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Particuology 6 (2008) 131–142

Utilization of chemical looping strategy in coal gasification processes

Liangshih Fan ∗ , Fanxing Li, Shwetha Ramkumar
Department of Chemical and Biomolecular Engineering, The Ohio State University, United States
Received 5 February 2008; accepted 11 March 2008

Abstract
Three chemical looping gasification processes, i.e. Syngas Chemical Looping (SCL) process, Coal Direct Chemical Looping (CDCL) process,
and Calcium Looping process (CLP), are being developed at the Ohio State University (OSU). These processes utilize simple reaction schemes to
convert carbonaceous fuels into products such as hydrogen, electricity, and synthetic fuels through the transformation of a highly reactive, highly
recyclable chemical intermediate. In this paper, these novel chemical looping gasification processes are described and their advantages and potential
challenges for commercialization are discussed.
© 2008 Chinese Society of Particuology and Institute of Process Engineering, Chinese Academy of Sciences. Published by Elsevier B.V. All
rights reserved.

Keywords: Chemical looping; Gasification process; Combustion; Hydrogen

1. Introduction carbon regulations would nevertheless impose a severe energy

Coal, as a vital energy source for the modern society,
accounts for 40% of the electricity generated world wide. At
present, more than 90% of the electricity generated from coal
is produced through coal-fired power plants, which emit nearly
2 gigatons of carbon into the atmosphere every year (World
Coal Institute, 2005).
In a typical coal-fired power plant, the heat released from
burning coal is used to generate high-pressure steam, which
drives a steam turbine-generator. Due to the highly corrosive
nature of steam, the turbine operating temperature is limited,
thereby curbing the efficiency of the process (Shinada, Yamada,
& Koyama, 2002). In most cases, traditional combustion power
plants convert only a third of the energy value of coal into elec-
tricity. Moreover, coal combustion with air produces a flue gas
stream at atmospheric pressure that consists of ∼80% N2 (by vol-
ume) and 10–15% CO2 . The low concentration of carbon dioxide
in the flue gas stream makes carbon capture from traditional coal
combustion power plants inefficient and uneconomical.
The global on-going R&D efforts on coal combustion encom-
pass enhancement of electricity generation efficiency to above
40% by the use of “super critical” and “ultra super critical”
steam boilers (Kitto, 1996). However, enforcement of future
∗ Corresponding author. Tel.: +1 614 688 3262.
E-mail address: fan@chbmeng.ohio-state.edu (L.S. Fan).
penalty to the ultra super critical power plants. It is estimated
by the USDOE that the incorporation of CO2 capture in ultra
super critical power plants would increase the cost of electricity
by 84% (NETL, 2007).
Other efforts such as chilled ammonia process and oxyfuel
combustion process focus on the cost reduction for CO2 cap-
ture in coal combustion plants. These carbon capture techniques,
however, would consume 25–28% of the total electricity gener-
ated from the power plant (Châtel-Pélage et al., 2005).
Another approach to utilize coal is through gasification. The
gasification processes, unlike traditional combustion processes
which fully oxidize carbonaceous fuels to generate heat, con-
vert the fuels such as coal or biomass into syngas via partial
oxidation reactions using oxygen and/or steam. In the coal gasi-
fication process, coal first reacts with steam and/or oxygen to
generate raw syngas. The raw syngas, with pollutants such as
H2 S, ammonia, and mercury, is then purified and sent to a gas
turbine-steam turbine combined cycle system for electricity gen-
eration and this is known as the integrated gasification combined
cycle (IGCC) process. The electricity generation efficiency of
the IGCC process can be higher than 45% without CO2 cap-
ture. Alternatively, the CO in the syngas stream can be further
converted to H2 through the water gas shift (WGS) reaction:
CO + H2 O → CO2 + H2
Thus, the resulting gas stream contains a high CO2 concen-
tration (up to ∼40% by 1 volume, dry basis). The CO2 in the

