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 3 6 ( 2 0 1 1 ) 4 8 8 7 e4 8 9 9

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Calcium looping gasification for high-concentration hydrogen

production with CO2 capture in a novel compact fluidized bed:
Simulation and operation requirements

Shiyi Chen, Dong Wang, Zhipeng Xue, Xiaoyan Sun, Wenguo Xiang*
School of Energy and Environment, Southeast University, Nanjing 210096, China

article info abstract

Article history: The coal/CaO/steam gasification system is one of the clean coal technologies being
Received 27 October 2010 developed for hydrogen production with inherent carbon dioxide separation. A novel
Received in revised form reactor configuration for the system is proposed in this paper. It consists of three major
26 December 2010 counterparts: a gasifier, a riser and a regenerator. A regenerable calcium-based sorbent
Accepted 29 December 2010 CaO is used to remove carbon dioxide. In the gasifier, the coal-steam gasification reaction
Available online 25 February 2011 occurs with in situ carbon dioxide removal by carbonation reaction. The removal of carbon
dioxide favors the gasification and watereshift reaction equilibrium and enables the
Keywords: production of a hydrogen-rich gas stream. CaO is regenerated in the regenerator by burning
Hydrogen production the unreacted char with oxygen, and a pure stream of carbon dioxide is separated after
Coal gasification a cyclone. The regenerated CaO then flows into the riser above the gasifier, and removes
Calcium sorbent the carbon dioxide in the outlet gases from the gasifier and drives the water-gas shift
CO2 capture reaction forward, further improving the hydrogen purity. In this work, the feasibility and
optimum process conditions of the proposed system were described. The hydrogen purity
can reach 96 vol% at a steam flow 80 mol/s and CaO recycle rate 30 mol/s when the carbon
conversion rate is 0.50. Increasing the steam flow and CaO recycle rate can enhance the
hydrogen yield and purity. With the rise of operation pressure from 1 bar to 10 bar, the
hydrogen yield and purity decrease and methane yield increases. High pressure leads to
higher calcination temperature. At 10 bar, the temperature for CaCO3 decomposition is


approximately 1100 C, at such temperature, the sorbent is easy to deactivate. The
appropriate temperatures in the gasifier and the riser are 700 and 600
C, respectively. An
analysis of heat integration is conducted. The maximum carbon conversion rate is w0.65.
A hydrogen production efficiency of 58.5% is obtained at a carbon conversion rate 0.50,
steam flow 60 mol/s and CaO recycle rate 30 mol/s, with a hydrogen purity of 93.7 vol%.
Crown Copyright ª 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All
rights reserved.

1. Introduction hydrogen on the earth is mainly contained in water and its

production consumes other energy sources, such as electricity,
Hydrogen is expected to be one of the most important energy natural gas, oil or coal. Currently, it is largely produced from
carriers in the next decades, which can be used in combustion steam-natural gas reforming and coal gasification [1,2].
engines and fuel cells with little pollution on the environment, Commercial production of hydrogen today is primarily for its
especially without CO2 emission. However, elemental use as a chemical feedstock. The potential for very large-scale

* Corresponding author. Tel.: þ86 25 8379 5545; fax: þ86 25 8771 4489.
E-mail address: [email protected] (W. Xiang).
0360-3199/$ e see front matter Crown Copyright ª 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2010.12.130
4888 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 3 6 ( 2 0 1 1 ) 4 8 8 7 e4 8 9 9

