Energy 46 (2012) 431e441

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Energy
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Progress and trends in CO2 capture/separation technologies: A review

Monoj Kumar Mondal*, Hemant Kumar Balsora, Prachi Varshney
Department of Chemical Engineering and Technology, Institute of Technology, Banaras Hindu University, Varanasi 221005, Uttar Pradesh, India

a r t i c l e i n f o a b s t r a c t

Article history: Coal-red thermal power plants are the major source of CO2 emission among fossil fuel power plants. In
Received 8 March 2012 thermal power plants, coal combustion produces ue gas containing a number of gases including
Received in revised form hazardous pollutants, such as CO2, mercury (Hg), sulfur dioxide (SO2), and oxides of nitrogen (NOx).
3 August 2012
Among all, CO2 is the largest contributor to global warming. CO2 capture and separation are therefore
Accepted 5 August 2012
essential to keep the environment safe and secure. The present paper delineates the existing literature to
Available online 28 August 2012
examine the current status of various methods and technologies used for CO2 capture and separation
from thermal power plant ue gas. Various emerging technologies like, chemical-looping combustion,
Keywords:
CO2 capture
integrated gasication combined cycle, enzyme based separation, dual-alkali absorption approach,
Separation facilitated transport membrane, hydrate based separations, mixed matrix membrane and, calcium
Combustion looping are also thoroughly discussed.
Various technologies 2012 Elsevier Ltd. All rights reserved.

1. Introduction research issue of global perspectives as more international attention

Increasing CO2 emissions in environment leads to global warm-
ing which is an issue of great concern today. The climate of the earth
is varying continuously due to various factors, viz., change in the
Earths orbit, change in the Suns intensity, change in ocean currents,
volcanic emissions and increase in greenhouse gas (GHG) concen-
trations. The greenhouse effect is the phenomenon where water
vapor, carbon dioxide (CO2), methane and other atmospheric gases
absorb outgoing infrared radiation causing an increase of Earths
temperature [1]. Excessive greenhouse gases in the atmosphere are
responsible for various environmental problems like continuous rise
of water-level in sea, the increasing number of ocean storms, oods,
etc. [2]. Among the GHGs, CO2 is the major contributor for global
warming and it has the greatest adverse impact which accounts
approximately 55% of the observed global warming. CO2 alone is
responsible for about 64% of the enhanced greenhouse effect [3].
According to the prediction of Intergovernmental Panel on Climate
Change (IPCC), by the year 2100, the atmosphere may contain up to
570 ppmv of CO2, causing a rise of mean global temperature of
around 1.9
C and an increase in mean sea level of 3.8 m.
Currently 85% of total world demanded energy is supplied by fossil
fuel thermal power plant including coal, oil and gas. Fossil fuel power
plants account roughly 40% of total CO2 emission and coal-red
power plant is the main contributor among them [4]. The capture
of CO2 from power plant ue gas accounts three quarter of the total
cost of carbon capture and storage. It has become an important
is focused on global warming [5]. To achieve mid to long term CO2
reduction targets, cost effective CO2 capture from fossil fuel power
plant and subsequent sequestration options need to be evaluated
keeping in view of worlds growing demand of energy. There are
several technologies available for CO2 capture such as absorption,
adsorption, gas separation, membrane, cryogenic separation, etc.
This paper briey reviews the existing and emerging technol-
ogies for the separation and capture of CO2 from point source
emissions. The aim of this literature review is to provide a current
understanding of the present development of various capture
technologies, existing technological options and the remaining
development challenges of the main capture technologies.
2. Various options for CO2 capture
Depending upon different plant congurations, CO2 emissions
from thermal power plant ue gas can be reduced by any of the
following methods:
 Pre-combustion capture
 Post-combustion capture
 Oxyfuel combustion
2.1. Pre-combustion capture

* Corresponding author. Tel.: 91 9452196638; fax: 91 5422367098. Pre combustion process is related to the treatment of synthesis
E-mail address: mkmondal13@yahoo.com (M.K. Mondal). gas (syngas) composed principally of CO and hydrogen [6]. Pre-

