in biogas upgrading process.

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In the study conducted by Kim et al. [42], hydrogen sulfide and carbon dioxide
were removed from biogas using the membrane separation process and the purified

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methane was used as the fuel of fuel cell. The requirement of product in Kim’s work
was CH4 purity above 99% and H2S concentration lower than 5 ppm, combined with
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CH4 recovery above 90%. The membrane CO2 permeance was around 75 GPU, and
membrane CO2/CH4 selectivity was around 15. Numerical solution obtained from
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MATLAB was employed to determine the relationship between CH4 recovery and
membrane area consumption of each stage in a multi-stage separation process with
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recycle stream. The three-stage membrane process with recycle stream was optimized
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to realize CH4 recovery of 91% and CH4 purity of 99.7% with a membrane area of
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454.3 m2 (equal to 65.4 m2 h/m3 CH4). Increasing operating pressure from 0.388 MPa
to 0.679 MPa would lead to the reduction of membrane area and also the decrease of
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CH4 recovery. As such, Kim concluded that the key optimization variables were the
operating pressure and membrane area for the removing of H2S and CO2 from biogas.
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Typically, membrane-based gas separation processes are modelled in steady state.

However, in practical, it is inevitable to encounter the fluctuation of feed gas
composition and flow rate during the operation. In these case, product composition
should be kept as constant through dynamic process control system during the
separation process. To resolve the above problem, Scholz et al. [43] presented
efficient process control schemes to maintain the product purity and CH4 recovery as
constant simultaneously during the biogas upgrading process. Two novel process
control schemes programmed in Aspen Custom Modeler and simulated in Aspen Plus
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Dynamics were designed to realize the above target, even if significant changes in the
feed gas conditions were still encountered. The membrane CO2 permeance was 60
GPU, and the CO2/CH4 selectivity was 60, with the operating temperature of 298 K
and feed pressure of 16 bar.

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Fig. 9. Two advanced control schemes which combine a conventional controller with a model predictive
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controller. (a) Model predictive controller (MPC) sets the permeate pressure of the first stage. (b) Model

predictive controller (MPC) sets the permeate pressure of the second stage permeate [43].
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The process control schemes depicted in Fig. 9 were able to maintain product
CH4 concentration as 96%. The conditions of feed gas were measured online, so as to
provide the necessary data for model predictive controller (MPC) that controlled
product purity. PID controller adjusted the pressure according to the product purity
measured. If the feed condition deviated from the design point, lower CH 4 recoveries
or increased cycle gas flow rate was expected. This process could be applied to the
start and shut down processes in gas permeation processes, and could also be used to
investigate the impact of material degradation on the gas process during the operation.
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The hybrid processes which combined membrane process with other traditional
gas separation processes such as pressurized water scrubbing, amine absorption and
cryogenic separation were investigated by Scholz et al. [44] for biogas upgrading. The
investigation of hybrid processes was simulated by Aspen Plus and the cost estimation
was based on Guthrie’s method. The combination of membrane technology and
existing separation techniques was proven to have better performance than merely

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using the traditional cryogenic separation process or amine absorption process, and
both lower cost and higher CH4 recovery could be obtained for the hybrid processes.

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As such, when the membrane process was incorporated into the established processes,
the energy consumption and capture cost could be further reduced.

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In most situations, a constant membrane permeance was often assumed for sake
of simplicity during the simulation. In the study conducted by Bounaceur et al. [45],
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the impact of pressure on the permeance of different gases was investigated
systematically based on solution-diffusion model. The result showed that constant
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permeance could lead to significant errors about membrane area consumption in

CO2/CH4 separation process. The author recommended that if the CO2 concentration
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difference between feed gas and residue gas was higher than 1%, the model assuming
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constant of membrane permeance was not accurate enough for predicting the
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membrane separation performance. Even though using average permeance could

provide a reasonable result, when the permeance for only one of the gases changed. If
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the permeance for all gases changed significantly during the separation process, the
required membrane area could not be correctly derived from the average permeance.
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Therefore, the impact of variable permeance should be taken into account during the
optimization of capital costs, operational costs and energy consumption, if a variable
permeance behavior was observed in membrane module.
It is speculated that membrane-based separation processes will be frequently
used as a practical biogas upgrading technology in the future. Both high CH4 purity
and high CH4 recovery can be achieved by two-stage membrane process. The
improvement of membrane CO2/CH4 selectivity and permeance further could reduce
the application cost of membrane-based gas separation process. There are still some
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conundrums needed to be resolved or investigated in the future as below.

