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The microstructure and stability of a Ni-nano-CaO/

Al2O3 reforming catalyst under
carbonationecalcination cycling conditions
Xiaochong Xue a, Sufang Wu a,b,*
a
b

College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China
Key Laboratory of Biomass Chemical Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China

article info

abstract

Article history:

The paper investigated the effect of carbonationecalcination cycling conditions on the

Received 27 May 2014

microstructure and CO2 sorption property of a sorption complex catalyst. The carbonation

Received in revised form

operation condition consisted of temperature of 600
C with 20% CO2e80% N2 and 20% CO2

14 November 2014

e80% steam atmosphere to simulate the methane reforming reaction conditions; the

Accepted 5 February 2015

calcination condition was 800
C with 100% N2. The BrunauereEmmereTeller (BET) surface

Available online 20 March 2015

area and thermogravimetric analysis (TGA) were measured to investigate the microstructure and variation in sorption property of the catalyst after multiple cycles under each

Keywords:

condition. Results showed that the microstructure and CO2 sorption capacity of the sorp-

Hydrogen

tion complex catalyst decayed significantly in the initial carbonationecalcination cycles,

Steam methane reforming

especially under a steam atmosphere. X-ray diffraction analysis revealed that a stable

Catalyst

compound Ca12Al14O33 formed gradually during the initial carbonationecalcination cycle

Carbonationecalcination cycles

seven at a temperature of 800
C. A model is proposed to explain the observed effect of

Calcium aluminate

carbonationecalcination cycling on Ca12Al14O33 formation. Furthermore, based on our

Stability

findings, a new sorption complex catalyst was prepared by pretreating at a high temperature of 900
C. Evaluation of the catalyst prepared by the ReSER hydrogen production
process through 10 circulations revealed significant improvement instability.
Copyright 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

Introduction
Hydrogen is an environmentally friendly energy source with a
wide array of applications in the chemical and petroleum industries. Among various feedstock, natural gas is the major
source for production of hydrogen via steam methane
reforming (referred to as SMR) [1,2]. In recent years, an
improved SMR-based method for hydrogen production called

sorption enhanced reaction process (referred to as SERP) has

attracted strong attention. SERP involves the use of a CO2
adsorbent to enhance the methane reforming process by in
situ removal of CO2. It has advantages of low reaction temperature, high concentration hydrogen outlet and controllable
emission of the greenhouse gas CO2 [3e5].
In a traditional SERP process, the CO2 adsorbent and nickel
reforming catalyst are mixed together mechanically, and CaO
wastypicallyselected as the CO2 adsorbent because of its high

* Corresponding author. College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China.
Tel.: 86 571 87953138; fax: 86 571 87953735.
E-mail address: wsf@zju.edu.cn (S. Wu).
http://dx.doi.org/10.1016/j.ijhydene.2015.02.032
0360-3199/Copyright 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

5618

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CO2 sorption capacity and natural abundance [6,7]. Recently,

Wu etal. [8] proposed a concept of reactive sorption-enhanced
methane reforming (referred to as ReSER)process based on the
use of a sorption complex catalyst that is a composite of a
nano-particulate CaO adsorbent and a Ni-based catalyst in a
single micro-spherical particle. Compared with mechanically
mixed adsorbent and catalyst, this sorption complex catalyst
can reduce resistance to heat and CO2 diffusion transfer during the reforming process and also offers other advantages
such as increased efficiency for enhanced reforming and
convenient handling in a fluidized bed reactor [9e11].
Despite the advantages of the sorption complex catalyst,
previous studies showed that its catalytic activity decreased
after several ReSER cycles [8]. Various methods have been
proposed to improve its stability and activity. Wang and Feng
[12,13] used ZrO2 and La2O3 as additives to improve the stability of the catalyst by increasing dispersion of nickel and
inhibiting the formation of NiAl2O4 spinel. Zhang and Tang
[14] used polyethylene glycol (PEG-6000) as a template to
expand the pore size and thereby enhance the dispersion of
nickel to increase the activity. All of the aforementioned solutions mainly focused on improving the stability and activity
of nickel catalyst, but ignored the influence of nanoparticulate CaO on the sorption catalyst. Since the
embedded CaO needs undergo multiple carbonationecalcination cycles to keep its sorption activity, this process may
have a negative influence on the sorption complex catalyst.
The effect of carbonationecalcination cycles on the stability of the catalyst is not clear, and the deactivation mechanisms of the catalyst are not well understood. Numerous
studies have found structural destruction and decline in
sorption activity of CaO-based absorbent after multiple carbonationecalcination cycles [15e18]. In addition, steam in the
carbonation process has been reported to accelerate the CaO
sintering rate, resulting in a rapid decline in its sorption
property [19e21]. However, no study has been undertaken to
understand structural destruction of CaO in the complex
sorption catalyst and its influence on catalyst activity during
carbonationecalcination cycles.
In this study, we prepared Ni-nano-CaO/Al2O3 sorption
complex catalyst and subjected it to three different carbonationecalcination cycling conditions to determine the
mechanism of micro-structural changes and activity decline.
Then, a Ni-nano-CaO/Ca12Al14O33 sorption complex catalyst
was prepared based on our findings in order to improve the
stability of the complex catalyst.