0360-5442/$ e see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.energy.2012.08.006
432 M.K. Mondal et al. / Energy 46 (2012) 431e441
combustion rate is premised on the production of syngas, removal of
CO2 and combustion of H2 [7]. In some ways it is oxymoron because
CO2 is obviously not normally available for capture prior to
combustion, as CO2 is a product of coal combustion, not a natural
precursor. All types of fossil fuels can be gasied (partially com-
busted, or reformed) with sub stoichiometric amount of oxygen at
elevated pressures typically in the range of 30e70 atm to produce
a syngas predominantly CO and H2. Thereafter steam is added to
syngas and passed through the bed packed with catalysts, onto
which water gas shift reaction takes place that convert CO into CO2.
In water gas shift reaction, the addition of steam and reduction of
temperature actually promote the conversion of CO into CO2 and
increase the yield of H2 [8]. From CO2 and H2 bearing stream, CO2 is
separated and sent to the compression unit and pure H2 is further
used as an input to a combined cycle to produce electricity (Fig. 1).
Another option currently being developed is to use the hydrogen to
power fuel cells with the intent of signicant rising of overall plant
efciency. In future H2 could also be used as transportation fuel [10].
The separation process typically uses a physical solvent such as
rectisol and selexol available at low cost. CO2 is dissolved at higher
pressure and then released as the pressure is reduced. No heat is
required to regenerate the solvent and CO2 can be released at above
atmospheric pressure. The energy requirement for CO2 separation
and compression in pre combustion capture can be in the order of
half of that required for post combustion capture [8]. This process
has a good advantage i.e. utilization of physical solvent which are
available at low cost and require low energy for regeneration [6].
The main disadvantage of pre-combustion capture is that it
requires a chemical plant in front of the turbine. Complicated
chemical processes normally cause extra shut-downs of the plant,
which can result to a lower power output. Other disadvantages are
non-gaseous feed stocks, requirement of the cleaned gas stream
and possible expensive scrubbing for high NOx emission control.
Presence of CO2 at much higher concentrations in syngas makes
CO2 capture less expensive for pre-combustion capture in
comparison with post-combustion capture. Currently, there are few
gasication plants in full-scale operation and capital costs are
higher than pulverized coal-red power plants [10].
2.2. Post combustion capture
Post combustion capture involves removal of CO2 from ue gas,
which comes from the thermal power plant combustion chamber
as shown in Fig. 2. Existing power plants use air for combustion and
generate a ue gas at atmospheric pressure and typically have a CO2
concentration of less than 15%. Thus the thermodynamic driving
force for low CO2 capture from ue gas is low creating a technical
challenge for the development of cost effective advanced capture
processes [6]. The low concentration of CO2 in power-plant ue gas
(13e15% for coal red power plant, 7e8% gas red power plant, etc.
(Table 1)) needs a large volume of gas to be handled, which results
in large equipment sizes and high capital costs. Technologies based
on chemical absorption appear to be best adapted to this
Fig. 1. Principle of pre-combustion CO2 capture [6,9,10].
Fig. 2. Principle of post-combustion CO2 capture [6,9,10].
separation. Other technologies, adsorption, membranes and cryo-
genic, are less suitable for post-combustion capture than pre-
combustion capture, mainly for the following reasons:
 A much lower partial pressure of CO2 in post-combustion
exhaust gases than in syngas originating from a gasier or
a reformer.
 The presence of larger quantities of dusts, impurities such as
SOx and NOx, and non-condensable gases particularly oxygen.
Post combustion capture technology has a higher thermal ef-
ciency for conversion to electricity than pre combustion Integrated
Gasier Combined Cycle (IGCC). It appears likely to give lower total
electricity costs than pre combustion capture for natural gas plants
[4,8]. Separation of CO2 from ue gas stream of post combustion
system is challenging for several reasons. The relatively high
temperature of the ue gases offers a design challenge. Another
challenge is that powerful chemical solvents have to be used for
low concentration of CO2 capture and regeneration of the solvents
to release CO2 will require a large amount of energy.
2.3. Oxy-fuel combustion
Oxy-fuel combustion is a promising technology for capturing of
CO2 from fuel gas or to modify the combustion process so that the
ue gas has a high concentration of CO2 for easy separation. In this
process fuel is burned in combustion chamber in the environment
of pure O2 (>95%) mixed with recycled ue gas (RFG) as pictured in
Fig. 3. In the most frequently proposed version of this concept,
a cryogenic air separation unit is used to supply high purity oxygen.
This high purity oxygen is mixed with RFG prior to combustion or in
the boiler to maintain combustion conditions similar to an air red
conguration. This is necessary because currently available mate-
rials of construction cannot withstand at high temperatures
resulting from coal combustion in pure oxygen. Flue gas stream
from this system contains mainly CO2 and water vapor. The water is
easily removed by condensation, and the remaining CO2 can be
puried relatively at low cost. The CO2 content of the dry ue gas
varies in the range of 70e95% depending upon the fuel, the process
used, the air in leakage, the O2 purity and the excess O2.
Table 1
Typical CO2 compositions in process streams [1,11].
Process CO2 concentration (vol.%)
Power plant ue gas
Coal red boiler 14
Natural gas red boiler 8
Natural gas combined cycle 4
Coaleoxygen combustion >80
Natural gas partial oxidation 40
Blast furnace gas
Before combustion 20
After combustion 27
Cement kiln off-gas 14e33
Oil reneries and petrochemical plant red heater 8
 M.K. Mondal et al. / Energy 46 (2012) 431e441
Fig. 3. Principle of oxyfuel combustion CO2 capture [6,9,10].
As a result of decreased ue gas volume and increased
concentration of CO2, the cost of carbon capture in oxyfuel
combustion is less than other conventional methods but the cost of
air separation and ue gas recirculation signicantly reduces the
economic benet. It uses oxygen instead of air for combustion of
fuel and thus no NOx will form. By utilizing this technology 60e70%
NOx emission is reduced compared to air-red combustion [10]. It
has potential to be operated at high pressure, therefore, less CO2
compression energy is required. Limitations of the oxyfuel
combustion are as follows:
 The auxiliary power consumption of a cryogenic air separation
unit is high and has a major impact on the overall efciency of
