chapter 14 - design considerations for postcombustion co2 capture...
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CHAPTER 14
Design Considerations for PostcombustionCO2 Capture With MembranesSimona Liguori, Jennifer WilcoxColorado School of Mines, Golden, CO, United States
1. Introduction
The design of low-energy intensive, low-cost, and efficient CO2 capture unit is of extreme
importance for the development of carbon capture and storage (CCS) technologies at
industrial scale (Davidson and Metz, 2005). This mainly holds for the postcombustion,
where the carbon dioxide is diluted in nitrogen with a volume fraction typically between
4% (i.e., gas turbine) and 15% (coal-fired power plant) and the flue gases to be treated are
at atmospheric pressure conditions (Table 14.1). These two specificities address a great
engineering challenge, especially in terms of the energy requirement of the separation
process (Steeneveldt et al., 2006; Herzog, 2001; Wilcox, 2012).
Several capture technologies are being developed and evaluated for CO2 capture
applications such as absorption, adsorption, cryogenic processes, membranes, and
chemical looping (Figueroa et al., 2008). The identification of the most efficient process is
subject to controversial debates. The ideal CO2 capture process should show (1) high
selectivity of CO2 with respect to the other gases, to reach a concentration above 95%; (2)
minimal energy requirement; (3) minimal environmental impact, which can be evaluated
from the waste produced by the CO2 capture unit and water footprint; (4) minimal overall
cost. By considering these characteristics, the absorption into a chemical solvent (such as
amine solution) is currently considered as the best available and most mature technology
(Steeneveldt et al., 2006). Amine solvents have been used for decades for natural gas
treatment. However, the two main drawbacks of the amine absorption process correspond
to a high-energy requirement (Steeneveldt et al., 2006) and waste production. Specifically,
almost 4 GJ/t of thermal energy, corresponding to 50% of the steam leaving the
intermediate pressure steam turbine module that has to be employed for solvent
regeneration, and the degradation of the solvent lead to additional material costs, high
disposal costs, and additional environmental pollution. New solvents or alternative
separation processes that would not exhibit these disadvantages are explored. In particular,
Current Trends and Future Developments on (Bio-) Membranes. https://doi.org/10.1016/B978-0-12-813645-4.00014-3
Copyright © 2018 Elsevier Inc. All rights reserved. 385
compared with other capture processes, CO2-selective membranes possess advantages that
include lower environmental impact and possible application as add-on equipment with
fewer modifications to the power plant (Zhao et al., 2012).
Initially, membrane separation processes were considered inadequate for CO2 capture
because of the difficulty in developing highly selective materials, high-energy requirement,
and prohibitive capital costs (Davidson and Metz, 2005; Figueroa et al., 2008; Favre,
2007). Nevertheless, the situation has, over the past decade, greater attention on
membranes as a possible alternative to chemical separation processes because of their ease
of application, limited maintenance, ability to perform separation with low-energy
penalties, and compatibility with a retrofit strategy without requiring complicated
integration (Abetz et al., 2006; Basu et al., 2004; Kohol and Nielsen, 1997; Mazur and
Chan, 1982; Perry et al., 2006; Wilcox et al., 2014).
However, although membrane processes are conceptually very simple, complicated
membrane process configurations are often employed in practice to meet product purity
and capture ratio constraints (Roussanaly et al., 2016). In this context, a critical analysis of
the benefits and drawbacks of membrane separation processes in a postcombustion capture
framework is proposed hereafter. In addition, different types of design possibilities for
membrane processes will be discussed in the next sections.
2. Membranes and Postcombustion Carbon Capture
Membrane processes are often listed as a potential candidate for CO2 separation for
postcombustion capture. Nevertheless, the main issue related to the limited application of
the membrane technology is the low CO2 concentration and the pressure of the flue gas,
which requires a huge membrane surface area to compensate for low driving force and
the use of membranes with high selectivities to fit the specification delivered by the
Table 14.1: Typical Conditions of a Flue Gas Stream From Various Sources (Metz et al., 2005)
Stream Sources CO2 Concentration (%) Pressure (bar)
CO2 Partial Pressure
(bar)
Gas turbine 3e4 1 0.03e0.04Fired boiler of oil refinery and
petrochemical plant8 1 0.08
Natural gas fired boiler 7e10 1 0.07e0.10Oil-fired boilers 11e13 1 0.11e0.13Coal-fired boilers 12e14 1 0.12e0.14
IGCC after combustion 12e14 1 0.12e0.14Cement process 14e33 1 0.14e0.33
IGCC, integrated gasification combined cycle.
386 Chapter 14
Department of Energy (January 2011), i.e., a target CO2 recovery of 90% with a target
product CO2 purity of 95%.
In fact, the major drawbacks of the membrane operation concern two different factors:
(1) membrane material aspect, which addresses the evaluation of the intrinsic separation
performances of the membrane and the (2) process engineering science aspect, which
focuses on the determination of the best design and operating conditions for a given
membrane material. Combining these two aspects, the installation size and the energy
requirement could be obtained (Zolandz and Fleming, 1995). Unfortunately, these two
fields are often separated. Specifically, numerous studies report only on material structure
and performances, while process design publications sometimes neglect the specificities of
membrane materials.
2.1 Membrane Material and Design for Power Plant Integration
The major hurdle in the engineering analysis of membrane processes in CO2 separation is
the large number and range of process variables, which are usually reduced by treating the
mixture as a binary mixture neglecting the effects of impurities and assuming a feed
mixture temperature, either close to or slightly above ambient temperature (e.g., 40�C).