1674-2001/$ – see inside back cover © 2008 Chinese Society of Particuology and Institute of Process Engineering, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.partic.2008.03.005
132 L.S. Fan et al. / Particuology 6 (2008) 131–142
Fig. 1. Schematic diagram of coal gasification processes for electricity, hydrogen, liquid fuel production.
gas mixture can be captured with ease to yield high-purity H2 .
The H2 can be used to generate electricity through a combined
cycle system or a fuel cell system without carbon emissions.
This represents a typical coal gasification scheme for hydrogen
production or electricity generation when CO2 capture is manda-
tory. Besides electricity and H2 generation, syngas can also be
converted to chemicals and liquid fuels such as diesel and gaso-
line through the Fischer–Tropsch (F–T) reactions given below:
(2n + 1)H2 + nCO → Cn H2n+2 + nH2 O
Fig. 1 shows a schematic diagram of coal gasification pro-
cesses for production of hydrogen, electricity and/or liquid fuels.
As can be seen in the figure, the major advantages of gasification
over combustion include product flexibility and ease in pollu-
tant control. Therefore, gasification is considered a favorable
candidate for use in next-generation coal-based plants (NETL,
2003, 2004, 2007; Stiegel & Maxwell, 2001). It is also consid-
ered to be a key enabling technology to the U.S. Department
of Energy (USDOE) Vision 21 program (National Research
Council, 2000).
Despite its various advantages over direct combustion,
gasification faces several challenges that impede its broad appli-
cations. Such challenges include intensive capital investment
and large operating cost, both of which result from the elab-
orate oxygen production and syngas cleaning procedures. It
has been estimated by Lewandowski and Gray (2001) that the
capital investment for an oxygen-blown IGCC power plant is
about $1241/kW, compared to $1170/kW for a pulverized coal
combustion power plant with an ultra-supercritical boiler. Both
technologies have similar energy conversion efficiencies.
Additionally, although CO2 can be captured from a coal
gasification system with ease compared to that from a coal
combustion system, CO2 capture would nevertheless impose
a significant penalty for the system economics. For example,
the state-of-the-art CO2 capture technique would increase the
cost of electricity by 25% in a coal based IGCC plant (NETL,
2007). Thus, future coal gasification processes should be sim-
plified through process intensification and coupled with more
efficient carbon capture schemes in order to reduce the capital
investment and to further increase the energy conversion effi-
ciency. The implementation of the chemical looping concept
in coal gasification processes represents a promising method to
achieve these goals.
The chemical looping concept has been widely applied to
combustion processes for electricity generation from gaseous
fuels (Ishida, Jin, & Olamoto, 1998; Mattisson, Johansson,
& Lyngfelt, 2006; Ryu, Jin, & Yi, 2004). During the last
decade, the chemical looping gasification strategy has been
applied to produce hydrogen from coal and coal derived syngas.
Among them, the GE fuel-flexible process (Rizeq et al., 2002)
and the ALSTOM hybrid combustion–gasification process
(Andrus et al., 2006) have been extensively studied. Both
technologies use two different types of particles to convert
coal into hydrogen: one type of particle is used to capture
CO2 while the other serves as an oxygen carrier. The mixing
between the two types of particles results in a decrease in
the energy conversion efficiency. In this paper, three novel
chemical looping gasification processes developed at OSU, i.e.
the syngas chemical looping (SCL) process, calcium looping
process (CLP), and coal/biomass direct chemical looping
(CDCL) process, are described (Fan, Gupta, & Iyer, 2007;
Fan, Li, Velazquez-Vargas, & Ramkumar, in press; Fan, Gupta,
Velazquez-Vargas, & Li, 2007; Gupta, 2006; Gupta, Velazquez-
Vargas, & Fan, 2007; Gupta, Velazquez-Vargas, Thomas, &
Fan, 2004; Iyer, Fan, & Ramkumar, 2007; Iyer, Ramkumar,
Wong, & Fan, 2006; Thomas, Fan, Gupta, & Velazquez-Vargas,
 L.S. Fan et al. / Particuology 6 (2008) 131–142
2005; Velazquez-Vargas, Thomas, Gupta, & Fan, 2004 ). Unlike
the GE and ALSTOM processes, each of these three processes
utilizes a single type of particle optimized for its specific energy
conversion scheme. The advantages and potential challenges of
these processes are discussed in the succeeding sections.
2. Syngas chemical looping (SCL) process
2.1. SCL Process for Hydrogen Generation
The SCL process co-produces hydrogen and electricity from
syngas based on the cyclic reduction and oxidation of specially
developed metal oxide composite particles (Gupta, Velazquez-
Vargas, Li, & Fan, 2006; Gupta et al., 2007). The SCL process
produces a pure hydrogen stream and a concentrated carbon
dioxide stream in two separate reactors. Therefore, additional
CO2 separation cost is avoided. Moreover, electricity can be effi-
ciently co-generated with hydrogen in the SCL process, making
it more flexible as well as economically attractive.
2.1.1. Process overview
The SCL process consists of five major components: an
air separation unit (ASU), a gasifier, a gas clean-up system, a
reducer and an oxidizer. Fig. 2 shows a simplified block diagram
of the SCL process.
In the SCL process, a high-purity oxygen stream (oxygen
concentration >95%) from an ASU is sent to the gasifier. The
gasifier utilizes the oxygen from the ASU to partially oxidize
coal forming high temperature raw syngas with contaminants
such as particulates, sulfur, mercury, and halogen compounds.
After the high temperature raw syngas quenching and particu-
Fig. 2. Simplified schematic of the syngas chemical looping process for hydrogen production from coal.
133
late removal steps, the pollutants in the gas stream are removed
from the raw syngas using gas cleanup units that include acid
gas removal (AGR) units and mercury removal units. These
steps are identical to the modern coal gasification to hydrogen
process shown in Fig. 1. The difference between SCL process
and the state-of-the-art coal-to-hydrogen process lies in the H2
generation strategy. Compared to the coal-to-hydrogen process
which requires a set of water–gas-shift reactors, CO2 separation
units, and pressure swing adsorption units for the production
of high-purity H2 from syngas, the SCL process utilizes only
three major units to convert syngas into pure hydrogen (purity
>99.95%) and electricity. The simplified overall energy conver-
sion scheme results from the utilization of chemical looping
strategy in modern coal gasification processes.
In a typical SCL configuration, the syngas is converted to
hydrogen in three major units, i.e. a reducer, an oxidizer, and a
combustion train.
2.1.2. Reducer
The purified syngas from the gas cleanup units is introduced
into the reducer, which is a moving bed of iron oxide compos-
ite particles, 2–10 mm in diameter, at 750–900 ◦ C and 30 atm.
In this reactor, the syngas is completely converted into carbon
dioxide and water while the iron oxide composite particles are
reduced to a mixture of Fe and FeO (reactions (1)–(4)).
Fe2 O3 + CO → 2FeO + CO2 (1)
FeO + CO → Fe + CO2 (2)
Fe2 O3 + H2 → 2FeO + H2 O (3)
FeO + H2 → Fe + H2 O (4)
134 L.S. Fan et al. / Particuology 6 (2008) 131–142