1. There is a lack of systematic investigation on how operating conditions and
membrane materials affect the operating cost with fixed product purity and recovery.
Therefore, systematic investigations of biogas upgrading involving both fixed
separation target and optimal operating cost are urgently needed.
2. Further improvement of membrane selectivity or permeance might not bring

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about additional benefits for biogas upgrading. Systematical investigations of the
impact of membrane selectivity, membrane permeance and operating pressure on

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capital cost, operational cost and energy consumption are required for researchers to
understand the required membrane permselectivity with optimal operating cost.

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3. Two-stage membrane process should be investigated with more detail, since it
is the simplest upgrading process to satisfy the requirement of CH4 concentration
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above 97% and the CH4 recovery above 98%, which is appealing for bio-methane
production.
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4. If the permeance of gases changes significantly during the membrane

separation process, membrane permeance calculated in membrane process should be
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adjusted according to the specific operating condition.

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5. The high selectivity membrane is of great importance to the realization of the

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biogas upgrade process. The PIM-1/Matrimid membrane [59] possesses a CO2/CH4

selectivity of 34.3 and CO2 permeance of 243.2 GPU, which is recommended for the
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potential application in biogas upgrade process.

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2.3 Natural gas carbon dioxide removal

Natural gas (NG) is one of the main sources of energy supply. Raw natural gas
[46] typically contains 75-90% CH4, carbon dioxide, nitrogen and hydrogen sulfide
etc. Actually, the CO2 concentration and H2S concentration varies in different
geographic locations, while methane is always the major component. Since CO2 could
reduce the heating value of natural gas, freeze to form dry ice, which would block

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pipeline and damage pumps, the U.S. rolled out increasingly stringent mandatory
measures to stipulate the US pipeline specifications of CO2 ≤ 2mol% and H2S ≤ 4
ppm for CO2 removal from natural gas [47]. Since 1980s, CO2/CH4 membrane has
been commercialized for natural gas carbon dioxide removal processes [46].
Membrane separation process provides significant advantages for the offshore
applications due to the small footprint and environmentally friendly operations. Many

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researchers [48, 49] proved the feasibility of membrane processes for natural gas
purification, for the driving force for membrane separation could be directly obtained

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by the high wellhead gas pressure of raw natural gas.
In order to achieve the US pipeline specifications (≤2mol% CO2 and ≤4 ppm

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H2S) of natural gas, single-stage and two-stage processes are two alternative kinds of
processes for the separation aim, and CO2-selective membrane and H2S-selective
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membrane are investigated to find out the most economical process design. In general,
natural gas was simulated by a ternary gas mixture containing 0–40% CO2 and 0–10%
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H2S balanced with CH4, and feed pressure was 800 psi (55.2 bar) and temperature was
35℃, and permeate pressure was 20 psi (1.38 bar). The results offered by Hao et al.
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[50] showed that natural gas containing large amount of H2S (≤10 mol%) and small
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amount of CO2 could be treated economically with H2S-selective membranes with

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CH4 permeance of 20 GPU, CO2/CH4 selectivity of 16 and H2S/CH4 selectivity of 75

in single membrane process. While natural gas containing large amount of CO2 (≤40
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mol%) and small amount of H2S (≤8 ppm) could be purified economically with
CO2-selective membranes with CH4 permeance of 1 GPU, CO2/CH4 selectivity of 60
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and H2S/CH4 selectivity of 15 in single membrane process. When both the amount of
CO2 (up to 40%) and the amount of H2S (up to 10%) were large enough, two-stage
membrane process with H2S-selective membrane in the first stage and CO2-selective
membrane in the second stage was the most economical process configuration. It was
obvious that the membrane area requirement acted as a function of both the CO2 and
H2S concentration in the feed gas. For example, if the feed gas contained 0-40 mol%
CO2 and 1 mol% H2S, total membrane area requirement varied from 2373.7 m2 to
3681.8 m2, and if the feed gas contained 1ppm-10 mol% H2S and 20 mol% CO2, total
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membrane area requirement varied from 14477.1 m2 to 128915.1 m2, and then the
processing cost also changed with the composition of feed gas. Therefore, by applying
different selective membranes in each stages, the two-stage membrane process with
recycle stream could bring about high CH4 purity, high recovery and low upgrading
cost.
Except for the commonly used two-stage membrane process and two-step