the power plant.
 Material of construction to withstand at high temperature is
needed.
 Recycling of ue gases increases the cost of the process.
3. Existing capture technologies
Several technologies are available to capture CO2 from fossil fuel
power plant. These include mainly physical and chemical absorp-
tion, adsorption, cryogenic and membrane processes.
3.1. Absorption process
Chemical or physical absorption processes are widely used in
the petroleum, natural gas and coal red power plants as well as
chemical industries for separation of CO2. It is based on the reaction
between the CO2 and chemical solvent such as aqueous solution of
mono-, di- and tri-amine, di-isopropanol amine, etc. [5,9]. In this
method absorber and regenerator are working continuously. Flue
gas stream containing CO2 is introduced at the bottom of the
absorber. Absorbent is introduced from top of the column that leads
counter current contact between ue gas and solvent and a selec-
tive absorption of CO2 takes place. Then CO2 rich stream is fed to the
regenerator, where desorption of CO2 occurs and regenerated
solvent is recycled for further use, desorbed CO2 is compressed and
sent to storage. Available literature reveals that the chemical
absorption holds good result in terms of removal efciency and can
be used for low concentration ue gases [12]. Chemical absorbents
such as monoethanol amine (MEA), diethanol amine (DEA), N-
methyldiethanolamine (MDEA), and di-2-propanolamine (DIPA)
are commonly used [13,14]. Other absorbents such as, diglycol-
amine (DGA), 2-(2-aminoethylamino) ethanol (AEE), 2-amino 2-
methyl 1-propanol (AMP), N-2-aminoethyl 1,3-propanediamine
(AEPDNH2), triethanol amine (TEA), triethylene tetra amine (TETA),
piperazine (PZ), glucosamine (GA), NaOH, NH3, K2CO3, KOH,
Na2CO3, etc. were also tested for CO2 removal, however their
individual limitations make them less suitable for large scale
industrial CO2 removal. For the concept of blending, in which
a solution of two or more solvents in varying concentrations are
mixed to produce absorbents with excellent absorption character-
istics as well as savings in energy requirements [15e19].
433
3.1.1. Absorption of CO2
Recently blends of alkanolamines are mostly preferred for
absorption of CO2. This process involves passing of gaseous CO2
through an amine solution until equilibrium is reached. The reac-
tion of CO2 with aqueous amine can theoretically be represented in
three individual steps as shown in Fig. 4 [5,20].
3.1.1.1. Dissolution of the gaseous CO2. Initially, diffusion of CO2
occurs from gas to liquid phase. This step is a purely physical process
and must occur prior to further reaction of CO2 in the liquid phase.
Very small quantity of CO2 remains in the form of aqueous CO2, and
this step is followed by bicarbonate and carbamate formation.
3.1.1.2. Formation of bicarbonate and carbamate. In this step, the
amine behaves simply as a base and reacts with carbonic acid
formed in the previous step with a CO2 to amine ratio of unity.
Obviously, the bicarbonate also exists in equilibrium with
carbonate and carbonic acid. The position of this equilibrium is
governed by pH and CO2 to amine ratio. The bicarbonate predom-
inates under absorber condition and this pathway is referred to as
the acid pathway [20].
Carbamate formation occurs at a CO2 to amine ratio of 0.5 which
means one molecule of CO2 is absorbed by every two molecules of
amine. One amine molecule is required to form carbamate, while
the second molecule acts as a base to react with the proton
released. This low CO2 to amine ratio results in a lower efciency
and lower CO2 capacity than that for the acid pathway. In addition,
carbamate formation is associated with a high enthalpy of reaction.
Reversing this reaction in the stripper consequently requires the
addition of large amount of energy, making the entire process
relatively energy intensive.
3.1.2. Reaction mechanism
An overview on the reaction mechanisms between CO2 and
alkanolamines in both aqueous and non aqueous solutions was
available in literature [21]. Danckwerts and McNeil proposed the
mechanism of reaction between CO2 and primary and secondary
alkanolamines in two-steps as given below [22]:
Step 1: Carbamate formation (Rate determining step)
CO2 R1 R2 NH4R1 R2 N COO H (1)
Step 2: Protonated alkanolamine formation (Instantaneous
reaction)
R1 R2 NH H 4R1 R2 NH
2 (2)
A second-order overall reaction is as follows:
CO2 2R1 R2 NH4R1 R2 NCOO R1 R2 NH
2 (3)
Fig. 4. CO2 absorption phenomena [20].
434 M.K. Mondal et al. / Energy 46 (2012) 431e441
A lot of work has been carried out on the reaction between CO2
and alkanolamines in aqueous solutions [23e28]. However, only for
MEA, as a primary amine, the overall reaction order and the value of
the kinetic constant are in accordance with the mechanism of Rxn.
(3). For other primary and secondary alkanolamines, the overall
reaction orders were found to be varying between 2 and 3, for both
aqueous and non aqueous solutions. For example, the overall reac-
tion order for DEA, as a secondary alkanolamine, was found to be 3
and some authors reported between 2 and 3. Therefore, the reaction
mechanism between CO2 and alkanolamines needs to be modied.
3.1.2.1. Zwitterion mechanism. This reaction mechanism was rst
proposed by Caplow [29] and reintroduced by Danckwerts [30] in
which the reaction between CO2 and alkanolamines results in the
formation of a zwitterion intermediate followed by the removal of
a proton by a base B:
CO2 R1 R2 NH4R1 R2 NH COO (4)
R1 R2 NH COO B4R1 R2 NCOO BH (5)
This mechanism comprises of formation of the CO2-amine zwit-
terion (Rxn. (4)) followed by base-catalyzed deprotonation of this
zwitterion (Rxn. (5)). Any base present in solution will contribute to
the deprotonation of the zwitterion. Hence, in an aqueous solution
of a single primary or secondary amine, the zwitterion deproto-
nation depends on free amines, H2O, and OH concentrations. By
using the pseudo-steady-state assumption for the zwitterions
concentration, the overall forward reaction rate can be written as:
kz2 CO2 R1 R2 NH
rCO2 (6)
k
1 P 1
kb B
where kz2 and k1 are the forward and reverse rate constants where
superscript z denotes zwitterion and kb [B] is the contribution to the
zwitterion deprotonation by all bases present in the solution.
3.1.2.2. Single-step-termolecular mechanism. Single-step-termo-
lecular mechanism was proposed by Crooks and Donnellan [31] in
which, amine bonding to CO2 and proton-transfer takes place
simultaneously, and was reviewed by da Silva and Svendsen [32].
The reaction uses the accepted mechanism proposed by Danck-
werts [30] in which the zwitterion intermediate is formed by
making the assumption that the reaction proceeds through
a loosely bound encounter complex as the initial product. The
forward reaction rate for this mechanism is
rCO2 kobs CO2  (7)
where,
kobs kT2 R1 R2 NH
h i

