Applied Energy 106 (2013) 143–151

Contents lists available at SciVerse ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

A review on carbon dioxide capture and storage technology using coal

fly ash
Jung-Ho Wee ⇑
Department of Environmental Engineering, The Catholic University of Korea, 43 Jibong-ro, Wonmi-gu, Bucheon-si, Gyeonggi-do 420-743, Republic of Korea

h i g h l i g h t s

" The potential of the CCS technology using coal fly ash (FA) is reviewed.
" Alkali species in FA are dissolved and consumed to sequestrate CO2 in the wet process.
" FA can be used as a support or as a raw material of dry sorbents to capture CO2.
" The technology can stabilize the harmful components in FA during the process.
" Therefore, the technology may be another option of CCS to a limited extent.

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

Article history: This work reviews the availability and the potential of the carbon capture and storage (CCS) technology
Received 1 October 2012 using coal fly ash (FA). Because the technology can be effectively applied on-site to coal fired power
Received in revised form 3 January 2013 plants and as FA contains sufficient alkali components, the technology may be another option of CCS tech-
Accepted 23 January 2013
nology to a limited extent.
Available online 16 February 2013
The technology can be divided into wet and dry processes. In the former, the available components for
CCS in FA are leached into solution by the solvent where they are subsequently consumed for carbonation
Keywords:
to store CO2. Particularly, the CO2 storage capacity of CaO-enriched FA solution mixed with brine under
Carbon dioxide capture and storage
Coal fly ash
high pressure may be equal to or greater than the true CO2 emission reduction achieved by applying FA as
Mineral carbonation a cement additive.
Leaching In the dry process, FA can be used as a direct support or as the raw material of the sorbent supports for
Dry sorbents CO2 capture. The dry process is effectively applied for CO2 capture rather than storage because the sor-
bents should be regenerated. Another advantage of the technology is the stabilization of the harmful
components present in FA, which are mostly co-precipitated with carbonated FA during the process.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction [14–17], the mineral carbonation with SWR is readily achieved to

The amount of solid waste residue (SWR) generated from the
large-scale industrial processes such as coal fired power plant
(CFPP), cement plant, steel, paper, oil shale industry and solid
waste incinerator is increasing every year and some SWRs are sub-
stantially harmful to the environment. Therefore, the SWR disposal
situation has been intensively aggravated to become an important
issue [1–5]. Considering that most of the processes that generate
SWR emit a great amount of CO2, SWR can be directly or indirectly
used as a material for on-site CO2 capture and storage (CCS), which
is another option of CCS technology [6–13].
This potential is based on the following reasons. Firstly, because
industrial SWRs contain substantial alkali and alkali earth metals
⇑ Tel.: +82 2 2164 4866; fax: +82 2 2164 4765.
E-mail addresses: jhwee@catholic.ac.kr, jhwee@korea.ac.kr
store CO2 and which may be a permanent solution compared to
geological and ocean storage. In addition, CO2 can be partially
recovered from the instable carbonated (or bi-carbonated) SWR
products. Secondly, they are geochemically instable and reactive
because they are generally formed at very high temperature (over
1200 °C) and subsequently produced by rapid cooling [7]. Finally,
they are porous materials with relatively high surface area.
The first study on CCS using SWR was conducted by Reddy et al.
group with alkaline byproduct of oil shale combustion process in
the mid-1980s [18] and they proposed the technology to increase
the reaction rate of former process in the early 1990s [19]. Both
works had inspired a number of subsequent literatures dealt with
mineral carbonation with various SWRs [8,20–22].
Among industrial SWRs, interest has focused on coal fly ash (FA)
generated from the pulverized CFPP because the CO2 emissions
from CFPP and the FA portion are the largest [23–28]. Although