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process, many other complex processes also have been investigated. Further studies
were conducted by Hao and coworkers [51], which investigated two-stage and

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three-stage membrane processes, with the same membrane permselectivity as reported
in Hao’s previous work [50]. A sensitivity analysis was made to find the optimal

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process design with best upgrading cost. The two-stage membrane process with
H2S-selective membrane in the first stage and either CO2 or H2S-selective membranes
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in the second stage was found to provide optimal upgrading cost. Under the
conditions assumed in Hao’s study, three-stage membrane process was found to be
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less economically competitive than two-stage membrane process. As a result,

two-stage membrane process with different kinds of membrane applied to each stage
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was proven to be a better process than three stage membrane processes, when applied
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to upgrade the low quality natural gas containing large amount of H2S and CO2.
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Fig. 10. Schematic diagram of single-stage and two-stage membrane process for natural gas carbon

dioxide removal.

In the work of Yang et al. [11], natural gas containing 10% CO2 and 90% CH4
was purified with single-stage and two-stage membrane processes shown in Fig. 10.
The results showed that the increase of feed pressure or the decrease of permeate
pressure could effectively reduce the membrane area consumption and improve the

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CH4 recovery. With membrane selectivity above 50, the separation target of CH4
recovery >95% and CH4 purity >98% could be achieved by the single-stage

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membrane process under the feed pressure of 5 MPa and the permeate side pressure of

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0.12 MPa. The total membrane area requirement should be tens of thousands of
square meters with a feed flow rate of 11.47 m3 (STP)/day [11]. For the two-stage
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membrane process, low membrane selectivity of 20 was proven to be high enough to
reach the same separation target, since the recycle gas managed to improve methane
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recovery. Hence, for the sake of reducing the membrane area consumption, moderate
selectivity (i.e., slightly lower than 100) and relatively high permeance were required.
The energy compression for two-stage membrane process was estimated to be 107.5
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KJ/Nm3, which was much lower than that of the amine absorption process, even
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considering the conversion factor between heat and electricity of 3-4.

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Most of the previous studies did not consider non-ideal effects such as pressure
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and temperature, which might have an impact on membrane permeance. With the
decrease of gas pressure, Joule-Thomson (JT) effect takes its place and it could lead to
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temperature drop in the permeate gas, which could progressively influence the
membrane permeance. Ahmad et al. [52] investigated the impact of JT effect on
membrane permeance for the separation of CO2 from natural gas with feed
temperature of 50 ℃, feed pressure of 5 MPa and permeate pressure of 0.12 MPa.
Pressure dependence of membrane permeance was compiled by Visual Basic (VB)
program using finite element method and implemented into Aspen HYSYS user
defined unit. The simulate results were validated by experimental data published, and
the two exhibited great agreement. The comparison between the results of ideal model

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and non-ideal model showed that non-ideal model provided higher retentate gas CO2
concentration, lower stage cut and lower methane loss than ideal model. Feed gas
with higher CO2 concentration intensified the non-ideal effect which significantly
could affect product purity, methane recovery, stage cut, compressor power
consumption and natural gas processing cost. Thus, it is important to take the
non-ideal effect into consideration, when accurate separation performance and

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economics of gas separation system is expected.
Scholz et al. [12] studied the non-ideal effect in membrane process with different

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feed temperature and feed pressure, and investigated more details (such as considering
concentration polarization, JT effect, pressure losses and real gas behavior, etc.) than