The two main parameters considered for the CO2 capture are the CO2 purity level (y) and
the capture ratio (R) (Deschamps and Pilavachi, 2004). The capture ratio of a single-stage
membrane unit is defined as
R ¼ qy
xin(14.1)
where q is the stage cut, corresponding to the ratio between the permeated flow rate (Qp)
and the feed flow (Qin), y is the CO2 purity corresponding to mole fraction of CO2 in the
permeate, and xin is the mole fraction of CO2 in the feed. Generally, an increase in q is
not linear with the capture ratio. For this reason, one of the major challenges is to
determine the relationship between the capture ratio (R) and the corresponding permeate
composition (y).
Any membrane separation process requires a driving force to be effective, classically
expressed through the pressure ratio, which corresponds to the ratio between the feed and
the permeate pressures.
J ¼ pf
pp(14.2)
The CO2 purity (y) depends on the feed composition and the material performances, i.e.,
the membrane selectivity, a, and is defined as the ratio between the CO2 and other gas
Design Considerations for Postcombustion CO2 Capture 387
permeabilities. In a large majority of cases, only the experimental permeabilities of the
pure compounds are known, leading to the so-called ideal selectivity of the material:
a ¼ PCO2
Pother�gases(14.3)
It is worth noting that the effective purity produced by a membrane unit not only depends
on the membrane selectivity but also by the module operating conditions, particularly the
pressure ratio (J). In addition, the capture ratio (R) also affects the purity level, due to
mass balance constraints. This qualitative analysis has shown how material and process
variables are closely interconnected, as discussed in the next sections.
3. Membranes Materials for Carbon Capture
A large number of CO2-selective membrane materials for gas applications has been
investigated over the years (Powell and Qiao, 2006; Brunetti et al., 2010). Specifically, a
great number of studies have been reported on different materials such as polymeric,
inorganic, hybrid organiceinorganic, and facilitated transport membranes (FTMs) (Ebner
and Ritter, 2009; Luis et al., 2012).
3.1 Polymeric Membrane
Polymeric membranes have been widely studied for gas separation applications. On the
one hand, application of polymeric membranes to CO2 capture is generally sustained
because they present low cost, facile processing, and high packing density, but on the
other hand, they are limited due to their low chemical, mechanical, and thermal stabilities
and their intrinsic low permeance. The polymeric materials mainly used for gas separation
are polyimide, polycarbonates, polyphenyl oxide, polysulfones, cellulose derivatives, and
poly (ethylene oxide) (Ebner and Ritter, 2009; Luis et al., 2012). Polyimides are the class
of polymers mainly studied. They combine excellent thermal and chemical stability with a
very wide range of CO2 permeabilities and show reasonable potential structural variations
and ease of membrane formation (Powell and Qiao, 2006). Du et al. (2012) summarized a
wide diversity of polyimides, in which those incorporated with the group of 6FDA shows
both high permeability and high selectivity. This is mostly due to the presence of the CF3group, which significantly enhances the stiffness of the chain so that the membrane
separates molecules more effectively on the basis of steric bulk. In 1996, Langsam
published an extensive review of the gas separation properties of polyimide.
Considerable research has been focused on the commercial polyimide, Matrimid 5218.
Postsynthesis modification by Hþ ion beam irradiation (Hu et al., 2007) and
functionalization by bromination (Stern, 1994) improve the permeability of CO2 and N2
simultaneously, leading to only a small decrease in CO2/N2 selectivity. Poly(ethylene-oxide)
388 Chapter 14
(PEO) membranes are considered attractive materials for CO2 separation because of the
polar ether oxygen in the polymer chain, which creates a strong affinity for CO2
(Brunetti et al., 2010). Much effort has been made in designing and synthesizing
polymers containing PEO. For example, a composite membrane based on a segmented
block copolymer (Polaris), a type of PEO copolymer, has been specifically designed for
carbon capture applications up to the industrial scale (spiral wound modules) (Merkel
et al., 2010). This material shows a CO2/N2 selectivity of 50 and CO2 permeance of
1000 GPU. Another example of block copolymers is PEOdpoly(butylenes terephthalate)
block copolymers with a selectivity of 75 and a CO2 permeance of 1000 GPU (Metz
et al., 2004). To date, these performances can be considered as the upper limit for
polymeric membranes based on a physical separation mechanism. Table 14.2 shows the
performance of polymeric membranes for CO2/N2 separation.
3.2 Inorganic Membrane
Inorganic membranes offer higher resistance against high temperature and pressure
conditions, and they can potentially show better performances in comparison with
polymeric membrane. Classical materials include carbon, alumina, zeolite, and silica
(Ebner and Ritter, 2009). Among them, zeolite membranes show interesting performance
for CO2 separation applications. In particular, two exceptional results have been obtained
by using tailor-made zeolites at the lab scale. Specifically, the NAY zeolite membrane
showed a CO2 permeance of 200,000 GPU with a CO2/N2 selectivity of 200 (Krishna and
van Baten, 2011). A higher selectivity of 500 and a CO2 permeance of 300 GPU have
been reported with another type of zeolite membrane (White et al., 2010). Recent patents
(Gobina, 2006; Ku et al., 2007) describe inorganic membranes consisting of a porous
separating layer, often silica, deposited on a ceramic support, such as Al2O3, which can be
used for CO2 separation applications. Xomeritakis et al. reported in their study a CO2
Table 14.2: Performance of Dense Polymeric Membranes
Membrane aCO2=N2CO2 Permeance (GPU) References
Polybenzodioxanes (PIM-1) 25 >12,000a Budd et al. (2008)Tetrazole-functionalized PIM-1
modified40 2,000a Du et al. (2011)
Polaris 50 1,000 Merkel et al. (2010)Poly(ethylene oxide) poly(butylene terephthalate)
75 1,000 Metz et al. (2004)
Poly(ether-block-ester) 60 1,850 Yave et al. (2010a) andLiu et al. (2005)
PTT-b-PEO copolymers 58 >500 Yave et al. (2010b)
aThe permeance is estimated from permeability considering 1 mm dense layer.