production of hydrogen as an alternative fuel to replace fossil It is exothermic. The product gas has a high concentration
fuels for motor vehicles appears to be very large. This use for of hydrogen. The unburned char flows into the regenerator for
natural gas should be considered an inappropriate technology combustion to provide the heat needed for CaO regeneration.
[3]. Coal is the most abundant fossil fuel in the world. In It is also called calcination or decarbonation:
a future hydrogen energy system [4], coal gasification will be
a potential support for the large hydrogen demand. However, CaCO3 4CaO þ CO2 DHQ298 ¼ 178:9 kJ=mol (8)
CO2 is a by-product in coal gasification. It is a greenhouse gas Char combustion:
and a major contributor to global warming in recent years [5]. If
the hydrogen production is implemented without CO2 capture, C þ O2 /CO2 DHQ298 ¼ 393:5 kJ=mol (9)
the increase in atmosphere temperature, ocean temperature
If pure oxygen is used for calcination, pure CO2 can be
and sea level caused by global warming is a huge threat to the
obtained from the regenerator, ready for sequestration and
survival of human being, and makes the hydrogen energy
storage. A simple sketch of the coal/CaO/steam process is dis-
system which is expected environmentally benign meaning-
played in Fig. 1. Coal and CaO is continuously fed into the
less. With in the many options and actions for mitigation of
gasifier where CO2 is captured in the form of CaCO3. CaCO3 and
greenhouse gas emissions, CO2 capture and sequestration is
unburned char are cycled to the regenerator, where the char is
emerging as a viable option. But CO2 capture and sequestration
burned with pure oxygen and the CO2 is released. In addition,
generally result in considerable energy penalties and signifi-
fresh sorbent may be introduced into the system accounting for
cant additional costs. In the longer term, it is very important to
the losses due to sintering and attrition of the sorbent. In the
develop potential methods for hydrogen production from coal
meantime, the deactivated sorbents, ash, unburned char and
with inherent CO2 capture. The coal/CaO/steam gasification
fines are also removed from the system. The temperature in the
system is one of these promising options.
gasifier is usually 600e700
C and >900
C in the regenerator.
The coal/CaO/steam gasification system consists of two
H2S would be generated during gasification of coal with
reactors: one is the gasifier and the other is the regenerator. In
a high content of sulfur. It reacts with CaO, forming calcium
the gasifier, the coal gasification process is achieved by reacting
sulfide (CaS) [6]. The calcium sulfide entering the regenerator
coal and steam at an appropriate temperature and pressure.
is oxidized to CaSO4 at a high temperature. Since the direct
Char gasification:
oxidization of CaS to CaSO4 is limited by a CaSO4 layer which
C þ H2 O4CO þ H2 DHQ298 ¼ 131:3 kJ=mol (1) prevents deeper oxygen diffusion to the unreacted CaS [7,8],
the solid sulfur components in the regenerator are a mixture
Water-gas shift reaction: of CaS and CaSO4. If the solid sulfur mixture is not removed
from the regenerator instantaneously, it would accumulate in
H2 O þ CO4CO2 þ H2 DHQ298 ¼ 41:2 kJ=mol (2)
the system and negatively affect the amount of CaO available
Other important chemical reactions, which influence the for carbonation. Therefore, a portion of the CaS/CaSO4 is also
distribution of the conversion products, are following: purged at the exit of the regenerator with deactivated sorbents
Steam-methane reforming: and ash to maintain an acceptable rate of CO2 capture in the
gasifier. Thus, the sorbents makeup and purge is required not
H2 O þ CH4 4CO þ 3H2 DHQ298 ¼ 206:1 kJ=mol (3)
only to keep a hydrogen stream with constant purity but also
Boudouard reaction: prevent the accumulation of inert materials (viz. deactivated
sorbents, ash, fines and CaSO4/CaS) in the cycle.
C þ CO2 42CO DHQ298 ¼ 172:4 kJ=mol (4) Circulating fluidized bed (CFB) is the most suitable reactor
Methanation: for the proposed process. The rapid solid mixing in the

C þ 2H2 4CH4 DHQ298 ¼ 74:8 kJ=mol (5) H2-rich gas CaCO3 CO2

Solid sorbent CaO has received the majority of attention as Char

a CO2 sorbent due to its ability to remove CO2 to a very low
concentration. Moreover, it is cheap and can be derived from
a wide range of abundant and inexpensive precursors, such as
limestone and dolomite. During the gasification process, CaO
is added into the reactor, absorbing CO2 in the form of CaCO3:

CaO þ CO2 4CaCO3 DHQ298 ¼ 178:9 kJ=mol (6)

Gasifier Regenerator

The reaction above is called carbonation, which has three

advantages: firstly, CO2 is carbonated and separated ready for
sequestration; secondly, the removal of CO2 from the reaction
system alters the equilibrium composition of the product gas
and promotes the hydrogen-rich gas; thirdly, carbonation CaO
H2O O2
reaction can compensate the heat needed in the gasification.
Coal
The net reaction in the gasifier is:
Fig. 1 e Schematic description of the coal/CaO/steam
C þ 2H2 O þ CaO4CaCO3 þ 2H2 DHQ298 ¼ 88:74 kJ=mol (7)
process.
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fluidized bed provides a good environment for heat and mass increasing the gasifier pressure, which was proposed by Lin
transfer and temperature uniformity [9]. Obviously, optimi- et al. [26] and other researchers in their published literatures.
zation of the fluidized bed design and the operation conditions However, their studies only focused on optimization of the
detailed for this near zero emission process would depend on gasifier for a higher hydrogen production and ignored the
the characteristics of specific coal and CaO. regenerator. There are two issues to be addressed in the system
The coupled gasification-CO2 capture process based on while increasing the pressure of the gasifier.
coal/CaO/steam is proposed by many researchers. This Suppose the system process uses interconnected circu-
process is also suggested as HyPr-RING [10], Zero emission lating fluidized bed reactors, increasing the pressure will
coal [11], SEHP [12] and LEGS [13]. As renewable sources such elevate the calcination temperature for CaO regeneration in
as biomass have received a majority of attention in recent equation (8). The equilibrium partial pressure of CO2 above
years, coal is substituted by biomass as feedstock to generate CaO as a function of temperature is plotted in Fig. 2, using the
hydrogen by many researchers [14e22]; however, the principle frequently quoted equilibrium equation of Baker [33].
of this sorbent enhanced hydrogen generation process is not
lg Pe ðatmÞ ¼ 7:079  8308=TðKÞ (10)
changed.
Lin et al. [10,23e29] have been doing a lot of work on the It can be seen that higher pressure typically increases the
production of hydrogen with simultaneous CO2 capture with calcination temperature. At 1.0 MPa, the regeneration
CaO in steam gasification of coal. They called this process temperature exceeds 1100
C. The high regeneration temper-
HyPr-RING. Their experiments were mainly carried out in ature is one of the major problems as the sorbents tend to
a batched high pressure reactor. They investigated many sinter and lose reactivity in multi-cycle operation [34]. This
factors influencing the gasification process, such as temper- has been recognized by many studies on calcium-looping for
ature, pressure, sorbents, pyrolysis process and coal rank etc. CO2 capture [35e37].
Gasification temperature range was usually of 650e700
C [25], Suppose the system process uses two separated reactors.
the carbon conversion of the coal was between 0.60e0.80 [27]. The gasifier is operated under high pressure, and the regen-
A hydrogen concentration, 85 vol% can be achieved in their erator is operated at atmosphere for a low calcination
experiments [24]. CO2 can be fixed into CaCO3 and CO can be temperature against sorbents deactivation, individually. The
completely shifted into hydrogen during reaction. The only system would be very complicated, and it is difficult to operate
hydrocarbon found in the gas products was methane [24]. But practically in industrial process.
this process is under a pressure as high as 6.0e11 MPa. In their Methods adopted to enhance the hydrogen production as
another process analysis based on HSC Chemistry [10], the mentioned above is usually increasing pressure, steam/C and
carbon conversion of coal in the gasifier was 0.53; a fuel gas Ca/C ratios. But the effects of these measures are limited
comprising an equilibrium mixture of 91 vol% hydrogen and when the hydrogen concentration has already reached
9 vol% methane can be obtained by gasification of coal at a certain degree, such as 85 vol% [24]. The crux is the ther-
650
C and 3.0 MPa. modynamic equilibrium and kinetics in a single-stage reactor.
Wang et al. [30] analyzed thermodynamic equilibrium of In this paper, a novel reactor set-up is proposed. The config-
this coal/CaO/steam process. They proposed that the opera- uration is shown in Fig. 3. It is in a loop with end-to-end
tion pressure in the gasifier should be 20e30 bar, the arrangement. It is comprised of two sections: the gasification
temperature should be between 625 and 850
C and more than section and the regeneration section. The innovation is the
70 vol% hydrogen can be obtained. Weimer et al. [13] analyzed gasification section, which is a gasifier with an extra riser
the gasifier operating conditions, and they found that to above it. It is similar to the compact fuel reactor as described
achieve a carbon capture of greater than 80%, it was necessary in chemical-looping hydrogen generation system [38]. The
to increase the pressure as the gasification temperature gasifier is a bubbling fluidized bed. It is designed for conven-
increases. Analysis on the gasification process was conducted tional gasification fed with steam, and the riser is for second
at temperature of 750
C, pressure of 2.0 MPa and carbon
conversion of 80%. The hydrogen composition was accounted 100

