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High Temperature CO2 Sorbents and Their Application For Hydrogen Production by Sorption Enhanced Steam Reforming Process
High Temperature CO2 Sorbents and Their Application For Hydrogen Production by Sorption Enhanced Steam Reforming Process
High Temperature CO2 Sorbents and Their Application For Hydrogen Production by Sorption Enhanced Steam Reforming Process
Review
h i g h l i g h t s
SESR is a forefront technology to produce highly pure H2 in one step.
High-temperature CO2 sorbents are the key element for successful SESR process.
Ca-based and alkaline-based sorbents are the most investigated high-temperature CO2 sorbents.
Capacity decay of Ca-based sorbents and slow kinetics of ceramics are the main challenges for industrial applications.
Development of efcient hybrid catalyst/sorbent materials is an interesting opportunity for research.
a r t i c l e
i n f o
Article history:
Received 2 April 2015
Received in revised form 10 June 2015
Accepted 11 June 2015
Available online 10 July 2015
Keywords:
High-temperature CO2 sorbents
CaO-based materials
Alkaline-based materials
Hybrid catalystsorbent materials
Sorption enhanced steam reforming
Review
a b s t r a c t
Among the available techniques for hydrogen production, the sorption enhanced steam reforming (SESR)
is an emerging technology consisting in the integration of reforming reaction (H2 production) and selective separation (CO2 sorption) in a single step, to shift thermodynamically the reforming reaction and
increase hydrogen production. It is a forefront technology to produce highly pure hydrogen that has several advantages against the conventional steam reforming operation. The key element for a successful
SESR process is the selection of suitable high-temperature CO2 sorbents. Due to the weakness of current
CO2 sorbents (capacity decay and/or slow kinetics), the improvement of their performance is crucial to
make the SESR process interesting for industrial applications. This review focuses on the main characteristics and preparation methods of CaO-based and alkaline-based sorbents, their advantages and
drawbacks, the available techniques to improve their behavior in severe operating conditions, as well
as the progress of their application in two important SESR processes, namely sorption enhanced steam
methane reforming (SESMR) and sorption enhanced steam glycerol reforming (SESGR).
2015 Elsevier B.V. All rights reserved.
Contents
1.
2.
3.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
High temperature CO2 sorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.
CaO-based sorbents. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.1.
Application of various sources of calcium to produce CaO sorbent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.2.
Metal-stabilized CaO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.3.
Additional treatments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.
Ceramic CO2 sorbents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.1.
Lithium zirconate (Li2ZrO3) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.2.
Lithium orthosilicate (Li4SiO4) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.3.
Sodium zirconate (Na2ZrO3). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.4.
Other ceramic materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.5.
Kinetic models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Hydrogen production by sorption enhanced steam methane reforming (SESMR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Corresponding author. Tel.: +1 418 656 2204; fax: +1 418 656 5993.
E-mail address: maria-cornelia.iliuta@gch.ulaval.ca (M.C. Iliuta).
http://dx.doi.org/10.1016/j.cej.2015.06.060
1385-8947/ 2015 Elsevier B.V. All rights reserved.
421
421
421
423
424
427
431
431
433
434
434
435
435
4.
5.
3.1.
Application of CaO-based sorbents in SESMR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.
Application of ceramic sorbents in SESMR . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Hydrogen production by sorption enhanced steam glycerol reforming (SESGR) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusion and recommendations for future works . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1. Introduction
Carbon dioxide (CO2) is a greenhouse gas (GHG) naturally present in the atmosphere. However, the increase of CO2 concentration due to human activities is the main factor that contributes
to Earths global warming. In May 2015 the CO2 concentration
reached 403 ppm, representing an increase by approximately 38%
in comparison with the middle of the 19th century [1]. Most
anthropogenic CO2 emissions come from the use of fossil fuels
for energy production in power plants, car engines and heating
processes. Hence, the continuous increase of global consumption
of energy is largely reected by the increase of CO2 emissions.
Among diverse possible approaches to lower the CO2 emissions,
the reduction of fossil fuel consumption by the increase of processes efciency and switch to less carbon-intensive fuels (e.g., natural gas) and/or to free-carbon energy sources (e.g., biomass) are
the most effective and economic methods to meet the goals of environmental rules [2]. In addition, the development of more efcient
and cost-competitive technologies to capture and storage the CO2
(CCS) has recently attracted considerable interest as an option to
control CO2 emissions. Post-combustion, pre-combustion and
oxy-combustion are the main methods for CO2 capture [3]. The
principle of post-combustion is to separate CO2 from combustion
exhaust gases that mainly contain CO2, N2 and O2. In the case of
oxy-combustion, pure oxygen is used rather than air for fuel combustion to avoid the dilution of CO2 by N2; as the resulting exhaust
practically contains only CO2 and water vapor, the CO2 can be easily
separated. The pre-combustion capture involves the gasication of
fossil fuels, which are rst converted into a mixture of hydrogen
and CO2; CO2 is therefore removed prior to combustion process.
Among several available technologies for CO2 capture like
chemical absorption, membranes and solid sorbents, the absorption based on chemical solvents (especially amine-based solutions)
is the most commonly used method for post-combustion CO2 capture due to its high CO2 removal efciency, particularly at low CO2
partial pressure. The use of solid sorbents is the most efcient technique for pre-combustion capture. Most available works in the
open literature are directed on high temperature solid sorbents like
lithium zirconate (Li2ZrO3) [4,5], sodium zirconate (Na2ZrO3) [6,7],
lithium silicate (Li4SiO4) [810] and CaO-based sorbents [1113].
High CO2 sorption capacity and adsorption/desorption kinetics
rate, relatively mild regeneration temperature, and multi-cycle stability are the most important parameters to be taken into account.
Therefore, there are still lots of challenges in the development of
efcient CO2 sorbents, especially related to long-term cyclic stability, capacity of sorption, regeneration condition and rate of CO2
capture.
Up to now, several research groups have provided review
papers about different strategies used to overcome the decay in
CO2 capture capacity of CaO-based sorbents over multiple carbonation/calcination cycles, including synthesis of CaO-based sorbents
from different precursors, stabilization of sorbents by incorporating CaO in support materials, and reactivation of sorbents with
hydration, thermal pretreatment and chemical pretreatment [14
17]. Wang et al. [18] provided a review on the synthesis methods,
CO2 adsorption/desorption characteristics and possible sorption
mechanisms for LixZryOz with different Li/Zr ratios, but it did not
421
436
438
439
440
441
441
422
Fig. 1. Sintering phenomenon of CaO; light grey: CaO phase and dark grey: CaCO3 phase [26].
Fig. 2. Typical weight changes vs. time for a repeated number of calcination/carbonation cycles of Piaseck limestone [23].
low temperature (550 C), whereas this value was higher for limestone derived CaO sorbent at high temperatures (600675 C). As a
matter of fact, at the beginning of the reaction, the growth of CaCO3
layer for limestone was faster than that of dolomite because of the
higher rate of reaction. Since Knudsen diffusion is related to the
square root of temperature, the diffusion through CaCO3 layer
enhanced as the temperature increased above 550 C. Therefore,
limestone showed a higher ultimate conversion at 600 and 675 C.
Some researchers studied the CO2 sorption behavior of limestone in long-term cyclic operation. Grasa and Abanades [23] evaluated the CO2 capture performance of limestone over 500
carbonation/calcination cycles and observed that the CO2 uptake
capacity signicantly decreased during the rst 20 cycles and then
stabilized along with the cycle number around 0.0750.08 residual
conversion up to 500 cycles. For CaO sorbent, Fig. 2 shows the
decrease of CO2 capture capacity along with the cycle number, as
well as the kinetic steps. In another study, Sun et al. [24] examined
the CO2 sorption behavior of limestone through more than 1000
carbonation/calcination cycles. They reported a calcium conversion
between 4% and 17% (depending on the carbonation time) after
150 cycles.
Some kinds of natural CaO sorbent containing MgO, such as
dolomite and huntite, possess better stability during cyclic operations. Silaban et al. [11] observed that after six adsorption/desorption cycles, the capture capacity of limestone was decreased from
61% to 35% of its theoretical value. However, dolomite was already
stable at a sorption capacity of 40%. The behavior of dolomite was
ascribed to the presence of MgO in its structure, which provided a
better structural stability. Bandi et al. [32] examined the CO2 capture activity of calcite, dolomite and huntite for 47 adsorption/desorption cycles. The experimental results showed that huntite could
423
Reaction conditions
Ads.