Design Considerations for Postcombustion CO2 Capture 389
permeance of 900 GPU with a CO2/N2 selectivity of 50 by using silica membrane.
Table 14.3 reports some performance obtained by using inorganic membranes.
3.3 Hybrid Membrane
Hybrid membranes consist of mixtures of organic and inorganic phases. Classically,
inorganic particles (adsorbents) are dispersed into a polymeric matrix. The corresponding
material is often called a mixed matrix membrane (MMM). This design offers the
possibility to combine the polymer’s easy processability and the superior gas separation
performance of inorganic materials (Mahajan et al., 1999).
The dispersed inorganic phase may act as a molecular sieve or as a selective surface flow
(SSF) material. In other cases, the interactions of the two phases can open interchain
distances, thereby improving both selectivity and permeability. The presence of inorganic
materials in a polymeric matrix can also improve the physical, thermal, and mechanical
properties for aggressive environments as well as stabilize the polymeric membrane
against change in permselectivity with temperature. Pera-Titus (2014) presented a review
of inorganic materials that may be suitable for use in polymer membranes for CO2
capture. Inorganic fillers have included zeolites (Bastani et al., 2013; Junaidi et al., 2014;
Nik et al., 2011; Sublet et al., 2012), carbon nanotubes (Ahmad et al., 2014; Aroon et al.,
2013; Rajabi et al., 2013), and metal organic frameworks (MOFs) (Nafisi and Hagg, 2014;
Perez et al., 2009). MOFs are organiceinorganic solids showing promise in gas separation
and purification (Li et al., 2012).
Jiang (2012) has provided a comprehensive review on MOF membranes and their
application for carbon capture. According to the author, unlike MOF sorbents, very little
work has been carried out on MOF membranes and they are still at their infancy. Recently,
molecular simulation studies have reported that it may be possible to obtain MgMOF-74
membranes with a permeance greater than 30,000 and a selectivity of about 30 (Krishna
and van Baten, 2012) compared with a MMM based on PEBAX-Silica (81:19) that has a
selectivity of about 118 and a CO2 permeance of 205 GPU (Kim and Lee, 2001).
Table 14.4 shows some performance data related to the hybrid membranes.
Table 14.3: Performance of Inorganic and Hybrid OrganiceInorganic Membranes
Membrane aCO2=N2CO2 Permeance (GPU) References
Faujasite or zeolite Y membraneon alumina support
>500 300 White et al. (2010)
NAY zeolite membrane(molecular simulation data)
200 200,000 Krishna and vanBaten (2012)
Zeolite membranes 69 2100 Ebner and Ritter (2009)Microporous silica membrane 50 900 Xomeritakis et al. (2007)
390 Chapter 14
3.4 Facilitated Transport Membrane
FTMs comprises a carrier (typically, metal ions) with a special affinity toward a target gas
component, and this interaction controls the rate of transport. In particular, a selective
reversible reaction between the gas of interest and a carrier agent incorporated in the
membrane takes place. The target gas is readily carried across the membrane, while the
diffusion of the other gases is inhibited. The driving force for gas transportation remains
the partial pressure difference across the membrane. However, by increasing the CO2
feed partial pressure the CO2 permeance and selectivity subsequently decrease. FTMs
can be divided in two categories: fixed-site-carrier membranes (FSCMs), where the
carrier is fixed to the polymer by chemical bonding and liquid membranes (LMs), where
the carrier can diffuse in the membrane. Both kinds of membrane categories have shown
attracting performances for CO2/N2 mixtures. Recently, a permeability above 6000
Barrer and a selectivity of about 500 have been reported for a membrane based on
poly(allylamine) as a fixed carrier and 2-aminoisobutyric acid-potassium salt as a mobile
carrier in a cross-linked PVA matrix (Huang et al., 2008). The main characteristic of
these membranes is represented by the request of water vapor for the selective reaction
toward CO2. Specifically, the separation performances of reactive membranes strongly
depend on humidity and a certain level of hydration has to be maintained on the two
sides of the membrane for correct operation. This is very interesting for the application
of CO2 separation from fossil fuel emissions because exhausted gases usually contain
saturated water vapor. In terms of design, the carrier in these membranes will become
saturated quicker if compression is used on feed side. This specificity logically has a
strong impact on the process design features. Table 14.5 reports some performance data
related to the FTMs.
3.5 Discussion on Membrane Material Design
For a given separation (such as CO2/N2 in postcombustion capture), the membrane should
ideally show both high selectivity and permeability (Zolandz and Fleming, 1995). High
selectivity is necessary to achieve the purity target, ideally in a single-stage process; the
high permeability will allow for minimizing the surface area required for a given
application. Moreover, according to Seader and Henley (2006) the membrane should show
Table 14.4: Performance of Hybrid OrganiceInorganic Membranes
Membrane aCO2=N2CO2 Permeance (GPU) References
MgMOF-74 30 >30,000 Krishna and van Baten (2012)(Pebax)-silica (90:10) 72 154 Kim and Lee (2001)(Pebax)-silica (81:19) 118 205 Kim and Lee (2001)(Pebax)-silica (73:27) 79 277 Kim and Lee (2001)
Design Considerations for Postcombustion CO2 Capture 391
chemical and mechanical compatibility with the process environment: stability, freedom
from fouling, reasonable life time, ease of fabrication and packaging, and resistance to
high pressures. Membranes used for carbon capture should have all these features.
However, most of the studies in the literature mainly analyze the permeability of pure
gases leading to an estimation of the CO2/N2 selectivity. Experiments with gas mixtures,
humid feeds, and/or other flue gas components, such as O2, SOx, NOx, NH3, to better
mimic real flue gas conditions, are ignored with a few exceptions (Hussain and Hagg,
2010; Merkel et al., 2010; Reijerkerk et al., 2011; Sada et al., 1992; Scholes et al., 2010).