for 53.5 vol%, the steam was 44.0 vol%, methane was 1.4 vol%
10
and the trace species were CO, CO2 and H2S. Corella et al.
CO2 equilibrium pressure /bar

[31,32] conducted experiments in a bubbling fluidized bed for 1

scaling up at atmosphere pressure, a gasification gas with an
hydrogen contents, as high as 80 vol% (dry basis), has been 0.1
obtained by gasification of coal with pure steam at 600e800
C,
0.01
the recommended CaO/C ratio was above 10e15. The range
was much higher than ratios investigated by other
1E-3
researchers in a small experimental set-up or simulation
[16,18,29], because the scaling-up experiments were con- 1E-4
ducted in atmosphere pressure.
Although the coupled gasification-CO2 capture process 1E-5
400 600 800 1000 1200 1400
based on coal/CaO/steam can generate hydrogen-rich product
Temperature /ºC
gas, the hydrogen purity is limited by thermodynamic equi-
librium and kinetics in a single-stage reactor. The method to Fig. 2 e Equilibrium partial pressure of CO2 above CaO as
enhance the hydrogen yield and carbonation was usually a function of temperature.
4890 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 3 6 ( 2 0 1 1 ) 4 8 8 7 e4 8 9 9

carbonation. The regeneration section is a riser for calcina- temperatures, what’s more, carbonation reaction itself in the
tion. The design focuses on maximizing the hydrogen riser is exothermic. Thus, the controlling of the riser temper-
concentration with the flue gas from the gasification section, ature is a challenging work. To maintain the lower tempera-
and the conventional loop seals can be used. The gasifier, riser ture of the riser, it is necessary to arrange heat exchange
and regenerator are operated under varied temperatures. Coal surfaces such as water-cooled wall along the riser tube to
is continuously fed into the gasifier and gasified with steam. maintain a temperature suitable for CO2 absorption. The heat
The gas product is syngas, which is a mixture of H2, CO, CO2 recovered from the riser can be also used to generate steam
and CH4. A majority of CO2 is simultaneously carbonated by for the gasifier.
CaO from the dipleg, forming CaCO3. The hydrogen-rich
syngas flows up to the upper riser. The unburned char and
CaCO3 are overflowed and enter the regenerator, where the 2. Technical approach and process
char burns with oxygen and CaCO3 decomposes to CaO and simulation
CO2. Regenerated CaO is raised with CO2. After cyclone, pure
CO2 is separated and then can be stored or utilized in an In the process of hydrogen production from coal gasification,
environmentally friendly way. Separated CaO is lead to the the bubbling fluidized bed gasifier (shorten as gasifier in the
upper riser above the gasifier; it is raised by hydrogen-rich later section) is operated at a temperature about 600e700
C,
syngas from the gasifier and absorbs the rest CO2 in the mixed while the riser is at a temperature 450e600
C. As coal is fed
gases, which also favors water-gas shift and methane into the gasifier, an exquisite contact between coal and
reforming reactions for hydrogen generation. At the outlet of sorbents occurs, followed by the intense exchange of heat and
cyclone, nearly pure hydrogen could be obtained after water mass. The mechanism for steam gasification of coal is char-
condensation and the separated solids CaO/CaCO3 fall into the acterized by a three-step sequence involving: pyrolysis,
gasifier for gasification carbonation. cracking and reforming of the volatiles and tars and char
From the thermodynamic equilibrium point of view, the gasification. The gasification process is endothermic; but the
riser would be operated at a temperature lower than the carbonation is exothermic, which can compensate some heat
gasifier and the regenerator, but the solids and gases circu- needed for gasification. The carbon conversion in a real gasifier
lating from the regenerator and the gasifier are at higher depends on many factors: thermodynamics, chemical
kinetics, hydrodynamics, heat and mass transfer, residence
time and even particle size distribution [39]. The gas stream
Gasification Regeneration from the gasifier is a mixture of H2, CO, CO2 and a small amount
H2 of CH4 and tar. The gaseous product independently exhausts
from the gasifier into the riser, whereas the unreacted char
with CaCO3 is back-passed into the regenerator where it is
CO2
burnt out to release heat demand for CaCO3 decomposition.
In the low-medium temperature gasification process, tar is
usually an undesired product. Catalyst particles can be added
into gasifier for tar decomposition. The catalyst has to be
strong enough to withstand the severe attrition conditions
encountered in both the high temperature fluidization envi-
ronment and the solid circulation loop. Nickel catalyst and the
Riser
sorbent itself, CaO [15], can meet the requirements of activity
and resistance. In addition, the rapid loss of catalytic activity
due to fouling by the tar or carbon deposition on the surface of
catalyst, which takes place in the process of gasification in the
bubbling fluidized bed, will be avoided, because the fouling on
the catalyst surface can be burnt out in the regenerator.
The decomposition of CaCO3 is an intensive endothermic
process. The heat needed is from the combustion of unburned
Regenerator char. The portion of unburned char in the coal mass between
the gasifier and the regenerator specifies the exothermic heat
in the regenerator and the efficiency of coal gasification. If the
Gasifier amount of char to the regenerator is too much, there must be
an excessive heat production inside the regenerator, but
Coal
the hydrogen production is less from char gasification in the
gasifier. On the contrary, too little char from the gasifier to the
H2O regenerator means insufficient heat supply to the decarbon-
ation. Thus, there is an optimum unburned char fraction
O2 between the gasifier and the regenerator.
In order to simulate the chemical processes of the
Fig. 3 e Proposed compact fluidized bed for the coal/CaO/ proposed compact fluidized beds, the software Aspen Plus is
steam process. applied. Based on mass balance, chemical equilibrium and
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energy balance, a model for the process is set-up. The flow

Table 1 e Analysis of Illinois 6# bituminous coal.
chart of simulation is sketched in Fig. 4. It consists of three
basic modules, a gasification module, a calcination module Proximate analysis/% Ultimate analysis/%
(mass, air dry) (mass, air dry)
and an absorption module. The gasification module is
comprised of a pyrolyzer and a gasifier. The pyrolyzer is Moisture 5.0 C 66.07
merely a decomposer, which corresponds to Ryield block in Ash 9.5 H 5.07
Aspen Plus. The gasification, calcination and absorption Fixed carbon 46.26 O 9.5
Volatile 39.24 N 1.19
modules correspond Rgibbs block. The Gibbs free energy is
S 3.67
minimal when the chemical equilibrium for the process is
Lower heating value (LHVfuel) (MJ/kg) 26.81
achieved. The assumptions are made based on the application
of Aspen Plus software:
methane produced per kilo of coal input to gasifier) varies with
(1) All the reactors are operated in a steady-flow state and the steam flow and CaO recycle rate in the proposed compact
reactions involved are in chemical equilibrium; fluidized beds. The gasifier temperature is 700
C; carbon
(2) Ash in coal is inert and tar is not taken into account in the conversion in the gasifier is defined as 0.50; the temperature in
simulation; the regenerator is 900
C and the temperature in the riser is
600
C. When the steam flow was 80 mol/s and CaO recycle
The coal used in this study was Illinois 6# bituminous coal. rate is 30 mol/s, the hydrogen purity can exceed w96 vol%,
The proximate analysis and the ultimate analysis of coal are which is much higher than other studies based on one single-
illustrated in Table 1; Operation conditions and primary stage gasification reactor configuration [25,27,30]. The gas
parameters in the modeling are summarized in Table 2. The compositions at the outlet of the gasifier and the riser are
CaO sorbent recycle rate is defined as the moles of Ca-based illustrated in Table 3.
sorbent flows into the gasifier. As expected, the hydrogen yield increases with steam flow
as shown in Fig. 5. This can be simply explained by chemical
equilibrium of the gasification reaction and water-gas shift
3. Results and discussion reaction. The increase of steam benefits the gasification reac-
tion (1) and water-gas shift reaction (2) towards the right
3.1. Effect of steam/coal ratio and CaO/coal ratio direction, i.e., those reactions are favored. It also promotes the
steam-methane reforming to yield hydrogen, and the methane
The primary gases from hydrogen cyclone are hydrogen and production decreases with increasing steam, whereas at a low
methane, and other traces i.e., H2S, CO and CO2. Fig. 5 shows steam flow, methane is the dominant product gas due to
how the gas yield (viz. the number of weight of hydrogen or insufficient gasification. But at a high steam flow, the hydrogen

Fig. 4 e Aspen flowsheet of the simulation.