kamine R1 R2 NH kH2 O H2 O k
OH OH R1 R2 NH (8)
Chemical absorption is the most mature and reliable technology
for post combustion CO2 removal from thermal power plant.
Among all types of amines, MEA has received much attention,
mainly due to its high rate of reaction, low solvent cost, and easy
regeneration [33e37]. MEA however has several drawbacks too,
including low CO2 loading capacity (0.5 mol CO2/mol amine), high
equipment corrosion rate, and amine degradation by SO2, NO2, HCl,
HF, and oxygen in ue gas which includes a high absorbent makeup
rate, high energy consumption during high temperature absorbent
regeneration [38e41]. Primary and secondary amines react rapidly
with CO2 to form carbamate with stoichiometric loading of 0.5 mol
CO2/mol amine. For tertiary amine, MDEA, loading value
approaches to 1.0 mol CO2/mol amine as it does not form carba-
mates. However its absorption rate is low as compared to primary
and secondary amines [42]. A commercially attractive alternative
solvent, AMP, which is sterically hindered amine, forms unstable
carbamate ions in its reaction with CO2, leading to higher absorp-
tion capacity. It has good regeneration capability, degradation
resistance, and higher absorption rate than MDEA [5] but its reac-
tion rate is lower than MEA at 40
C [43]. It is therefore used with
other solvents to enhance the absorption performance. A compar-
ative test performed by different authors [44,45] reveals that MEA
is superior to AMP in the CO2 removal efciency but AMP is more
suitable than MEA in CO2 absorption amount. In absorption/
regeneration process, reaction rate constant of blended MEA/AMP
solutions increases and CO2 loading of rich amine decreases with an
increase of MEA contents. On the other hand, with the increase of
AMP contents, CO2 loading has increased. The MEA/AMP blend
showed more satisfactory removal than MDEA/MEA [46].
PZ is the solvent which is used as an activator for CO2 removal
solvents. It is a diamine that acts as a promoter for amine systems to
improve kinetics, such as MDEA/PZ or MEA/PZ blends. The CO2
absorption rate with aqueous PZ is more than double as that of MEA
and volatility at 40
C ranges from 10 to 19 ppm. Thermal degra-
dation is negligible in concentrated PZ solutions up to a tempera-
ture of 150
C [47,48]. Various studies on PZ blend, viz., MDEA/PZ
[49,50], glycine (GLY)/PZ [2], DEA/PZ [42], etc. revealed that CO2
loadings at corresponding partial pressures were higher than
individual solvent without PZ. Thus the blended solvent has shown
good result as compared to single solvent. Literature on blended
solvent is scared and need to more research for understanding the
mechanism of this process.
Amine based CO2 absorption process has several limitations
among these the main focused on regeneration cost of solvent
(roughly 70e80% of total operating cost of the system). Imple-
mentation on this, a new method pH swing has also been proposed.
The principal feature of this process is adding the acid to process
stream just before the regeneration step to lower the pH so that the
regeneration will take place at low temperature and nally the
overall cost of the process will be reduced. The addition of few
weak acids (suberic, pathalic and oxalic acid) was reported for
desorption rate of CO2 and found that the CO2 released much faster
and in much larger quantity [40].
3.2. Adsorption process
Adsorption is a process for removal of one or more components
of a mixture with the help of a solid surface. The adsorption
processes are based on signicant intermolecular forces between
gases (including CO2) and the surfaces of certain solid materials
(such as molecular sieves and activated carbon). Depending on the
temperature, partial pressure, surface force and adsorbent pore
sizes, single or multiple layers of gases can be adsorbed [51].
In CO2 capture by adsorption technology, a packed column is
mainly lled by spherical adsorbent and CO2 bearing stream is passed
through the column. CO2 is attracted towards the adsorbent and
adheres on the surface of adsorbent. After achieving the equilibrium,
desorption takes place to get CO2 in pure form and regenerated
adsorbent can be utilized for further cycle. This process can be carried
out in different manners as discussed in the preceding section.
3.2.1. Pressure swing adsorption (PSA)
In PSA, the gas mixture ows through bed at elevated pressure
and low temperature until the adsorption of CO2 approaches to
 M.K. Mondal et al. / Energy 46 (2012) 431e441
equilibrium conditions at the exit of bed [51]. The beds are then
regenerated by stopping the ow of the feed mixture, reducing the
pressure and elutriating the adsorbed constituents with a gas
having low adsorptivity. Once regenerated, the beds are ready for
another adsorption cycle.
3.2.2. Temperature swing adsorption (TSA)
Alternative procedure is temperature swing adsorption in which
ue gas is passed over bed. Selective adsorption takes places on the
adsorbent until to reach equilibrium. The desorption of gas can be
done at elevated temperature by supplying the additional heat.
Additional requirement of heat in TSA makes it costlier than PSA [51].
3.2.3. Electrical swing adsorption (ESA)
In this method low voltage electric current is passed through the
adsorbent [52]. The ESA has the potential to reduce the cost of CO2
capture compared with other conventional adsorption technolo-
gies as reported in literature [53,54]. Therefore, ESA can be believed
to be able to make the process of CO2 capture more cost-effective
than TSA and PSA.
3.3. Cryogenic process
Cryogenic separation method is widely used commercially for
separation of CO2 from streams having high CO2 concentrations
(typically more than 50%). It is not normally used for dilute CO2
streams such as ue gas from coal/natural gas red boilers as the
amount of energy required for refrigeration is uneconomical for the
plant [55].
This process involves compression and cooling of the gas
mixtures in several stages to induce phase changes of CO2 in ue
gases and invariably other components present in the mixture.
Depending on the operating conditions the CO2 can arise as a solid
or liquid together with other components from which it can be
distilled. Water vapor in the CO2 feed mixture leads to the potential
formation of solid CO2 clathrates and ice, and can result in major
plugging problems [51]. The main advantage of cryogenic CO2
capture is that no chemical absorbent is required and the process
can operate at atmospheric pressure. Moreover it directly produces
liquid CO2, which is needed for economical transport, such as
transport in ship and pipeline [55].
The main disadvantage of this system is that the water content in
the feed stream to the cooling units should be minimal in order to
prevent the plugging by ice or unacceptably high rise in pressure
drop during operation. Therefore, several costly steps are required to
remove all water traces from the ue gas. In addition the increasing
layer of solid CO2 onto heat exchanger surfaces during the capture
cycle will adversely affect the heat transfer which in turn reduces
the process efciency [56]. The most promising application for
