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 5 ( 2 0 1 0 ) 8 5 8 0 e8 5 9 1

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Investigation of coal gasification hydrogen and electricity

co-production plant with three-reactors chemical
looping process

Wenguo Xiang*, Shiyi Chen, Zhipeng Xue, Xiaoyan Sun

School of Energy and Environment, Southeast University, Nanjing 210096, China

article info abstract

Article history: This paper analyzes a novel process for producing hydrogen and electricity from coal,
Received 24 December 2009 based on chemical looping combustion (CLC) and gas turbine combined cycle, allowing for
Received in revised form intrinsic capture of carbon dioxide. The core of the process consists of a three-reactors CLC
25 April 2010 system, where iron oxide particles are circulated to: (i) oxidize syngas in the fuel reactor
Accepted 29 April 2010 (FR) providing a CO2 stream ready for sequestration after cooling and steam vapor
Available online 8 June 2010 condensation, (ii) reduce steam in the steam reactor (SR) to produce hydrogen, (iii)
consume oxygen in the air reactor (AR) from air releasing heat to sustain the thermal
Keywords: balance of the CLC system and to generate electricity. A compacted fluidized bed,
Hydrogen production composed of two fuel reactors, is proposed here for full conversion of fuel gases in FR. The
Electricity production gasification CLC combined cycle plant for hydrogen and electricity cogeneration with
Coal gasification Fe2O3/FeAl2O4 oxygen carriers was simulated using ASPEN
PLUS software. The plant
Chemical-looping combustion consists of a supplementary firing reactor operating up to 1350
C and three-reactors SR at
CO2 separation 815
C, FR at 900
C and AR at 1000
C. The results show that the electricity and hydrogen
efficiencies are 14.46% and 36.93%, respectively, including hydrogen compression to 60 bar,
CO2 compression to 121 bar, The CO2 capture efficiency is 89.62% with a CO2 emission of
238.9 g/kWh. The system has an electricity efficiency of 10.13% and a hydrogen efficiency of
41.51% without CO2 emission when supplementary firing is not used. The plant perfor-
mance is attractive because of high energy conversion efficiency and low CO2 emission.
Key parameters that affect the system performance are also discussed, including the
conversion of steam to hydrogen in SR, supplementary firing temperature of the oxygen
depleted air from AR, AR operation temperature, the flow of oxygen carriers, and the
addition of inert support material to the oxygen carrier.
2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.

1. Introduction systems is the conversion of fossil fuel into carbon-free energy

Concerning about global climate change has led to the research
on low CO2 emission energy systems. Various fossil fuel power
plant concepts, which are intended to reduce CO2 emission in
the process of energy conversion, are proposed. One of such
carriers, hydrogen (H2) and electricity, with CO2 capture and
storage. Coal is a feedstock of particular interest because of its
great abundance, widespread geographical distribution, and
low cost. Coal based H2 and electricity will play an important
role during the transition to a H2-based energy economy.

* Corresponding author. Tel.: 86 25 8379 5545; fax: 86 25 8771 4489.

E-mail address: wgxiang@seu.edu.cn (W.G. Xiang).
0360-3199/$ e see front matter 2010 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2010.04.167
 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 5 ( 2 0 1 0 ) 8 5 8 0 e8 5 9 1 8581

Gasification of coal is a promising technology for the Oxygen depleted air H2,H2O
production of H2 and electricity. The coal is prepared and fed
to the gasifier. In the gasifier, the feedstock reacts with steam CO2,H2O
and oxygen at high temperature and pressure. The resulting
syngas is composed primarily of H2, CO, and smaller quanti-
ties of CH4 and CO2, and then undergoes additional processing SR
to separate and purify H2 with CO2 capture. A series of studies Fe0.947O
have investigated the thermodynamics and economics of
AR FR
converting coal to H2 and electricity with CO2 capture,
including numerous plant designs, operating parameters and Fe2O 3
choices of technology.
Kreutz, Consonni et al. [1e4] studied performances, costs Fuel Steam
and prospects of using commercially ready technology to
convert coal to H2 and electricity with CO2 capture and
Fe3O4
storage. In the co-production plants, coal is gasified to syngas
and then shifted to primarily H2 and CO2. CO2 is then removed
from the syngas using Selexol; after being stripped from the Air
solvent, CO2 is dried and compressed for pipeline transport
and underground storage. High purity H2 is extracted from the Fig. 1 e Conceptual scheme of three reactors CLC for
H2-rich syngas via a pressure swing adsorption (PSA) unit and hydrogen generation.
compressed for usage. The PSA purge gas is compressed and
burned in a conventional gas turbine combined cycle to
generate co-product electricity. Results show that technology
allows transferring 57e58% of coal lower heating value (LHV) 1:803Fe2 O3 1:601CO/1:601CO2 3:807Fe0:947 O DH298
to decarbonized hydrogen, while exporting to the grid decar-
21:64kJ=mol (1)
bonized electricity amounting to 2e6% of coal LHV.
Chemical looping combustion (CLC) is a novel process for
heat and power production with inherent CO2 capture. An 1:803Fe2 O3 1:601H2 /1:601H2 O 3:807Fe0:947 O DH298
oxygen carrier performs the task of bringing oxygen from the 86:48kJ=mol (2)
air to the fuel. Suitable oxygen carriers are small particles of
in the steam reactor (SR), the reduced Fe0.947O reacts with
metal oxide such as hematite (Fe2O3), nickel oxide (NiO). A
steam to form magnetite (Fe3O4) and H2, the latter represent-
basic CLC system has two reactors, one for air and one for fuel.
ing the final product of the process. The reaction (3) is
The oxygen carrier circulates between the reactors. In the fuel
exothermic. Extra steam is needed to achieve an acceptable
reactor (FR), it is reduced by the fuel, which in turn is oxidized
metal oxidation and therefore the gaseous outlet steam is
to CO2 and H2O (steam vapor). In the air reactor (AR), the
a mixture of H2 and H2O (vapor).
reduced metal oxide is regenerated (oxidized) with oxygen
from the combustion air. 3:807Fe0:947 O H2 O/1:202Fe3 O4 H2 DH298 88:1kJ=mol (3)
There has been significant work regarding a suitable choice
Fe3O4 is fully oxidized to Fe2O3 in the AR. The highly
of oxygen carrier for such a process. Gupta et al. [5] found that
exothermic reaction (5) sustains the thermal balance of the
Fe2O3 provided the highest conversion of syngas to combus-
three reactors CLC. The oxygen depleted air is discharged
tion products. Additionally, acceptable conversion of steam to
from the reactor.
H2 was only achieved with oxygen carriers consisting of iron
or tin, the latter proving unsuitable owing to its low melting 4Fe3 O4 O2 3:762N2 /6Fe2 O3 3:762N2 DE298
point. Svoboda et al. [6] compared oxygen carriers containing
479:5kJ=mol (4)
iron, nickel, copper, manganese and chromium. Iron (Fe) was
proved most suitable, since it displayed satisfactory reactivity The overall reaction (5) therefore corresponds to water-gas
during both reduction and oxidation. Mattison et al. [7] found shift reaction which results in the oxidization of CO to CO2.
both the rates of reduction and oxidation for the iron-based
CO H2 O/H2 CO2 DH298 41:20kJ=mol (5)
carriers sufficiently rapid for use in a fluidized bed. Further-
more, iron is safe, and is relatively inexpensive. The chemical looping hydrogen reactors have several
CLC can also be used to generate H2 with inherent CO2 potential benefits compared with conventional water-gas
separation, when iron oxides are used as the oxygen carriers, shift reaction. The exhausts from the oxidation reactor (SR)
as shown in Fig. 1. The three reactors chemical looping consist mainly of H2 and steam vapor. The gas from the
arrangement is able to produce separated streams of H2 and reduction reactor consists of CO2 and steam vapor, so
CO2. In the FR, the iron oxides, in the oxygen rich hematite a condenser is the only equipment needed to obtain almost
state (Fe2O3), are mostly reduced to wustite state (Fe0.947O) by pure CO2 and H2.
oxidizing the fuel gas (taking syngas as an example) according Hacker, Fraser et al. [8e11] investigated H2 production by
to the strongly endothermic reaction (1) and (2). The gaseous steameiron process. The process was studied in a laboratory
outlet stream is composed of H2O (vapor) and CO2 in which fixed bed reactor in the temperature range of 750e900
C.
CO2 is ready for storage after water vapor condensation. Study shows that high operation temperatures are favored for
8582 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 5 ( 2 0 1 0 ) 8 5 8 0 e8 5 9 1

