Membrane based carbon capture from flue gas

Chapter 1a Introduction

Citation(s):
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polymeric membrane systems for flue gas applications." Recent Patents on Chemical Engineering 1.1
(2008): 52-66.

[2] Khalilpour, Rajab, et al. "Membrane-based carbon capture from flue gas: a review." Journal of
Cleaner Production (2014).

[3] Powell, Clem E., and Greg G. Qiao. "Polymeric CO2/N2 gas separation membranes for the capture
of carbon dioxide from power plant flue gases." Journal of Membrane Science 279.1 (2006): 1-49.

[4] Richard, W. BAKER. "Membrane technology and applications." John Wiley & Sons Ltd (2004).

[5] Hongqun Yang et. al. “Progress in carbon dioxide separation and capture: a review.” Journal of
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[6] Arunkumar Samanta, An Zhao, George K. H. Shimizu, Partha Sarkar and Rajender Gupta, “Post-
combustion CO2 capture using solid sorbents: A review”, Ind. Eng. Chem. Res. 51 (2012) 1438-1463

[7] J.C.M. Pires, F.G. Martins, M.C.M. Alvim-Ferraz, M. Simoes, “Recent Developments on Carbon
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[8] Kenji Sumida, David L. Rogow, Jarad A. Mason, Thomas M. McDonald, Eric D. Bloch, Zoey R. Herm,
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[9] A. L. Ahmad, Z. A. Jawad, S. C. Low and S. H. S. Zein “Prospect of Mixed Matrix Membrane
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[10] Deanna M. D’Alessandro, Berend Smit and Jeffrey R. Long “Carbon Dioxide Capture: Prospect
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General Overview
a. In United Nation’s Earth Summit (1992 in Brazil), Nations Framework Convention on Climate
Change (UN-FCCC) was made in order to stabilize greenhouse gas concentration in atmosphere so
that the anthropogenic emission could not interfere with the climate system [2, 7]. In subsequent
years, Kyoto Protocol (1997), based on the United Nations Framework Convention on Climate
Change (UNFCCC) was made [6], and to the most recent case, UN Climate Change Conference in
Cancun, Mexico (December 2010) [6].
b. First commercial interest in the separation of CO2 from flue gas was the application for the
Enhanced Oil Recovery (EOR) which started in 1970s and has proved to be an effective economic
approach over the years [2]. This is because as compared to using water, it is cited as a more
environmentally feasible and attractive alternative [10].
c. Intergovernmental Panel on Climate Change (IPCC)’s fourth assessment report states that, as a
result of anthropogenic CO2 emission, global atmospheric concentration from a preindustrial value
of ~ 280 ppmv to ~379 ppmv in 2005 and ~390 ppmv in 2011 [6]. As compared to the fluctuation in
CO2 in past 400 000 years, it is at the range of 100 – 300 ppm [8]. IPCC predicts that by the year 2100,
the atmosphere may contain up to 570 ppmv of CO2, which leads to a rise of mean global
temperature of around 1.9 oC and increase in mean sea level of 38 m, which also accompanied with
species extinction [5]. Global CO2 emissions due to fossil-fuel use have grown by ~80%, from ~21 Gt
in 1970 to ~38 Gt in 2004 (about 77% of total anthropogenic GHG emission in 2004) [6, 8]. These
emission levels are projected to increase further over the next several decades owing to the rise in
energy demands associated with a growing global population and economic as well as industrial
development [8]. Global temperatures are projected to rise between 1.4 and 5.8 oC by 2100 in the
absence of climate change policies [3] (6.4 oC [8])
d. Transition of existing infrastructure from carbon-based sources to cleaner alternatives would be
ideal [8]. However, it requires a considerable modifications to the current energy framework, and
many of the proposed system are not yet sufficiently developed to facilitate large-scale industrial
implementation [8]. Thus, CCS technology (Carbon capture) from existing emission sources will play
a vital role until a more significant modifications to the energy infrastructure can be realized [8].