0306-2619/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.apenergy.2013.01.062
144 J.-H. Wee / Applied Energy 106 (2013) 143–151
the characteristics of FA differ substantially according to the coal
and combustion conditions [29], currently generated FA is mostly
used as cement and concrete additives [30,31]. However, its utili-
zation ratio remains less than 30% of the total generated amount
[32] in terms of the worldwide production, which is estimated at
700 million tons per year. In US, at least 150 million tons FA is gen-
erated annually and 27% is reused, while the remaining is landfilled
or surface-impounded [30].
Although CO2 emission reduction using FA can be achieved via
some methods, the primary technology is based on mineral car-
bonation because FA contains a high content of alkali components,
which are essential materials for mineral carbonation [33–35]. For
example, the CaO and MgO contents are more than 20% in Class-C
FA (FA generated from younger lignite or sub-bituminous coal
burning). Furthermore, the CaO concentration is very high in FA
collected at flue gas desulfurization (FGD) process [36]. Therefore,
several attempts have been made to use FA as the caustic material
to increase the pH of the acidic brine solution generated from oil
and gas production.
One of the advantages of FA use for CO2 emission reduction is its
on-site application in CFPP. This is very effective to minimize the CCS
cost while saving or reducing the current transfer, treatment and
disposal costs of FA. In addition, the final carbonated FA products
have the potential to be effectively reused as construction materials
or additives because their physical structure might be changed, and
their mechanical strength and leaching resistance are improved.
Therefore, these can substantially enhance the economy of the
carbonation process and decrease the environmental impact of FA.
Many papers have reported the FA carbonation effect by leach-
ing process, irrespective of CCS. However, the research focusing on
the application of FA to one of the CCS technologies began to be re-
ported since the late 1990s. The present paper reviews the CCS
technologies using FA based on previously reported studies. Firstly,
the technology using FA is divided into two categories: wet and dry
processes. Secondly, the features and performance of each technol-
ogy are investigated in detail. Finally, the availability and CO2
emission reduction potential of the technology are discussed.
2. Status of coal fly ash (FA) in Korea
2.1. Amount of FA generated
Total amount of coal ash, including FA, generated per year since
2001 in Korea is listed in Table 1.
The nation’s total electricity production in 2010 was
433,604 GW h [37], of which 45%, 195,000 GW h, was generated
from CFPP via 5 major electric utilities. For this electricity genera-
tion, 78.89 million tons of coal was consumed to generate 8.41 mil-
lion tons of coal ash [38–40]. The amount of generated FA was
estimated to be 5.29 million tons [41], of which more than 90%
was utilized as additives in cement, concrete and brick.
2.2. Application as a cement additive
As aforementioned, most FA is currently used as a cement addi-
tive. When FA is mixed with the Portland cement, SiO2 and Al2O3 in
FA react with slaked lime and water according to the Pozzolan reac-
tion. Therefore, calcium silicate and calcium aluminate hydrates are
Table 1
Annual coal ash and coal fly ash (FA) generation in Korea.
Year 2001 2002 2003
Coal ash (million tons) 4.92 5.14 5.19
Coal fly ash (million tons) 3.09 3.23 3.26
produced, which substantially increase the chemical resistance and
the long-term strength of the cement [42]. Therefore, this Portland
FA cement (PFAC) is generally used as the concrete in dam
construction.
Another effect of FA application as a cement additive is to re-
duce CO2 emission by reducing the cement consumption. In Korea
Standards, PFAC is classified into three types according to the FA
content: A (10% of FA), B (10–20%) and C (20–30%). Currently,
type B is most widely used. Therefore, the average portion of FA
in PFAC is assumed to be 15%. When 1 ton of Portland cement is
produced, 0.83 ton of CO2 is known to be emitted, of which
0.46 ton is generated from sintering of CaCO3 and the balance is
due to energy consumption [43]. Therefore, assuming that the en-
ergy consumption is unchanged and considering the portion of FA
substitution for CaCO3, the CO2 emission reduction achieved by
using FA as a cement additive is roughly estimated to be
0.069 ton per ton of cement production.
However, the true CO2 emission reduction by FA replacement
with cement is less because of the additional CO2 emissions gener-
ated from FA treatment as a cement additive such as fractionation,
mixing and transportation processes. Due to these penalties, the
CO2 emission reduction contribution of FA as a cement additive
may be substantially less than this value.
Therefore, when FA is used as a direct or indirect material for
CCS in CFPP on-site, its detailed effects should be analyzed com-
pared to FA application in cement plant. In this case, various con-
ditions should be considered such as additional energy
consumption to treat FA for wet or dry based application. The ben-
eficial effects should be also considered which include reuse of car-
bonated FA products as construction materials and stabilization of
harmful components in FA precipitated during carbonation.
Although, this feasibility study based on all these conditions would
very meaningful, the present review does not include this study.
The paper focuses on the CCS capacity of FA or its potential when
it is used as a material for CCS.
Except as a cement additive, FA application to other fields has
been extensively investigated, including ceramic balls for water
purification, zeolite synthesis, polish materials of steel plate,
anti-flaming, building and fill materials [44]. However, these are
minor applications in terms of CO2 emission reduction.
3. Study on CCS technology using fly ash (FA)
Recently, many papers have investigated the development of
CCS technology using FA. These studies can be divided into three
classifications according to the applied technology. The first cate-
gory is wet and dry processes. In wet technology [32,45–51] CCS
components in FA such as Ca, Na, Mg and K are leached by aqueous
(acidic) solution and then consumed on carbonation reaction to
store CO2. In the dry process [52–55], FA and some additives are
used as direct CCS materials. In addition, FA is used to support
the catalytic sorbent for CO2 capture [56–58] and as a raw material
of zeolite [59–63]. The second classification is based on the level of
pressure during the carbonation. The reaction can be carried out in
atmospheric or high pressurized condition. Generally, carbonation
with high pressure is carried out in an autoclave with the object of
CO2 storage. Final classification depends on the number of pro-
cesses involved. In a one-step process, FA treatment and carbon-
2004 2005 2006 2007 2008 2009 2010
5.38 5.95 5.84 6.02 7.61 8.35 8.41
3.38 3.74 3.67 3.79 4.79 5.25 5.29
 J.-H. Wee / Applied Energy 106 (2013) 143–151 145

Table 2
Process features and carbon dioxide storage capacity of wet-based FA application to CCS, as reported in the literature.