Experiment
Preparation of catalyst
Preparation of Ni-nano-CaO/Al2O3 sorption complex catalyst
The Ni-nano-CaO/Al2O3complex catalyst was prepared by
impregnating Ni(NO3)2 solution on the nano-CaO/Al2O3 support as described in the literature [13]. The support was prepared by mixing nano-CaCO3 (70 nm, >95% purity, Hu Zhou
LingHua Co., Ltd., China) with alumina sol (10%, Zibo Longao
Co. Ltd., China). The mixed slurry was dried and extruded into
a cylinder with a diameter of approximately 2 mm. The final

Ca/Al molar ratio in the slurry was 1:1.4. The support was
calcined at 550
C for 2e4 h and ground to 1.3e1.5 mm. A 0.2 M
Ni(NO3)2 solution (98% purity, Shanghai HengXin Chemical
Reagent Co., Ltd., China) was prepared and infused into the
nano-CaCO3/Al2O3 support, and the catalyst was dried at
100e150
C and calcined at 500e800
C. The final Ni content
was about 15%, and the catalyst was named CA-cat1.

Preparation of Ni-nano-CaO/Ca12Al14O33 sorption complex

catalyst
Preparation of the sorption complex catalyst was similar to
that of the catalyst described in section Preparation of Ninano-CaO/Al2O3 sorption complex catalyst. The nanoCaCO3/Al2O3 support was obtained in the same way and
calcined at 900
C for 2 h to form nano-CaO/Ca12Al14O33. Then
impregnated the same Ni(NO3)2 solution as described above.
The catalyst was named CA-cat2.

Characterization of the sorption complex catalyst

Surface area and pore structures of the sorption complex catalyst were characterized by nitrogen physical sorption in liquid
N2 at 77 K using an apparatus (BELII-mini Japan). Surface area
was calculated according to the BrunauereEmmetteTeller (BET)
formula, and pore size distribution was calculated using the
BarretteJoynereHalenda (BJH) model. Micro-crystallinity of the
samples was measured by X-ray diffraction (XRD) on a Rigaku D/
MAX-RA X-ray diffractometer (Japan) equipped with a copper
anode. The measurement conditions were: voltage 40 kV, current 40 mA, and diffraction angle 2q with a range of 10
to 80
.
Thermogravimetric analysis (Pyris1, PerkineElmer, USA)
was used to measure the sorption property of the samples.
The sorption process was conducted at 600
C under 0.02 MPa
of CO2 in N2. Regeneration was performed at 750
C in pure N2.
The sorption capacity was calculated according to Equation (1):
Sorption capacity

CO2 sorption mol amount

Mass of catalyst
 1000mol=kg

(1)

Evaluation of catalyst
Evaluation of CA-cat1 by carbonationecalcination cycling
A fixed-bed reactor was used for the carbonationecalcination
cycling test. Further details of the fixed-bed are provided
elsewhere [12,13]. Mass flow controllers and water pump were
utilized to achieve the desired inlet gas concentrations. Two
cyclic carbonation conditions were employed: 600
C for 1 h
with 20% CO2e80%N2, and 20% CO2e80% H2O respectively. All
calcinations were carried out at 800
C with 100% N2 for 1 h. To
determine the effect of temperature variation, a cyclic condition in which the temperature was varied between 600
C
and 800
C with 100% N2 for the same time was used. A total of
30 carbonationecalcination cycles were performed and 10 g of
catalyst was used to obtain different samples that were tested
after the 1st, 3rd, 7th, 15th, and 30th cycles. The samples were
designated as Sn-m where n represents the carbonation
condition and m represents the number of cycle. The condition with pure N2 without carbonation was defined as S1-m