high H2 productivity. Increasing the temperature does result pH2 O

gH2 (6)
in a better redox potential of syngas and oxidation, which is pH2 O pH2
not favored thermodynamically, yielding approximate similar
For CO:
H2:H2O ratio as with lower temperature. Akiyama [12] studied
the reactive property between steam and iron carbide by pCO2
gCO (7)
thermal analysis with a mass spectrometer. Li and Fan [13,14] pCO pCO2
investigated iron based on a chemical looping process for
Here, gi is the gas yield of component (i), and pi is the partial
direct coal gasificationdcoal direct chemical looping (CDCL)
pressure of gaseous species (i) in the product gas. Mattisson
process. The CDCL process has three main reactors, i.e., the
et al. [22,23] simulated chemical reactions and performed
coal reactor, the hydrogen reactor, and a combustion reactor.
equilibrium calculations. The equilibrium composition is
The coal reactor converts the coal into CO2 and H2O while
calculated using the Gibbs energy minimization method.
reducing Fe2O3 to a mixture of Fe and FeO. The hydrogen
Svoboda et al. [24,25] studied the reduction of Fe3O4 by H2, CO,
reactor oxidizes the reduced Fe/FeO particles to Fe3O4 using
CH4 and model syngas (mixtures CO H2 or H2 CO CO2)
steam while producing a H2 rich gas stream. The combustion
from the thermodynamic and chemical equilibrium point of
reactor pneumatically transports Fe3O4 particles from the
view. In their simulations, the conversion of H2 and CO is
hydrogen reactor outlet to the AR inlet using air and Fe3O4
complete for the Fe2O3/Fe3O4 systems, while the gas yield to
particles are reoxidized to Fe2O3 during the conveying process.
CO2 for the systems Fe3O4/Fe0.947O and Fe0.947O/Fe is low in the
ASPEN
PLUS simulation studies showed a very high conver-
entire temperature. At 800
C, the gas yield of CO to CO2 for the
sion efficiency from coal to hydrogen. Ryden et al. [15]
system Fe3O4/Fe0.947O is 0.5408 and that of H2 is 0.5264
proposed a natural gas fueled H2 production process by
whereas for Fe0.947O/Fe system the gas yield is 0.3681 for CO
steam reforming with inherent capture of carbon dioxide by
and 0.3548 for H2. And at 1000
C, the conversion of Fe3O4/
chemical-looping combustion. The process resembles
Fe0.947O system is 0.6820 for CO and 0.7841 for H2, whereas that
a conventional circulating fluidized bed combustor with
of Fe0.947O/Fe is 0.2898 for CO and 0.4086 for H2.
reforming taking place in reactor tubes located inside a bubble
From above analysis it can be concluded that the reduction
fluidized bed. Process layout and expected performance were
of Fe2O3 to Fe0.947O by CO and H2 in a single step results in low
evaluated and a preliminary reactor design was proposed. It
conversion of CO and H2 using Fe2O3 as oxygen carriers in
was found that the proposed process had potential to achieve
a CLC. In order to increase the fuel conversion, two FRs
better selectivity towards hydrogen than conventional steam
arrangement is proposed here for the simulation of CLC H2
reforming plants. Chiesa et al. [16] analyzed a three reactors
and electricity cogeneration system, as shown in Fig. 2. The
chemical looping process for producing H2 from nature gas
iron oxides, in the oxygen rich hematite state Fe2O3 from AR,
using iron oxide particles as the oxygen carriers with intrinsic
are partially reduced to magnetite Fe3O4 by oxidizing the
capture of carbon dioxide. Results showed that an impressive
unconverted fuel gases from FR1 according to the exothermic
potential exists for chemical looping systems for H2 produc-
reactions (8) and (9) in FR2. The gaseous outlet stream is
tion, and it was deserved for substantial R&D activities in the
composed of steam vapor and CO2 in which CO2 is ready for
near future. Cleeton et al. [17] investigated a CLC system using
storage after water condensation.
Fe2O3 as an oxygen carrier in conjunction with a steamecoal
gasification process. Full heat integration was considered for 3Fe2 O3 CO/CO2 2Fe3 O4 DH298 43:2kJ=mol (8)
a range of operating conditions. Gnanapragasam et al. [18]
proposed coal direct chemical looping (CDCL) substituting 3Fe2 O3 H2 /H2 O 2Fe3 O4 DH298 2:7kJ=mol (9)
the gasification process in syngas chemical looping (SCL). In
their study, operating conditions were assessed for CDCL and Fe3O4 and the remaining Fe2O3 go up and down to FR1 after
SCL, directed towards H2 production from coal. The author a cyclone, where they are reduced to Fe0.947O by fuel gases
[19e21] modeled the integration of CLC for power generation according to the endothermic reactions (1), (2), (10) and (11).
or H2 and electricity cogeneration with the gasification of coal
1:202Fe3 O4 CO/CO2 3:807Fe0:947 O DH298 47:6kJ=mol (10)
with pure oxygen. In this paper, the main purpose is to
investigate the thermodynamics performance of converting
1:202Fe3 O4 H2 /H2 O 3:807Fe0:947 O DH298 88:1kJ=mol (11)
coal to H2 and electricity with three reactors CLC and to
explore the plant designs, operating parameters by means of Fe0.947O from FR1 is led to SR where it is oxidized to form Fe3O4
ASPEN
PLUS software. by steam and H2 is generated in the meantime according to
the reaction (3). H2 is the final product of the process. Large
excess steam is needed to achieve an acceptable metal
2. Configuration of fuel reactor oxidation and therefore the gaseous outlet steam is a mixture
of H2 and H2O. The iron oxide Fe3O4 is fully oxidized to Fe2O3 in
In CLC, it is important to convert a high fraction of the the AR according to the strongly exothermic reaction (4)
incoming fuel to CO2 and H2O. The fuel studied here is syngas sustaining the thermal balance of the whole system. Oxygen
mainly comprised of H2 and CO. To gauge the degree of fuel depleted air is discharged from the AR.
conversion to CO2 and H2O (vapor), the gas yield was defined The FR1 and FR2 can be compacted in one fluidized bed
as the fraction of the fuel which is oxidized to CO2 or H2O, and proposed here as shown in Fig. 3. The fluidized bed is
is given by equations (6) and (7) below for the different fuels composed of two parts. Upper one is a circulating fluidized
investigated.For H2: bed, where Fe2O3 from AR is induced and is reduced by the
 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 5 ( 2 0 1 0 ) 8 5 8 0 e8 5 9 1 8583