Paper Carbonated system Experimental Storage capacity Remarks

conditions
Reactor type
Temperature
Solid (FA)/liquid
(solvent)
CO2 partial
pressure
Stirring speed
Time
Others
[45] Aqueous solution mixed with N.A. – S in leachates enhanced CaCO3 production rate
Ca(OH)2 and FA leachates – Mg in leachates hindered CaCO3 formation
– Storage capacity of solution was independent of CO2 flow rate
and concentration
[46] Moderately wetted FA (Humidity Batch – – CaO addition to FA enhanced carbonation rate
portion in FA; 5–50%) 25–50 °C – Humidity, CO2 concentration and partial pressure were
– strongly dependent on carbonation
50–125 psi
–
24–72 h
–
[47] Class-C FA (10%) and NaOH Autoclave – 2.77 g CO2 and 29.63 g ppt/L – Mineral carbonation was effectively available with components
added brine filtrates and slurry 20 °C filtrates in brine and in FA
– – 22.88 g CO2 and 21.9 g ppt/L – FA addition to brine increased pH of brine from 3.8 to 8.3
1.36 MPa slurry within 1.5 h
– – NaOH addition to FA brine slurry increased carbonation rate
2h
–
[48] Lignite FA-water slurry Batch (3.7 L) – 0.23 g CO2/g FA – Storage capacity was proportional to CO2 partial pressure, stir-
25–75 °C ring speed, temperature and solvent/FA ratio
50 g/L
0.01–0.3 MPa
600 rpm
4.5 h
–
[32] FA-water slurry Autoclave – 0.026 g CO2/g FA – Carbonation efficiency was independent on the initial pressure
30–60 °C of CO2
100 g/1 L – Carbonation was not significantly affected by reaction temper-
40 bar ature (20–60 °C) and fly ash dose (50–150 g)
450 rpm
2h
–
[49] Aqueous mixed slurry of Class-C Closed MFR – 33.4 g CO2 at 23.6% solids in – Synergistic effect of saline cations and dissolved CCS compo-
FA and saline Ambient slurry by weight (FGD) nents of FA in slurry was observed 2 h later from the start
– – 1.54 g CO2 at 23.3% solids in
9.62 psi g slurry by weight (Class-C)
1500 rpm
2h
Gas feeding
rate; 300 mL/
min
[50] Lignite FA- water slurry Autoclave – 0.055 g CO2/g FA (average) – Carbonated FA (CO2 bonding FA) used as construction materials
35 °C was estimated 1.3 million tons per year in Poland
1.5:1 (by
weight)
1 MPa
Shaken
24 h
–
[51] Aqueous mixed slurry of Autoclave (6 L) – 0.072 g CO2/g 20–150 lm – CaO composition of FA with the particle size of 20–150 lm was
fractionated FA and brine 90 °C sized FA the highest (9.3%) and >150 lm was the least (5.89%)
1 – 0.036 g CO2/g > 150 lm sized – Concentration of significant trace elements in FA was reciprocal
4 MPa FA to FA particle size
600 rpm
2h
–

ation are almost simultaneously carried out. On the other hand, in
multi-unit involved process, components in FA are firstly extracted
or FA is modified before they are subsequently used for carbon-
ation reaction. Generally, the multi process is not desirable because
it involves solvent regeneration and side reactions. In the present
paper, many studies are classified according to their wet and dry
basis and they are reviewed in the next section. In addition, their
critical information such as carbonated system, experimental con-
dition and storage capacity of FA is summarized in Tables 2 and 3.
3.1. Wet process
In 1992, Schramke [45] carried out the mineral carbonation
feeding CO2 into Ca(OH)2-added FA leachates manufactured by
146 J.-H. Wee / Applied Energy 106 (2013) 143–151

Table 3
Process features and carbon dioxide capture capacity of dry-based FA application to CCS, as reported in the literature.

Paper Carbonated system Experimental Capture capacity Remarks

conditions
Reactor type
Temperature
CO2 partial
pressure
[52] KOH added and CPAHCL impregnated FA DRIFTSa/TPDb – 0.008 g CO2/g fresh – KOH was not essential component to increase capture
120 °C sorbent performance of the sorbent
10.1 kPa – 0.006 g CO2/g regen-
erated sorbent
[53] PEI (50%) impregnated MCM41 generated from FA TGA – 0.112 g CO2/g sorbent – Sorption and desorption rates was rapid
(K2CO3 added, 40 mol%) 75 °C – 0.003 g CO2/g PEI free
10.1 kPa sorbent
[54] Li4SiO4 generated from FA (K2CO3 added, 40 mol%) TGA – 0.107 g CO2/g sorbent – Sorbents was maintained its original capacity during
600 °C 10 regeneration cycles
101.3 kPa – Maximum capture capacity reached within reaction
time of 15 min
[55] FA Fluidized bed – 0.207 g CO2/g FA – SO2 and Hg was co-precipitated in carbonated FA
43–54 °C
15 kPa
a
Diffuse reflectance infrared transform spectroscopy.
b
Temperature programmed desorption.

extraction of FA using water as the solvent. Originally, the work did
not aim to store CO2 but to control the pH of the FA leachates
absorbing CO2. The author measured the neutralizing effect of
CO2 injection and Ca(OH)2 addition to FA leachates. As a result,
the author claimed CO2 was substantially converted and stored
in the form of precipitated CaCO3 in the leachates. Many Ca compo-
nents inherent in FA were also substantially included in the car-
bonates. Therefore, the paper demonstrated that FA could be
used as a CCS material via mineral carbonation.
In 1995, Tawfic et al. [46] reported the effect of high pressurized
CO2 injection to moderately wetted FA. This study was not focused
on CO2 storage. The authors intended to reduce the pH of wetted
FA and simultaneously to eliminate the trace metals presented in
FA such as Cd, Pb, Cr, As and Se co-precipitating with CaCO3. Final-
ly, however, the result of the paper led to interest in the FA appli-
cation to CO2 storage.
Therefore, these two papers [45,46] may offer insight into many
subsequent works dealing with the CCS technology using FA.
In 2006, Soong et al. [47] investigated the carbonation effect of
FA in mixed slurry and filtrates of FA, NaOH and brine solution. To
utilize Ca, Mg, and Fe in the brine as the CCS components, the ini-
tial pH of brine, which is approximately 3–5, should be firstly in-
creased to over 7.8. Therefore, the authors used FA to increase
the pH of the brine. Among five kinds of FA, Class-C FA was selected
and FA mixed-brine slurry and filtrates were prepared. Thereafter,
mineral carbonation with the slurry was carried out according to