It is important to understand the role of minor components because they affect the design
and operation of membranes for carbon capture. Indeed, as reported by Koros and Fleming
(1993), the permeability of a gas at pure versus mixture conditions may vary remarkably
due to different molecules competing in both diffusion and sorption processes. The effect
of water vapor can be considered as an example. Indeed, it has been hypothesized that
water negatively affects the CO2 permeation because of its higher permeability compared
with CO2. Nevertheless, Merkel et al. (2010) have reported that the presence of water has
a positive effect on CO2 permeation because it can be considered as an internal sweep,
which dilutes the permeate by increasing the permeation driving force through the
membrane. Similar results have been found by Hussain and Hagg (2010) by using FTMs
and by Reijerkerk et al. (2011) with poly(ethylene oxide)-based block copolymers.
Table 14.5: Performance of Facilitated Transport Membranes
Membrane aCO2=N2
CO2 Permeance
(GPU) References
Polyvinyl amine (PVAm) and polyvinylalcohol (PVA) blend membrane
150 >300 Deng et al. (2009)Deng and Hagg (2010)Matsuyama et al. (1999)
Fixed carrier in a solvent-swollenmembrane and water-swollen chitosan(poly(D) glucosamine) membrane
120 320 El-Azzami and Grulke(2008)
Poly (allylamine) as a fixed carrier2-aminoisobutyric acid-potassium salt as
a mobile carrier in a cross-linkedPVA matrix
500 >6000 Huang et al. (2008)
Composite membranes (coating PPOand PSf with high-molecular PVAm)
500 840 Sandru et al. (2010)
PVAm composite membranes with PHcontrol
>500 >1800 Kim et al. (2013)
Amine-modified mesoporous silicamembranes
800 300 Barillas et al. (2011)
DEA supported on poly(vinyl alcohol)membranes
200 100 Francisco et al. (2010)
Enzyme supported on polymer 820 52 Zhang et al. (2010)
392 Chapter 14
The opposite result was demonstrated by Scholes et al. (2010) by using a polydimethyl
siloxane (PDMS) rubbery membrane. The negative effect of water vapor on the
permeability of CO2 was due to the hydrophobic nature of PDMS resulting in very low
water sorption. Jiang (2012) noticed that by using MOFs the effect of water may be
positive on CO2 separation at a certain pressure range and negative at another pressure
range. Therefore, future investigations under realistic flue gas conditions will be crucial for
the successful design and development of materials for carbon capture.
4. Membrane Module Configurations for Carbon Capture
Apart from the membrane material, the configuration of the membrane module is an
additional parameter that must be considered for CO2 separation. In particular, they have
to show low production cost and energy consumption, in addition to high packing density.
The module configurations described are in reference to only polymeric membranes
because polymeric membrane technology is currently applied at the industrial level despite
many scientific studies that involve different kinds of membrane applications to CO2
capture. Three types of module configurations are mostly used: hollow fiber (Esposito
et al., 2015), spiral wound (Zhao et al., 2011; Nadir, 2016), and envelope (Borsig, 2016).
Each module configuration shows different characteristics, which are summarized in
Table 14.6.
An important parameter to evaluate the membrane module is the packing density, which
indicates the surface area of the membrane per unit volume inside the module. A hollow
fiber module generally shows the highest packing density (up to 30,000 m2/m3), followed
by the spiral wound (between 300 and 1000 m2/m3), and then the envelope, which shows
the lowest packing density (less than 500 m2/m3) (Mulder, 1996). Fig. 14.1 illustrates the
structures of three types of membrane modules (Wang et al., 2017).
As a general comparison, the hollow fiber configuration has advantages over the two other
types in terms of cost and packing density. However, fibers may be easily blocked by the
particulate matter and must be completely replaced, which may not be very cost-effective
for an existing power plant.
Table 14.6: Comparison of Membrane Modules
Spiral-Wound Envelope Hollow Fiber
Packing density (m2/m3) <1000 200e500 <10,000Pressure drop High and longer permeate path Moderate High in fibers
Cleaning Hard Medium Chemical washing or replacedManufacturing Easy and cheap Easy CheapCost ($/m2) 9e44 47e176 2e9
Design Considerations for Postcombustion CO2 Capture 393
4.1 Hollow Fiber Membranes
Hollow fiber membranes comprise thin polymeric tubes, with a diameter of 50e200 mm
(Baker, 2004). The selective layer is on the outside surface of the fibers, facing the high-
pressure gas. A hollow fiber membrane module normally contains tens of thousands of
parallel fibers sealed at both ends in epoxy tube sheets (Baker, 2004). These membranes
are compact, require low energy consumption, and show high flux with moderate
selectivity in a full-scale system (Sandru et al., 2010). Moreover, they are cleanable by
reversing the permeate flow, they require low area cost and low holdup volume.
Figure 14.1Membrane modules: (A) spiral wound; (B) hollow fiber; (C) envelope (Wang et al., 2017).
394 Chapter 14
4.2 Spiral Wound Membranes
Spiral wound membranes are compact, which means that high membrane packing density
results in more efficient use of the footprint. In addition, they are stable and require minimum
energy consumption and low capital and operating costs. Generally, sheets of membranes that
are 1e2 m long are cut and folded and subsequently packaged as spiral wound modules
(Kashemekat et al., 1991). A single module may contain as many as 30 membranes.
Drawbacks of these membranes are that they are not suitable for very viscous flow and are
difficult to clean. In addition, if the membrane fails the entire module needs to be replaced.