Fig. 2 e ASPEN
flowsheet of a three reactors CLC with two FR arrangement.

unconverted fuel gases from the lower bed, and the lower one
is a bubble fluidized bed, where Fe3O4 and the remaining Fe2O3
from the upper circulating fluidized bed are reduced to
Fe0.947O by fuel gases. The reduced Fe0.947O in the lower bubble
fluidized bed is overflowed to SR. To keep the fluidized velocity
in the upper circulating bed, CO2 from flue gas may be used as
the secondary air to the middle of the compacted bed.
Based on the above two FRs arrangement, we simulated the
compositions from two FRs. Assuming that AR temperature is
1000
C and the ratio of oxygen carriers Fe0.947O/Fe3O4 from
FR1 is 95%:5% (in mole fraction). The composition of syngas
as the fuel is assumed as H2-27.5%, CO-62.4%, CO2-2.7%,
H2O-2.1%, N2-4.0%-, and Ar-1.4%. The compositions of outlet
stream from FR1 and FR2 are calculated as shown in Table 1.
The unconverted CO from FR1 is 21.92% and the unconverted
H2 is 7.81%, while the CO and H2 from FR2 are almost con-
verted into CO2 and H2O completely.

3. System description

The coal fueled H2 and electricity cogeneration system

combining CLC and gas turbine combined cycle in this work
is shown in Fig. 4. Coal is gasified in the Shell gasifier
(w40 bar). The hot raw gas is cooled to w900
C by recycling
syngas, and then is cooled for cleaning in convective heat
exchangers to w340
C. The recovered heat is used to
superheat steam and reheat the steam from high pressure
(HP) steam turbine. The syngas is used as the fuel gas of the

Table 1 e Flue gas composition from FR.

Components CO CO2 H2 H2O N2 Ar

FR1 stream, Vol.% 21.92 46.81 7.81 21.22 0.86 1.37

Fig. 3 e Proposed compact fluidized bed for iron oxide
FR2 stream, Vol.% <0.01 68.69 <0.01 29.03 0.86 1.37
CLC FR.
8584 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 5 ( 2 0 1 0 ) 8 5 8 0 e8 5 9 1

Fig. 4 e Schematic layout of a three-reactors chemical-looping-based hydrogen and electricity plant.

three reactors CLC process in conjunction with gas turbine
combined cycle. The CO2 rich stream from the FR is
expanded in a CO2 expander (EX1) and then the waste heat is
recovered in a heat recovery steam generator (HRSG1). After
compression and removal of condensate, the CO2 stream is
liquefied (121 bar) for piping. Steam is led to SR where H2 is
produced. The H2 rich stream from SR is expanded in a H2
expander (EX2) and the heat is further recovered in HRSG2.
H2 is compressed to 60 bar for usage. The oxygen depleted air
from the AR is led to gas turbine for power generation after
supplementary firing (SF) and the waste heat is recovered in
the HRSG for steam generation. The system can be divided
into 4 parts: gasification process, chemical looping hydrogen
generation process, power generation, CO2 separation and H2
compression.
Gasification process
Shell gasification process is selected for this study. The pre-
treated coal powder is fed to the gasifier using CO2 instead of
N2. Oxidant reagent is 95% pure oxygen with 4% Ar and 1% N2
from air separation unit (ASU) at a pressure of 40 bar. Illinois 6#
coal is selected and the analysis data is shown in Table 2. The
ASU is not modeled here; rather we adopt the composition
 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 5 ( 2 0 1 0 ) 8 5 8 0 e8 5 9 1
Table 2 e Proximate and ultimate analyses of coal.
Proximate Ultimate Qnet,ad/MJ$kg1
analysis/%(mass, analysis/%(mass,
air dry) daf)
M A V FC C H O N S ratio 17, turbine inlet temperature (TIT) 1350
C) is used as the
5.0 10.0 39.24 46.26 67.07 5.07 9.5 1.19 3.67 26.81
and specific work (0.246 kWh/kg of 95% O2) [26]. And the work
of compressing O2 to 48 bar is 0.125 kWh/kg. The power for
coal powder preparation is 0.022 kWh/kg. The mass ratio of O2
to coal is set about 0.90. Coal is gasified at 32 bar in an
entrained-flow Shell gasifier. Oxygen and steam are injected
into the reaction chamber where the syngas is produced.
Gasification operation conditions: temperature 1371
C,
carbon conversion 99.5, pressure loss 6%, heat loss 0.5%. The
raw syngas (26.1% H2, 59.2% CO, 4.9% H2O, 3.5% CO2, 3.8% N2,
1.3% Ar, 1.2% H2S and traces of COS and NH3) is cooled to
w900
C in the syngas quencher (QC) by recycling the clean
syngas after compression, and further cooled to 340
C in two
convective heat exchangers in waste boiler (WB), a HP super-
heater (HSH2) and a reheater (RH), for steam superheating and
steam reheating. After removal of particulates and desulfur-
ation in a syngas cleaning equipment (GC), the resulting gas
(27.5% H2, 62.4% CO, 2.1% H2O, 2.7% CO2, 4.0% N2, 1.4% Ar, and
traces of COS, H2S and NH3) at temperature of 150
C can be
used as the fuel of the three reactors and gas turbine supple-
mentary firing (SF).
Chemical looping hydrogen generation process
The three reactors described in the former section are
comprised of an AR, an SR and an FR. The states of the oxygen
carriers are in Fe2O3, Fe0.947O/Fe3O4 and Fe3O4, respectively.
Oxygen carriers Fe2O3 from AR are reduced to Fe0.947/Fe3O4
(95%:5% in mole fraction) by syngas in FR, and then in SR
Fe0.947O/Fe3O4 are oxidized to Fe3O4, which are regenerated to
Fe2O3 in AR. The operation conditions are as follows: AR
temperature 1000
C, SR temperature 815
C, FR temperature
w900
C, pressure loss in the reactors 8%, and heat loss 0.5%.
Inert support material FeAl2O4 is also taken into consideration
to improve the reactivity, durability and fluidizability of the
oxygen carriers.
Power generation
The CO2-rich stream (68.72% CO2, 29.04% H2O, 0.86% N2, and
1.37% Ar according to the simulation results) from the FR is
expanded in the CO2 expander (EX1) for power generation, and
then the heat of CO2-rich exhaust stream is recovered in
HRSG1 for steam generation. Steam to the SR is throated from
HP steam turbine (HPST) outlet and reacts with Fe0.947O
generating H2. H2 rich stream from the SR is expanded in the
hydrogen expander (EX2) for power generation, and then the
heat of H2-rich exhaust stream is recovered in HRSG2 for
steam generation. Air to AR comes from gas turbine
compressor (C) and is heated to 1000
C. Temperature of the
oxygen depleted air from AR is further risen to w 1350
C by
supplementary firing (SF). The high temperature oxygen
8585
depleted air from SF is expanded in gas turbine (T) to a back
pressure of 1.047 bar. The exhaust flue gas from the gas
turbine is supplied to the HRSG. Flue gas rejects heat in
different sections of HRSG to water/steam at two pressures
and is finally rejected to stack. F-class gas turbine (pressure
model for this study. For steam generation, heat integrations
between three HRSGs and a waster boiler were taken into
consideration. Reheat steam cycle with two pressure levels is
employed in HRSG side. The HP steam 12.5MPa/565
C,
reheating steam 2.86MPa/565
C, and low pressure (LP) steam
0.4MPa/230
C [27]. The heat exchangers arranged in HRSG are
in series of HP superheater (HPSH), HP steam evaporator
(HPEV), HP economizer (HPEC2), LP superheater (LPSH), HP
economizer (HPEC1), LP steam evaporator (LPEV), and LP
economizer (LPEC). HP steam is superheated first in HSH1 and
then in the HSH2 of syngas WB. After the expansion of HP
steam, the outlet steam from HP steam turbine (HPST) is
divided into two parts: one for the H2 production to SR and the
other for reheating to RH. The hot reheat steam is led to
intermediate pressure steam turbine (IPST) and further
expanded in low pressure steam turbine (LPST) combining
with the steam from LPSH for power generation. Assumptions
are pinch point 8
C, approach point 10
C in HRSG, back
pressure in condenser 3.6 kPa, HPST isotropic efficiency 88%,
IPST isotropic efficiency 92% and LPST isotropic efficiency 90%.
CO2 Separation and H2 compression
The H2-rich stream and the CO2-rich stream are compressed
in stages and cooled through circulating water following each
stage. Meanwhile, condensate is removed. H2 is compressed
to 60 bar in 3 intercooled stages and CO2 is to 121 bar in 4
intercooled stages.
4. Performance evaluation
The electricity efficiency and the hydrogen efficiency are
defined on LHV basis as the following,
Wnet
hnet (12)
mcoal $LHVcoal
LHVH2 $mH2
hH2 (13)
mcoal $LHVcoal
where hnet is the plant electricity efficiency, %; Wnet is the net
power of the co-production plant, kW; mcoal is the coal mass
flow, kg/s; LHVcoal is coal LHV, kJ/kg; hH2 is the hydrogen
production efficiency, %; LHVH2 is coal LHV, kJ/kg and mH2 is
the hydrogen production, kg/s. For the purpose of comparison
with other co-production technologies with CO2 capture,
a total energy efficiency as the equivalent energy efficiency is
defined here [28]:
hnet
hE hH2 (14)
0:58
in which 0.58 corresponds to the electricity efficiency of
natural gas fueled F-class gas turbine combined cycle, and
8586 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 5 ( 2 0 1 0 ) 8 5 8 0 e8 5 9 1