Fig. 1. Conceptual process for CO2 sequestration via brine and fly ash (FA) [47].
 J.-H. Wee / Applied Energy 106 (2013) 143–151 147

Fig. 3. Schematic experimental system for mineral sequestration of CO2 by aqueous

carbonation of fly-ash in a stirred reactor [32].
Fig. 2. Reaction progress in fly ash (FA) experiment with water and CO2 (s/l-
ratio = 75 g/L; initial pCO2 = 0.02 MPa; stirring rate=300 rpm). A: pH, pCO2 and EC.
B: total uptake of CO2, precipitated amount of carbonate, total dissolved inorganic
carbon (TDIC) and dissolved contents of Ca and Mg per gram FA [48].

the process shown in Fig. 1, which includes FA recycling, separa-

tion and causticization.
As a result, the authors claimed that the CO2 was substantially
captured in the solution and stored as the precipitated material
(ppt). However, the carbonation was conducted at high pressure
in an autoclave and the reported Ca composition of 17–29% in FA
was very high compared to traditional FA.
In 2008, Back et al. [48] reported the mechanism of the mineral
carbonation conducted with the mixed slurry of lignite FA and
water. In addition, they investigated the effect of various condi-
tions such as CO2 concentration and temperature on the carbon-
ation. After analyzing the variation of pH, electrical conductivity
(EC) and CO2 conversion rate during the reaction, they claimed that
the carbonation in the slurry was carried out via the three consec-
utive stages shown in Fig. 2. Fig. 4. XRD spectra of starting fly-ash and solid products after carbonation during
The first step with a slurry pH over 12 proceeded during the ini- 2 h. C: calcite, M: mullite, Q: quartz, L: lime. These spectra demonstrate the total
tial 30 min where CO2 and Ca began to be dissolved, which initi- consumption of lime and the production of calcite [32].
ated CaCO3 formation. They claimed that the CO2 dissolution was
maximized in this stage and became the rate controlling step.
The second step was the period between 10 and to 60 min from duced by the rapid carbonation in the slurry, as confirmed by the
the start, during which the pH was under 10.5. The carbonation XRD analysis shown in Fig. 4.
was dominantly carried out to CaCO3 in this stage. The authors also estimated the conversion ratio of CaO to CaCO3
The slight dissolution of MgO into water was significantly in- as 82%. However, the glass-phase Ca, which was not converted
volved in the final stage, in which soluble MgHCO3 was generated. CaCO3, was substantially remained with a concentration of
Based on this mechanism, the authors calculated the CO2 storage 800 mg/L [64] of slurry after carbonation. In addition, they high-
capacity of FA to be 90% of the acid neutralizing capacity value of lighted the heavy metals in FA such as Se, which was co-precipi-
FA. In addition, they highlighted that the Ca conversion ratio into tated with CaCO3, as well as Mg and S, which hindered the
CaCO3 was over 75% of the dissolved Ca from FA. formation of CaCO3. Furthermore, they claimed that the CaCO3
In 2009, Montes-Hernadez et al. [32] investigated the CO2 stor- co-precipitated with SO2
4 and Mg components was more soluble
age capacity of FA (4.1% of CaO)-water slurry conducting the highly than pure CaCO3.
pressurized carbonation in an autoclave, as shown in Fig. 3. In 2009, Dirmore et al. [49] reported the carbonation perfor-
They reported that the carbonation was carried out according to mance of a mixed slurry of FA collected from the FGD unit and sal-
two reactions. Firstly, CaO in FA was dissolved by water, which ine waste water. The Ca composition in this FA was substantially
rapidly increased the pH of the slurry. Thereafter, CaCO3 was pro- high because the lime had previously been used in the FGD process
148 J.-H. Wee / Applied Energy 106 (2013) 143–151

to eliminate SOx in the flue gas, so that substantially more Ca re-
mained than in traditional FA. The authors claimed that the
amount of CO2 stored by FGD-based FA was even larger than that
of Class-C FA, as listed in Table 2, and it was proportional to the
FA feeding amount. Moreover, they investigated whether the haz-
ardous elements were extracted from the carbonated FA by mea-
suring their composition in the carbonated FA leachates. As a
result, Ba was solely traced in leachates, leading them to claim that
most hazardous materials were stabilized during the FA
carbonation.
In 2009, Uliasz-Bocheńczyk et al. [50] carried out the carbon-
ation of the mixed slurry of water and CaO-enriched lignite FA,
with a weight ratio of 1.5. The carbonation was conducted by shak-
ing an autoclave filled with slurry and highly pressurized CO2 for a
very long time. As a result, the authors claimed that the CO2 stor-
age capacity was very strongly dependent on the reaction time,
being 35 and 79 g of CO2 per kg of FA after the initial 15 min and
25 days later, respectively. However, the water content in the slur-
ry was very high compared to those of other works.
In 2011, Nyambura et al. [51] investigated the carbonation of
aqueous slurry mixed with fractionated Class-F FA (FA generated
from harder and older anthracite or bituminous coal burning)
and brine. As a result, CaCO3, plagioclase (NaAlSi3O8–CaAl2Si2O8)
and anhydrite (CaSO4) were confirmed to be produced, as shown
in Figs. 5 and 6.
The FA used in the study was previously fractionated according
to particle size and the authors claimed that the CO2 storage capac-
ity of the relatively smaller FA with a size of 20–150 lm was larger
than that of the larger FA. They ascribed this result to the fact that
the smaller FA contained more CaO (9.3%). Furthermore, they re-
ported that the composition of trace elements such as S, Sr, and
Ba in smaller FA were higher than that of larger FA. In addition,
they noted that the brine substantially enhanced the degree of
carbonation.