Carbon Capture and Sequestration (CCS) Technology

a. Enhanced oil recovery (EOR), where the CO2 is injected into underground geological formation
[others, 8]
b. With regards to CCS Technology, there are two main points to be taken care of:
= Any chemical employed to capture CO2 will rapidly exhaust its global supplies if it is used in a once-
through manner, thus it must be assured that the capture materials can be regenerable [10]
= If CO2 is used as a reactant in chemical transformation (e.g. to a certain commodity in the market),
it will lead to rapid saturation of the market, as CO2 emission is tremendous (about 30 Gt per year) [8,
10]. Thus, a more promising scenario that can be utilized would be its conversion into a fuel for
transportation, provided efficient methods for carrying out the conversion via a renewable energy
sources [8].
c. CCS system must capture CO2 from the flue gas in an efficient, reversible fashion [8]. However, the
most significant challenge for CO2 capture at present in the large energy penalty associated with the
capture process, which about 70% of the cost of CCS is associated with the selective capture of CO2
from the power plant flue gas [8]. This value is required to be reduced so as to ensure CCS to be
viable, which the cost is mainly from the large energy input needed to regenerate the capture
material [8].
d. The deployment of CCS schemes is a multifaceted problem that requires shared vision and
worldwide collaborative efforts from governments, policy makers and economist, as well as scientist,
engineers and venture capitalist [10]
e. Besides, the slow deployment of fully integrated commercial CCS scheme is due to the
considerable cost of the capture phase, which represents approximately 2/3 of the cost of CCS [10].
Regeneration energy and the capital cost of capture-specific equipment are the two major variables
that contributed significantly to the cost of CO2 capture. However, this will be improved if the
separation efficiency is enhanced, which there is a serious need for research on innovative new
materials in order to reduce the time to commercialization [10].
CO2 capture at stationary point sources
a. In a typical post-combustion flue gas, owing to relatively low concentration of CO2 (15 – 16%) and
large quantities of N2 (73 – 77%) originating from the air in which the coal is combusted, a high
selectivity toward CO2 is critical, such that only pure CO2 is captured and subjected to sequestration
[8].
b. Aqueous amine absorbents capture CO2 from the gas mixture with high selectivity but carry
energy penalty of approximately 30% of the pore produced at the power plant [8]. This is due to the
energy required to break C-N bond (CO2 and amine interaction) during desorption process [8]. Thus,
it is required to explore new materials that offer lower energy penalty, ideally close to the
thermodynamic minimum of approximately 10 – 20% [8].

Current CO2 Capture Material

a. Optimization should allow the energy penalty and cost of CO2 capture to be lowered, enabling
widespread implementation under various scenarios [8].
b. Selectivity is the most crucial performance parameter in CO2 capture [8]. High selectivity is needed
so that CO2 can be completely removed for subsequent sequestration [8].
c. Affinity of materials towards CO2 is related to the optimization of energy penalty for capture. If the
interaction is too strong, this leads to high energy requirement for desorption of the captured CO 2. If
the interaction is too weak, despite it lowers the energy cost, it would lead to lower selectivities for
CO2 over other components of the flue gas.
d. Materials should exhibit a high stability under the conditions of capture and regeneration, such
that it can be deployed for the lifetime of the power plant [8].
e. Adsorption capacity: materials should take up CO2 at a high density such that the volume of the
adsorbent bed can be minimized [8].

Kaya’s Identity [7]

a. It is an relationship between CO2 emissions (CD) with population (P), economic development
(GDP), energy production (E), carbon based fuel used for energy production (C) and CO2 sinks (𝑆𝐶𝑂2 ):
𝐺𝐷𝑃 𝐸 𝐶
𝐶𝐷 = 𝑃 − − 𝑆𝐶𝑂2 [7]
𝑃 𝐺𝐷𝑃 𝐸
= Reduction of population and decline of economy output is not feasible as policy decision
= Increase in energy efficiency (E/GDP) and change of fossil fuels to non-carbon forms of energy
(renewable and nuclear energy) are measures to reduce CO2 emissions to the atmosphere.
= CO2 sinks (Contribution of CCS technology), which is more a feasible option to reduce CD