hE is the total energy efficiency or equivalent energy efficiency. flow of the plant, kg/s. To evaluate the CO2 emission, CO2
The plant net power is calculated according to equation (15): emission parameter is defined as

Wnet WGT WEX1 WEX2 WST  WO2  WQ  WH2 mCO2

ECO2 (17)
Wnet
 WCO2  WCP 15
in which ECO2 is CO2 emission, g/kWh.
in which W represents power generation or assumption, kW;
GT- gas turbine; EX1- CO2 expander; EX2- H2 expander; ST-
steam turbine; O2- ASU; Q- compressor for quenching recycle
gas; H2 - hydrogen compression unit; CO2- CO2 separation 5. System performance
unit; and CP- coal preparation unit. To measure the CO2
capture performance of a system, the CO2 capture efficiency is The primary assumptions used to simulate plant performance
defined as are detailed in Table 3. ASPEN PLUS software is used to simu-
late the plant, and the simulation results shown in Table 4 are
mCO2
hCO2 (16) based on two conditions, one with supplementary firing to
mCO2 ;total
a TIT of 1350
C and the other without supplementary firing at
where hCO2 is CO2 capture efficiency, %; mco2 is CO2 flow from a TIT of 1000
C.
FR after steam vapor condensing, kg/s; mco2 ;total is the total CO2 As listed in Table 4, the plant has an electricity efficiency of
14.34% and a hydrogen efficiency of 36.93% with a total energy
efficiency of 61.66% at a TIT of 1350
C after supplementary
firing. CO2 capture efficiency is 89.62% with CO2 emission of
Table 3 e Assumptions Adopted for Performance 238.9 g/kWh. Oxygen carriers are 10.65 kg/s Fe0.947O and
Simulation. 0.62 kg/s Fe3O4 from FR, 11.9 kg/s Fe3O4 from SR and 12.32 kg/s
Assumption from AR based on 1 kg/s coal. The oxygen depleted air from AR
is composed of O2 13.81% and N2 85.62%, and then O2 10.68%,
Gasification process Temperature, 1371
C; pressure, 32 bar;
carbon conversion rate, 99.5%; O2/coal ratio,
N2 82.84% and CO2 4.0% after supplementary firing. Because
0.9; pressure loss, 5%; heat loss, 0.5% of controlled by the COeCO2 and H2eH2O equilibrium in the
input LHV; pressure loss, 5%; syngas outlet reduction of Fe2O3 or Fe3O4 to Fe0.947O, there exist unconverted
temperature, 900
C; coal flow, 1 kg/s. fuel gases from FR1 (CO -21.92%, H2-7.81%). But the uncon-
Convective heat Pressure loss, 2%; approach point DT , 10
C verted fuel gases are burnt in FR2 because of fully conversion
exchangers in WB
of H2 and CO in the reduction of Fe2O3 to Fe3O4. The CO2 rich
Gas cleaning Particulate removal pressure loss, 6%;
stream from FR2 is composed of CO2 68.69%, H2O 29.03%, N2
desulfurization, MEDA method; removed
sulfur, 98%; desulfurization pressure loss, 6%. 0.86%, and Ar 1.37%. After heat recovery, steam vapor
Oxygen carrier AR out, Fe2O3; FR out, Fe0.947O/Fe3O4; SR out, condensation and compression to 121 bar, CO2 is liquefied
Fe3O4; inert support, FeAl2O4. ready for pipeline, and the unliquefied gases are mainly
steam reactor (SR) Temperature, 815
C; pressure loss, 8%, comprised of Ar and N2, 3% of total. The hydrogen stream is
thermal loss, 0.5% of thermal input comprised of H2 99.93% and H2O 0.07% after compression to
fuel reactor (FR) Temperature, 900
C; pressure loss, 8%;
60 bar and steam vapor condensation. For the case of no
thermal loss, 0.5% of thermal input
Air reactor (AR) Temperature,1000
C; pressure loss, 8%;
thermal loss, 0.5% of thermal input
Gas turbine Discharge pressure, 1.047 bar; turbine
polytropic efficiency, 90%; mechanical/ Table 4 e Power balance and plant performance.
generator efficiency, 99%/99%.
TIT 1350
C TIT 1000
C
HRSG Approach point DT, 10
C; pinch point DT,
(with SF) (without SF)
8
C; pressure loss, 10%; thermal loss, 0.7%
of thermal input. LHV of input coal, kW 26 805 26 805
CO2 compression Single-stage compression ratio of CO2 CO2 compression power, kW 908.45 1120.08
compressor, 3.5; compressor stage H2 compression power, kW 716.80 809.57
isentropic efficiency, 85%; cooling water AUS power, kW 1202.04 1202.04
inlet temperature, 15
C; pressure loss in Syngas compressor, kW 56.89 56.89
the heat exchanger, 3%; temperature at Coal preparation power, kW 79.20 79.2
intercooler outlet, 30
C; mechanical/ BOP kW 80.67 75.46
electric efficiency, 99%/99%; liquid CO2 to EX1(CO2 expander) power, kW 1369.83 1528.48
disposal, 30
C and 121 bar. GT power, kW 1665.0 851.4
H2 compression Single-stage compression ratio of H2 ST power, kW 2026.23 1676.49
compressor, 3.5; compressor stage EX2(H2 expander) power, kW 1827.34 2003.27
isentropic efficiency, 85%; cooling water Plant net power, kW 3844.35 2716.39
inlet temperature, 15
C; pressure loss in H2 production, kg/hr 294.79 331.61
the heat exchanger, 3%; temperature at Power efficiency (LHV), % 14.34 10.13
intercooler outlet, 30
C; mechanical/ H2 efficiency (LHV), % 36.93 41.51
electric efficiency, 99%/99%; 99.9% pure Total efficiency, % 61.66 59.98
hydrogen, 30
C and 60 bar. CO2 capture efficiency, % 89.62 100
Balance of plant (BOP) Pump efficiency, 75%. CO2 emission, g/kWh 238.9 0
 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 5 ( 2 0 1 0 ) 8 5 8 0 e8 5 9 1 8587