Fig. 5. Phase identification and quantification of fresh FA by XRD; M (mullite), Q (quartz), Mt (magnetite), L (lime), H (hematite) [51].

Fig. 6. Phase identification and quantification for carbonated FA by XRD; (90 °C, 4 MPa, bulk ash at an S/L ratio of 1); M (mullite), Q (quartz), C (calcite), A (anhydrite), P
(plagioclase), B (bassanite), Mt (magnetite) [51].
 J.-H. Wee / Applied Energy 106 (2013) 143–151 149

Fig. 7. XRD profiles of samples FA-1 (Pure FA) and FA-1⁄ (Li4SiO4 synthesized with FA) [54].

3.2. Dry process In 2010, Olivares-Marín et al. [54] manufactured Li4SiO4 via so-
lid state method using SiO2 in FA as the raw materials and reported
Recently, research on dry sorbents for CO2 capture has been its CO2 capture capacity. Li4SiO4 was reacted with CO2 to produce
intensively conducted due to its relatively more advantageous fea- Li2SiO3, according to Eq. (1).
tures compared to the wet process. As aforementioned, FA can be
directly used as a support for the sorbent in CO2 capture and as Li4 SiO4 ðsÞ þ CO2 ðgÞ ! Li2 SiO3 ðsÞ þ Li2 CO3 ðsÞ ð1Þ
the raw material of supports such as zeolite. Dry sorbents can be
The sorbent was synthesized by sintering the mixture of FA and
effectively used for CO2 capture rather than mineral carbonation
Li2CO3 at 950 °C and it was confirmed to be Li4SiO4 via XRD analy-
because the sorbents are generally regenerated. The works on
sis, as shown in Fig. 7.
dry sorbents using FA are reviewed below.
Thereafter, CO2 capture and desorption tests were carried out
In 2004, Graya et al. [52] analyzed the CO2 capture performance
many times and their performance was compared to the refer-
of the amine-enriched dry sorbents manufactured by using Pitts-
enced original Li4SiO4. In addition, they analyzed the effect of
burgh-seam coal FA as the sorbent supports. FA was treated before
K2CO3 addition to the sorbent. The authors claimed although the
use by solvent via the authors’ own agglomeration process. The
capture performance of their sorbent was less than that of the ref-
primary CO2 absorption component in the sorbent was 3-chloro-
erence sorbent, as shown in Fig. 8, their sorbent was better in
propylamine-hydrochloride, which was impregnated onto FA with
terms of sorbent regeneration.
KOH in the aqueous solution. CO2 capture with the sorbents was
Furthermore, the authors explained that K2CO3 addition to the
carried out in their manufactured reactor under a CO2 composition
sorbent substantially increased the capture capacity of the sorbent
of 10% with the balance of He mixed humid gases. The reported
in a temperature dependent manner up to 600 °C.
CO2 capture capacity of the fresh and regenerated sorbents is listed
in Table 3. In the paper, the authors also claimed although the per-
formance of the sorbent was only 9% of the commercialized one,
the performance based on the unit surface of the sorbent was
higher.
In 2009, Majchrzak-Kuceba et al. [53] investigated the perfor-
mance as a sorbent support of MCM-41, which is produced by FA
collected in a circulating fluidized bed. This meso-porous sub-
stance was manufactured via a hydrothermal process where the
supernatants in FA were used as its main raw materials and surfac-
tants were added as the structure-directing agents. Thereafter,
polyethylenimine (PEI), which is a CO2 capture component, was
impregnated onto MCM-41 to produce the sorbent. The reported
CO2 capture capacity of their sorbents is listed in Table 3. The
absorption was conducted with a gas mixture in which the CO2,
O2 and N2 compositions were 10%, 10% and 80%, respectively. In
addition, the authors analyzed the desorption rate of the sorbent.
Therefore, they concluded that micro-sized FA can be used as the Fig. 8. CO2 sorption profiles of P-Li4SiO4 (Pure Li4SiO4) and FA-1⁄ (Li4SiO4
raw material for meso-porous substance such as MCM-41. synthesized with FA) in 100 vol% CO2 at 500 °C [54].
150 J.-H. Wee / Applied Energy 106 (2013) 143–151
Fig. 9. Preliminary experiment set-up for CO2 capture and mineralization (Inset shows the testing at the plant) [55].
In 2011, Reddy et al. [55] carried out a pilot-scale mineral car-
bonation experiment with an FA content of 100–300 kg, as shown
in Fig. 9.
In the pre-experiment, the carbonation effect of FA was investi-