4.3 Envelope Membranes
In the envelope configuration, sets of two membranes are placed in a sandwich-like
fashion with their feed sides facing each other. A suitable spacer is placed in each feed,
and permeate side and baffles are introduced to establish a uniform flow distribution and
to reduce channeling (Mulder, 1996). The benefits of the envelope configuration are the
use of flat membranes without the use of glue and the exchange ability of single
membranes. However, this configuration is in need of sealing and shows low packing
density. Moreover, pressure drop can take place inside the module.
5. Membrane Design for Carbon Capture Applications
The design of a membrane process is aimed at optimizing the entire process system
configuration to achieve the required purities at minimum capital and operational
expenditures and to enhance the overall performance of the membranes. Modeling and
optimization are the main keys to reaching this objective.
A reasonable membrane system design based on feasible membranes should take into
account the following factors: separation target (CO2 recovery rate and purity); operating
conditions such as temperature, pressure, and composition of CO2 in the feed gas; trade-
off balance between material cost and energy consumption. The flue gas of coal-fired
power plants has a low CO2 concentration (Herzog, 2001) at ambient pressure, and to
achieve the desired CO2 recovery rate of >90% and CO2 purity >95 mol% (Department
of Energy, January 2011), which is feasible with the competing technology (chemical
absorption) and required for pipeline transport (Conturie, 2006; Hagedoorn, 2007), two
strategies should be considered, i.e., a single-stage membrane with high selectivity or
optimized multistage membrane systems.
5.1 Single-Stage Membrane
There have been numerous efforts in the simulation of membrane-based gas separation
over the last six decades. Today, the possibility to accurately predict the separation
Design Considerations for Postcombustion CO2 Capture 395
performances of a unit through a series of key equations and associated assumptions is
abundantly documented (Bounaceur et al., 2006; Kaldis et al., 2000; Chowdhury et al.,
2005; Coker et al., 1999; Matson, 1983; Zanderighi, 1996). Fig. 14.2A shows all
significant parameters for a single-stage membrane process. Specifically, as in any process
design study, a series of variables has to be first defined, and then a fixed number of
unknowns can be identified through analytical or numerical resolution. For carbon capture
studies, two key limitations are imposed: the CO2 capture ratio (R) (Eq. 14.1) and the CO2
purity produced on the permeate side (y).
The separation performance is obtained by considering the CO2 capture ratio and the CO2
purity. For a single-stage, these two parameters are calculated by simulation combining the
operating boundary conditions and membrane parameters. Anyhow, membrane separations
show a high parametric sensitivity unlike other carbon capture processes, and the
following variables play important roles:
• composition of CO2 in the feed (xin);
• driving force, expressed as the pressure ratio across the membrane (Eq. 14.2);
• ideal selectivity (Eq. 14.3) and the CO2 permeance, which are related to the membrane
material.
The influence of these variables will be discussed hereafter.
5.1.1 Relation Between the Pressure Ratio and Ideal Selectivity for a Target CO2 Purity
There is a strong interaction among the pressure ratio, the ideal selectivity, and the CO2
purity. Specifically, the required pressure ratio decreases as the desired permeate CO2
purity increases, which induces an increase in the energy requirement. Moreover, for a
Figure 14.2(A) Parameters for a single-stage membrane process; (B) single-stage membrane module.
396 Chapter 14
given pressure ratio, the higher the membrane selectivity, the higher the permeate purity.
Also, as reported by Merkel et al. (2010) and Bounaceur et al. (2006), at low pressure
ratios (high driving force), the pressure ratio limitation is reduced and the role of
membrane selectivity becomes significant.
For a given target purity, the pressure ratio depends strongly on the CO2 composition in
the feed. In particular, it decreases with increasing CO2 composition. As a consequence,
when low CO2 composition has to be treated and when high CO2 purity is desired, the
membrane selectivity plays a key role and the energy requirement increases (Belaissaoui
et al., 2012a). As an example, for a target CO2 purity of 95% and an inlet CO2
composition of 15%, the ideal selectivity necessary to attain the target is 200 (Zhao et al.,
2012). Nevertheless, owing to the trade-off between the membrane permeability and
selectivity, the selectivity of the state-of-the-art commercial polymeric membrane is not
above 60 (Zhao et al., 2009). Consequently, it is impossible to reach the required CO2
purity using a single-stage membrane, and the use of a multistage process became
necessary. However, it should be noted that the possibility of achieving high selectivity
with nonpolymeric membranes (Tables 14.3e14.5) could be attractive because it offers the
possibility to theoretically use a single stage unit for coal-fired power plants.
5.1.2 Compression Strategy and Energy Requirement
The driving force, and consequently the pressure ratio through the membrane, can be
obtained by choosing two different configurations: feed compression (Fig. 14.3); vacuum
or sweep gas on the permeate side (Fig. 14.4).
The feed compression strategy is most often selected for gas separations. However, for
carbon capture, it leads to a huge energy requirement due to the compression of the total
feed flow rate (Merkel et al., 2010; Bounaceur et al., 2006). The vacuum pumping strategy
is recommended when a minimal energy requirement is necessary. In this case, the energy
requirement will be in principle lower than the direct compression strategy because a
smaller flow rate has to be pumped. However, this option has drawbacks such as the
energy efficiency of the vacuum pumps can be much lower than compressors and the
vacuum operation can be difficult at large scale. Comparing the two options, it is worth
noting that the feed compression strategy leads to a notably lower membrane area than
that required for the vacuum pumping strategy. This analysis shows that there is a
compromise between the energy requirement and membrane surface area, which means
that an optimum low cost/high CO2 recovery exists for each option.