Table 5 e comparison with other technologies.

technologies Power efficiency, % Hydrogen efficiency, % Total efficiency, % CO2 capture efficiency, % References

Texaco/E-gas, Selexol 0 43 43 97 [28]

2 50 53.45 92 [28]
4.11 57.45 64.3 90.4 [3,4,29]
Texaco, Pd membrane 1.2 62 59.93 100 [3,4,29]
Texaco/Shell, Selexol 0 53.5e58.3 53.5e58.3 93e96 [30,31]
4.28e12.85 33.53e28.61 40.9e50.7 92.35 [30,31]
Shell, Selexol 0 56.6 56.6 100 [32]
12.1e18.8 37.4e24.7 57.1e58.26 85 [32]
Shell/Texaco, Selexol 31 3 56.5 90 [33]
E-gas, amines 2 45.4 48.8 100 [34,35]
E-gas, Selexol 1.4 51.9 54.3 92 [36]

supplementary firing, the electricity efficiency is 10.13% and
hydrogen efficiency is 42.83% with a total energy efficiency of
59.98%, and there is no CO2 emission.
The performances are attractive because of theoretically
high hydrogen composition from SR, high energy conversion
efficiency, and low CO2 emission. The process does not require
additional gas treatments (reforming, shift) and separation
processes. Compared to coal gasification, water-gas shift, CO2
removal, and H2 purification technologies for electricity and
hydrogen co-production, as reported in Table 5, the proposed
configuration co-production plant has better total energy
efficiency, relatively higher power generation share in energy
conversion and a potential for investment cost savings. From
hydrogen production point of view, this system cannot meet
the requirement of fully hydrogen production, i.e. there must
be power output, but the ratio of power generation to
hydrogen generation can be adjusted, which will be discussed
in the next section.
6. Sensitivity analysis and discussion
6.1. Effect of different steam conversion ratio
The conversion of steam to hydrogen in SR according to
reaction (3) is a key parameter to the plant performance. The
rise of the conversion decreases the steam flow to SR and heat
loss from HRSG2, and increases the steam turbine power
generation. As to the conversion, Hackers researches
[10,11,37] showed that the steam conversion rate was w28% at
800
C. S. D. Fraser [11] made an explanation of the reaction
between H2 and Fe3O4 to form Fe0.947O. The concentration of
H2 on equilibrium, i.e. the conversion, is 40.9% and the
concentration of H2O is 59.1%. It means that the concentration
of H2 in SR will not be more than 40.9% after reaction equi-
librium is reached. M. Steinberg [38] indicated that the steam
conversion rate was 37% when the reaction temperature was
between 815 and 870
C. Chiesa et al. [16] selected a conversion
rate of 50% in their simulation. Because different researchers
use different data in their research, the effect of steam
conversion rate is discussed here. From the thermodynamic
and chemical equilibrium point of view, the equilibrium
concentration of H2, i.e. the steam to H2 conversion, decreases
with the rise of operation temperature. Lower temperature
benefits the system efficiency, but it decreases the power
generation of H2 expander. And the reactivity of reaction (3) is
thermodynamically slow at lower temperature, especially
lower than 700
C according to the atmospheric thermogra-
vimetric apparatus (TGA) results by the authors of this paper.
The concentrations from SR under temperatures of
750e850
C are reported in Table 6, and conversion of 36.67%
at 815
C is applied for this study.
The system performances vs. SR temperature are simu-
lated at a TIT of 1350
C after supplementary firing, as shown
in Fig. 5. The steam flow to SR decreases along with the
increase of steam conversion rate i.e. with the decrease of SR
temperature. At lower SR temperature, the power of hydrogen
stream expander (EX2) drops prominently because of lower
stream flow and lower temperature, whereas at higher
temperature, more steam flow to SR results in power drop in
steam turbine and heat losses from HRSG2 exhaust stream.
There exists an optimal temperature of 800
C. At this
temperature, the plant net efficiency is 14.42%, and hydrogen
efficiency is 37.15% with a total energy efficiency of 62.01%. In
addition, as the SR temperature goes up, the heat from SR to
AR carried by oxygen carriers increases, the net heat released
to AR rises, which increases air flow. Fuel gas for supple-
mentary firing increases along with the rise of air flow, and the
CO2 capture efficiency decreases. At the same time, the fuel to
FR, the reduced oxygen carriers Fe0.947O from FR and hydrogen
production in SR decrease. The hydrogen efficiency goes
down. With the rise of SR temperature from 750
C to 850
C;
the CO2 capture efficiency decreases from 91.99% to 88.32%,
CO2 emission increases from 199.2 g/kWh to 267.5 g/kWh; and
the hydrogen efficiency diminishes from 37.91% to 36.31%.
Uncertainty remains as to the steam to hydrogen conver-
sion. Simulation on the influence of the conversion (0.3e0.5)
has also been made, assuming SR temperature 815
C, AR
temperature 1000
C, FR temperature 900
C, and TIT 1350
C.
Simulation results are quiet different from the above discus-
sion. At a constant SR temperature, the hydrogen efficiency
Table 6 e Concentration of hydrogen from SR under
different temperature.
Temperature,
C 750 800 815 850
H2, vol.% 46.34 38.72 36.67 32.29
H2O, vol.% 53.66 61.28 63.33 67.71
8588 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 5 ( 2 0 1 0 ) 8 5 8 0 e8 5 9 1
Electricity efficiency
14.8
Hydrogen efficiency
CO2capture efficiency
Electricity efficiency %
14.4
14.0
13.6
13.2
740 760 780 800 820 840
SR Temperature oC
Fig. 5 e Plant performance vs. SR temperature.
keeps unchanged, whereas the net power efficiency increases
along with the rise of the conversion. Keeping the operation
condition of three reactors, the change of the conversion only
affects the steam flow to SR, and the flow of oxygen carriers
from FR to SR is unchanged. So hydrogen production keeps
constant. The rise of the conversion decreases the steam flow
to SR, so steam flow to IPST increases which increases the
steam turbine power generation. CO2 capture efficiency keeps
constant, while the CO2 emission decreases due to the rise of
power generation. The plant electricity efficiency increases
from 13.64% to 14.93% (total energy efficiency from 60.46% to
62.68%) and CO2 emission decreases from 251.1 g/kWh to
229.4 g/kWh as the conversion increases from 0.3 to 0.5.
6.2. Effect of turbine inlet supplementary firing
The temperature at the AR outlet is relatively lower than F-
class gas turbine TIT 1350
C. Because increasing TIT can raise
the plant electricity efficiency, supplementary firing is used to
increase temperature of the oxygen depleted air. Assuming SR