gated by directly subjecting the FA to contact with the flue gas of
the CFPP in a fluidized reactor. They claimed that the concentration
of CO2 and SO2 in the flue gas was decreased from 13% to 9.6% and
from 107.8 ppmv to 15.1 ppmv within 2 min, respectively. In addi-
tion, the concentration of Hg in the flue gas was substantially re-
duced. The authors claimed that if FA is exposed to flue gas, CO2
is preferably reacted with Ca and other oxides in FA to generate
CaCO3 and various other carbonates such as thaumasite (Ca3-
Si(SO4)CO3(OH)612H2O) dawsonite (NaAl(CO3)(OH)2), and alum-
ohydrocalcite (CaAl2(CO3)2(OH)43H2O). In addition, the authors
highlighted the small amount of acid presented in the flue gas such
as H2SO4 and HNO3. Such remnant components are inevitable be-
cause the flue gas had previously been passed through the scrub-
bing process to eliminate SOx and NOx, so that various
components in FA such as Al, Fe, Ca, Mg, Na, K, and S were slightly
dissolved and then co-precipitated in the carbonated FA. In fact,
the amorphous silicate in FA is known to be substantially soluble
and reactive in acidic condition [65]. From their results, the authors
claimed that when 90% of the CO2 emitted from a 532 MW CFPP is
stored, the estimated cost is $11/t CO2, which equates to a CO2
storage capacity of 207 kg CO2/t of FA. However, they did not de-
scribe the treatment of carbonated FA, which is a critical issue.
4. Conclusions
The present paper has discussed the availability and the poten-
tial of CCS technology using FA by analyzing the results from pre-
vious studies in this field. From the reviews, the following
conclusions were obtained.
 The technology is applicable to CFPP on-site and FA contains
sufficient alkali components such as CaO. Therefore, FA may
be effectively used as a material for CCS.
 The technology can be classified into wet and dry processes. In
the former, the available components for CCS in FA such as Ca,
Na, Mg and K are dissolved into solution by leaching and subse-
quently consumed for carbonation to store CO2.
 Currently, most FA is used as a cement additive. The CO2 emis-
sion reduction achieved by FA substitution to cement material
was roughly calculated to be less than 0.069 ton per ton of
cement.
 Class-C FA (particularly lignite coal based), FA collected from
the FGD unit in CFPP, and FA with a size of 20–150 lm were
the most effective materials for CO2 storage in the wet process
due to their higher CaO composition. In addition, the CO2 stor-
age capacity of brine solution mixed with CaO-enriched FA
under high pressure can be significantly increased to a level that
might be sufficiently competitive to the case of FA application
to cement.
 In the dry process, FA is directly used to support the sorbent on
which CO2 capture components such as amine can be impreg-
nated. In addition, FA can be the raw material of meso-porous
substances, zeolite and SiO2, which can be the sorbent supports
for CO2 capture. Therefore, the dry process can be effectively
used for CO2 capture rather than storage because the sorbents
should be regenerated. However, FA may be used as a CCS com-
ponent for direct contact with the flue gas of the CFPP in the flu-
idized reactor. The storage capacity in the process was reported
to be 0.207 g CO2/g FA.
 If the technology with the highest storage capacity reported by
dry process were applied to Korean situation, the annual CCS
potential is estimated to be 1.10 million tons. In the same
way, the global CCS potential is calculated to be 144.9 mil-
lion tons per year and which equates the total CO2 emissions
of a medium-sized European country like Belgium.
 Another advantage of CCS technology using FA is the stabiliza-
tion of the harmful components present in FA such as Cd, Pb,
Cr, As, Se, Al, and S. These toxins are mostly co-precipitated with
carbonated FA during the process.
Acknowledgements
This research was supported by Basic Research Program
through the National Research Foundation of Korea (NRF) funded
by the Ministry of Education, Science and Technology (2010-
0009938) as well as supported by the Catholic University of Korea,
Research Fund, 2012.
 J.-H. Wee / Applied Energy 106 (2013) 143–151 151