Reactor
Number
of cycles
TGA
TGA
TGA
TGA
TGA
TGA
TGA
27
17
9
57
100
60
20
0.49
0.5
0.66
0.19
0.17
0.39
0.39
[13]
[13]
[39]
[39]
[30]
[45]
[45]
FB
FB
TGA
TGA
TGA
TGA
TGA
TGA
9
9
11
20
20
9
9
9
0.303
0.285
0.40
0.51
0.2
0.32
0.1
0.25
[40]
[40]
[34]
[46]
[46]
[35]
[35]
[35]
Reg.
Calcium acetate
Calcium acetate
Calcium D-gluconate
Calcium D-gluconate
Nano-CaCO3 (40 nm)
Calcium naphthenate (FSP-made CaO)
Calcium naphthenate (FSP-made CaO)
700 C,
700 C,
650 C,
650 C,
650 C,
700 C,
700 C,
30%
30%
15%
15%
15%
30%
30%
CO2,
CO2,
CO2,
CO2,
CO2,
CO2,
CO2,
CaAc2
CaCO3
CaCO3
Ca(NO3)24H2O
Ca(NO3)24H2O
CaO
CaCO3
Ca(OH)2
650 C,
650 C,
650 C,
650 C,
650 C,
750 C,
650 C,
650 C,
15.30% CO2
15.30% CO2
15% CO2, 2 h
15% CO2, 15 min
15% CO2, 15 min
100% CO2, 40 min
100% CO2, 30 min
100% CO2, 40 min
300 min
10% H2O, 300 min
30 min
30 min
20 min
300 min
5 min
preserve around 84% of its initial capacity, while dolomite and calcite were able to maintain 55% and 38% of their initial capacity,
respectively. However, huntite possessed less CO2 uptake capacity
in comparison to dolomite and calcite because of its higher content
of inactive MgO. According to these studies, the deactivation of
CaO sorbent derived from natural sources is unavoidable.
Different strategies have therefore been proposed to improve the
CO2 sorption performance of CaO sorbent, such as (i) application
of various sources of calcium to produce CaO sorbent, (ii) incorporation of stable inert materials into CaO structure, and (iii) reactivation and treatment of sorbent.
2.1.1. Application of various sources of calcium to produce CaO sorbent
Many research groups have focused on the production of CaO
sorbents from various calcium precursors, including CaCO3 [33
35], Ca(OH)2 [3537], organometallic [13,3843] and nano-sized
CaO/CaCO3 [39,42,4449], with the aim of providing a CaO-based
sorbent with meso- and macroporous structure, high specic surface area, large pore volume, and small particle size (Table 1).
These specications are mandatory for a sorbent with high and
stable CO2 capture capacity. The performance of CaO sorbents
derived from two most promising groups, organometallic and
nano-sized CaO/CaCO3 precursors are further discussed.
2.1.1.1. Organometallic precursors. Up to now, a number of studies
have reported the production of CaO sorbents from various
organometallic precursors (OMPs) and the relation between the
structural characteristics of OMPs-derived CaO sorbents with their
CO2 uptake performance [13,3843]. The decomposition of OMPs
leads to the formation of meso- and macroporous structures with
large surface area, which results in the enhancement of CO2 capture performance [13,39]. In an earlier work, Silaban et al. [43]
found that CaO synthesized from calcium acetate possessed a
higher CO2 capture capacity than CaO synthesized from calcium
carbonate independent of the calcination temperature. Similarly,
Lu et al. [13] examined the CO2 capture activity of the CaO sorbents
derived from calcium acetate monohydrate, calcium carbonate,
calcium hydroxide, and calcium nitrate tetrahydrate. According
to the experimental results, the CaO sorbent obtained from calcium
acetate demonstrated the best performance with a CO2 sorption
capacity of 0.49 g of CO2/g of sorbent after 27 cycles (carbonation
at 700 C under 30% CO2/He balance and calcination at 700 C
under He), because of its large BET surface area and pore volume.
The SEM images revealed that this sorbent contained a uffy structure, which contributed to its high surface area and large pore volume. In a further study, Liu et al. [39] prepared CaO sorbents using
CO2 uptake at
last cycle (g-CO2/g-ads)
Ref.
2.1.1.2. Nano-sized CaO and CaCO3. For porous CaO with critical particle size less than 44 nm or a large single CaO crystal with critical
crystal size less than 220 nm, the carbonation reaction completes
within the fast kinetically-controlled regime and the slow
solid-state diffusion controlled regime does not exist [47,50].
Therefore, different research groups studied nano-sized CaO and
CaCO3 as calcium precursors [39,42,4449]. All of these studies
show that nano-sized sorbents possess much better CO2 capture
activity in comparison to micro-sized CaO. However, there are
two primary hurdles for using the nano-sized CaO sorbents in practical applications: (i) the nano-sized CaO sorbents synthesized
from nano-sized particles are susceptive to sintering because of
higher surface area [44]; (ii) the methods used for the synthesis
424
Table 2
Summary of investigations on metal oxide stabilized CaO-based sorbents.
Stabilizer
Stab.
content (wt%)
Reaction conditions
Ca12Al14O33
Ca12Al14O33
Ca12Al14O33
Ca12Al14O33
Ca12Al14O33
Ca12Al14O33
Ca12Al14O33
Ca12Al14O33
Ca12Al14O33
Ca12Al14O33
Ca9Al6O18
Ca12Al14O33
Ca12Al14O33
Ca12Al14O33
Ca12Al14O33
Ca12Al14O33
Ca12Al14O33
Ca12Al14O33
Ca12Al14O33
Al2O3
Al2O3
Al2O3
Ca9Al6O18
Ca9Al6O18
Ca9Al6O18
Ca9Al6O18
Ca9Al6O18
Ca9Al6O18
Ca3Al2O6
Ca3Al2O6
Cement
MgO
MgO
MgO
MgO
MgO
MgO
CaZrO3
CaZrO3
CaZrO3
CaZrO3
CaZrO3
CaZrO3
CaZrO3
CaZrO3
TiO2
TiO2
Mesoporous silica shell
Silica
Y2O3
Y2O3
25
25
25
25
25
65
15
7.7
7.7
9.2
20
42
42
7.7
25
14.7
?
39
19
19
8
20
20
20
7.5
7.5
22.1
34
9
10
26
25
25
25
25
25
58
10
30
30
N.a.
30
26.2
58.16
10
43
14.7
20
20
690 C,
690 C,
700 C,
700 C,
690 C,
650 C,
750 C,
690 C,
650 C,
750 C,
650 C,
700 C,
850 C,
650 C,
700 C,
675 C,
550 C,
600 C,
600 C,
750 C,
700 C,
710 C,
650 C,
650 C,
650 C,
650 C,
650 C,
650 C,
690 C,
650 C,
850 C,
758 C,
700 C,
750 C,
650 C,
650 C,
700 C,
700 C,
650 C,
650 C,
650 C,
800 C,
700 C,
650 C,
600 C,
600 C,
400 C,
675 C,
675 C,
650 C,
650 C,
Ads.
Reactor
Number
of cycles
Ref.
TGA
TGA
TGA
TGA
TGA
TGA
FB
TGA
TGA
TGA
TGA
TGA
TGA
TGA
TGA
TGA
PB (Packed-bed)
TGA
TGA
TGA
TGA
TGA
TGA
TGA
TGA
TGA
TGA
TGA
TGA
TGA
TGA
TGA
TGA
TGA
TGA
TGA
TGA
TGA
TGA
TGA
TGA
PB (packed bed)
TGA
TGA
TGA
TGA
TGA
TGA
TGA
TGA
TGA
13
13
50
56
45
50
20
30
30
30
28
100
100
30
100
31
10
150
40
30
10
15
35
35
50
31
31
25
45
100
30
50
60
1250
24
44
50
100
30
30
20
90
1050
25
15
40
1
31
31
10
10
0.45
0.333
0.41
0.22
0.26
0.19
0.26
0.37
0.22
0.55
0.51
0.4
0.25
0.6
0.4
0.27
0.34
0.130.15
0.4
0.36
0.31
0.62
0.52
0.2
0.48
0.57
0.33
0.33
0.45
0.35
0.17
0.53
0.44
0.17
0.56
0.46
0.54
0.3
0.37
0.31
0.48
0.34
0.30
0.29
0.15
0.23
0.2
0.24
0.15
0.57
0.49
[12]
[12]
[65]
[65]
[66]
[67]
[68]
[76]
[80]
[79]
[63]
[69]
[69]
[52]
[74]
[61]
[194]
[72]
[83]
[75]
[75]
[73]
[195]
[195]
[51]
[78]
[78]
[71]
[77]
[64]
[125]
[86]
[53]
[54]
[87]
[55]
[88]
[45]
[92]
[92]
[29]
[93]
[91]
[71]
[90]
[56]
[58]
[61]
[61]
[62]
[62]
Reg.