temperature 815
C (steam to hydrogen conversion of 0.37), AR
temperature 1000
C, and FR temperature 900
C, the influ-
ences of supplementary firing TIT (1000e1450
C) were simu-
lated, as shown in Fig. 6. The change of supplementary firing
Fig. 6 e Plant performance vs. supplementary firing
temperature.
temperature re-assigns the fuel gas flows between FR and SF,
38.0
and affects the hydrogen generation and electricity power. As
92
seen from Fig. 6, the electricity efficiency, the total energy
CO2capture efficiency %
Hydrogen efficiency %
efficiency, and CO2 emission increase, whereas the hydrogen
37.5
efficiency and CO2 capture efficiency decrease with the rise of
SF temperature. As the rise of supplementary firing TIT, the
90
fuel gas flow to SF goes up, which increases the gas turbine
37.0
power, whereas the fuel gas flow to FR goes down, which
decreases the CO2 expander power. The plant power goes up
because of the higher increase in gas turbine power. The
36.5 88
decrease of fuel gas flow to FR diminishes the CO2 stream flow
and the circulating oxygen carriers flow, so steam needed to
860 880 oxidize the oxygen carriers and the hydrogen production in SR
reduce, which increases steam turbine power. Air flow to AR
for oxidization of the oxygen carriers reduces, which dimin-
ishes the gas turbine compressor power consumption. As to
gas turbine, the power is increased in spite of the reduction of
air. Moreover, the exhaust temperature from gas turbine gets
raised, and the energy efficiency of HRSG increases by main-
taining the exit temperature of HRSG. But the CO2 capture
efficiency drops and the CO2 emission goes up. At TIT of
1450
C, the plant electricity efficiency, hydrogen efficiency
and total energy efficiency are 15.26%, 36.01%, and 62.33%,
respectively and the CO2 emission is 286.4 g/kWh.
6.3. Effect of AR temperature
AR temperature is determined by the temperature endurance
of oxygen carriers. AR temperature further affects the FR
temperature because of the heat balance of CLC reactors. AR
temperature is another key parameter for the electricity and
hydrogen cogeneration plant. The effects of AR temperature
(or the temperature endurance of oxygen carriers) on the plant
performance are simulated, as shown in Fig. 7, assuming that
supplementary firing TIT is kept at 1350
C, AR temperature at
815
C. According to the simulation, the theoretical tempera-
ture of AR is 1094
C because of relatively lower heat release
from the oxidation of Fe3O4 to Fe2O3 when the gas turbine
pressure ratio is 17. At 1090
C AR temperature, FR temperature
reaches 1020
C, and the supplementary firing temperature can
only be set at 1250
C because of lower O2 composition in the
oxygen depleted air. The air flow of gas turbine decreases with
the rise of AR temperature, so the average temperature of
Fig. 7 e Plant performance vs. AR temperature.
 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 5 ( 2 0 1 0 ) 8 5 8 0 e8 5 9 1
turbine inlet stream (GT and CO2 expander) decreases, which
leads to the decrease of the plant net power and plant elec-
tricity efficiency, as shown in Fig. 7. Fuel gas used for supple-
mentary firing diminishes, which results in the reduction of
CO2 emission and the increase of CO2 capture efficiency. It also
leads to the rise of hydrogen efficiency, but the total efficiency
drops. At AR temperature of 1090
C, there is a drop in the
electricity efficiency because of relatively lower SF tempera-
ture of 1250
C. As AR temperature increases from 950
C to
1090
C, electricity efficiency, hydrogen efficiency, CO2 capture
efficiency and CO2 emission change from 16%, 34.62%, 84.08%,
and 328.2 g/kWh to 11.75%, 40.42%, 98.17%, and 51.4g/kWh,
respectively. If no supplementary firing is used, the CO2
emission is 0 and the plant electricity efficiency and the total
efficiency are improved with the rise of AR temperature. To get
better plant performance, AR temperature should be kept at
a possible high level whether SF is used or not, i.e. it is
necessary to develop an oxygen carrier to endure a high
temperature for the three reactors chemical looping hydrogen
process.
6.4. Effect of circulating oxygen carrier mass flow
Different from the two reactors CLC gasification combined
cycle [21], oxygen carrier flow affects performances of the
three reactors CLC cogeneration plant, shown in Fig. 8. The
operation conditions of three reactors remain unchanged (FR
temperature 900
C, SR temperature 815
C, AR temperature
1000
C, and TIT 1350
C), and the flow ratio of oxygen carriers
increases from 1 (representing the base solids circulation rate)
to 1.6 (times of the base value). Simulation results show that
the change of the oxygen carrier flow affects the ratio of power
generation and hydrogen generation. The reduction of Fe2O3
by fuel gas has 3 states, Fe3O4, Fe0.947O and Fe, which depend
on the equilibriums of reaction gases. The states of oxygen
carriers from FR are altered if the oxygen carrier circulation
ratio is changed. The states of oxygen carriers from FR change
from Fe3O4/Fe0.947O to Fe0.947O/Fe with the decrease of the
circulation ratio, or they change from Fe3O4/Fe0.947O to Fe3O4
with the rise of the circulation ratio. The ratio of Fe3O4 to
Fe0.947O in the oxygen carriers from FR increases with the rise
of the oxygen carrier circulation ratio. Relation of heat
Fig. 8 e Plant performance vs. oxygen carriers circulation
ratio.
8589
released in the three reactors changes. At the ratio of 1.5,
reactions in FR become exothermic instead of endothermic
because of reaction (8) and reaction (9). Furthermore, heat
released in AR and heat carried by oxygen carriers from AR to
FR and from FR to SR rise. The FR temperature in FR reaches
1000
C at the ratio of 1.6. Air flow to AR increases, and it leads
to the rise of fuel gas to supplementary firing and gas turbine
power. Because more heat released in three reactors, more
steam in three HRSGs is generated more steam, which
increases steam turbine power. As a result, the electricity
efficiency goes up. Furthermore, hydrogen production
decreases because of the decrease of fuel gas to FR and Fe0.947O
flow in oxygen carriers to SR which results in the decreases of
hydrogen efficiency.
The ratio of hydrogen production to electricity production
can be changed by adjusting the oxygen carrier circulation
ratio. When the circulation flow rises from the base value to
1.6 times of the base value, the ratio of hydrogen to electricity
is changed from 2.57:1 to 1:1.15. The CO2 capture efficiency
decreases slightly from 89.62% to 84.36%, whereas the CO2