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sorption complex catalyst, 45 mL/min CH4, 180 mL/min H2O,

reaction at 600
C and calcination at 800
C with 100% N2.
Before the reaction, the sorption catalyst was calcined at
800
C with 100% N2 and then reduced under 20%H2, 80%N2
with total gas flow of 100 mL/min. GC analysis was used to
detect the outlet production mixtures. The conversion of
methane was calculated according to Equation (2), where
XCH4 % is the conversion of methane, FCH4 mL=min is the
flow rate of methane, Fout mL=min is the effluent flow rate of
the product gas, and yCH4 (%) is the methane content.
XCH4

FCH4  Fout  yCH4

 100%
FCH4

(2)

Multiple reactions and regeneration runs were conducted

to evaluate the stability of the sorption complex catalyst.

Fig. 1 e Variation of specific surface area of CA-cat1 under

S1, S2, S3 conditions.

Results and discussions

Effect of carbonationecalcination cycles on microstructure
and sorption property of the catalyst

for comparison. The carbonation condition with 20%

CO2e80%N2 was defined as S2-m. The carbonation condition
with 20% CO2e80% H2O was defined as S3-m.

Evaluation of CA-cat2 by the ReSER hydrogen production

process
Evaluation of the CA-cat2 complex catalysts was carried out
in the same fixed-bed as described in section 2.2.1. The condition for ReSER hydrogen production was as follows: 5 g

The specific surface area of all carbonationecalcination

cycling test samples was shown in Fig. 1. The results showed
that the S1 condition of use N2 as the environmental gas has
a little change of surface area. Temperature variation between
600
C and 800
C had little effect on the catalyst microstructure with a slightly specific surface area fluctuation at
20 m2 g1. Alternatively, conditions of S2 and S3 which all
contain CO2 as the environmental gas have an obvious

Fig. 2 e Pore size distribution of CA-cat1 under S1, S2, S3 conditions. (a) 1st cycle, (b) 7th cycle, (c) 15th cycle, (d) 30th cycle.

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Fig. 3 e Sorption capacity of CA-cat1 samples treated under

S1, S2, S3 conditions.

decrease of surface area. And contain the steam and CO2 both
of S3 condition has a big decrease of surface area. The rapid
decay of S2 andS3 in the initial three cycles indicates that
the catalyst microstructure changes strongly during the initial
carbonationecalcination cycles, while the presence of steam
during carbonation appeared to accelerate the decay rate. No
significant variation was observed in the later cycles, which
implies that the catalyst structure was stable.
Fig. 2(a), (b), (c), (d) show a comparison of the evolution of
pore size distribution of the catalyst under S1, S2, S3 three
different test conditions after 1, 7, 15, 30 cycles respectively.
Two types of meso-pores were found with the main part
around 8e10 nm and the subordination part around 35 nm,
and we defined them as SPs and LPs, respectively. The LPs
appeared stable during the 30 carbonationecalcination cycles
at all cycling conditions while the SPsvaried significantly
with changes in the cycling conditions. The maximum in the
curve of dVp/drp vs. rp shifted slightly from 8 nm to 13 nm in
the comparison cycles, which indicated expansion of the pore.
The structure of SPs decayed strongly during the carbonationecalcination cycles in the initial 15 cycles with the
presence of steam accelerating the decay rate, while a stable
trend was observed in subsequent 15 cycles. The pore volumes of pores with a diameter of about 13 nm appeared
relatively stable at all cyclic conditions after 30 cycles. These
results show that apart from the influence of high temperature variation, the carbonationecalcination process has a
major effect on pore evolution, with the small pores decaying
during the initial cycles.
To investigate the influence of cycles on CO2 sorption capacity, each sample obtained under S1, S2, S3 conditions was
tested by thermogravimetric analysis, and the results are
shown in Fig. 3. The declining trend in sorption capacity was
similar to the decrease in the specific surface area, suggesting
that they are related; higher specific surface area could provide more sorption reactive sites and thereby increase the CO2
sorption capacity. In the cyclic condition of S1, the CO2
sorption capacity declined from 3.3 mol/kg to 2.5 mol/kg
during 30 cycles, and the decline of S2, S3 was significant in
the initial 15 cycles, but only modest in the subsequent 15
cycles. Sintering of CaO during the cycles may have caused

Fig. 4 e XRD test result of the 30th sample of CA-cat1 under

S1, S2, S3 conditions.

decay of the catalyst's microstructure and sorption capacity,

but further detailed investigation should be conducted to
determine the exact relationship between decay rate and
carbonationecalcination cycles.