14% CO2, 30 min
14% CO2, 30 min
20% CO2, 30 min
20% CO2, 30 min
15% CO2, 30 min
33% CO2, 10 min
14% CO2, 8.3 min
15% CO2, 30 min
15% CO2, 10 min
40% CO2,20 min
15% CO2, 30 min
30% CO2, 10 min
100% CO2, 10 min
15% CO2, 30 min
90% CO2
100% CO2, 20 min
7% CO2, 27% H2O, 12 min
20% CO2, 25 min
100% CO2, 10 min
40% CO2, 20 min
40% CO2, 20 min
100% CO2, 30 min
15% CO2, 30 min
15% CO2, 30 min
0.015 MPa CO2, 30 min
100% CO2, 30 min
100% CO2, 30 min
15% CO2, 30 min
15% CO2, 30 min
20% CO2, 30 min
100% CO2, 10 min
100% CO2, 30 min
90% CO2
25% CO2, 20 min
15% CO2, 30 min
15% CO2, 30 min
20% CO2, 10 min
30% CO2, 30 min
15% CO2
100% CO2
100% CO2, 60 min
50% CO2, 5 min
100% CO2, 30 min
15% CO2, 30 min
100% CO2, 30 min
20% CO2, 10 min
100% CO2, 30 min
100% CO2, 20 min
100% CO2, 20 min
20% CO2, 30 min
20% CO2, 30 min
precursors as well as synthesis method [12,63,64]. The inert support materials are distributed between the CaO particles during
the synthesis procedure and prevent the sintering phenomenon
during multiple carbonation/calcination cycles resulting in the
enhancement of CO2 capture performance. One of the earliest
reports about the synthesis of Al-stabilized CaO-based sorbents
has been published by Li et al. [12,65]. They developed
Ca12Al14O33-stabilized CaO sorbent from aluminum nitrate nonahydrate (Al(NO3)39H2O) and calcium oxide precursors via wet
mixing method. The synthesized sorbent consisting of 75 wt.%
CaO and 25 wt.% Ca12Al14O33 presented the highest adsorption
capacity of 0.41 g of CO2/g of sorbent at the end of the 50th cycle
under mild calcination conditions (850 C, 100% N2). Using more
realistic calcination conditions (980 C, 100% CO2) reduced the
adsorption capacity to 0.22 g of CO2/g of sorbent after 56 cycles.
However, it is still more than the CO2 capture capacity of dolomite
(0.16 g of CO2/g of sorbent).
Encouraged by the promising results reported by Li et al.
[12,65], several attempts have been made to incorporate aluminum compounds to the CaO structure, mainly focusing on the
application of different calcium and aluminum precursors
[63,66,67], optimization of Ca/Al ratio [6870], and use of different
synthesis methods [64,7180].
Zhou et al. [63] employed a wet-mixing technique to synthesize
Al-stabilized CaO sorbents from various calcium and aluminum
precursors. They found that different inert support materials,
including Al2O3, Ca12Al14O33 or Ca9Al6O18, could be produced
depending on calcium and aluminum precursors used during the
synthesis process. According to the experimental results, most of
the Al-stabilized CaO sorbents showed higher CO2 sorption capability and stability during multi-cyclic carbonation/calcination
operation in comparison to pure CaO, which was attributed to
the bimodal pore size distribution with an adequate number of
small pores, the high specic surface area of sorbents, and the uniform distribution of inert support materials among CaO particles.
Among the developed sorbents, CaO/Ca9Al6O18 derived from calcium citrate and aluminum nitrate presented the best performance
with the CO2 capture capacity of 0.51 g of CO2/g of sorbent after 28
cycles. The authors also proposed a formation mechanism for the
support materials (Fig. 3). The transition between steps 3 and 4
depends on the precursors used during the synthesis step, which
can limit Ca2+ diffusion into the stabilizer structure for further
reaction.
Pacciani et al. [68,70] prepared a number of CaO/Ca12Al14O33
synthetic sorbents with different CaO/inert material ratios.
Among the studied materials, the sorbent consisting of 85 wt.%
CaO and 15 wt.% Ca12Al14O33 showed the highest activity in a uidized bed reactor with a CO2 capture capacity of 0.26 g of CO2/g
of sorbent after 20 cycles (adsorption under 14% CO2 ow and
regeneration under pure N2), which decreased to 0.17 g of CO2/g
of sorbent after 110 cycles. In another study, Koirala et al. [69]
applied the single nozzle ame spray pyrolysis method to synthesize Al-stabilized CaO sorbents with different Al/Ca ratios. They
found that a higher Al doping into CaO improved the sorbent stability. According to the multiple carbonation/calcination experiments, the synthetic sorbent with the Al/Ca molar ratio of 3:10
exhibited the best performance with a CO2 uptake capacity of
0.40 g of CO2/g of sorbent, which was stable over 100 cycles. The
improved durability of Al-stabilized CaO sorbents was owing to
the uniform distribution of Ca12Al14O33, which was produced in
(1)
(2)
Ca & Al precursors
CaCO3 +Al2 O3
CaO+Al2 O3
CO2 , H 2O
CO2
( 3)
( 4)
425
the synthesis step, among the CaO particles. The sorbent with the
Al/Ca molar ratio of 3:10 also performed well under severe calcination conditions, indicating a residual sorption capacity of 0.25 g
of CO2/g of sorbent at the 100th cycle. These results revealed that
the presence of CO2 in the regeneration step led to the accelerated
structural sintering.
Recently, different research groups have developed various synthesis methods with the aim of increasing surface area and pore
volume and obtaining high dispersion of inert supports within
the sorbent structure: wet mixing [12,63,65,66,68,70], limestone
acidication by citric acid followed by two step calcination [71],
solid-state reaction [72], ultrasonic spray pyrolysis (USP) [73],
combination of precipitation and hydration [74], co-precipitation
[75], citrate preparation [64], solgel [77,79], citrate-assisted sol
gel technique followed by two-step calcination [78], single nozzle
ame spray pyrolysis (FSP) [69], and precipitation [80]. Some of
these techniques result in Al-stabilized CaO sorbents with a great
performance in cyclic carbonation/calcination experiments.
Sayyah et al. [73] developed a series of Al-stabilized CaO sorbents
using ultrasonic spray pyrolysis (USP) method. The precursors, calcium nitrate tetrahydrate (Ca(NO3)24H2O) and aluminum nitrate
nonahydrate (Al(NO3)39H2O), were solved in ethanol. The
obtained solution was nebulized via ultrasound, followed by carrying through a furnace tube (set at 600 C) by argon gas. The synthesized sorbents were tested in carbonation (710 C, 100% CO2) and
calcination (950 C, 100% N2) cyclic operations. The results showed
that the optimum value for Al/Ca ratio is around 0.08. The CO2
adsorption capacity of this sorbent decreased from 0.65 g of
CO2/g of sorbent to 0.62 g of CO2/g of sorbent over 15 calcination/carbonation cycles. The high performance of the sorbents showed
the capability of USP method in homogenous dispersion of additives in the CaO matrix and production of materials with high surface area and high stability. Zhang et al. [64] applied the citrate
preparation route to synthesize a Ca-based sorbent consisting of
9 wt.% Al2O3 and 91 wt.% CaO from aluminum nitrate, citric acid,
and CaCO3. The developed sorbent was activated by a four-step
activation procedure instead of the common one-step activation
mode that promoted the formation of porous structure because
of the release of CO2, H2O, and NO2 step by step under the mild
activation conditions. Therefore, the developed CaOAAl2O3 sorbent
showed a larger pore volume (0.85 cm3/g) and higher specic surface area (958 m2/g) compared to the untreated CaO (pore volume:
0.03 cm3/g, specic surface area: 5 m2/g). Moreover, XRD patterns
exhibited the formation of the stabilizer Ca3Al2O6 in the developed
CaOAAl2O3 sorbent after 16 carbonation and calcination cycles,
which prevented the severe sintering of CaO particles. The developed CaOAl2O3 and untreated CaO sorbents showed the CO2 capture capacity of 0.35 g of CO2/g of sorbent after 100 cycles and
0.2 g of CO2/g of sorbent after 50 cycles, respectively (carbonation
at 650 C under 20% CO2 and calcination at 850 C under 100% N2).