The overall reaction occurring in the reducer can be either Fe3 O4 to Fe2 O3 :
slightly endothermic or slightly exothermic depending on the
syngas composition, reaction temperature, as well as the par- 4Fe3 O4 + O2 → 6Fe2 O3 (7)
ticle reduction rate. The mild endothermic to mild exothermic The high pressure high temperature spent air (mainly N2 )
nature of the reducer simplifies the heat integration of the reducer produced from the combustion train can be used to drive a
reactor, since heat can be easily carried in or out of the reactor gas turbine-steam turbine combined cycle system to generate
by the particles. electricity for parasitic energy consumptions. In yet another
Since the syngas is completely oxidized by the Fe2 O3 com- configuration, a portion or all of the reduced particles from the
posite particles, the exhaust gas from the reducer contains only reducer reactor can be directly sent to the combustion train with-
CO2 and steam. Steam can be condensed out by extracting heat out reacting with steam in the oxidizer reactor. By doing this,
from the high temperature exhaust gas. This would result in more heat would be available for power generation at the cost
a concentrated high-pressure CO2 stream that can be directly of decreased hydrogen production. In a typical SCL configu-
transported for sequestration. ration, the reducer is installed on top of the oxidizer and the
particles move from the inlet of the reducer all the way to the
2.1.3. Oxidizer outlet of the oxidizer under gravity. The particles discharged
Having been reduced in the reducer, the particles are then from the oxidizer are then conveyed back to the reducer inlet by
introduced into the oxidizer. In the oxidizer, the reduced particles the combustion train. As can be seen, the SCL system can be
react with steam to produce a gas stream that contains solely H2 considered as a special type of circulating fluidized bed in which
and unconverted steam. Once the steam is condensed out from the reducer and the oxidizer serve as the downer while the com-
the gas stream, a H2 stream with a very high purity (>99.7%) bustion train is the riser. The step of combusting the reduced
can be obtained. The reactions involved in the oxidizer include: particles is known as chemical looping combustion, which dif-
fers from the chemical looping reforming step in that the particle
Fe + H2 O(g) → FeO + H2 (5)
regeneration is performed with steam rather than oxygen. Hence,
3FeO + H2 O(g) → Fe3 O4 + H2 (6) the utilization of both chemical looping reforming and chemi-
cal looping combustion concepts in the SCL system makes it
The steam used in the oxidizer is produced from the syngas flexible to adjust the ratio between H2 and electricity product.
cooling units and reducer/oxidizer exhaust gas cooling units. Moreover, only one type of highly reactive particle is circulating
The oxidizer reactor operates at 30 atm and 500–750 ◦ C. Under
such reaction conditions, both reactions (5) and (6) are slightly
exothermic. The heat released from the oxidation of the parti-
cles to Fe3 O4 is used in the same reactor to preheat the steam
feedstock. By introducing pressurized steam with a temperature
lower than the oxidizer operating temperature, the oxidizer can
be adjusted to operate under thermally neutral conditions. The
reactor design is thus simplified.
In the SCL process, hydrogen is produced using the chemical
looping reforming concept, i.e. the syngas is indirectly con-
verted to hydrogen with the assistance of iron oxide particles.
This is fundamentally different from the traditional coal-to-
hydrogen process where the syngas is shifted to make hydrogen
and followed by a CO2 removal operation. By using the syngas
chemical looping process, the CO2 and hydrogen are produced
from two different reactors, thereby eliminating the energy con-
suming CO2 separation and compression step. Since a significant
portion of the carbon management cost is associated with the
separation and compression of CO2 , the SCL process offers a
major advantage over the traditional coal-to-hydrogen process.