emission drops from 238.9 g/kWh to 210.6 g/kWh because of
the increase of the plant power. And the total energy effi-
ciency increases from 61.66% to 64.23%. However, the range of
ratio of hydrogen to electricity is relatively narrow because the
oxygen carrier circulation ratio is limited by the heat balance
of three reactors. At a circulation ratio of 1.7, the AR temper-
ature of 1000
C reaches the theoretical temperature, whereas
at a circulation ratio lower than 0.9, FR temperature cannot be
maintained at 900
C and oxygen is needed to sustain the FR
temperature.
6.5. Effect of inert support material addition
in oxygen carriers
In order to improve the reactivity, durability and fluidizability
of the oxygen carriers, FeAl2O4 is used as the inert support
material and the influences of the addition of the inert support
material are simulated, as shown in Fig. 9. It is assumed that
no extra pressure loss occurred in the three reactors, AR
temperature 1000
C, SR temperature 815
C, and maximum
supplementary firing TIT 1350
C determined by the O2
composition in the oxygen depleted air from AR. With the rise
Fig. 9 e Plant performance vs. mass flow ratio of inert
support material to oxygen carriers.
8590 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 5 ( 2 0 1 0 ) 8 5 8 0 e8 5 9 1
of inert support material addition, heat carried by oxygen
carriers to FR increases and the FR temperature goes up. When
the addition of inert support reaches a certain value (w0.8
times of the oxygen carrier flow), AR temperature of 1000
C
approaches the theoretical temperature. As a result, air flow to
AR drops and oxygen composition in the oxygen depleted air
is near zero which means that supplementary firing cannot be
used. In Fig. 9, the rise of inert support material addition in
oxygen carriers gives rise to the decrease of the air flow to AR,
which leads to the decent in the net power and plant elec-
tricity efficiency. On the other hand, fuel gas used for
supplementary firing goes down and fuel gas for FR goes up,
which results in the increase of the hydrogen production and
hydrogen efficiency. Furthermore, the CO2 capture efficiency
goes up and the CO2 emission goes down. When the inert
support material mass flow is 0.75 times of the oxygen
carriers, there is a drop in electricity efficiency, because 1.1%
O2 in the oxygen depleted air cannot meet the need of
supplementary firing and TIT is kept at 1000
C. All the fuel gas
is used as the fuel of FR, so hydrogen generation and hydrogen
efficiency ascend, and all the CO2 can be captured. At this
point, plant electricity efficiency, hydrogen efficiency and
total energy efficiency are 10.28%, 41.17%, and 59.07%,
respectively. There exists an optimum total energy efficiency
of 62.17% at 0.25 times of the oxygen carrier flow.
7. Conclusion
This paper investigated the possibility to exploit the charac-
teristics of iron oxides to assemble a process that produces
electricity, H2 and sequestration ready CO2. The system inte-
grates coal gasification gas turbine combined cycle with
a three-reactors chemical looping using iron oxides as the
oxygen carriers for electricity and hydrogen co-production.
Although the system is rather complicated and the costs for
electricity and hydrogen must be high, it shows a rather good
total energy efficiency and an excellent environmental
performance according to our calculations, so the key tech-
nology of the three reactors chemical loping hydrogen
generation is deserved for substantial R&D activities. The
following are some of the inferences from the analysis of the
current work:
1. With a Shell gasification process, AR temperature of 1000
C
and SR temperature of 815
C, the proposed three-reactors
cogeneration plant has a sound performance of electricity
efficiency 10.13%, hydrogen efficiency 41.51% (total energy
efficiency 59.98%) and zero CO2 emission. If temperature of
the oxygen depleted air from AR is risen to 1350
C by
supplementary firing, the plant has an electricity efficiency
of 14.34% and a hydrogen efficiency of 36.93% (a total energy
efficiency of 61.66%) with CO2 emission of 238.9 g/kWh.
2. Higher steam to hydrogen conversion in SR benefits the
plant electricity and the total energy efficiency.
3. Supplementary firing TIT is a key parameter affecting the
plant performance. The electricity efficiency, the total
energy efficiency and CO2 emission increase, whereas the
hydrogen efficiency and CO2 capture efficiency decrease
with the rise of supplementary temperature.
4. At a gas turbine pressure ratio of 17, the theoretical
temperature in AR is 1094
C. Maintaining supplementary
firing TIT at 1350
C, the plant electricity efficiency and total
energy efficiency decrease, whereas CO2 capture efficiency
increases with the rise of AR temperature.
5. The ratio of hydrogen production to electricity production
can be changed by adjusting the oxygen carrier circulation.
With the increase of the oxygen carrier circulation, the
plant electricity production can be increased and the plant
total energy efficiency goes up whereas the CO2 capture
efficiency slightly decreases. However, the range of the
ratio of hydrogen production to electricity production is
relatively narrow because the oxygen carrier circulation
flow is limited by the heat balance of three reactors.
6. Addition of inert support materials in the oxygen carriers
affects the system performance. The increase of addition
of inert support material in oxygen carriers gives rise to
the decrease of plant power and the increase of the
hydrogen production and CO2 capture efficiency. When
the addition of inert support reaches a certain value (w0.8
times of the oxygen carrier flow), AR temperature of
1000
C approaches the theoretical temperature. There is
a drop in electricity production, because oxygen in the
oxygen depleted air cannot meet the requirement of
supplementary firing.
Acknowledgement
The authors would like to acknowledge the National Natural
Science Foundation of China (50776018) and the Special Fund
of the National Priority Basic Research of China
(2007CB210101) for financial support of this project.
references
[1] Lorenzo L, Kreutz T, Chiesa P, Williams R. Carbon-free
hydrogen and electricity from coal: options for syngas
cooling in systems using a hydrogen separation membrane
reactor. Proc ASME Turbo Expo Nevada USA; June 2005.
[2] Consonni S, Vigano F. Decarbonized hydrogen and electricity
from natural gas. Int J Hydrogen Energy 2005;30:701e18.
[3] Chiesa P, Consonni S, Kreutz T, Williams R. Co-production of
hydrogen, electricity and CO2 from coal with commercially