5.2 Multistage Membrane
The single-stage system cannot provide the desired product with both high CO2 recovery
and purity. This is because the separation process is constrained on one hand by the low
Design Considerations for Postcombustion CO2 Capture 397
CO2 partial pressure difference and on the other hand by the trade-off relationship between
CO2 recovery and CO2 purity (Zhao et al., 2008; Robeson, 1991). Therefore, multistage or
cascade membrane separation becomes a viable option, where a combination of a
membrane containing multiple stages, in parallel or in series to reach higher qualities of
permeate, may be considered. Unfortunately, such arrangements result in both higher
capital and operating costs due to high membrane surface area and high compression
costs, respectively. In such scenarios, membranes seem to not be the best available
technology, and other separation technologies might be competitive. However, the process
synthesis, configuration, and design will play a key role in the success of the membrane
system.
5.2.1 Cascade Membrane System
The first two-stage system for carbon capture was presented for the first time by Pfefferle
(1960), and the system comprised a two-stage membrane with permeate recycling to reach
a high-purity permeate. Two decades later, Kakuta et al. (1978) and Ozaki et al. (1978)
introduced a cascade membrane system for a binary gas mixture separation, and later
Gruzdev et al. (1984) proposed the cascade system for a multicomponent gas mixture.
The cascade model shown in Fig. 14.5 represents the most general multistage membrane
design. The design idea came from a multistage operation such as a distillation or
extraction system (Treybal, 1955). The cascade model comprises both the upstream and
downstream. The first stream strips the remaining traces of the gas of interest to desired
values, whereas the second one enriches the permeate to higher purities of the gas
of interest. However, in many processes only one of the two streams is required.
Figure 14.3Single stage with feed compression configuration.
Figure 14.4Single stage with vacuum configuration.
398 Chapter 14
For example, in the oxygen separation process from air, the upstream is the only stream
required, whereas in the natural gas sweetening, both streams are necessary.
However, it is well known that the most technoeconomically optimal configuration is
represented by the two- or three-stage membrane system (Ozaki et al., 1978; Pettersen and
Lien, 1995), except in case of very low feed concentrations (Li et al., 1990) or low-
efficiency membranes (Avgidou et al., 2004). Indeed, it has been shown that the
introduction of more stages slightly decreases the membrane surface area and compression
energy while subsequently increasing the number of compressors, thereby neutralizing that
benefit (Pettersen and Lien, 1995).
5.2.2 Two- and Three-Stage Membrane Systems
There have been a number of studies that have focused on the optimal configurations of
two- and three-stage membrane systems. Regarding the two-stage systems, Kao et al.
(1989) compared two different configurations: the continuous column membrane or CMC
(Fig. 14.6) and the two strippers in series permeator system, TSSP (Fig. 14.7). They
reported that TSSP shows better performance compared with the CMC configuration
except if the aim is to reduce the membrane area or to have high-purity permeate.
Figure 14.5Schematic of cascade membrane system with recycle.
Figure 14.6Two stage with continuous column membrane configuration.
Design Considerations for Postcombustion CO2 Capture 399
Qiu et al. (1989) have obtained similar results affirming that TSSP is the best
configuration if the purpose is to reach a high-quality retentate, whereas in the case of a
high-quality permeate, CMC is more efficient.
Bhide and Stern (1993) investigated the minimum cost for different one-, two-, and three-
stage configurations. They found that the best configuration corresponds to the three-stage
system with a single permeation stage in a series with a two-stage permeation cascade
with recycle (Fig. 14.8).
Pettersen and Lien (1995) analyzed the intrinsic behavior of different single-stage and
multistage permeator systems. They found that the upstream section of the cascade
(stripping) is the best choice if the aim is to have a retentate stream with the minimum
concentration of the gas of interest, whereas the downstream section (enriching) is chosen
in the case of a high-purity permeate product. Datta and Sen (2006) evaluated several
configurations and conveyed that the best configuration highly depends on the feed quality,
separation purposes, and market prices.
In summary, it is clear that the selection of the multistage design depends on the
separation strategy, which is influenced by the economical input. Specifically, when the
gas of interest is in the retentate side and, its partial loss with the permeation is not
Figure 14.7Two stage with two strippers in series permeator system.
Figure 14.8Three-stage system with single-permeation stage in series with two-stage permeation.
400 Chapter 14
economically significant, then the stripping option is simply used. In this case, the design
consists of a two-stage or three-stage membrane system as shown in Figs. 14.7 and
Fig. 14.9, respectively.
Conversely, when the aim is a high-purity permeate, then the enriching option will be
chosen and the design would be the two- or three-stage membrane system shown in
Fig. 14.10.
However, there are situations where high-quality of both retentate and permeate is desired.
In this case, a combined design of Figs. 14.7, 14.9, and 14.10 can be used. According to
Seader and Henley (2006), the best approach in designing cascade systems is to select
parameters in a way that the composition of the recycled permeate to any stage i is similar
to that of the feed entering the same stage. In recent years, there have been numerous
efforts to develop the best design for the cascade membrane system, the so-called
“superstructures” for membrane process synthesis (Agrawal, 1996; Qi and Henson, 2000;
Uppaluri et al., 2004; Saif et al., 2009; Alshehri et al., 2013; Gassner and Marechal,
2010). The first study in this field was made by Vandersluijs et al. (1992) who investigated
the qualities of single-stage and two-stage cascade membrane systems for postcombustion
capture by using membrane modeling with the assumption of binary CO2/N2 flue gas.
They found that for high-purity CO2 product (>80%), the two-stage system could perform
Figure 14.9Three-stage stripping system.
Figure 14.10Two- and three-stage enriching system.
Design Considerations for Postcombustion CO2 Capture 401
remarkably better than the single-stage process. Analogous results were reported by
Carapellucci and Milazzo (2003) who pointed out that the best option for enriching the
CO2 stream is the two-stage design while the addition of the third stage increases the
complexity of the process without particularly improving the CO2 purity. Ho et al. (2008)
studied the single-stage and two-stage cascades with and without retentate recycle. In
addition, they investigated two different configurations: feed compression and vacuum.