References [30] Rostami H, Brendley W. Alkali ash material: a novel fly ash-based cement.
Environ Sci Technol 2003;37:3454–7.
[31] Ahmaruzzaman M. A review on the utilization of fly ash. Prog Energy Combust
[1] Lange LC, Hills CD, Poole AB. Preliminary Investigation into the Effects of
2010;36:327–63.
Carbonation on Cement-Solidified hazardous Wastes. Environ Sci Technol
[32] Montes-Hernandez G, Pérez-López R, Renard F, Nieto JM, Charlet L. Mineral
1996;30:25–30.
sequestration of CO2 by aqueous carbonation of coal combustion fly-ash. J
[2] Huijgen WJJ, Comans RNJ. 2005. Carbon dioxide sequestration by mineral
Hazard Mater 2009;161:1347–54.
carbonation, Literature review update 2003–2004. ECN-C-05-022. Energy
[33] Fauth DJ, Soong Y, White CM. Carbon sequestration utilizing industrial solid
Research Center of The Netherlands, Petten, The Netherlands.
residues. Prepr Paps Am Chem Soc Div Fuel Chem 2002;47:37–8.
[3] Costa G, Baciocchi R, Polettini A, Pomi R, Hills CD, Carey PJ. Current status and
[34] Teir S, Eloneva S, Fogelholm C-J, Zevenhoven R. Fixation of carbon dioxide by
perspectives of accelerated carbonation processes on municipal waste
producing hydromagnesite from serpentinite. Appl Energy 2009;86:214–8.
combustion residues. Enciron Monit Assess 2007;135:55–75.
[35] Reddy KJ, Tawfic TA, Gloss SP, Drever JI. Development of a carbon dioxide
[4] Bobicki ER, Liu Q, Xu Z, Zeng H. Carbon capture and storage using alkaline
pressure technique for chemical stabilization of alkaline clean coal technology
industrial wastes. Prog Energy Combust Sci 2012;38:302–20.
(CCT) ash. EPRI TR-104840;1995.
[5] Kaithwas A, Prasad M, Kulshreshtha A, Verma S. Industrial wastes derived solid
[36] Anthony EJ, Bulewicz EM, Dudek K, Kozak A. The long term behaviour of CFBC
adsorbents for CO2 capture: a mini review. Chem Eng Res Des
ash–water systems. Waste Manage 2002;22:99–111.
2012;90:1632–41.
[37] http://www.kpx.or.kr.
[6] Bertos MF, Simons SJR, Hills CD, Carey PJ. A review of accelerated carbonation
[38] http://www.epic.or.kr/cont/yearbook/2010/yb2010_chap02_8.pdf.
technology in the treatment of cement-based materials and sequestration of
[39] =http://www.ceric.net/news/detail_02.asp?p=CERIC&tb=pubnews&code=ceric
CO2. J Hazard Mater 2004;B112:193–205.
news&num=14736&ref=&page=1&start
[7] Huijgenm WJJ, Comans RNJ. 2005. Mineral CO2 sequestration by carbonation of
page=1&key=&k_s=0&k_e=0&k_w=0&section_code=3.
industrial residues, Literature overview and selection of residue. ECN-C-05-
[40] http://www.dailian.co.kr/news/news_view.htm?id=131278.
074. Energy Research Center of The Netherlands, Petten, The Netherlands.
[41] http://www.hankyung.com/news/app/newsview.php?aid=2010041470741.
[8] Huijgen WJJ, Witkamp GJ, Comans RNJ. Mineral CO2 sequestration by steel slag
[42] http://www.ssycnt.co.kr/news_plant3.asp.
carbonation. Environ Sci Technol 2005;39:9676–82.
[43] http://ckdwhwk.egloos.com/10474132.
[9] Huijgen WJJ, Witkamp GJ, Comans RNJ. Mechanisms of aqueous wollastonite
[44] http://www.flyash.co.kr.
carbonation as a possible CO2 sequestration process. Chem Eng Sci
[45] Schramke JA. Neutralization of alkaline coal fly ash leachates by CO2 (g). Appl
2006;61:4242–51.
Geochem 1992;7:481–92.
[10] Bonenfant D, Kharoune L, Sauvé S, Hausler R, Niquette P, Mineault M, et al. CO2
[46] Tawfic TA, Reddy KJ, Gloss SP. Reaction of CO2 with clean coal technology ash
sequestration potential of steel slags at ambient pressure and temperature. Ind
to reduce trace element mobility. Water Air Soil Poll 1995;84:385–98.
Eng Chem Res 2008;47:7610–6.
[47] Soong Y, Fauth DL, Howard BH, Jones JR, Harrison DK, Goodman AL, et al. CO2
[11] Uibu M, Uus M, Kuusik R. CO2 mineral sequestration in oil-shale wastes from
sequestration with brine solution and fly ashes. Energy Convers Manage
Estonian power production. J Environ Manage 2009;90:1253–60.
2006;47:1676–85.
[12] Jiang JG, Du XJ, Chen MZ, Zhang C. Continuous CO2 capture and MSWI fly ash
[48] Back M, Kuehn M, Stanjec H, Peiffer S. Reactivity of alkaline lignite fly ashes
stabilization, utilizing novel dynamic equipment. Environ Pollut
towards CO2 in water. Environ Sci Technol 2008;42:4520–6.
2009;157:2933–8.
[49] Dilmore RM, Howard B, Soong Y, Griffith C, Hedges SW, DeGalbo AD, et al.
[13] Sanna A, Dri M, Hall MR, Maroto-Valer M. Waste materials for carbon capture
Sequestration of CO2 in mixtures of caustic byproduct and saline waste water.
and storage by mineralization (CCSM) – a UK perspective. Appl Energy
Environ Eng Sci 2009;26:1325–33.
2012;99:545–54.
[50] Uliasz-Bocheńczyk A, Mokrzychi E, Piotrowski Z, Pomykala R. Estimation of
[14] Huijgenm WJJ, Comans RNJ. 2003. Carbon dioxide sequestration by mineral
CO2 sequestration potential via mineral carbonation in fly ash from lignite
carbonation, Literature review. ECN-C-03-016. Energy Research Center of The
combustion in Poland. Energy Procedia 2009;1:4873–9.
Netherands, Petten, The Netheranlds.
[51] Nyambura MG, Mugera GW, Felicia PL, Gathura NP. Carbonation of brine