ready technology. Part A: performance and emissions. Int J
Hydrogen Energy 2005;30:747e67.
[4] Kreutz T, Williams R, Consonni S, Chiesa P. Co-production of
hydrogen, electricity and CO2 from coal with commercially
ready technology. Part B: economic analysis. Int J Hydrogen
Energy 2005;30:769e84.
[5] Gupta P, Fan LS. Syngas redox (SGR) process to produce
hydrogen from coal derived syngas. Energy Fuels 2007;21:
2900e8.
ly M.
[6] Svoboda K, Siewiorek A, Baxter D, Rogut J, Pohore
Thermodynamic possibilities and constraints for pure
hydrogen production by iron based chemical looping process
at lower temperatures. Energy Convers Manag 2008;49:221e31.
[7] Mattison T, Lyngfelt A, Cho P. The use of iron oxide as an
oxygen carrier in chemical-looping combustion of methane
with inherent separation of CO2. Fuel 2001;80:1953e62.
 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 5 ( 2 0 1 0 ) 8 5 8 0 e8 5 9 1
[8] Hacker V, Fankhauser R, Faleschini G, Fuchs H, Friedrich K,
Muhr M, et al. Hydrogen production by steameiron process. J
Power Sourc 2000;86:531e5.
[9] Hacker V. A novel process for stationary hydrogen
production: the reformer sponge iron cycle (RESC). J Power
Sourc 2003;118:311e4.
[10] Hacker V, Faleschini G, Fuchs H, Fankhauser R, Simader G,
Ghaemi M, et al. Usage of biomass gas for fuel cells by the SIR
process. J Power Sourc 1998;71:226e30.
[11] Fraser SD, Monsberger M, Hacker V. A thermodynamic
analysis of the reformer sponge iron cycle. J Power Sourc
2006;161:420e31.
[12] Akiyama T, Miyazaki A, Nakanishi H, Hisa M, Tsutsumi A.
Thermal and gas analyses of the reaction between iron
carbide and steam with hydrogen generation at 573K. Int J
Hydrogen Energy 2004;29:721e4.
[13] Li FX, Fan LS. Clean coal conversion processes e progress
and challenges. Energy Environ Sci 2008;1:248e67.
[14] Fan LS, Li FX, Ramkumar S. Utilization of chemical looping
strategy in coal gasification processes. Particuology 2008;6:
131e42.
[15] Ryden M, Lyngfelt A. Using steam reforming to produce
hydrogen with carbon dioxide capture by chemical-looping
combustion. Int J Hydrogen Energy 2006;31:1271e83.
[16] Chiesa P, Lozza G, Malandrino A, Romano M, Piccolo V.
Three-reactors chemical looping process for hydrogen
production. Int J Hydrogen Energy 2008;33:2233e45.
[17] Cleeton J, Bohn C, Muller C, Dennis J, Scott S. Clean hydrogen
production and electricity from coal via chemical looping:
identifying a suitable operating regime. Int J Hydrogen
Energy 2009;34:1e12.
[18] Gnanapragasam N, Reddy B, Rosen M. Hydrogen production
from coal using coal direct chemical looping and syngas
chemical looping combustion systems: assessment of
system operation and resource requirements. Int J Hydrogen
Energy 2009;34:2606e15.
[19] Xiang WG, Chen YY. Hydrogen and electricity with carbon
dioxide separation using chemical looping reactors. Energy
Fuels 2007;21:2272e7.
[20] Xiang WG, Mou J, Di T. Investigation of chemical-looping
combustion based gasification combined cycle with iron
oxide as oxygen carrier. In: Proc 9th Int Gas Turbine
Congress, Tokyo, Jpn; December 2007.
[21] Xiang WG, Wang S, Di T. Investigation of gasification
chemical looping combustion combined cycle performance.
Energy Fuels 2008;22:961e6.
[22] Mattisson T, Lyngfelt A. Capture of CO2 using chemical-
looping combustion. Goteborg, Sweden: Nordic Section of the
Combustion Institute; April 2001. Proceedings of First
Biennial Meeting of the Scandinavian.
[23] Jerndal E, Mattisson T, Lyngfelt A. Thermal analysis of
chemical-looping combustion. Chem Eng Res Des 2006;84
(A9):795e806.
[24] Svoboda K, Siewiorek A, Baxter D, Rogut J, Pohorely M.
Thermodynamic possibilities and constraints for pure
hydrogen production by a nickel and cobalt-based chemical
8591
looping process at lower temperature. Energy Convers
Manag 2008;49:221e31.
[25] Svoboda K, Slowinski G, Rogut J, Baxter D. Thermodynamic
possibilities and constraints for pure hydrogen production by
iron based chemical looping process at lower temperatures.
Energy Convers and Manag 2007;48:3063e73.
[26] Wang B, Jin H, Han W, Zheng D. IGCC system with
integration of CO2 recovery and the cryogenic energy in air
separation unit. In: Proceedings of ASME Turbo Expo, Vienna,
Austria; June 2004.
[27] Xiang WG, Chen Y. Performance improvement of combined
cycle power plant based on the optimization of the bottom
cycle and heat recuperation. J Therm Sci 2007;16:84e9.
[28] Damen K, Troost M, Faaij A, Turkenburg W. A comparison of
electricity and hydrogen production systems with CO2
capture and storage. Part A: review and selection of
promising conversion and capture technologies. Prog Energ
and Combust 2006;32:215e46.
[29] Kreutz T, Williams R, Socolow R, Chiesa P, Lozza G.
Production of hydrogen and electricity from coal with CO2
capture. In: Gale J, Kaya Y, editors. Sixth international
conference on greenhouse gas control technologies, Kyoto,
Japan. Amsterdam: Pergamon; 2003. p. 141e7.
[30] Cormos C, Starr F, Tzimas E, Peteves S. Innovative concepts
for hydrogen production processes based on coal gasification
with CO2 capture. Int J Hydrogen Energy 2008;33:1286e94.
[31] Cormos C. Assessment of hydrogen and electricity co-
production schemes based on gasification process with
carbon capture and storage. Int J Hydrogen Energy 2009;34:
6065e77.
[32] Davison J, Arientib S, Cotoneb P, Mancusob L. Co-production
of hydrogen and electricity with CO2 capture. Energy
Procedia 2009;1:4063e70.
[33] Tzimas E, Cormos C, Starr F, Garcia-Cortes C. The design of
carbon capture IGCC- based plants with hydrogen co-
production. Energy Procedia 2009;1:591e8.
[34] Spath P. Capital and operating cost of hydrogen production
from coal gasification, http://www.Fischer-tropsch.org/DOE/
DOE_reports/40465/40465-FNL.%202003/DE-AM26e
AM99FT40465-ES.pdf.
[35] Spath P, Amos W. Technoeconomic analysis of hydrogen
production from low-btu western coal augmented with CO2
sequestration and coalbed methane recovery including
delivered hydrogen costs. NREL; September 1999.
[36] Rutkowski M, Klett M, White J, Schoff R, Buchanan T.
Hydrogen production facilities plant performance and cost
comparisons, http://www.fischer-tropsch.org/DOE/DOE_
reports/40465/40465e4FNL,%202002/40465-FNL,%202002_toc.
htm; March 2002. Final report.
[37] Kindermann H, Kornberger M, Hierzer J, Besenhard JO,
Hacker V. First investigations of structural changes of the
contact in the RESC process for hydrogen production. J Power
Sourc 2005;145:697e701.
[38] Steinberg M, Cheng H. Modern and prospective technologies
for hydrogen production from fossil fuels. Int J Hydrogen
Energy 1989;14:797e820.