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the study of Ahmad and coworkers. The results showed that the non-ideal behavior
caused by JT effect during the separation of CH4 and CO2 should be taken into
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account when the feed pressure was above 10 bar. The differences of the retentate gas
CO2 concentration between ideal gas and non-ideal model became more pronounced
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with feed pressure more than 30 bar. Compared with non-ideal behavior caused by JT
effect, the impact of pressure loss and concentration polarization was negligible.
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Therefore, JT effect should be taken into account for large-scale process design with
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feed pressure above 10 bar. As such, it was expected that researches on natural gas
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carbon dioxide removal should address the JT effect in the separation process, if the
operating pressure was equal to the wellhead gas pressure.
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Khalilpour et al. [53] investigated the impact of feed gas quality, feed pressure,
membrane area, selectivity and permeance on separation performance to better
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understand the design optima in single-stage membrane process for natural gas carbon
dioxide removal. The results showed that medium selectivity of 60 combined with
medium permeance of 300~500×10−10 mol m-2 s-1 Pa-1 (90~150 GPU) at the feed
temperature of 25 ℃ was more advantageous in terms of process cost. High
selectivity or permeance was shown not to be necessary for natural gas carbon dioxide
removal. The optimal selectivity or permeance could be determined through
techno-economic analysis.
Kwon et al. [54] investigated different membrane configurations via a new
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approach that visualized the economic performance for CO2 removing from natural
gas through a case study using hollow fiber membrane with the feed pressure of 80
bar, permeate pressure of 4 bar and flow rate of 32.8 Nm3 s-1. The membrane
maintained a CO2 permeance of 40 GPU, CO2/CH4 selectivity of 36, C2H6/CH4
selectivity of 0.27 and C3H8/CH4 selectivity of 0.054. Response surface methodology
(RSM) was adopted in Kwon’s work to find the optimal operating parameters with

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minimum economic cost. Based on this method, the results were presented in a 3-D
graph in which the effects of different parameters could be compared simultaneously

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to identify the optimal condition based on the same separation criteria. Two-stage
membrane system was found to exhibit low membrane area consumption to match the

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pipeline specification (CO2 concentration below 2%), and it was taken as the most
profitable configuration in Kwon’s study. The graphs of response surface could be
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used to find out the most appropriate configuration with the minimal investment cost,
showing large numbers of design parameters simultaneously. Therefore, RSM could
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be a very useful optimization method in process design.

According to the discussions above, there are some suggestions for the natural
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gas carbon dioxide removal processes below.

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1. It is the high pressure that makes the gases behave non-ideally and the
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Joule-Thomson effect rather pronounced, which could reduce the membrane

temperature and permeance, then progressively causing the increase of membrane
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area consumption. As a result, for natural gas membrane separation process,

Joule-Thomson effect should be taken into consideration when the membrane process
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is operated at a high pressure above 10 bar.

2. If the H2S concentration in raw natural gas is too high to be neglected, the
membrane process with H2S-selective membrane and CO2-selective membrane in
different stages should be discussed with more details.
3. The two-stage membrane process was found to be more economically
competitive than three-stage membrane process. Over time, the optimization of
two-stage membrane process will increase the competitiveness of membrane
processes for natural gas carbon dioxide removal.
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4. When membrane selectivity is above 20, the separation target of CH4

recovery >95% and CH4 purity >98% could be achieved by two-stage membrane
process under the feed pressure of 5 MPa. Besides, for the sake of reducing the
membrane area consumption further, higher selectivity (i.e., 20-100) and relatively
high permeance are required.
The typical designs for membrane-based gas separation processes include

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single-stage, two-stage/two-step, and even three-stage membrane process. It is worth
mentioning that when the three-stage process is applied, the immense complication

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and high energy consumption are incurred for the separation process. As for single
stage/two-step membrane processes, it is hard to achieve both high product purity and

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high recovery, based on the membrane properties (selectivity and recovery) reported.
Therefore, it is the two-stage membrane process, as this paper mainly reviewed, that is
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well recommended to achieve both high purity and high recovery, with the most cost
and energy saving way.
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3. Conclusions
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This paper systematically reviews the membrane-based gas separation processes

for post-combustion CO2 capture, biogas upgrading and natural gas carbon dioxide
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removal. Depending on the specific applications (such as feed pressure, compositions

of feed gas, etc.) of the CO2 membrane, the corresponding requirements on membrane
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materials and operating conditions have significant differences. Single-stage

membrane process is not an effective option if the feed gas CO2 concentration is too
low or the product purity requirement is too high. As a result, two-stage membrane
processes as well as multi-stage membrane processes can be regarded as an effective
option for CO2 separation. Validated by genetic algorithm and systematic analysis,
two-stage membrane processes are proven to be more attractive than multi-stage (>2)
membrane processes for the realization of high product purity and recovery, when low

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energy consumption and operating cost are desired. As such, being an immature
technology, two-stage membrane system, which is on the path from laboratory to
industrial scale, should still be investigated deeply with more details in the future.
Therefore, the pilot scale process plays a really critical role, and it is urgent for the
researchers to provide more data in pilot scale test to accelerate the industrialization
of membrane-based CO2 separation process.

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