4892 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 3 6 ( 2 0 1 1 ) 4 8 8 7 e4 8 9 9

a low steam flow (<w40 mol/s), there is not sufficient steam for
Table 2 e Operation conditions and primary parameters
in the modeling. gasification reaction; the major product gas is methane and the
hydrogen production is limited by gasification reaction equi-
Atmosphere pressure (bar) 1.01325
librium. At a high steam flow (>w40 mol/s), the increase of CaO
Atmosphere temperature (
C) 25
Coal flow rate (kg/s) 1.0 recycle rate promotes the absorption of CO2 and benefits the
Steam temperature (
C) 500 gasification reaction, and especially the water-gas shift reac-
Gasifier temperature (
C) 700 tion in the riser. When CaO recycle rate exceeds approximately
Regenerator temperature (
C) 900e1100 30 mol/s, there is enough CaO to absorb CO2 in the gasifier and
Riser temperature (
C) 450e600 riser, and the surplus sorbents are only circulating around the
System pressure (bar) 1e10
beds without reacting. Therefore, hydrogen production is
Calcium recycle rate (mol/s) 10e60
Molar flow rate of steam (mol/s) 10e150
independent on the CaO recycle rate. However, in a practical
Oxygen flow rate (kg/s) 8 munburned char(kg/s)/3 application, sintering and deactivation of sorbents is inevitable
CaO/ash purged ratio (%) 10 over multiple cycles, leading to the decay in CO2 capture.
Therefore, the factual CaO recycle rate would be higher than
theoretical calculation to ensure a sufficient CO2 capture
increment declines and any surplus steam will be a waste of
capacity.
heat load on the system. Additional steam in the system mostly
passes through the gasifier and leaves as unconverted steam.
At a relative high steam flow, i.e., above 60 mol/s, the increase 3.2. System pressure
of CaO recycle rate will enhance the hydrogen production in
the initial stage (CaO recycle rate: 0e30 mol/s), but when the Fig. 6 shows how the gas yield (viz. the number of weight of
CaO recycle rate is higher than w30 mol/s or the system is at hydrogen or methane produced per kilo of coal input to gasifier)
a low steam flow (<w40 mol/s), the hydrogen production is varies with steam flow and CaO recycle rate at 10 bar. The
independent on CaO recycle rate. There is an explanation, at temperature in the gasifier is 700
C; the regenerator is at

Fig. 5 e a-Hydrogen production (kg/h) varying with steam flow rate and CaO flow rate (both in mol/s), p [ 1 bar, gasifier
feed [ 1 coal kg/s, b-Methane production (kg/h) varying with steam flow rate and CaO recycle rate (both in mol/s), p [ 1 bar,
gasifier feed [ 1 coal kg/s, c-Hydrogen purity varying with steam flow rate and CaO recycle rate (both in mol/s), p [ 1 bar,
gasifier feed [ 1 coal kg/s.
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atmosphere in Fig. 5, however, it is noted that there is

Table 3 e The gas composition (dry basis) at the outlet of
the gasifier and the riser, p [ 1 bar, gasifier coal feed a dramatic increase of calcination temperature from 1 bar to
rate [ 1 kg/s, steam flow [ 80 mol/s, CaO recycle 10 bar. At 10 bar, the decomposition temperature of CaCO3
rate [ 30 mol/s. exceeds 1000
C, where there is a further consideration of
Gas component Gasifier Riser sorbent activity. At such temperature higher than 1000
C, the
sorbent CaO is easily prone to deactivate after several cycles
kg/h vol% kg/h vol% [40,41]. In general, increasing the system operation pressure
CO 630.614 7.76 35.456 0.48 has an adverse effect on the hydrogen production, while the
CO2 984.805 7.71 74.505 0.64 hydrogen absolute yield decreases with the pressure
H2 477.923 82.29 511.407 96.00 increasing; the increase of methane also dilutes hydrogen in
CH4 13.917 0.30 32.445 0.76
the product gas at the same time. More importantly, high
N2 42.738 0.53 42.569 0.57
pressure will elevate the regenerator temperature, causing
H 2S 139.772 1.41 140.389 1.55
NH3 0.124 trace 0.330 trace deactivation of CaO. That is the major problem at elevated
COS 1.152 trace 0.065 trace pressure. Therefore, the optimal pressure of the system should
be atmosphere.