They reported that the two-stage system operated under vacuum and with the recycle
shows the best performance in terms of CO2 purity. However, they found that the vacuum
strategy requires larger membrane surface area but could save 35% of the capture cost.
Another membrane strategy for carbon capture is the design of a two-stage, two-step
membrane system with CO2 recycling. In comparison with the two-stage design, the
retentate stream exiting the first stage is sent to a second stage where a sweep gas is used
in a countercurrent flow configuration to further remove CO2. Combustion air is used as a
sweep gas, which carries the permeated CO2 back to the boiler along with the feed air.
The retentate stream is vented while the permeated CO2 product is compressed for
transport and storage. Merkel et al. (2010) investigated the two-stage membrane system
with and without sweep gas. For their case study, they studied a 600-MW power plant
with 90% CO2 capture using membrane technology, and they reported that the membrane
area needed to decrease from 3.0 to 1.3 million square meters and the power from 145 to
97 MW by adopting the sweep gas technology. Alshehri et al. (2013) developed a
superstructure considering n-stage membranes to find the optimal configuration for a 300-
MW coal-fired power plant. Specifically, in their model they considered a multicomponent
gas model, and they solved an objective function that minimized the costs associated with
operating and capital expenses. The model was able to identify two best configurations
depending on the CO2/N2 selectivity. In particular, if the membrane had a CO2/N2
selectivity of 100, then the two-stage membrane system was the best, whereas for a
selectivity of 50, the three-stage membrane system showed the best performance.
5.3 Hybrid Membrane Design
The development of CO2 capture systems has principally focused on the study of a single
technology. Only few studies have investigated a hybrid capture system by combining
multiple separation technologies (Yuan et al., 2017). For example, Membrane Technology
and Research, Inc. (MTR) and the University of Texas at Austin (UT Austin) developed a
hybrid membrane absorption capture technology, consisting of the MTR Polaris membrane
contactor combined with UT Austin’s piperazine advanced flash stripper capture
technology (Freeman et al., 2014). They designed two different configurations, where the
chemical absorption and the membrane are in series and in parallel, respectively. In the
first configuration, the chemical adsorption unit is followed by the membrane system and
402 Chapter 14
the total CO2 removal reaches 90%. In the second arrangement, the flue gas stream is split
and directed to the absorption column and membrane system, with the benefit of having
only half of the absorber size. It can be concluded that in the series arrangement the
energy required for solvent regeneration is less and in the parallel configuration the capital
costs decrease compared with a conventional chemical absorption process. Zhao et al.
(2014) and Belaissaoui et al. (2012) investigated via modeling analysis the hybrid process
consisting of the cryogenic and membrane technologies. In both studies, the process
arrangement is in series where the membrane is installed before the cryogenic unit to
concentrate CO2. However, the main difference between the two studies is the specific
configurations of the cryogenic unit. Specifically, 3 GJ/ton of CO2 are consumed by the
process simulated by Belaissaoui et al. (2012) with CO2 capture above 85% and CO2
purity higher than 89%, whereas the hybrid process of Zhao et al. (2014) possesses lower
efficiency loss than amine absorption and cascade membrane system when the CO2
separation is less than 90%. By considering these few studies, the hybrid system appears
to be more energy saving and economical. This design can be a possible future direction
for advanced carbon capture technology, although there are not enough data to prove that
the hybrid membrane is truly feasible.
6. Cost Consideration and Membrane System Design
Several technoeconomic analyses have been carried out that evaluate the feasibility of
membrane systems to remove CO2 from flue gases and improve the viability of membrane
technology for carbon capture. One of the first technoeconomic studies was made by
Vandersluijs et al. (1992), who analyzed the technical feasibility and mitigation costs of
polymeric membranes for carbon capture. They used a model for cross-flow permeation to
establish the CO2 reduction costs that depend on the separation targets. Specifically, for
CO2 recovery of 75% with purity of 50%, the minimum possible cost was estimated to be
$48=tCO2�avoided. By increasing the recovery and purity at 90% and 95%, respectively, the
cost increases up to $71=tCO2�avoided. The authors report that in order for the membrane to
become economically competitive, it should show a CO2/N2 selectivity higher than 200 in
addition to a high permeability. The selectivity value was cited by other membrane studies
(Aresta, 2003; Favre, 2007; Feron et al., 1992; Wolsky et al., 1994).
Kazama et al. (2004) performed an economic analysis to evaluate the cardo polyimide
hollow fiber membrane, which they developed. The membrane showed a high CO2
permeance of 1000 GPUs and CO2/N2 selectivity of 40. They reported that the membranes
can become economically advantageous and present an alternative to the existing amine-
based capture systems if the CO2 concentration is around 25% or more. Matsumiya et al.
(2005) evaluated the energy consumption of a novel ultrafiltration hollow fiber module for
CO2 separation from flue gas and studied the effects of the permeate-side pressure,
Design Considerations for Postcombustion CO2 Capture 403
temperature, and the inner diameter of the hollow fiber membranes. Regarding the latter
parameter, the author reported that the energy consumption was in the range of
0.072 kWh/kg-CO2 (0.259 GJ/tonne-CO2) to 0.211 kWh/kg-CO2 (0.796 GJ/tonne-CO2)
when the hollow fiber inner diameter varied from 1.4 to 0.8 mm. In addition, they studied
two different configurations: feed compression and vacuum. They found that by using a
vacuum, the energy required to create a given driving force is less than the one required
by feed compression. A similar result was reported by Zhai and Rubin (2013) by
considering a two-stage membrane system.