Angeli et al. [77] developed a CaOACa3Al2O6 sorbent by a modied
solgel method. TEA (complexing agent) was added into a mixture
of Ca(NO3)24H2O and Al(NO3)39H2O diluted in distilled water at
the temperature of 50 C to obtain a molar ration of 1:1
(TEA/metals). A brown viscous solution was obtained when the
most of the water was evaporated. This solution was dried overnight at 185 C and then calcined at 900 C for 1.5 h in air. This sorbent indicated a high CO2 uptake capacity of 0.45 g of CO2/g of
sorbent (corresponding to 84% carbonation conversion), which
was maintained through 45 cycles under mild conditions (calcination at 800 C under 100% N2). The high and stable CO2 uptake
capacity was attributed to the synthesis procedure. The TEA
decomposition emitted a large amount of gases, which led to the
formation of coral-like structure. In addition, the TEA-ion complexes formed during the preparation step resulted in the uniform
dispersion of Al and Ca ions. It is worth mentioning that the
426
proposed sorbent represented higher stability compared to previously reported Ca-based sorbents at severe conditions. It maintained approximately 40% of its initial CO2 uptake capacity at the
end of the 100th cycle under severe conditions (calcination at
950 C under 100% CO2). Radfarnia and Sayari [78] employed a
citrate-assisted solgel technique followed by two-step calcination
procedure (under inert and air atmosphere) to develop an efcient
Al-stabilized CaO sorbent (92.5 wt.% CaO/7.5 wt.% Al2O3). After 31
carbonation/calcination cycles, the CO2 capture capacity of the synthetic sorbent was 0.57 and 0.33 g of CO2/g of sorbent under mild
and severe calcination conditions (mild condition: 800 to 900 C,
100% N2; severe condition: 930 C, 100% CO2), respectively. They
reported no loss of activity during 31 cycles, when calcination
was performed at 800 C under pure N2 ow. The high stability
of the proposed sorbent was on account of the uniform dispersion
of Ca9Al6O18 binder throughout the CaO matrix, which controlled
the structural sintering.
Ca-based sorbents derived from Ca-Al layered double hydroxides (LDHs) exhibit high stability during multiple carbonation/calcination cycles due to the uniform distribution of calcium
aluminates between CaO particles [8184]. Chang et al. [82]
applied a solgel method to develop CaAAl LDH-derived
mixed-metal oxides by using Al(OiPr)3 and Ca(NO3)2 as the precursors and hexadecyl trimethyl ammonium bromide (CTAB) as the
structure-directing agent. For the developed sorbents with a
Ca2+/Al3+ ratio of 1:1, only the Ca12Al14O33 phase was identied
after calcination at 600 C. For the sorbents with a higher
Ca2+/Al3+ ratio, the CaO phase was observed along with
Ca12Al14O33. The CaAAl mixed-metal oxides (CAMO) displayed
high specic surface areas of up to 191 m2 g1 and a pore size distribution in the range of 36 nm, allowing rapid diffusion of CO2
throughout the sorbent, inducing relatively rapid CO2 absorption
kinetics and enhancing the sintering-resistant nature through multiple carbonation/calcination cycles for CO2 capture. The CAMO
showed a high CO2 capture capacity of 49 wt.%, as well as a fast
CO2 absorption kinetics in considerably short period of 5 min for
the Ca2+/Al3+ = 7 composition. Moreover, this sorbent exhibited
highly stable CO2 capture capacity at high temperatures with only
26% capacity decay after 50 multiple carbonation/calcination
cycles. As a conclusion, the CAMO framework is a good insulator
for inhibiting the aggregation of CaO particles and therefore, it is
suitable for long-term cyclic operation at high temperatures.
Chang et al. [83] developed CaAAl LDH nanoparticles by a reverse
microemulsion method. The results showed no apparent reduction
in CO2 sorption capacity over multi-cycle carbonation/calcination
experiments because of the formation of Ca12Al14O33 oxide during
nanoparticle synthesis, which could avoid the intimate contact
between CaO nanoparticles. Yu et al. [84] employed an hydrothermal method to synthesize calciumAaluminum carbonate
(CaAAlACO3) sorbents with the Ca/Al molar ratio of 1:1 to 30:1
from calcium acetate and aluminum nitrate. By increasing the
Ca/Al molar ratio, the CO2 capture capacity increased from 13.4
to 74.2 wt.% because more Ca2+ loading in CaAAlACO3 formation
resulted in higher concentration of CaO in the synthetic sorbents
after calcination. However, the stability of the sorbent in cyclic
operation might decline with high Ca/Al ratio. The stability of the
CaAAlACO3 sorbent with the Ca/Al molar ratio of 7:1 during 10
cycles was 99% in TG analyzer (regeneration at 750 C under
100% N2) and 76% in the reactor (regeneration at 750 C under
40% CO2).
2.1.2.2. Mg-stabilized CaO. MgO is another inert support material
that is capable of stabilizing the CO2 uptake because of its high
Tammann temperature (1276 C). To obtain a very high and stable
CO2 capture capacity, it is imperative to mix the Ca and Mg ions on
a molecular level. The Mg-stabilized CaO-based sorbents that are
427
428
Table 3
Summary of investigations on treated CaO sorbents.
Sorbent
Treated by
Reaction conditions
Ads.
Limestone
CaCO3
Limestone
Limestone
Limestone
Limestone
Limestone
Limestone
Limestone
Limestone
Limestone
Al2O3-stabilized CaO-based
Pelletized Al2O3-stabilized CaO-based
Ca(OH)2
Limestone
Limestone
Limestone
Limestone
Limestone
Limestone
Limestone
Acetic acid
Propionic acid
Pyroligneous acid
Citric acid
Ethanol
Steam (hydration)
Steam (hydration)
Pre-heat
Ethanol/water solution with the
volume ratio of 3
Pre-heat (950 C, 100% air, 12 h) and
recarbonation (850 C, 90% CO2,
3 min)
Steam (hydration)
Acetic acid
Steam
Steam
Acetic acid
Vinegar
Formic acid
Oxalic acid
10 wt% Aluminate cement, 10% Starch
Steam (hydration)
Steam
Steam
Pre-heat
Recarbonation after each carbonation
(800 C, 100% CO2, 5 min)
Heat-pretreated
Heat-pretreated
Heat-pretreated & recarbonation at
800 C in 90% CO2 for 3 min
Ground + Heat-pretreated (850 C,
12 h)
Ground + Heat-pretreated (950 C,
12 h)
Liquid water and steam hydration
650 C,
700 C,
700 C,
700 C,
700 C,
700 C,
780 C,
800 C,
600 C,
Number
of cycles
920 C,
850 C,
850 C,
750 C,
920 C,
850 C,
960 C,
800 C,
700 C,
DFR
DFR
DFR
TGA
DFR
TGA
TGA
TGA
TGA
20
100
103
18
15
10
10
30
11
0.39
0.24
0.26
0.485
0.31
0.55
0.47
0.39
0.62
[121]
[120]
[122]
[123]
[118]
[104]
[105]
[110]
[119]
Ref.
TGA
50
0.27
[116]
650 C,
650 C,
650 C,
650 C,
650 C,
650 C,
650 C,
650 C,
700 C,
650 C,
600 C,
600 C,
650 C,
650 C,
900 C,
920 C,
925 C,
925 C,
850 C,
850 C,
850 C,
850 C,
900 C,
940 C,
900 C,
900 C,
850 C,
875 C,
TGA
TGA
TGA
TGA
TGA
TGA
TGA
TGA
FB (Fluidized-bed)
TGA
TGA
TGA
TGA
10
20
15
15
20
20
20
20
10
5
10
10
50
75
0.40
0.09
0.11
0.16
0.23
0.15
0.22
0.25
0.65
0.37
0.52
0.31
0.17
0.13
[97]
[126]
[96]
[96]
[124]
[124]
[124]
[124]
[127]
[106]
[95]
[95]
[113]
[115]
TGA
TGA
TGA
20
20
20
0.09
0.05
0.03
[117]
[117]
[117]
TGA
10
0.37
[114]
TGA
10
0.45
[114]
TGA
100
0.23
[109]
Limestone
Limestone
Limestone
Limestone
Limestone
Limestone
CaCO3
Limestone
Ca(Ac)2
Reactor
Reg.