cryogenic is expected to remove CO2 from high pressure gases, such
as in pre-combustion capture processes or oxyfuel combustion in
which input gas contains high concentration of CO2 [55].
3.4. Membrane technology
A relatively novel capture concept is the use of selective
membranes to separate certain components from a gas stream,
which can be CO2 from ue gas (post-combustion system), CO2
from natural gas (natural gas processing), and CO2 from hydrogen
(pre-combustion systems) or oxygen from nitrogen (oxyfuel
combustion system). Membranes are semi-permeable barriers able
to separate substances by various mechanisms (solution/diffusion,
adsorption/diffusion, molecular sieve and ionic transport). These
are available in different material types, which can be either
organic (polymeric) or inorganic (carbon, zeolite, ceramic or
435
metallic) and can be either porous or non-porous. With regards to
CO2 capture, the membrane processes are classied into two types:
 Gas separation membrane
 Gas absorption membrane
3.4.1. Gas separation membrane
Fig. 5 shows gas separation membranes which operate on the
principle of preferential permeation of mixture constituents through
the pores of the membrane causing one component diffuses through
the membrane faster than the others. The main design and opera-
tional parameter of membrane are selectivity and permeability. In
this process, the gas stream containing CO2 is introduced at elevated
pressure into the membrane separator consisting typically a large
number of hollow cylindrical membranes arranged in parallel. CO2
selectively permeates through membrane and is recovered at
reduced pressure on the shell side of the separator [51,58].
Various types of gas separation membranes including ceramic,
polymeric and combination of both materials or mixed matrix
membranes are available [55]. The separation of the gases is relied
on solubility or diffusivity of gas molecules in the membrane and
difference in partial pressure is driving force for gas separation.
3.4.2. Gas absorption membrane
Gas absorption membrane consists of micro porous solid
membrane which is used as contacting device between the gas and
liquid ow as shown in Fig. 6. From Fig. 6, it is evident that CO2 to be
separated from ue gas is diffused through membrane, and then is
recovered by liquid absorbent by absorption. This process gives
higher removal rate than gas separation membrane due to high
driving force at any instant. The advent of independent control of
gas and liquid ow results minimum entrainment, ooding,
channeling and foaming. The equipment used also tends to be more
compact than conventional membrane separator [51].
Membrane processes are highly capable of maintaining product
purity even though the capacity is reduced down to 10% of the
initial design value. It can be done by either reducing feed pressure,
increasing permeate pressure, or by isolating modules from the
system. Moreover it is a low cost process for separating gases and
extremely reliable with respect to the on-stream factor. The
membrane separation process is continuous and has few control
Fig. 5. Principle of gas separation membrane [57].
436 M.K. Mondal et al. / Energy 46 (2012) 431e441
Fig. 6. Principle of gas absorption membrane [57].
components which can cause a shutdown. The response time of
membrane systems is essentially instantaneous, and corrective
action has immediate results. The start-up time required by the
process is extremely short. There are number of losses associated
with the CO2 capture from ue gases, which limit the use of
membrane. The membrane systems can be considered highly
exible only when the CO2 concentration is higher than 20%. For
CO2 concentration lower than 20% the membrane system offer
a very low exibility [58]. A further reduction in CO2 concentration,
in fact, produces a reduction of the driving force with a consequent
decrease in CO2 recovery and in product purity. However, the main
problem related to limited use of membrane technology is lower
concentration of CO2 in ue gases. For high temperature applica-
tion, membrane technology needs additional pre-treatment (cool-
ing for reduced temperature) [52,58].
4. Limitations and implementation on existing technologies
4.1. Absorption process
Chemical absorption capture technologies are best suitable for
post combustion. Various solvents are available which have the
tendency to absorb CO2 such as MEA, DEA, and MDEA, K2CO3,
Na2CO3, NaOH, NH3, AMP, etc. Among these MEA provides a good
absorption capacity, but regeneration is lower than AMP. Recently
blended solvents provide an enhancement in overall efciency than
individual solvent [5]. However, several limitations to absorption
process such as, solvent degradation, corrosion, solvent regenera-
tion efciency, etc affect the efciency of CO2 removal. So much
research is needed in the direction of:
 Improvement of solvents.
 Modication in gaseliquid contacting devices.
 Development of degradation and corrosion inhibiters.
 Development of alternative solvents such as ionic liquids,
blended solvents, etc.
4.2. Adsorption process
Solid adsorbents such as activated carbons, zeolites, meso-
porous silicates, alumina, and metal oxide have been extensively
used for gas separation [59]. Adsorption of CO2 from a gas stream is
a dry process and hence it has no by-product such as wastewater in
conventional absorption process. Moreover it requires low energy
as compared to that of cryogenic and absorption processes. But
there are some limitations that make this process less effective such
as:
 Low selectivity and capacity of available adsorbent for CO2.
 Lower removal efciency as compared to other technologies
such as absorption and cryogenic [5,58].
 Regeneration and reusability of adsorbent.
In view of the above, much attention is required for developing
the new adsorbents or modication on surface chemistry of exist-
ing adsorbents so that the adsorbents can operate at higher
temperatures in the presence of steam with increased capacity and
improved selectivity. Recently, gas adsorption by activated carbon
bers and carbon ber composites has been identied as a prom-
ising alternative. Lately, structured porous monolith material made
from carbon bers has the ability to selectively adsorb gases due to
their molecular sieving characteristics [59]. Combination of PSA
and TSA such as PTSA (pressure and temperature swing adsorp-
tion), or ESA can be used for CO2 removal. PTSA reduces power
consumption required for separation as compared to PSA system by
11% [55].
4.3. Cryogenic process
Cryogenic process is inherently difcult to apply for CO2 capture,
because mostly CO2 occurs in conjunction with other gases (SOx,
NOx, H2O) which severely interfere with cooling and cause corro-
sion, fouling and plugging [51]. There is a need to remove all trace
water from feed which leads to increase the CO2 capture cost.
Furthermore the phase behavior of CO2 is complex and it easily
leads to the formation of solids which plug equipment and severely
reduce heat transfer rates resulting in the reduction of process
efciency [51,56]. In light of these limitations and high cost of
refrigeration, this process can be used only for special circum-
stances as an adjunct to other processes.