Amine-based carbon capture technologies (Solvent absorption [1])

a. It is a regenerative chemical absorption processes using aqueous solution of amine, which have
been widely practiced for several years for CO2 capture from gas streams [6]
b. Amine-based carbon capture technologies (i.e. solvent-based PCC) despite being the best
available technology for dealing with various flue gas stream, may not be a long-term desired
technology for PCC due to its high energy penalty associated with solvent regeneration [2], which is
of high energy intensive [6]. Corrosive nature of the solvent also limits its application [9].
c. A recent analysis has shown that the thermodynamic minimum energy penalty for capturing 90%
of the CO2 from the flue gas of a typical coal-fired power plant is approximately 3.5%, assuming the
flue gas containing 12 – 15% CO2 at 40 oC. By comparison, conventional CO2 capture using amine
scrubbers will increase the energy consumption of a plant by 25-40%. Besides, conventional
regenerative amine scrubbing systems have predicted an increased cost of electricity of $0.06 kWh,
or an “avoided cost of capture” of $57-60/tonne CO2 [10]

Adsorption Process
a. Using novel solid sorbents are capable of reversibly capturing CO2 from flue gas streams have
many potential advantages compared to other techniques for CO2 capture such as reduced energy
for regeneration, greater capacity, selectivity, ease of handling, etc. [6]
b. Adsorption on porous solid media using PSA/TSA approach seeks to reduce the cost associated
with the capture size, with the regeneration energy requirement for CO2 capture is significantly
reduced [6]. Smaller heat capacity of the solid sorbent than aqueous amine solvent is also an
important advantages [6].

Temperature and Pressure Swing Adsorption

a. Regeneration of a solid sorbent is accomplished by temperature swing adsorption (TSA), pressure
swing adsorption (PSA), vacuum swing adsorption (VSA) or other combination of these processes [8].
b. Solid adsorbent is packed into a large fixed-bed column and the adsorbate would be desorbed
form the material by increasing temperature (TSA) or reducing the pressure (for PSA and VSA) of the
bed [8]
c. TSA is relatively more promising as compared to PSA and VSA due to it is still possible to use low-
graded heat from the power plant as a source of energy for regeneration [8].
d. In post-combustion carbon capture, compressing or applying a vacuum to such a high volume of
gas is usually difficult. Therefore, TSA is the most viable process [8].
e. In the pre-combustion carbon capture, as the gas stream is inherently pressurized after the
conversion reactions, PSA cycle is most appropriate [8].
f. Regeneration strategies must be designed to minimize the total cost of capturing CO2, thus there
will be a trade-off between maximizing the working capacity (amount of CO2 captured in a given
adsorption cycle) and minimizing the energy required for regeneration [8].

Membrane Technology
a. Membrane technology have been investigated for over 150 years [3]. It was originally proposed
by Graham in 1866 with Loeb and Sourirajan developing the first anisotropic membrane in 1961, and
the membrane developed is mainly for the application of RO membrane [1]. Gas separation were
first commercialized in 1977 when hydrogen recovery system was first introduced [1].
b. Membrane technology is a physical separation process (i.e. act as a filter [1]) where gas mixture
consisting of two or more components are separated by a semi-permeable barrier into a retentate
stream and a permeate stream [2]. In such a way, membrane technology is attractive due to its
energy efficiency and simplicity of membrane gas separation [1].
c. Advantages of membrane separation against other technologies are: compactness, modularity,
ease of installation by skid-mounting, ability to be applied to remote area, flexibility in operation and
maintenance and in most cases, lower capital cost (low usage of chemicals as compared to other
processes) as well as lower energy consumption [2]
d. Membrane research and development for CO2 capture are mainly categorized into membrane
material design (MMD: synthesize membranes of desirable permeance and selectivity while having
chemically and physically stable structure) and membrane system engineering (MSE) [2]
f. Although review (2005) had mentioned that the most promising method is liquid absorption (e.g.
using monoethanolamine (MEA); however the development of membrane (e.g. ceramic and
metallic membrane) will be significantly more efficient than liquid absorption, especially when the
gas separation using membrane was not yet been trailed in large scale system, with their
reliability and cost are not fully evaluated at that time. [2]
f. Although membrane treatment had been used in natural gas sweetening (removal of CO2 and
H2S at high pressure), but it does not necessary ensure the feasibility of membrane for flue gas
treatment. This is because (1) membrane are good for bulk separation but are generally not
economical option for the case with either low feed concentration or high-purity product
requirement; (2) flue gas streams are typically at atmospheric pressure, thus costly compression or
vacuum pumping is required to generate driving force for membrane gas separation; (3) different
molecular characteristics of CH4/CO2 separation and CO2/N2 separation involved in membrane
separation [2]