They reported that although the presence of steam with the concentration of 15% for carbonation led to a 15% point increase in
conversion after 15 cycles, the presence of steam with the concentration of 40% for calcination only led to a 5% point increase after
15 cycles. However, Rong et al. [97] mentioned that steam addition
during carbonation (20 and 40 vol.%) resulted in only 23%
increase in the carbonation conversion of CaO sorbent after 10 carbonation/calcination cycles by decreasing the diffusion resistance
through the CaCO3 product layer. The poor enhancement of carbonation conversion by hydration treatment during carbonation
was justied by the limited increase of carbonation conversion in
the diffusion-control stage. In overall, steam hydration during carbonation and calcination processes have less impacts on the carbonation conversion in comparison to the separate hydration
treatment.
Introducing water or steam to CaO after regeneration is the
most important hydration approach. Calcium hydroxide
(Ca(OH)2) is produced during this hydration treatment and leads
to the agglomerate breakage because of its expanded molar volume. Therefore, separate hydration treatment after calcination
increases the specic surface area and pore volume of spent sorbent, resulting in the sorbent reactivation. This approach is briey
called steam reactivation. In an early work, Manovic and
Anthony [104] investigated the steam reactivation of spent limestone in a pressurized reactor at 200 C. According to the cyclic carbonation/calcination experiments, the reactivated limestone
showed the average CO2 capture capacity of about 0.55 g of
CO2/g of sorbent over 10 cycles, which was considerably higher
than that of the original sorbent (0.27 to 0.31 g of CO2/g of
sorbent).
Rong et al. [97] showed that different parameters such as steam
concentration, hydration temperature, and hydration frequency
affected the spent sorbent reactivation. Increasing the steam concentration during hydration treatment led to a better reactivation
performance by retaining more small pores and therefore, increasing the ultimate conversion of the fast kinetically control phase of
carbonation. However, hydration treatment at high temperatures
resulted in a lower carbonation conversion during carbonation/calcination cycles, which was on account of more severe sintering of
Ca(OH)2 at a higher hydration temperature. With respect to the
hydration frequency, hydration after every 3 cycles and once hydration did not represent satisfying reactivation performance during
cyclic CO2 sorption operation because of more severe sintering of
CaO sorbents derived from Ca(OH)2. The activity of the spent sorbent was recovered by separate steam hydration after every calcination step. Recently, Coppola et al. [106] assessed the effects of
water hydration on the CO2 capture capacity and attrition tendency
of a limestone-derived CaO sorbent. The results demonstrated that
the CO2 capture capacity of sorbent increased from 0.04 g of CO2/g
of sorbent in the last carbonation before hydration to 0.320.37 g of
CO2/g of sorbent in the rst carbonation after hydration, because of
particle swelling and development of active porosity. However, the
capacity quickly decayed along with the cycles due to the severe
sintering of Ca(OH)2-derived CaO sorbents. In addition, the sorbent
hydrated for 60 min showed larger CO2 capture capacity, as well as
limited attrition tendency. In fact, two distinct time scales should
be considered for the optimal design of hydration stage: (i) the time
required for full hydration of the free lime (water uptake) and (ii)
the time required for improving the connectivity and mechanical
stability of particles by wet chemical sintering. Although 10 min
was enough for water uptake, wet chemical sintering was not
achieved during this time. Moreover, more soaking time (more than
60 min) led to a decrease of CO2 uptake capacity without any significant improvement in its attrition resistance.
Hydration treatment of the spent limestone not only recovers
its CO2 capture capacity but also signicantly increases its attrition
429
430
431
cement and 510 wt.% starch indicated a higher and more stable
CO2 capture capacity in multi-cyclic carbonation/calcination
experiments in comparison to the natural limestone. After 10 carbonation (at 700 C in 15% CO2/air balance) and calcination (at
900 C in air) cycles, the pellets containing 10 wt.% aluminate
and 10 wt.% starch offered a capture capacity of 0.65 g of CO2/g
of pellets, which was higher compared to pellets of natural limestone (0.5 g of CO2/g of pellets). The excellent performance of
the pellets developed with aluminate cement and starch was
attributed to the increase of pore volume of pellets because of
starch decomposition during calcination and the deceleration of
sintering due to the presence of alumina which has a high melting
point.
2.2. Ceramic CO2 sorbents
In addition to CaO-based sorbents, alkaline ceramic materials
have also been proposed as potential candidates for CO2 removal
processes such as SESR [4,6,128137]. However, their kinetic limitations during the CO2 capture still remain their main hurdle. The
literature data for lithium zirconate (Li2ZrO3), lithium orthosilicate
(Li4SiO4), and sodium zirconate (Na2ZrO3), which are the most
investigated ceramic sorbents, is summarized in Table 4. The carbonation reactions for the most well-known alkaline oxide sorbents are as follow:
Li2 ZrO3 s CO2 g $ Li2 CO3 s ZrO2 s DH 298 160 kJ=mol
2
Na2 ZrO3 s CO2 g $ Na2 CO3 s ZrO2 s DH 298 149 kJ=mol
3
Li4 SiO4 s CO2 g $ Li2 CO3 s Li2 SiO3 s DH 298 143 kJ=mol
4
2.2.1. Lithium zirconate (Li2ZrO3)
In 1998, Nakagawa and Ohashi [4] proposed Li2ZrO3 as a
promising candidate for CO2 adsorption. The material has a theoretical uptake capacity of 0.28 g of CO2/g of sorbent in the temperature range of 450600 C. They employed solid-state reaction of
Li2CO3 and ZrO2 precursors to prepare Li2ZrO3. The synthesized
sorbent showed the CO2 capture capacity of 0.22 g of CO2/g of sorbent at the temperature of 500 C under a ow containing 20 vol.%
CO2 and 80 vol.% H2. In a further study, the same research group
[135] synthesized potassium carbonate doped Li2ZrO3 (K-Li2ZrO3)
via solid-state reaction method. The developed sorbent showed a
higher CO2 adsorption rate in comparison to the undoped
Li2ZrO3. The signicant improvement in kinetic rate was ascribed
to the formation of a eutectic molten carbonate layer of Li2CO3
and K2CO3 above 500 C, which considerably increased the CO2 diffusion rate. Later, Ida and Lin [136] proposed a comprehensive
double-shell model to explain the mechanism of CO2 chemisorption on pure and potassium-doped Li2ZrO3 sorbents. According to
their model, CO2 reacts with Li+ and O2 ions after diffusion to
the surface of Li2ZrO3 to form ZrO2 and Li2CO3. These materials
form a double solid shell around the unreacted Li2ZrO3 (Fig. 5).
At this step, Li+ and O2 have to diffuse through the ZrO2 layer to
react with CO2 and also CO2 molecules have to diffuse through
the Li2CO3 layer for reaction. Therefore, the adsorption rate begins
to decrease. In the case of K-Li2ZrO3, the formation of a eutectic
molten carbonate layer of Li2CO3 and K2CO3 enhances the adsorption kinetic rate by increasing the CO2 diffusion rate through the
external layer. However, Ochoa-Fernandez et al. [138] showed that
despite the positive effect of potassium carbonate doping into
Li2ZrO3 on the kinetic rate of CO2 adsorption, the CO2 capture
432
Table 4
Summary of investigations on ceramic-type sorbents.
Sorbent
Synthesis technique
Reaction conditions
Li2ZrO3
Li2ZrO3
Li2ZrO3
Li2.2ZrO3.1
KALi2ZrO3a
K0.2ALi1.6ZrO2.9
K0.2ALi1.6ZrO2.9
KALi2ZrO3b
Li2ZrO3
Citrate solgel
Co-precipitation
Liquid-state
Liquid-state
Solid-state
Citrate solgel
Liquid-state
Solid-state
Ultrasound-assisted
surfactant-template
Solid-state
Solid-state
Solid-state
Solid-state
Solid-state
Solid-state
Liquid-state
Liquid-state
Surfactant template/
ultrasound assisted
500 C,
550 C,
575 C,
575 C,
550 C,
550 C,
575 C,
500 C,
575 C,
650 C,
690 C,
650 C,
630 C,
800 C,
675 C,
630 C,
750 C,
690 C,
100%
100%
100%
100%
100%
100%
100%
100%
100%
525 C,
580 C,
580 C,
680 C,
550 C,
550 C,
700 C,
600 C,
550 C,
575 C,
575 C,
850 C,
700 C,
700 C,
800 C,
550 C,
550 C,
700 C,
780 C,
800 C,
680 C,
840 C,
60 min
100% N2, 15 min
100% N2, 15 min
100% N2, 10 min
100% N2, 90 min
100% N2, 90 min
100% N2, 30 min
100% N2, 65 min
100% N2, 55 min
100% Ar
100% Ar, 30 min
Ads.