1100
C and the riser is at 600
C. The amount of hydrogen is

slightly suppressed with the increase of pressure, whereas 3.3. Riser temperature
methane production is enhanced. It is contrary to the experi-
mental result by Lin [26] because this work does not take into Fig. 7 displays gas yields and hydrogen concentration varying
account kinetics limitations. As the pressure increases to with riser temperature. The gasifier is at 700
C, the regenerator
10 bar, methanation reaction (5) is favored and methane has is at 900
C, and the system is at atmosphere. The inlet steam
a slight increase, causing the decrease of hydrogen fraction in flow is 60 mol/s and heated to 500
C; the CaO recycle rate is
the product gas. The curves tendency is the same as that at 30 mol/s. It is observed that the gas production is almost

Fig. 6 e a-Hydrogen yield (kg/h) varying with steam flow rate and CaO flow rate (both in mol/s), p [ 10 bar, gasifier feed [ 1 coal
kg/s, b-Methane yield (kg/h) varying with steam flow rate and CaO flow rate (both in mol/s), p [ 10 bar, gasifier feed [ 1 coal
kg/s, c-Hydrogen purity varying with steam flow rate and CaO recycle rate (both in mol/s), p [ 10 bar, gasifier feed [ 1 coal kg/s.
4894 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 3 6 ( 2 0 1 1 ) 4 8 8 7 e4 8 9 9

1800 1.00 rate and the last is carbon conversion. If the temperature is too
1600 high, CaO will not react with carbon dioxide in the gasifier due
1400 0.95 to chemical equilibrium. For example, at 750
C carbon dioxide
cannot be carbonated in the gasifier and the outlet sorbents

H2 concentration (dry)
Gas yields /kg h-1

1200
are CaO unreacted. When the gasifier is at too low tempera-
1000 HO 0.90
CO
ture, the reaction rate will be poor. The temperature recom-
800 CO mended in literatures was between 600 and 700
C
H
600 CH
0.85
[10,16,22,23,25e27]. In this paper, 700
C was chosen for
400
further investigation. At a fixed gasifier temperature, the
0.80 carbon conversion expected can be achieved by adjusting the
200
gasifier design. As mentioned above, the carbon conversion
0
0.75
rate in the gasifier is dependent on thermodynamics, chem-
450 500 550 600 650 700 ical kinetics, hydrodynamics, heat and mass transfer, resi-
The riser temperature/ dence time and particle size distribution. In a practical device,
Fig. 7 e Gas yields varying with different riser temperature, to achieve a certain conversion rate, one of the feasible
measures is to control the residence time of coal particles by
gasifier at 700
C, regenerator at 900
C, p [ 1 bar, coal feed
optimizing the bed height and the fluidized velocity in the
rate [ 1 kg/s, steam flow [ 60 mol/s, CaO recycle
bubbling fluidized gasifier.
rate [ 30 mol/s.

3.5. Heat integration

independent on the riser temperature when it is below 550
C.
As the riser temperature increases from 550 to 700
C, methane In the coal/CaO/steam system, there are three reactors: the
yield decreases slightly, and carbon monoxide, carbon dioxide gasifier, the regenerator and the riser. In the riser, the domi-
and steam increases dramatically and the hydrogen concen- nant reaction is carbonation. It is exothermic, and the riser
tration declines. The hydrogen yield is almost the same in the requires no extra heat. In the gasifier, the net reaction (7) is
temperature range and declines slightly at 700
C. There is an exothermic, but it is an ideal assumption that all elemental
explanation. At higher temperature, the capability of CaO carbon is carbonated to CaCO3. Due to chemical equilibrium,
absorption is limited by chemical equilibrium, thus more the reactions included in the gasifier are not merely the ideal
CaCO3 decomposes to CaO at high temperature: net reaction; some carbon dioxide and carbon monoxide from
the gasification reaction cannot be fully carbonated; it can be
CaCO3 /CaO þ CO2 validated by product gases at the outlet of gasifier. Table 4
high partial pressure of carbon dioxide suppresses the water- presents the gas composition at the outlet of gasifier. The
gas shift reaction and favors its reverse reaction: outlet gases include hydrogen, carbon monoxide and carbon
dioxide; the carbon monoxide and carbon dioxide derive from
CO2 þ H2 /CO þ H2 O coal gasification, which is strongly endothermic and should
which increases the steam concentration. At the same time, not be neglected. Even though the carbonation reaction is
the hydrogen production decreases slightly. At high steam exothermic, the heat released cannot fully compensate the
partial pressure, steam-methane reforming reaction is endothermic gasification. Thus, the gasifier is endothermic
enhanced: and demands extra heat. Some experiments results also
proved that the heat generated by carbonation cannot
CH4 þ H2 O/CO þ 3H2 compensate for heat consumed by coal gasification [32]. The
heat compensation can be from two sources: one is the partial
and then the methane production decreases.
oxidization of the product gas; the other is from char
In general, this proposed configuration is equivalent to the
combustion in the regenerator. The latter is more complicated
traditional one single-stage gasification reactor set-up when
compared to fuel partial oxidization, where it needs extra heat
the riser is at 700
C; through Fig. 7, it can be also seen that’s
why addition of a riser at a lower temperature can improve the
hydrogen concentration.
Temperature is an important parameter in any chemical Table 4 e Gas composition at the outlet of gasifier,
p [ 1 bar, gasifier coal feed rate [ 1 kg/s, steam
reaction. The reaction rate is restrained by chemical kinetics if
flow [ 60 mol/s, CaO recycle rate [ 30 mol/s.
temperature is too low. But at high temperature, the decom-
Gas component kg/h vol%
position of CaCO3 increases carbon dioxide, suppressing
water-gas shift reaction, and promotes the reverse water-gas H2O 1526.407 23.11
shift reaction, increasing carbon monoxide in the product gas CO 857.107 8.34
dramatically. The suitable riser temperature is 600
C. CO2 828.329 5.13
H2 449.415 61.23
CH4 38.201 0.65
3.4. Gasifier temperature N2 42.729 0.42
H2S 139.48 1.12
NH3 0.135 trace
The selection of gasifier temperature involves three major COS 1.662 0.01
considerations: the first is carbonation; the second is reaction
 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 3 6 ( 2 0 1 1 ) 4 8 8 7 e4 8 9 9 4895