4.4. Membrane process
In membrane technology for CO2 separation, the required
energy per unit mass of CO2 captured is least in the range of
0.5e6 MJ/kg of CO2 as compared to other existing technologies [58].
But low removal efciency and low purity of CO2 make this process
ineffective. Also its feasibility is decreased when concentration of
CO2 in feed stream is below 20% [52,58]. Since, the membrane
cannot usually achieve high degree of separation it cant be opti-
mized for large volume of gas separation. So, multiple stages and/or
recycle of one of the streams are necessary and also membranes are
sensitive to sulfur compounds and other traces [52,55]. Thus much
attention is needed in the direction for improving the transport
properties of membrane:
 Development of some alternative membranes.
 Combination of two membrane materials to produce
composite membrane for enhanced removal of gases.
Facilitated transport membrane, mixed matrix membrane etc.
are good enhancement in membrane technology. Also the
membrane process in combination with other existing processes
may increase the overall efciency of the process, e.g. membrane
with cryogenic [60] and membrane with absorption process [52].
 M.K. Mondal et al. / Energy 46 (2012) 431e441
5. Progress in CO2 capture
5.1. Chemical looping combustion (CLC)
A promising technology for fossil fuel combustion uses the
concept of preventing CO2 dilution with ue gases by avoiding the
direct contact between ue and combustion air [61e63]. In this
process oxygen required for combustion of fuel is supplied in the
form of metal oxide as in solid phase. Transition metal oxides such
as nickel, copper, cobalt, iron and manganese are good oxygen
carriers. In CLC process, two interconnected uidized beds are used
as air reactor and fuel reactor, respectively. A gaseous fuel is fed into
the fuel reactor, where it is oxidized by lattice oxygen of metal
oxide, which is circulating between the reactors. Complete
combustion in fuel reactor produces condensable water vapor and
CO2. Therefore, the CO2 formed can be readily recovered by
condensing water vapor, eliminating the need of an additional
energy intensive CO separation process [4,10,52,62]. The water free
CO2 can be sequestrated and used for other applications.
A generalized description of the overall reaction stoichiometry
in the fuel reactor can be written as follows:
2n mMy Ox Cn H2m /2n mMy Ox1 mH2 O nCO2 (9)
Once fuel oxidation completed the reduced metal oxide MyOx1
(or metal) is transported to the air reactor where it is reoxidized
according to the following reaction:
My Ox1 1 2 O2 air/My Ox N2 air excess O2
=
(10)
The outlet gas stream of the air reactor contains nitrogen and
unreacted oxygen. These gases can be released to the atmosphere
with minimum negative environmental impact. This process has
several advantages in comparison with conventional combustion
process. The CLC does not bring any enthalpy gain because the
overall heat generation is equal to the heat of combustion. Its main
advantage, however, resides in the inherent separation of both CO2
and H2O from the ue gases. In addition, CLC also minimizes NOx
formation since the fuel burns in the fuel reactor in an air free
environment and the reduced oxygen carrier is re-oxidized in the air
reactor in the absence of a fuel at comparatively lower temperatures.
5.2. Integrated Gasication Combine Cycle (IGCC)
The IGCC is a very promising power generation technology for
pre combustion process. The gasication system converts coal or
other carbon based feedstock such as petroleum coke, heavy oils,
biomass etc. into synthesis gas (syngas) which consists of hydrogen
and CO [6,9,64]. The syngas with added steam is then sent to a shift
converter where the water gas shift reaction converts CO to CO2
and additional H2. The CO2 is separated from the H2, which is mixed
with steam or nitrogen from air separation unit and sent to
a combustion turbine. The hot exhaust gas from the combustion
turbine goes to a heat recovery steam generator system to produce
steam for the steam turbine that generates additional power and
increases the overall efciency [6]. Gasiers applied for IGCC fueled
with bituminous coal are typically oxygen-blown entrained ow
gasiers operating at pressures between 30 and 70 bar and
temperatures from 1000 to 1500
C [9].
A major bottleneck for large scale commercial application is
relatively high investment costs in comparison to post combustion.
Moreover, IGCC is a technically more complex system than post
combustion, leading to a relatively low availability and poor oper-
ational exibility. In order to increase plant efciency to a level of
85e90%, a spare gasier might be required which will increase total
investment costs [9].
437
5.3. Dual-alkali absorption approach
The Solvay process employs a dual alkali approach with
ammonia as a catalyst to aid the reaction of CO2 with sodium
chloride for the production of sodium carbonate [65]. The reaction
was performed by saturating brine with ammonia, and then with
CO2 [4,52]:
CO2 NaCl NH3 H2 O/NaHCO3 Y NH4 Cl (11)
Product sodium carbonate is obtained by heating sodium
bicarbonate:
2NaHCO3 /Na2 CO3 s H2 O CO2 g (12)
The ammonia is recovered by reacting ammonium chloride with
lime:
2NH4 Cl CaOH2 /2NH3 CaCl2 2H2 O (13)
However, this approach poses several drawbacks when applied
to CO2 capture from ue gas. The use of limestone as source of lime
for the regeneration of ammonia makes the process ineffective
because of the consumption of limestone, production of CO2, and
extensive energy requirement during calcination. In the Solvay
process, for every 2 mol of CO2 captured, 1 mol of CO2 is released
from calcination of limestone. This can be seen from the overall
reactions:
CaCO3 /CaO CO2 (14)
2NaCl 2CO2 CaO H2 O/2NaHCO3 CaCl2 (15)
To overcome the drawbacks of the Solvay process, a new dual
alkali method was developed using MEA to replace ammonia as
primary alkali. The MEA was used as an effective primary alkali
with the following reaction:
CO2 NaCl2 HOCH2 CH2 CH3 NH H2 O)/NaHCO3 Y
HOCH2 CH2 CH3 NH,HCl (16)
The CO2 absorption capacity of methylaminoethanol (MAE) is
greater than that of MEA. The maximum CO2 absorption capacity of
an amine is 0.5 mol CO2/mol amine for carbamate and 1.0 mol CO2/
mol amine for bicarbonate formation. So theoretically, the CO2
absorption capacity of an amine increases with an increase of
bicarbonate in the products. The second step of the dual-alkali
approach involves a secondary alkali to regenerate the rst alkali.
In order to regenerate ammonia, and to make the process effective,
activated carbon (AC) was used in place of limestone to regenerate
ammonia at 25
C, the primary alkali in the Solvay process
according to the following reaction:
NH4 Cl AC/NH3 AC:HCl (17)
The basicity of the AC is responsible for the adsorption of HCl
molecules from NH4Cl solution with the liberation of ammonia.
This group of research does not require any secondary alkali to
regenerate the primary alkali like MAE [52].
6. Emerging technologies
6.1. Enzyme based separation
In this process, CO2 is removed from gas mixture based upon
naturally occurring reactions of CO2 in living organism (enzyme).