Li2CO3/K2CO3-doped Li2ZrO3
KALi4SiO4
NaALi4SiO4
Li4SiO4
Li4SiO4
Ball milled Li4SiO4
Li4SiO4
Na2ZrO3
Na2ZrO3
Na2ZrO3
Na2ZrO3
a
b
c
d
e
Reactor
Number
of cycles
TGA
TGA
TEOM
TEOM
TGA
TGA
TEOMc
TGA
IGAd
3
3
100
8
6
4
8
5
11
0.26
0.23
0.24
0.24
0.2
0.23
0.18
0.26
0.22
[143]
[134]
[5]
[138]
[130]
[144]
[138]
[142]
[145]
TGA
TGA
TGA
TFBe
TGA
TGA
TGA
TGA
TGA
TEOM
IGA
12
25
25
15
10
10
16
2
2
8
4
0.083
0.15
0.07
0.3
0.044
0.154
0.28
0.24
0.15
0.15
0.13
[139]
[150]
[150]
[149]
[147]
[147]
[148]
[6]
[207]
[7]
[156]
Reg.
N2, 50 min
N2, 10 min
Ar
N2
N2, 30 min
N2, 50 min
N2
N2, 230 min
Ar, 30 min
Ref.
Li2CO3:ZrO2:K2CO3 (1.15:1.0:0.2).
91.3% Li2ZrO3 + 3.4% Y2O3 + 0.2% Al2O3 + 5.1% K2O.
Tapered Element Oscillating Microbalance.
Intelligent Gravimetric Analyzer.
Twin Fixed-Bed Reactor.
433
modied it by the ball milling process. The characterization analysis of both Li4SiO4 sample and ball milled Li4SiO4 sample showed
that the crystal size was decreased from >500 to 175 and the
surface area was increased from 0.4 to 4.9 m2 /g. The modied
Li4SiO4 sample showed better efciencies during the CO2 chemi
sorptiondesorption process without further sintering effects.
Shan et al. [148] prepared Li4SiO4-based sorbents from diatomite (as an inexpensive source of silicon) by the solid-state reaction method at 700 C. They studied the effect of different molar
ratios of raw materials on CO2 adsorption capacity in a gas mixture
of CO2 and N2 (50 vol.%). They found that the CO2 adsorption capacity reached the largest value (30.32 wt.%) at Li2CO3/SiO2 molar
ratio of 2.6. They also observed that the CO2 adsorption capacity
decreased by only 6.44 wt.% during 16 adsorptiondesorption
cycles because of the specic morphologies of Li4SiO4-based sorbents synthesized from diatomite. Wang et al. [149] developed
Li4SiO4-based sorbents from Li2CO3 and different types of silica
(citric acid pretreatment rice husk ash (CRHA), nano-structured
Aerosil, and crystalline Quartz powders) by the solid-state reaction
method and studied the effects of the type of silica on the
microstructure and CO2 capture performance of developed sorbents. Among all developed sorbents, CRHA-Li4SiO4 sorbent
showed the best performance with the highest CO2 capture capacity of 30.5 wt.% more rapid adsorption/desorption process and better regenerability during multicyclic adsorption/desorption
experiments (only 2.1 wt.% decrease of CO2 capture capacity after
15 cycles). The excellent performance of this sorbent was attributed to its lower crystalline of pure Li4SiO4, smaller particle size, and
larger specic surface area, as a result of the favorable microstructure of nanoparticles and the strong sintering-resistant character of
CRHA.
Seggiani et al. [150] applied the solid-state reaction method to
synthesize Li4SiO4-based sorbents containing 10, 20, 30 wt.% of
alkali carbonates (K2CO3, Na2CO3), binary (K2CO3/Li2CO3,
Na2CO3/Li2CO3) and ternary (K2CO3/Na2CO3/Li2CO3) eutectic carbonate mixtures. The CO2 adsorption characteristics of the developed sorbents were investigated at high temperatures in the
range of 500600 C and low CO2 partial pressure of 0.04 atm.
According to the results, the CO2 sorption rate and capacity of all
the promoted Li4SiO4-based sorbents were obviously improved in
comparison to pure Li4SiO4 sorbent. This was attributed to the
much faster diffusion of CO2 through the molten carbonate shell,
compared to that through the solid Li2CO3 shell in no-promoted
Li4SiO4. Furthermore, the CO2 sorption rate and capacity of the promoted sorbents containing alkali carbonates were higher than
those of the promoted sorbents containing binary or ternary eutectic carbonate mixtures. For the promoted sorbents containing
alkali carbonates, (K/Li)CO3 and (Na/Li)CO3 eutectic melt were
formed on the Li4SiO4 surface during the CO2 sorption. However,
for the promoted sorbents containing binary and ternary eutectic
carbonate mixtures, a eutectic liquid phase was already present
on the surface of Li4SiO4 at the beginning of CO2 sorption and
CO2 had to diffuse through this molten layer in order to reach
the surface of Li4SiO4. Therefore, this molten layer acted as an additional diffusional resistance. For all the promoted Li4SiO4-based
sorbents, 580 C was reported as optimum sorption temperature,
because the equilibrium temperature was around 590 C at CO2
partial pressure of 4.04 atm, and therefore, the desorption process
was activated at temperatures higher than 580 C. At 580 C, promoted Li4SiO4-based sorbents containing 30 wt.% of K2CO3 or
Na2CO3 indicated the best CO2 adsorption characteristics with
sorption capacity of 0.23 g of CO2/g of sorbent corresponding to a
Li4SiO4 conversion of 80%. However, the promoted sorbent containing Na2CO3 indicated a considerable degeneration of CO2 capture capacity during multi-cyclic adsorption/regeneration
experiments due to the structural sintering. On the contrary, the
434
435
436
437
Reaction conditions
M
M
22.0
18
Ni commercial cat./CaO:Ca12Al14O33
Ni commercial cat./dolomite
Ni commercial cat./CaO:Ca12Al14O33
NiO/CaO/Ca12Al14O33
NiO/CaO
La2O3/NiO/CaO/Al2O3
ZrO2/NiO/CaO/Al2O3
NiO/CaO/HTlc (Al-Mg)
NiACaOACa12Al14O33
NiOAHTlc (AlAMg)/Al-stabilized CaO
NiOAHTlc (AlAMg)/CaO:Ca9Al6O18
Ni commercial cat./Li2ZrO3
Ni commercial cat./Na2ZrO3
NiOAHTlc (AlAMg)/Li2ZrO3
NiOAHTlc (AlAMg)/Na2ZrO3
NiO-c-Al2O3/CaOACa9Al6O18
NiAMgAlO/CaOACa9Al6O18
NiAHtlc/CaOACa12All4O33
M
M
M
H
H
H
H
H
H
M
M
M
M
M
M
M
M
M
NiOACaO/Ca9Al6O18
CaOAZr/NiO
H
H
20
(a)
18
20
(b)
N.a
(c)
(d)
7
(e)
(g)
N.a.
N.a.
(f)
(f)
5
N.a.
47 wt.% in
catalyst (for Ni)
25
650 C, 1 bar, S/C: 4
20.5
650 C, 1 bar, S/C: 4
Reac.
Reg.
Ref.