Mechanism of the influence of carbonationecalcination on

catalysts
The experiments were designed use CA-cat1 under S1, S2, S3
conditions for 30 cyclic carbonationecalcination runs to study
the relation between the conditions and the formation of
Ca12Al14O33.
XRD was used to measure phase transformation of the
samples after different cycling operations. Data on the sample
from the 30th cycle under each cyclic condition is presented in
Fig. 4. From Fig. 4, there are obvious Ca12Al14O33 peak under S3
condition, and a few Ca12Al14O33 peak is under S2 condition,
and few Ca12Al14O33 peak appeared under S1 condition. The
result of the Ca12Al14O33 peak was the most intense of sample
S3-30 indicates the sample contained the largest amount of
Ca12Al14O33.

Fig. 5 e TEM image of the sample CA-cat1.

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 0 ( 2 0 1 5 ) 5 6 1 7 e5 6 2 3

Fig. 6 e XRD results of samples under the S3 condition.

The cyclic reaction between CaO and CO2 may push the
catalyst to an unstable state, and the Al2O3 in the catalyst
support may react with CaO [22,23] according to Equation (3):
12CaO 7Al2 O3 /Ca12 Al14 O33

(3)

Normally, the reaction shown in Equation (3) occurs only at

temperatures greater than 900
C [22]. However, in this study,
Ca12Al14O33 was found to be formed at temperatures as low as
800
C. A possible reason for this behavior is the use of nanosized CaO as CO2 sorbent, and in most previous studies,
micro-sized CaO was used as the CO2 sorbent.
Fig. 5 showed the TEM image of sample of CA-cat1. The
dark point presents the NiO before reduced to Ni as a size of
5e20 nm. And the other is the support of a mixture of CaO/
Al2O3. The size is also under 100 nm. The results proved the
both NiO and CaO/Al2O3 are under a nanometer scale.
To determine the relationship between formation of
Ca12Al14O33 and cycling conditions, we characterized the

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samples cycled under the S3 condition in detail s as shown in

Fig. 6. From Fig. 6, Ca12Al14O33 was not detected during the
original three cycles, but was easily detected after the 7th
cycle. This indicates that the quantity of Ca12Al14O33 formed
accumulated during cycling as the as the carbonationecalcination cycles running on. The catalyst we prepared was a
complex of alumina sol and nano-CaCO3, which has a relatively low decomposition temperature [24]. The nano-CaCO3
in the catalyst likely decomposed into nano-CaO at 800
C.
Hence, the reaction shown in Equation (3) must have occurred
during each calcination cycle under a temperature of 800
C.
A possible mechanism of Ca12Al14O33 formation under
different cycling conditions is proposed in Fig. 7. First, after
initial calcination at 800
C, nano CaCO3 decomposed into
nano-CaO, which immediately reacted with Al2O3 to form
Ca12Al14O33. Owing to the smaller molar volume of CaO
compared to that of CaCO3, a pore channel was simultaneously formed. If the channel was not filled-in during subsequent cycles, it would prevent continued reaction between
CaO and Al2O3, as shown case 1 in Fig. 7. Therefore, cycling
performed under N2 atmosphere did not lead to accumulation
the quantity of Ca12Al14O33. However, if the channel became
blocked during carbonation, as shown in cases 2 and 3 in
Fig. 7, a new phase interface between CaCO3 and Al2O3 would
have formed and led to the formation of Ca12Al14O33 during
subsequent calcination. This may explain why Ca12Al14O33
accumulated as the number of cycles increased. The effect of
steam is explained as follows: since steam may accelerate
carbonation rate by forming the intermediate Ca(OH)2, the
amount of CaCO3 may have increased during carbonation in
our experiments, thereby resulting in increased amounts of
Ca12Al14O33 after calcination.
A comparison of the sintering behavior of the sorption
complex catalyst under different conditions revealed that
formation of Ca12Al14O33, which consumed the porous Al2O3
carrier, played the largest role in the evolution of microstructure of the catalysts. As a result, the specific surface area
of catalysts cycled under the S2 and S3 conditions decreased

Fig. 7 e Mechanism of Ca12Al14O33formation during the carbonationecalcination cycle.