Ho et al. (2006) compared the viability of a single-stage membrane process for
postcombustion carbon capture with respect to the amine-based system, and they studied
the effects of membrane characteristics, operating parameters, and system design on
capture costs. In particular, they considered three membranes: poly(phenylene oxide)
(PPO), polyimide (PI), and PEO. The total capture cost was in the range of US$55 to
61=tCO2�avoided. Their study confirmed that the membrane cannot economically compete
with the amine process. In another study the same authors, Ho et al. (2008) compared the
feed compression and the vacuum approaches. They found that the vacuum strategy
required relatively high membrane area, although it could realize 35% less capture cost
per tonne of CO2 avoided.
Merkel et al. (2010) synthesized a new membrane, which shows higher permeance than
the commercial CO2 membrane. In their study, they reported that the enhancement of the
CO2 permeance plays a more important role than the CO2/N2 selectivity to reduce the
overall cost. In a recent study, Zhai and Rubin (2013) studied the performance and the
costs of single- and multistage membrane configurations. The latter have allowed them to
reach high recovery and purity, i.e., 90% and 95%, respectively. In addition, they found
that the multistage membrane can be competitive with the amine-based capture process.
Maas et al. (2016) made an energetic and economic analysis for a membrane-based
separation process for carbon capture, and they found that the cascade membrane system
design achieves the lowest energy consumption. From their research it emerges that the
cost of CO2 allowances has to exceed $44=tCO2to make membrane separation technology
economically advantageous. Table 14.7 shows some energetic and economic estimates of
membrane-based processes and some of the results are compared with chemical
adsorption. It can be seen that a membrane-based separation process does not have
apparent advantages with respect to the chemical absorption technology (Table 14.8), in
terms of energy and cost at 90% CO2 recovery. Membrane technology is less competitive
than initially expected because of the large membrane surface area and mechanical work
necessary to do the CO2 separation.
404 Chapter 14
Table 14.7: Energetic and Economic Evaluations of Membrane-Based Separation Process
Output of
Power Plant
(MW) T (�C)Permeance
(Nm3/m2 h bar)
CO2
Recovery (%)
Membrane
Area (Mm2)
FirsteSecond
CO2
Avoidance
Cost ($/tCO2)
CO2 Capture
Cost ($/tCO2)
CO2 of
Electricity
($/MWh) References
600 30 0.5 50 6.62e0.24 Zhao et al.(2010)70 13.92e0.34
3 70 2.44 36450 30 1000 (gpu) 90 85a 49a 125a Zhai and
Rubin(2013)
55b 36b 105b
600 25 3 0.40e0.07 Maaset al.(2016)
30 4.3 90 0.29e0.04 53 10750 5 0.24e0.03
aWithout sweep gas.bWith air as sweep gas.
Design
Considerations
forPostcom
bustionCO
2Capture
405
7. Conclusion
The application of membrane separations for postcombustion carbon capture has attracted
attention in recent years. Significant improvements have been made in the development of
membrane materials, membrane performance, and process design. The research on
polymeric membranes for carbon capture is addressed toward the chemical and physical
modification of the membrane to greatly enhance the separation performance. Specifically,
agentsdorganic or inorganicdare added into the matrix of the membrane and, currently,
the FTMs, which incorporate a carrier molecule, seem to be promising for carbon capture.
Selectivity and permeability are the key factors for a good membrane. In addition, the
membrane must exhibit chemical and mechanical compatibility with the process
environment, stability, long life time, easiness to fabrication and packaging, and resistance
to high pressures. However, most of the present studies on CO2 capture membrane
materials are focused on improving the performance in terms of selectivity and
permeability without paying attention to other important requirements, i.e., the impacts of
minor gas components such as water vapor, SOx, NOx, O2. Indeed, the membrane use at
the industrial level might not be possible without analyzing these critical technical and
operational issues in various perspectives. Therefore, despite numerous efforts and
remarkable improvements in the performances of membrane materials, the best application
and role of membrane units remain still unclear.
Regarding the design of membrane, it can be concluded that the single-stage membrane
configuration is not a feasible solution for carbon capture because of the low CO2 content
of flue gas, even for membranes with high permselectivities. In addition, it has been shown
in several studies that the vacuum configuration has a positive impact in reducing the
system energy penalty. Multistage or hybrid systems offer the most promising solutions for
the use of membrane systems for carbon capture, although these configurations are
unexplored up to now. Only few studies have used the membrane-based process to treat
realistic flue gas compositions, obtaining promising experimental results (Merkel et al.,
2010; Hagg et al., 2012; Sandru et al., 2012).
Table 14.8: Energetic and Economic Evaluations of Chemical Absorption Process Using MEA
Output
of Power
Plant (MW)
CO2
Recovery
(%)
CO2
Avoidance
Cost ($/tCO2)
CO2 Capture
Cost ($/tCO2)
CO2 of
Electricity
($/MWh) References
600 90 e 43 66 Abu-Zahra et al.(2007a,b)
450 90 62 93 73 MassoodRamezan (2007)
406 Chapter 14
In summary, the priority of the research has to be addressed to support (1) design studies
for multistage and/or hybrid systems, (2) membrane material, and (3) economic analysis.
However, a deep and complete analysis is needed to help investigate trade-offs between
performance and cost objectives and recognize the most promising system design and
targets of material properties for competitive membrane capture technologies.
List of Acronyms
CCS CO2 capture and storageCMC Continuous column membraneFSCMs Fixed-site-carrier membranesFTMs Facilitated transport membranesLMs Liquid membranesMMM Mixed matrix membraneMOFs Metal organic frameworksMTR Membrane Technology and Research, Inc.PEO Poly(ethylene-oxide)SSF Selective surface flowTSSP Two strippers in series permeator system
List of Symbols
R Capture ratioq Stage cuty CO2 purity corresponding to mole fraction of CO2 in the permeatexin Mole fraction of CO2 in the feedJ Driving forcepf Feed pressurepp Permeate pressurea Ideal selectivityP Permeability
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