Enzyme mainly proteins catalyzes the chemical reaction. The
process using carbonic anhydrase (CA) in a hollow ber with liquid
438 M.K. Mondal et al. / Energy 46 (2012) 431e441
membrane has demonstrated the potential for 90% CO2 capture
followed by regeneration at ambient conditions in laboratory-scale
operation. The CA process has been shown a very low heat of
absorption that reduces the energy penalty typically associated
with absorption processes.
The rate of CO2 dissolution in water is limited by aqueous CO2
hydration and CO2 carrying capacity is limited by buffering
capacity. Addition of CA enzyme to solution enhances the CO2
dissolution and forms carbonic acid. CA has the ability to catalyze
the hydration of 600,000 molecules of CO2 per molecule of CA per
second compared to a theoretical maximum rate of 1,400,000. This
fast turnover rate minimizes the amount of enzyme required [6].
Finally by pressure-swing desorption, solid carbonate precipitation,
chemical treatment, or some other means, the process must
incorporate a mechanism by which CO2 can be released from the
system as a concentrated stream [66].
The idea behind this process is to use immobilized enzyme at
the gas/liquid interface to increase the mass transfer and separation
of CO2 from ue gas. Technical challenges of this technology include
membrane boundary layers, pore wetting, surface fouling loss of
enzyme activity, long-term operation, and scale-up of the process.
Small amount of CA requirement and life of the CA around 6
months and also high catalyzed ability indicate that it will be
a great improvement in cost and performance of CO2 capture in
large scale power plants [6,65]. So, this can be an alternative for
existing technology for CO2 capture.
6.2. Facilitated transport membrane (FTM)
A facilitated transport membrane for CO2 separation was
patented by Hagg [67]. It has received a lot of attention in gas
separation because it offers higher selectivity and larger ux.
Higher selectivity in FTM is achieved by incorporating a carrier
agent into membrane such as cross linked polyvinylamine, which
reacts reversibly with the penetrating species [4,58]. The perme-
ating species dissolves in the up stream portion of the membrane
and reacts with the carrier agent inside the membrane to form
complex. This complex diffuses across and releases permeate on
the downstream side of the membrane, while the carrier agent is
simultaneously recovered and diffuses back to the feed side. In case
of CO2 separation, a xed carrier helps so that the CO2 molecules in
combination with moisture to form HCO 3 , which is then quickly
and selectively transported through the membrane. This tech-
nology is effective and eco-friendly (as the membranes are based
on nanostructure material) and can be used for practically all types
of CO2 removal from other gases. Its effectiveness increases pro-
portionally to the concentration of CO2 in the gas [58].
6.3. Hydrate based separation
Hydrate-based separation as a promising technology has
attracted more attention. This process begins by forming the
hydrate by exposing the exhaust gas stream containing CO2 to
water under high pressure. As the hydrate forms, the CO2 is
captured. The hydrate is then separated and dissociated by
releasing CO2 in pure form. Gas hydrates are crystalline composed
of water and gas under suitable condition of low temperature and
high pressure. When gas hydrates are formed from mixture of
gases, the concentration of the gases in the hydrate phase is
different as that in the gas phase. Consequently, the component
that forms hydrate more easily might be enriched in the hydrate
phase. Because hydrates have the capacity to store large amount of
gas [68], hydrate based technology can be attracted much attention
as a potential means for capturing CO2.
The process of hydrate based CO2 capture was systematically
studied with tetrahydrofuran (THF) as an additive [69,70]. The
result shows that the addition of THF reduces the operating pres-
sure and enhances the corresponding kinetic rate. It is veried that
the hydrate-based gas separation process makes it possible to
recover more than 99% of CO2 from ue gas. Although the result is
promising, the separation process with THF as an additive has some
problems:
 Very low temperature is required in the process (0.6
C).
 THF is harmful to health/safety and well known contaminant to
the environment.
 The hydrate formation rate is slow.
Recently, tetra-n-butyl ammonium salts such as tetra-n-butyl
ammonium bromide (TBAB) and tetra-n-butyl ammonium uo-
ride (TBAF) have received much attention as attractive additive for
CO2 capture [68].
6.4. Mixed matrix membrane
Mixed matrix membranes are a well-known route to enhance
the properties of polymeric membranes. Their microstructure
consists of an inorganic material in the form of micro- or nano-
particles incorporated into a polymeric matrix. The use of two
materials with different ux and selectivity provides the possibility
to design an efcient membrane for CO2 capture, allowing the
synergistic combination of polymers for easy process ability and
superior gas separation performance of inorganic materials.
Furthermore the addition of inorganic materials in a polymer
matrix offers enhanced physical, thermal and mechanical proper-
ties for aggressive environments and represents a way to stabilize
the polymeric membrane against change in permeability with
temperature [4,58].
Many researches direct at mixed-matrix membranes specially
the polymer-zeolite pairs which include polydimethylsiloxane-
silicalite [71], polyimide-carbon molecular sieve, polyimide-silica
[72], naon-zirconium oxide [73], HSSZ-13-polyetherimide, acry-
lonitrile butadiene styrene-activated carbon [74]. It is known that
the permeability of a gas through a zeolite-lled polymeric
membrane depends on the intrinsic properties of zeolite and the
polymer [71]. However their performances are suffered from
defects caused by poor contact at the molecular sieves/polymer
interface. This can allow gases to ow non-selectively around the
solid particles. Sonication and decantation techniques have been
suggested to overcome this issue. The successful implementation of
this membrane process depends on both, the selection of polymeric
matrix and inorganic zeolite, and the elimination of interfacial
defects [74]. Mixed matrix membranes offer very interesting
properties, however, their cost, difculty of commercial scale
manufacturing and brittleness remain important challenges.
Researchers proposed some criteria for material selection and
preparation protocols in order to match the necessary transport
characteristics of materials to prepare high performance mixed
matrix membranes for CO2 capture [58,75,76].
6.5. Calcium looping CO2 capture
This technology utilizes the concept of reversible reaction
between CaO and CO2 to form calcium carbonate in calcium looping
cycle [4,77,78]. The use of CaO-based solids to capture CO2 at high
temperature is the core of several CO2 capture and zero emission
power plant concepts [79,80]. Similar to CLC, there are two reactors
in this system. Primary fuel combustion takes place in the
 M.K. Mondal et al. / Energy 46 (2012) 431e441 439