Reactorb Number H2
of cycles concentration
(molar %)
FB
FB
1
25
>95
>95
[192]
[190]
FB
FB
FB
FB
FB
FB
FB
FB
FB
FB
FB
FB
FB
FB
FB
FB
FB
PB
12
4
13
1
1
30
20
10
4
10
1
1
1
1
1
1
35
10
>90
>98
>92
90
80
>92
>90
99
95
99
97
85
97
68
97
89.1
98
99
[193]
[187]
[191]
[201]
[199]
[202]
[56]
[203]
[74]
[196]
[200]
[207]
[207]
[128]
[128]
[206]
[195]
[194]
30
10
>95
>95
[204]
[205]
(a) Ni loading: >12 wt%; (b) Ni loading: 12.5 wt%; (C) Ni loading: 15 wt%; (d) Ni loading: 45 wt%; (e) Ni loading: 47 wt%; (f) Ni loading: 40 wt%; (g) Ni:Mg:Al (atomic ratio in
HTlc catalyst) = 0.5:2.5:1
a
Mixture (M) or hybrid (H).
b
Fixed-bed (FB) or Packed-bed (PB).
Ni-based catalyst was tested in the SESMR process at 600 C and S/C
of 4. The H2 concentration during the prebreakthrough stage was
98%. During 10 successive reforming-regeneration cycles, the
methane conversion and different species concentrations remained
almost constant, demonstrating the good performance of the
CaO-based sorbent developed by solgel technique. Broda et al.
[196] used a mixture of Ni-HTlc-derived catalyst (47 wt.% Ni, prepared by co-precipitation) and a synthetic Ca-based sorbent (CaO
supported on calcium aluminate). The sorbent pellets were synthesized from limestone and commercial calcium aluminate (CA-14:
71% Al2O3 and 28% CaO). At 550 C and S/C of 4, 99 vol.% H2 (dry
and N2-free basis) was obtained in the reforming process. After 10
sorption/regeneration cycles, the CO2 capture capacity was 0.41 g
of CO2/g of sorbent, in comparison with limestone (0.22 g of CO2/g
of sorbent). The appropriate thermal stability of CO2 sorbent was
attributed to the uniform dispersion of Ca12Al14O33 among CaO
particles.
For large-scale hydrogen production units where mass transfer
limitations can signicantly affect the process efciency, the catalystsorbent mixing conguration is an important parameter to
be considered. Besides a physical admixture of catalyst with sorbent, hybrid catalystsorbent patterns which integrate the catalytic
reaction and the CO2 sorption in a single pellet can present some
advantages such as the elimination of mass diffusional limitation
and the reduction of reactor volume [197,198]. Several studies have
been performed on the development of hybrid catalystsorbent
materials for SESMR process [199206]. A rst attempt to combine
CaO-based sorbent and catalyst in a single pellet was performed by
Martavaltzi and Lemonidou [201] who developed a hybrid
NiACa12Al14O33ACaO catalystsorbent. The optimum NiO loading
of 20 wt.% was shown to lead to a H2 concentration of 90% at
650 C and S/C of 3.4, as well as CO2 and CO efuent concentrations
of 2.8% and 2%, respectively. The process was only limited to one
cycle. Wu and Wang [56] further investigated the application of
ZrO2-stabilized NiOACaO/Al2O3 hybrid catalystsorbent in the
SESMR during 20 cycles. The authors reported a H2 concentration
of more than 90%. The favorable stability and activity of the proposed hybrid material during cyclic operation was found to be on
account of avoiding the formation of NiAl2O4 phase by incorporating ZrO2 particles. Feng et al. [202] developed a La2O3-stabilized
NiO-CaO/Al2O3 hybrid catalystsorbent prepared by two-step
impregnation of lanthanum and nickel precursors. At 600 C and
S/C of 4, H2 concentration of more than 92% was achieved during
30 SESMR cycles. The incorporation of La2O3 could improve both
stability and nickel grain dispersion over the substrate.
Besides the suitability of CO2 sorbent, appropriate Ni dispersion
and surface area of catalyst are also important parameters in H2
production. A HTlc-based hybrid catalystsorbent was synthesized
by Broda et al. [203] via co-precipitation technique. The hybrid
material contained both Ni reforming catalyst and Ca-based CO2
sorbent dispersed in the HTlc structure containing Mg and Al
(Fig. 7). The appropriate surface area (54 m2/g) and the high dispersion of Ni and Ca in the HTlc structure resulted in a high H2 production efciency of 99 vol.% (a dry basis composition is always
mentioned, if otherwise specied) and adequate thermal stability
over cyclic SESMR operation. The proposed hybrid material produced a better H2 purity compared to a mixture of limestone and
NiSiO2 or nickel HTlc-derived catalyst. However, the loading of
CaO in the hybrid structure was only 21 wt.%, requiring the use of
a high amount of hybrid material in the reaction to obtain an adequate CO2 adsorption capacity. As stated by the authors, the CO2
uptake capacity of the hybrid material averaged only 0.074 g of
CO2/g of sorbent over 10 cycles. Kim et al. [74] studied the synthesis
of hybrid CaOACa12Al14O33ANi composite from calcium nitrate
tetrahydrate, aluminum nitrate nonahydrate, and Ni precursor by
combination of precipitation and hydration methods, and its application in the SESMR (S/C of 3, 630 C). Ca12Al14O33 made spacious
pathway available for CO2 diffusion via forming porous structure,
thus providing an excellent cyclic stability for Ca-based sorbent.
The SESMR experiments using hybrid CaOACa12Al14O33ANi composites with different loading of Ni precursor (3, 5, 7, and
10 wt.%) revealed that 7 wt.% of Ni loading led to the best
438
performance (CH4 conversion and H2 production). The H2 concentration was maintained at 9495% for 70 min (prebreakthrough)
during SESMR. It was also found that the presence of a high Ni loading (10 wt.%) caused Ni self-agglomeration. Radfarnia and Iliuta
[204] developed NiOACaO/Ca9Al6O18 hybrid catalystsorbent
materials with various nickel loading (12, 18, and 25 wt.% NiO)
via a simple wet-mixing method (limestone acidication coupled
with two-step calcination technique) and investigated their application in SESMR operation (S/C of 4, 650 C and 1 bar). According
to the experimental results, the best performance belonged to the
hybrid material containing 25 wt.% NiO, which showed an average
H2 production efciency of 96.1% during 10 cycles (180 min reaction per cycle). Moreover, the long-term application (30 cycles,
45 min reaction per cycle) led to an average H2 production efciency of 97.3%, proving its high efciency in the SESMR process.
The excellent performance of this catalystsorbent hybrid material
was attributed to the easy access of Ni sites resulted from higher Ni
loading and proper distribution of Ni on the substrate. The same
authors also developed a CaOAZr/Ni (13, 18, 20.5 wt.% NiO) sorbentcatalyst material by wet-mixing/sonication technique and
its application in the SESMR showed that the one with 20.5 wt.%
NiO loading presented the most suitable activity (H2 yield of 91%
at the end of the 10th cycle) [205].
In a recent study, Barelli et al. [206] employed wet mixing methods to prepare three different catalystsorbent materials for
SESMR:
NiOACaO/Ca9Al6O18
composite
(M1),
NiOACaO/
Ca12Al14O33 composite (M2), and a physical mixture of
CaO/Ca9Al6O18 and NiO/cAAl2O3 (M3). M3 showed the best performance in cyclic carbonation/decarbonation experiments, where the
initial CO2 capture capacity of 0.55 g of CO2/g of sorbent decreased
to 0.495 g of CO2/g of sorbent after 14 cycles (reduction of 17%). For
comparison, the CO2 capture capacity of standard pure CaO
decreased from 0.49 g of CO2/g of sorbent to 0.288 g of CO2/g of sorbent over 14 cycles (reduction of 57.5%). XRD, SEM and TEM analysis of the used materials justied the performance of all three
materials during cyclic CO2 adsorption/desorption process. While
no change was observed in the porous structure and morphology
of M3 sorbent, agglomeration of CaCO3 on the surface of
Ca9Al6O18 and partial loss of roughness and porosity of used M1
led to much lower cyclic CO2 adsorption/desorption performance
in comparison with M3. In addition, the formation of NiAl2O4 and
the deterioration of the porous structure during the cyclic CO2
adsorption/desorption process caused the poorest performance of
M2. The material with the best performance (M3) was further
applied in SESMR process at different temperatures between 500
and 650 C. Although the molar fraction of H2 at the reactor outlet
reached 89.1% during the pre-breakthrough period at 650 C (S/C
of 2.85), it was still much lower than that at equilibrium. This could
be due to difcult contact between gas and solid because of the particle size of the catalyst, low catalyst load and residence time.
439
during the second cycle of operation for both Na2ZrO3 and Li2ZrO3.
Even if the reason was not very clear, this behavior seemed to be
due to catalyst poisoning in the presence of impurities present in
the sorbents.