[15] Stolaroff JK, Lowry GV, Keith DW. Using CaO- and MgO-rich industrial waste
impacted fractionated coal fly ash: implications for CO2 sequestration. J
streams for carbon sequestration. Energy Convers Manage 2005;46:687–99.
Environ Manage 2011;92:655–64.
[16] Baciocchi R, Corti A, Costa G, Lombardi L, Zingaretti D. Storage of carbon
[52] Graya ML, Soong Y, Champagne KJ, Baltrus J, Stevens Jr RW, Toochinda P, et al.
dioxide captured in a pilot-scale biogas upgrading plant by accelerated
CO2 capture by amine-enriched fly ash carbon sorbents. Sep Purif Technol
carbonation of industrial residues. Energy Procedia 2011;4:4985–92.
2004;35:31–6.
[17] Arm M, Suer P, Arvidsson H, Lindqvist J-E. Technical and environmental long-
[53] Majchrzak-Kuceba I, Nowak W. Development of fly ash-based sorbent to
term properties of industrial residues – summary of field and laboratory
capture CO2 from flue gas. In: Proceedings of the 20th international conference
investigations. Waste Manage 2011;31:101–7.
on fluidized bed combustion; 2009. p. 596–602.
[18] Reddy KJ, Lindsay WL, Boyle FW, Redente EF. Solubility relationships and
[54] Olivares-Marín M, Drage TC, Maroto-Valer MM. Novel lithium-based sorbents
mineral transformations associated with recarbonation of retorted shales. J
from fly ashes for CO2 capture at high temperatures. Int J Greenh Gas Con
Environ Qual 1986;15:129–33.
2010;4:623–9.
[19] Reddy KJ, Drever JI, Hasfurther VR. Effects of a CO2 pressure process on the
[55] Reddy KJ, John S, Weber H, Argyle MD, Bhattacharyya P, Taylor DT, et al.
solubilities of major and trace elements in oil shale solid wastes. Environ Sci
Simultaneous capture and mineralization of coal combustion flue gas carbon
Technol 1991;25:1466–9.
dioxide (CO2). Energy Procedia 2011;4:1574–83.
[20] Schramke, JA. EPA solidification/stabilization resource guide. EPA/542-B-99-
[56] Chang HL, Chun CM, Aksay IA, Shih WH. Conversion of fly ash into mesoporous
002; 1999.
aluminosilicate. Ind Eng Chem Res 1999;38:973–7.
[21] Meima JA, Van Der Weijden RD, Eighmy TT, Comans RNJ. Carbonation
[57] Chandrasekar G, Son WJ, Ahn WS. Synthesis of mesoporous materials SBA-15
processes in municipal solid waste incinerator bottom ash and their effect
and CMK-3 from fly ash and their application for CO2 adsorption. J Porous Mat
on the leaching of copper and molybdenum. Appl Geochem 2002;17:1503–13.
2008;16:545–51.
[22] Eche H, Menad N, Lagerkvist A. Carbonation of municipal solid waste
[58] Maroto-Valer MM, Zhe L, Yinzhi Z, Zhong T. Sorbents for CO2 capture from high
incineration fly ash and the impact on metal mobility. J Environ Eng
carbon fly ashes. Waste Manage 2008;28:2320–8.
2003;129:435–40.
[59] Querol X, Umaña JC, Plana F, Alastuey A, Lopez-Soler A, Medinaceli A, et al.
[23] Fang J, Zeng T, Yang LIS, Oye KA, Sarofim AF, Beér JM. Coal utilization in
Synthesis of zeolites from fly ash at pilot plant scale. Examples of potential
industrial boilers in China – a prospect for mitigating CO2 emissions. Appl
applications. Fuel 2001;80:857–65.
Energy 1999;63:35–52.
[60] Cama J, Ayora C, Querol X, Ganor J. Dissolution kinetics of synthetic zeolite
[24] Arenillas A, Smith KM, Drage TC, Snape CE. CO2 capture using some fly ash-
NaP1 and its implication to zeolite treatment of contaminated waters. Environ
derived carbon materials. Fuel 2005;84:2204–10.
Sci Technol 2005;39:4871–7.
[25] Sun Y, Paikh V, Zhang L. Sequestration of carbon dioxide by indirect
[61] Hui KS, Chao CYH. Effects of step-change of synthesis temperature on
mineralization using Victorian brown coal fly ash. J Hazard Mater 2012;209–
synthesis of zeolite 4A from coal fly ash. Mesoporous Mater 2006;88:
10:458–66.
145–51.
[26] Jo HY, Kim JH, Lee YJ, Lee M, Choh S-J. Evaluation of factors affecting mineral
[62] Lee KM, Jo YM. Synthesis of zeolite from waste fly ash for adsorption of CO2. J
carbonation of CO2 using coal fly ash in aqueous solutions under ambient
Mater Cycles Waste 2010;12:212–9.
conditions. Chem Eng J 2012;183:77–87.
[63] Karamanis D, Vardoulakis E. Application of zeolitic materials prepared from fly
[27] Chen S, Xiang W, Wang D, Xue Z. Incorporating IGCC and CaO sorption-
ash to water vapor adsorption for solar cooling. Appl Energy 2012;97:
enhanced process for power generation with CO2 capture. Appl Energy
334–9.
2012;95:285–94.
[64] Pérez-López R, Cama J, Nieto JM, Ayora C. The iron-coating role on the
[28] Gerbelová H, Versteeg P, Ioakimidis CS, Perrão P. The effect of retrofitting
oxidation kinetics of a pyritic sludge doped with fly ash. Geochim Cosmochim
Portuguese fossil fuel power plants with CCS. Appl Energy 2013;101:280–7.
AC 2007;71:1921–34.
[29] Wu Y, Wang C, Tan Y, Jia L, Anthony EJ. Characterization of ashes from a
[65] Yang YF, Gai GS, Cai ZF, Chen QR. Surface modification of purified fly ash and
100 kWth pilot-scale circulating fluidized bed with oxy-fuel combustion. Appl
application in polymer. J Hazard Mater 2006;133:276–82.
Energy 2011;88:2940–8.