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Table 1 e Microstructure variation of CA-cat2 and NCA.

Name

Pore
Adsorption
Surface Average pore
size
volume
capacity
area
(nm)
(cm3$g1)
(mol/kg)
(m2$g1)

NCA-0
NCA-7
CA-cat2-0
CA-cat2-10

Fig. 8 e Evaluation of CA-cat2 catalyst by the ReSER

hydrogen production process. (reaction temperature of
600
C, calcination temperature of 800
C, steam methane
molar ratio of 4, reaction pressure of 1 atm).

substantially, whereas that of the catalyst cycled under the S1

conditions decreased only slightly. The reasons for these behaviors are similar in that the sorption capacity changes with
consumption of CaO during the carbonationecalcination
cycling process. Since Ca12Al14O33 is thermally stable at temperatures less than 1000
C [25], it serves as an inert component to maintain the skeleton of the complex catalyst and to
prevent further sintering during cycling. This may explain
why the microstructure and sorption capacity stabilized after
several cycles.

Results of CA-cat2 evaluation by the ReSER hydrogen

production process
Based on our finding that formation of Ca12Al14O33led to a
more stable microstructure and sorption properties, a new

33.4
10.7
5.2
5.4

17.2
19.8
49.3
41.1

0.198
0.055
0.064
0.055

2.1
0.9
1.4
1.1

sorption catalyst Ni-nano-CaO/Ca12Al14O33 was obtained to

improve the stability of sorption complex catalyst as illustrated above (section Preparation of Ni-nano-CaO/Ca12Al14O33
sorption complex catalyst).
Results of stability evaluation of CA-cat2 based on ReSER
hydrogen production are presented in Fig. 8. Ten runs of the
ReSER hydrogen production were conducted. The first
reforming reaction showed the highest activity with 96.2% (v/v)
hydrogen content and 86.1% methane conversion. The sorption catalyst showed an improvement in stability in the initial 8
reaction cycles with >90.0% (v/v) hydrogen content in the
outlet. Comparison of our results with the previous study [13]
that investigated the stability of Ni-nano CaO/Al2O3 is shown
in Fig. 9. The catalyst Ni-nano CaO/Ca12Al14O33 shows greater
stability than NCA with improvement of six reaction cycles.
The sorption complex catalysts were characterized before
and after ReSER hydrogen production by N2 nitrogen physicsorption to investigate variation in the microstructure, and
by TGA testing to define the reason of sorption capacity stability. As is evident from Table 1, the surface area and pore
volume of CA-cat2-0 was much smaller than that of NCA-0,
and the average pore diameter was much larger than that of
NCA-0. However, the microstructure of NCA changed significantly after 7 ReSER cycles while the CA-cat2 remained almost
the same after 10 ReSER cycles. This improvement in microstructure stability may have contributed to stability of sorption capacity, making the catalyst highly suitable for ReSER
hydrogen production.

Conclusions

Fig. 9 e Evaluation the stability of CA-cat2 and NCA

catalysts by the ReSER hydrogen production process.
(reaction temperature of 600
C, calcination temperature of
800
C, steam methane molar ratio of 4, reaction pressure
of 1 atm).

In this paper, the influence of carbonationecalcination conditions on microstructure of the sorption catalyst was studied.
The results showed that microstructure and CO2 sorption
capacity of the sorption complex catalyst decayed significantly during the carbonationecalcination cycle, especially
under a steam atmosphere during the initial cycles. This was
caused not only by sintering of CaO to effectively decrease the
surface area, but also because the reaction between Al2O3 and
CaO to form Ca12Al14O33, which decreased the Al2O3 and
reactive CaO content, occurred even at 800
C. A model for
formation of Ca12Al14O33 is proposed. Meanwhile, our results
suggest that formation of Ca12Al14O33 is the main factor
contributing to stability of the subsequently cyclic process.
Based on these results, a new catalyst was prepared by
pretreatment of the nano-CaCO3/Al2O3 support at a high
temperature to improve the stability of the sorption complex
catalyst. Ten cycles of ReSER process of hydrogen production
has proved the more stable of conversion of methane, while

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 0 ( 2 0 1 5 ) 5 6 1 7 e5 6 2 3

the catalyst without pretreatment yielded only four cycles of

stable of conversion of methane.

Acknowledgment
We gratefully acknowledge financial supports from the National Natural Science Foundation of China (NSFC,Grant No.
21276234).

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