4. Hydrogen production by sorption enhanced steam glycerol
reforming (SESGR)
As mentioned in the previous section, methane reforming is
commonly used in industrial applications for hydrogen production
[176,177,180182]. The steam methane reforming provides about
48% of worldwide produced hydrogen [209]. However, hydrogen
production from methane deals with serious difculties such as
environmental problems and drastic reduction of fossil fuel
sources. Therefore, extensive works were directed on the development of alternative renewable sources such as water and biomass
or biomass-derived oxygenates. Glycerol, a by-product of the transesterication of renewable biological sources (i.e., vegetable oils
and animal fat oils), may be considered an interesting renewable
source of hydrogen [210214]. The production of 10 kg of biodiesel
generates around 1 kg of crude glycerol [210]. Hence, the rapid
growth in the production of biodiesel from 2000 year has resulted
in great increase of crude glycerol. It is anticipated that the annual
production of glycerol will reach to about 3 megatons in 2020,
whereas the industries consume only 500 kilotons glycerol each
year [214,215]. The increase of the availability of this industrial
waste, as well as the renewability and the low cost of glycerol, make
it very attractive as an alternative source of hydrogen [211].
Pyrolysis, partial oxidation, steam reforming, autothermal
reforming, and aqueous-phase reforming are some promising
methods for converting glycerol into hydrogen. By now, steam
reforming is the most common method for converting glycerol into
hydrogen [213,215,216]. This global process consists of complex
reactions, which lead to the formation of several by-products and
therefore, affect the nal purity of H2 adversely [213]. Glycerol
pyrolysis (9) and WGS (6) are the main reactions in this process:
9
6
Consequently, the overall reaction of glycerol reforming is represented by Eq. (10), where one mole of glycerol can theoretically
produce 7 mol of hydrogen:
10
The side reactions that can occur in the steam reforming of glycerol are presented in Table 6. The steam glycerol reforming process
is carried out at temperatures of 500900 C, 1 atm and
water/glycerol molar ratio of 69, in the presence of Ni, Co and
noble metals (such as Pt, Pd and Rh) based catalysts. H2, CO, CO2,
and CH4 are the main gaseous products [213216].
One of the obstacles to the utilization of hydrogen obtained from
steam glycerol reforming for energy production is the high CO and
CO2 content. In particular, the presence of large amount of CO2 signicantly drops the efciency of fuel cells, while CO strongly poisons the catalyst of proton-exchange membrane fuel cells
(PEMEC) [217]. Furthermore, the cost of hydrogen separation from
a H2-rich gas containing impurities causes major cost penalties.
Therefore, a better system is needed to achieve high purity hydrogen. The application of the sorption enhanced process is therefore
an interesting option to produce high purity hydrogen in a single
step [210,211,214]. Compared to the traditional steam reforming,
the in-situ CO2 removal increases glycerol and steam conversions
as well as hydrogen purity [214,215]. Moreover, the in-situ CO2 capture during the steam glycerol reforming decreases the risk of coke
Table 6
Side reactions during steam glycerol reforming.
Entry
Reaction
DH298 (kJ/mol)
1
2
3
4
5
6
7
CO 3H2 $ CH4 H2 O
CO2 4H2 $ CH4 2H2
H4 CO2 $ 2CO 2H2
2CO $ CO2 Cs
CH4 $ 2H2 Cs
CO H2 $ H2 O Cs
CO2 2H2 $ 2H2 O Cs
206
165
247
172
75
131
306
formation and the reforming reactions can be carried out at relatively low steam/carbon ratios [212]. Dou et al. [214] provided an
overview on some issues and challenges of SESGR process such as
selecting suitable sorbents, extending operation time, and nding
a way for continuous reaction/regeneration in order to achieve
high-efciency hydrogen production from SESGR process.
To date, much fewer studies have been performed on the
sorption enhanced steam glycerol reforming (SESGR) compared to
SESMR. In the presence of CaO as the CO2 sorbent, it was found that
the in-situ CO2 removal resulted in a signicant enhancement of H2
production and thermal efciency as well as an important reduction of CO concentration [210,218220]. Chen et al. [221] performed thermodynamic analyses on the SESGR process based on
the principle of Gibbs free energy minimization for chemical reactions. They evaluated the effect of temperature (327727 C), pressure (14 bar), S/C ratio (14), percentage of CO2 removal through
adsorption (099%), and carrier gas to feed reactants molar ratio
(15) on the reforming reactions and carbon formation. The results
demonstrated that the in-situ CO2 removal led to the enhancement
of glycerol conversion to hydrogen. The maximum hydrogen yield
was increased from 6 to 7 moles/mole of glycerol by the in-situ CO2
removal via adsorption. The analyses proposed that the most
favorable conditions for the SESGR process were: temperature
range around 527577 C at atmospheric pressure and S/C of
around 3.0. The most favorable temperature for the SESGR process
was approximately 100 C lower than that for the traditional steam
glycerol reforming without in-situ CO2 removal. As carbon formation can occur at low S/C ratios, the in-situ CO2 removal can considerably reduce the lower limit of the S/C ratio to limit the carbon
formation [221]. He et al. [211] studied the SESR process of pure
glycerol by using the CoANi/HTls as reforming catalysts and calcined dolomite as CO2 sorbent, at 500650 C and S/G of 3, 4, and
9. The CoANi/HTls catalysts (25%Co15%Ni/HTls and 30%Co
10%Ni/HTls)
were
developed
by
co-precipitation
from
Ni(NO3)26H2O, Co(NO3)3, Mg(NO3)36H2O and Al(NO3)39H2O.
According to the experimental results, the hydrogen purity reached
approximately the theoretical value at temperatures beyond
575 C or S/G no less than 4 (for example, both hydrogen purity
and yield reached around 99% for a S/G of 9). Such a high H2 yield
obtained in the SESGR process was attributed to the enhancement
of methane steam reforming and watergas shift reactions and the
elimination of non-catalytic reactions in the SESR process. Below
550 C and a low S/G of 3, hydrogen production was compromised
because of the high tendency of pyrolysis and the low efciency of
steam reforming. Dou et al. [222] studied the SESGR process in a
xed-bed reactor using a mixture of commercial Ni-based catalyst
(18 wt.% NiO/82 wt.% Al2O3) and CaO-based sorbent derived from
dolomite (weight ratio of catalyst to sorbent of 1:1), at temperatures in the range of 400700 C, 1 atm, and S/C of 3. The experimental results demonstrated that the SESGR is an efcient
process for obtaining hydrogen purity of more than 90%. 500 C
was shown to be the optimum temperature, with the highest H2
purity of 97% and the longest CO2 breakthrough period.
One of the most important parameters that affect the economic
benets of H2 production by SESGR is the price of glycerol. Up to
440
sorbent. In the air reactor, sorbent regeneration, catalyst oxidization and coke combustion were carried out at 900 C in an air atmosphere. The NiO/NiAl2O4 catalyst containing 42.1 wt.% NiO was
developed by co-precipitation from Ni(NO3)26H2O and
Al(NO3)39H2O precursors. The experimental results showed that
the increase of temperature and S/C value enhanced the H2 purity.
The best results (hydrogen purity higher than 90%) were obtained
at temperatures of 500600 C and S/C of 1.53.0.
the evaluation of their efciency and stability under severe operation conditions and cyclic operation.
In terms of the application of CO2 sorbents in the SESGR process,
few works have been done by using CaO-based sorbents and various catalysts. In all these works, the catalyst and sorbent were
mixed physically and none of them considered using hybrid catalystsorbent arrangement up to now. In this context, systematic
studies on the development of efcient hybrid catalystsorbent
materials and the evaluation of their stability under severe operating conditions and cyclic operation represent interesting opportunities for research. Although the SESR of crude glycerol is more
attractive compared to pure glycerol to obtain H2 with a lower
price, the SESR of crude glycerol has been very scarcely investigated. The main challenge in the SESR of crude glycerol is the carbon formation because of the presence of heavy compounds, such
as fatty acid methyl esters. Therefore, the production of pure H2
from crude glycerol is still a challenge due to the composition complexity of crude glycerol.
Acknowledgments
Financial support from Natural Sciences and Engineering
Research Council of Canada (NSERC), FRQNT Centre in Green
Chemistry and Catalysis (CGCC) and Centre de Recherche en
Catalyse et Chimie Verte (C3V, Laval University) is gratefully
acknowledged.
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