exchange utility. Here an analysis of heat integration over the sensible heat compensation of solids between the gasifier and
entire system is performed. The heat demanded in the gasifier regenerator will increase, i.e., the heat required for heating
is from the regenerator. solids from 700 to 900
C will increase, which decreases the
capability of regenerator to supply heat, especially when the
(1) The heat for heating and evaporation of water to steam steam flow and CaO recycle rate are both high. More heat is
into the gasifier is from the riser; demanded in the gasifier and to compensate solids sensible
(2) The heat for heat compensation in the gasifier is supplied heat. If the regenerator cannot meet this heat load, heat
by regenerator; integration is broken.
(3) Gasifier is at 700
C, regenerator is at 900
C and riser is at With the increase of steam flow, the heat load demanded
600
C; for heating and evaporation of water to produce a stream of
(4) Energy consumed for pure oxygen into the regenerator is saturated steam for gasification will be enhanced. The riser
not included for simplicity. cannot meet this heat load. At some medium-high steam
flows (70e150 mol/s), the region cannot meet the criteria (1)
Fig. 8 displays potential operating regions for a system at above, and it is necessary to seek other steam vapor sources.
atmosphere pressure at a carbon conversion rate 0.50. The
molar flow rate of steam into the gasifier varies from bottom 3.6. The maximum carbon conversion rate
to top, and the molar flow rate of CaO varies from left to right.
The white region represents unsuitable operating conditions Carbon conversion rate is an important parameter in heat
where the criteria set above are not met, whilst the gray region integration. At a high carbon conversion rate, more char
where both the criteria are successfully met, i.e., in this region reacts with steam and generates more H2, CO2 and CaCO3. On
the system is fully heat integrated. one hand, gasification process demands higher heat load; on
At the carbon conversion rate 0.50, when CaO recycle rate the other hand, more heat is needed for CaCO3 decomposition
is less than 30 mol/s and the steam flow is higher than in the regenerator. If the amount of unburned char into
40e70 mol/s, the heat supplied by regenerator to gasifier is regenerator is too small, the heat cannot be integrated in the
insufficient. At a steam flow higher than 40e70 mol/s, the system. At a low carbon conversion rate, less char is used for
gasification reaction becomes dominant. CO2 is a major gas gasification and the heat load for gasification is small. If too
product and more CaCO3 is formed. The heat load for CaCO3 much unburned char flows into the regenerator, and the heat
decomposition increases in the regenerator and leads less load (gasification and decarbonation) is smaller than supply,
heat supply to gasifier. Therefore, at higher steam flows, the the surplus heat will be a waste of energy.
heat cannot be integrated. At a low steam supply, less than Practically, the carbon conversion rate in the gasifier is
40 mol/s, methane is the major gas product and elemental a function of temperature, pressure, steam/carbon ratio, gas-
carbon is mainly in the form of methane; so there is less solid solid heat transfer and other factors. The minimum flow rate of
product CaCO3 from the gasifier, which alleviates the heat unburned char into the regenerator is required at least meeting
load of regenerator for CaCO3 decomposition. Meanwhile, the heat load for CaCO3 decomposition, and other heat demand
methanation is exothermic. Thus, the regenerator can supply for endothermic gasifier can be from partial fuel combustion. If
enough heat to gasifier. At a medium CaO recycle rate, the carbon conversion rate is too high in the gasifier, the rest
30e40 mol/s, the regenerator can provide full heat demanded unburned char may not provide sufficient heat for CaO
in the gasifier, but with increase of solids recycle rate, the regeneration. Fig. 9 shows a regime at two varied carbon

150
140
130
120
110
100
H2O /mol s-1

90
80
70
60
50
40
30
20
10
20 25 30 35 40 45 50 55 60
-1
CaO /mol s
Fig. 8 e Suitable operating regimes for varying steam in-flow and CaO recycle rate, p [ 1 bar, coal feed rate [ 1 kg/s.
4896 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 3 6 ( 2 0 1 1 ) 4 8 8 7 e4 8 9 9

a 150
140
130
120
110
100
H2O /mol s-1

90
80
70
60
50
40
30
20
10
20 25 30 35 40 45 50 55 60
-1
CaO /mol s
b
150
140
130
120
110
100
H2O /mol s-1

90
80
70
60
50
40
30
20
10
30 35 40 45 50 55 60
-1
CaO /mol s
Fig. 9 e a- Regimes that the regenerator requires no extra heat at a carbon conversion rate 0.65, the temperature in the
gasifier, regenerator and riser is 700, 900, and 600
C, respectively, b- Regimes that the regenerator requires no extra heat at
a carbon conversion rate 0.70, the temperature in the gasifier, regenerator and riser is 700, 900, and 600
C, respectively.