Table 2
Comparative analysis of different technologies.

Sr no. Parameter Absorption Adsorption Membrane Cryogenic

1. Operating exibility Moderate Moderate High (CO2 > 20%) Low [5,40,51]
Low (CO2 < 20%)
2. Response to variations Rapid (5e15 min) e Instantaneous Slow [40,51]
3. Start-up after the variations 1h e Extremely short (10 min) 8e24 h [40]
4. Turndown Down to 30% Down to 10% Down to 50% [40]
5. Reliability Moderate Moderate 100% Limited [13,51]
6. Control requirement High High Low High [40,81]
7. Ease of expansion Moderate Moderate Very high Very low [13,40,51]
8. Energy requirement 4e6 MJ/kgCO2 2e3 MJ/kgCO2 0.5e6 MJ/kgCO2 6e10 MJ/kgCO2 [81e83]
9. CO2 recovery 90e98% 80e95% 80e90% >95% [13,51,52]

carbonator and CaO reacts with CO2 in the same reactor achieving absorption process for improved overall removal efciency of CO2
in-situ CO2 capture. The reaction is as follows: such as:

CaOs CO2 g/CaCO3 s (18)  Development of new solvent/or blended solvent.

Temperature is in the range of 650e700
C depending on
pressure of the system. CaCO3 is heated to regenerate CaO in
calciner as given by Rxn (11) and the heat is provided by burning
a secondary fuel such as petroleum coke.
CaCO3 s/CaOs CO2 g (19)
Depending on the partial pressure of CO2 temperature can rise
above 900
C. The CO2 thus regenerated in the calciner is delivered
for storage. The overall thermal efciency has been shown to be
comparable to that of a current combustion system without CO2
capture [4,78]. The carbonation can either occur at in-situ or ex-situ
and heat released from exothermic carbonization can be used to
run steam cycle.
There are intrinsic benets to be gained from utilizing this
carbonationecalcination cycle to separate CO2. The most important
fact is that, as it is a high-temperature CO2 separation process, there
will be modest efciency penalties and opportunities for a high
degree of integration in the combustion plant (for example, at
atmospheric pressure the heat required for calcination at temper-
ature over 900
C is recovered in the carbonation step at 650
C).
Secondly, there are plentiful sources of cheap, widely available
sorbent (limestone) and furthermore, there is an increasing back-
ground of knowledge for the reactions required in these separation
processes [79,80]. Despite the known limits to the maximum
carbonation conversion, the reaction rates are sufciently high
even at low temperatures, to allow compact reactor designs for the
carbonator. Recently, this has been conrmed in post combustion
tests reported using three different interconnected uidized bed
installations [78].
 Modication on process system or integration with other
conventional process (e.g. absorption membrane).
 Development of suitable corrosion inhibitors.
A comparative analysis of different technologies is presented in
Table 2. The CO2 capture/separation depends on status, level of
maturity, cost and limitations of various technologies available for
sustainable power generation system [84,85]. If CO2 composition in
the ue gas streams, extent of CO2 separation/capture and uses of
separated CO2 are well dened then from this analysis we can
suggest a suitable technology for CO2 capture.
8. Conclusions
A comprehensive overview of the current status of existing
technologies for CO2 capture has been discussed. Absorption is
matured technology for post combustion capture but solvent los-
ses, corrosion and high cost of separation are the main issues for
this process. Low selectivity and low capacity of the available
adsorbents make adsorption process ineffective for large scale
industrial applications. Membrane process has several advantages
over conventional processes but high capacity and stability are still
uncertain. Cryogenic process has produced liquid CO2 and no
separation media is required. Very high cost of separation and
necessary control requirement make this process only suitable for
special circumstances. All existing technologies have their own
advantages and limitations but their reliability, stability and
removal efciency are main challenges. There is a great need for
understanding the existing technology to improve the perfor-
mance, and reduce the cost and energy required for CO2 separation.

Acknowledgment
7. Discussion
Authors are thankful to Banaras Hindu University, India for
The major improvements of various technologies to existing providing all necessary facilities to undertake the work.
processes are highly novel approaches for CO2 capture. Chemical
looping, IGCC are great modication to the existing combustion Nomenclature
based capture systems. FTM, mixed-matrix membrane are well
routes for enhancing the properties of the membrane. Hydrate and AC activated carbon
enzyme based separations are two different alternative technology AEE 2-(2-aminoethylamino) ethanol
for CO2 capture. Dual-alkali approach and blended solvents have AEPDNH2 N-2-aminoethyl 1,3-propanediamine
resulted satisfactory performances of the absorption process. AMP 2-amino 2-methyl 1-propanol
Regarding to adsorption process, activated carbon and carbon ber CA carbonic anhydrase
composite have been identied as promising alternative adsor- CLC chemical looping combustion
bents. The PTSA or ESA alone can be used for effective CO2 removal. DEA diethanol amine
There is no unique solution for CO2 capture. Same kind of DGA diglycolamaine
approaches can be considered and can be implemented in the DIPA di-2-propanolamine
440 M.K. Mondal et al. / Energy 46 (2012) 431e441
ESA electrical swing adsorption
GA glucosamine
IGCC Integrated Gasier Combined Cycle
IPCC Intergovernmental Panel on Climate Change
MAE methylaminoethanol
MDEA N-methyldiethanolamine
MEA monoethanol Amine
PZ piperazine
PSA pressure swing adsorption
PTSA pressure and temperature swing adsorption
syngas synthesis gas
RFG recycled ue gas
TBAB tetra-n-butyl ammonium bromide
TBAF tetra-n-butyl ammonium uoride
TEA triethanol amine
TETA triethylene tetra amine
THF tetrahydrofuran
TSA temperature swing adsorption
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