conversions, 0.65 and 0.70, which is different from Fig. 8. The compensation from gasifier to regenerator, which also
gray regime represents that the regenerator is exothermic; and consumes some heat released in the regenerator. That’s why
the white regime represents that the regenerator needs extra the unsuitable regime starts from the right upper blocks. With
heat for CaCO3 decomposition, which is not suitable for the the increase of carbon conversion rate in the gasifier, more
process at all. It can be seen that the white regime is enlarging CaCO3 is produced but less char is available for CaCO3
from the upper left corner with carbon conversion rate decomposition, so at a carbon conversion rate 0.7, much of the
increasing. There is an explanation, on one hand, a high steam regime cannot provide enough heat for regenerator. Even
flow drives more CaCO3 yield in the gasifier, leading more heat though some blocks at 0.7 meets heat demand, the hydrogen
load for decomposition in the regenerator; on the other hand, yield or purity is poor in these areas. Therefore, the maximum
a high solid recycle rate demands more sensible heat carbon conversion rate is approximately 0.65.
 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 3 6 ( 2 0 1 1 ) 4 8 8 7 e4 8 9 9 4897

3.7. The role of riser Section 3.3 Riser temperature. These effects are counteracted
and there is only a slight increase in hydrogen yield, but the
The solid into the riser is regenerated CaO; the gases into the hydrogen purity is improved dramatically due to further
riser from the gasifier are a mixture of steam, hydrogen, carbon absorption of carbon dioxide. Therefore, the role of the riser is
monoxide, carbon dioxide and methane. Regenerated CaO to increase the hydrogen purity, not to increase the absolute
absorbs CO2 and drives the water-gas shift reaction to the right. hydrogen yield.
The riser is operated at a low temperature (600
C), which
favors the water-gas shift reaction. The principle is similar to 3.8. Efficiency
that of Calcium Looping Process (CLP) proposed by Fan et al.
[42]. They have recently proposed that CaO is used to improve According to the regime suitable for the heat integration,
the hydrogen purity after the gasifier by driving the water-gas hydrogen production efficiency is studied. The hydrogen yield
shift reaction forward. There is another reaction, which should efficiency h is defined in equation (11):
not be neglected in the riser, the steam-methane reforming
reaction. The reforming reaction is endothermic and favored at mH2 LHVH2
h¼ (11)
high temperature; but in this simulation, the riser temperature mcoal LHVcoal
is not high but relatively low, which favors the reverse where mH2 is the mass of hydrogen produced by mcoal kilogram
reforming reaction, and the methane production has a slight of coal, LHVH2 is the lower heating value of hydrogen,
increase through the riser. For example, at CaO 35 mol/s and 119.95 MJ/kg and LHVcoal is the lower heating value of coal
steam 90 mol/s, the methane is 9.07 kg/h at the outlet of the which is 26.81 MJ/kg. A typical feasible regime with heat
gasifier, whereas the methane is 19.39 kg/h after the riser. On integration is selected for calculation. The carbon conversion
one hand, hydrogen increases due to water-gas shift reaction; is 0.50. The steam flow is 60 mol/s and the CaO recycle rate is
on the other hand, hydrogen decreases with the reverse steam- 30 mol/s; the pressure is atmosphere. The details are shown in
methane reforming reaction. This has been discussed in Fig. 10. The hydrogen yield efficiency is approximately 58.5%.

H2=471.06kg/h
CO=51.21kg/h
CO2=59.90kg/h
CH4=110.46kg/h
600 Heat

Material
Riser
125.4MJ/h
600
H2O=60mol/s Deacativated
25 CaO=672kg/h
Ash=342kg/h
CaO=6056.36kg/h 900
Ash=3078kg/h
13167MJ/h 900

CO2=8271.75kg/h
H2O=1526.41kg/h CO=0.002kg/h
CaO=3714.91kg/h
CO=857.11kg/h O2=3.06kg/h
CaCO3=4179.04kg/h
CO2=828.33kg/h CaO=6729.29kg/h 900
Ash=3078kg/h
H2=449.42kg/h Ash=3420kg/h
600 CH4=38.20kg/h 900
700
H2O=60mol/s
500 Char=1189.26kg/h
Ash=3420kg/h
3636.60MJ/h
CaO=1068.93kg/h
CaCO3=8901.59kg/h
Gasifier 700 Regenerator
700 15800.40MJ/h
900
Fresh
Coal=1kg/s 25 CaO=672kg/h
LHV=26.81MJ/kg 25

O2=3171.36kg/h
25

Fig. 10 e A typical calculation of hydrogen efficiency at a CaO recycle rate 30 mol/s, steam flow 60 mol/s and a carbon
conversion rate 0.50, p [ 1 bar.
4898 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 3 6 ( 2 0 1 1 ) 4 8 8 7 e4 8 9 9

The composition of the product gas is H2 93.7 vol%, CH4 2.7 vol composition and system efficiency, and the optimum condi-
%, CO 0.73 vol%, CO2 0.54 vol% and other gases. The impurities tions may change in a real system.
in the product gas can be absorbed by PSA unit. However, the
calculation is based on ideal assumption (chemical equilib-
rium, fixed carbon conversion rate, steady material and heat
flows), which may be deviate from the practical operation Acknowledgements
condition. The proposed reactor set-up can be also integrated
with combined cycle, but the detailed configuration is The authors gratefully acknowledge the National Natural
complicated and not discussed in this paper. Science Foundation of China (gs1) (50776018) and the Special
Fund of the National Priority Basic Research of China (gs2)
(2007CB210101) for financial support of this project.

4. Conclusions
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