2.1.4. Combustion train

The Fe3 O4 formed in the reducer reactor is regenerated to
Fe2 O3 in a unit called the combustion train. The combustion
train is a riser driven by compressed air with a pressure slightly
higher than 30 atm in order to compensate the pressure drop
throughout the train. This unit serves as a pneumatic conveyor to
transport solid discharged from the oxidizer reactor to the inlet
of the reducer reactor. It also serves as a heat generator since
significant amount of heat is produced during the oxidation of Fig. 3. Bench scale demonstration unit (2.5 kWth ) for SCL process.
 L.S. Fan et al. / Particuology 6 (2008) 131–142 135

among the three units, thus minimizing the solid circulation rate
within the system.
The operations of all three major reactors in the SCL process
have been demonstrated individually with satisfactory results.
The reducer and oxidizer were individually tested in a bench
scale chemical looping demonstration unit while the combus-
tion train was simulated in an entrained bed reactor assembly;
both units were constructed at OSU. Fig. 3 shows the chemi-
cal looping demonstration unit, which is a moving bed reactor
with a capacity of 2.5 kW thermo. The reactor allows for a
large degree of flexibility in reaction conditions such as tem-
perature, particle size, gas–solid contacting pattern and solid
and gas flow rates. Gas and solid composition profile can be
obtained over the length of the reactor bed once steady state
operation is established. Useful information such as the reaction
rates and gas–solid conversions can be elucidated by analyzing
the demonstration results.
Current demonstration results (Gupta et al., 2007) show
>99.9% syngas conversion in the reducer and >99.95% purity
hydrogen stream from the oxidizer. Nearly full conversion of
gaseous hydrocarbons such as CH4 is also obtained in the
SCL demonstration. Based on the bench scale demonstration
results, an ASPEN® simulation model was constructed in order
to evaluate the performance of the SCL process (Fig. 4b). The
simulation outcomes for the SCL process were compared to
those obtained from an ASPEN® model for the state-of-the-art

Fig. 4. ASPEN® simulation model. (a) State-of-the-art coal-to-hydrogen process; (b) SCL process.
136 L.S. Fan et al. / Particuology 6 (2008) 131–142
coal-to-hydrogen process (Fig. 4a) based on identical assump-
tions. The simulation results show that the overall efficiency for
SCL process to be 64% (HHV) with 100% carbon capture as
compared to 57% (HHV) for state-of-the-art coal-to-hydrogen
process (Stiegel & Ramezan, 2006) (Fig. 4a).
2.2. Application of SCL process in coal-to-liquids processes
Other than serving as a stand alone hydrogen/electricity pro-
ducer, the SCL process can be integrated into other processes to
improve the overall energy conversion scheme. The integration
of the SCL process in the sate-of-the-art coal-to-liquids (CTL)
process (Fan, Gupta, Velazquez-Vargas et al., 2007) exemplifies
such novel application of the SCL process.
There are several different configurations to incorporate the
SCL system into the CTL process. In one conservative config-
uration, the SCL process is used as a retrofit to the traditional
CTL plant. The role of SCL system is to compensate for the
hydrogen deficit in the syngas from the modern gasifier. The
schematic flow diagram of such configuration is illustrated in
Fig. 5.
In a state-of-the-art CTL plant using cobalt based catalyst, the
syngas generated from the gasifier has a hydrogen concentration
(30–40%) much lower than the optimum H2 content for liquid
Fig. 5. Syngas chemical looping enhanced coal-to-liquids (SCL–CTL) process.
fuel synthesis (67%). This deficit in hydrogen is usually met by
converting a significant portion of the syngas from the gasifier
into hydrogen using the traditional coal-to-hydrogen approach.
Meanwhile, the Fischer–Tropsch (F–T) reactor converts only
part of the syngas (60–85%) into a wide variety of hydrocarbons
ranging from methane to hard wax. The gaseous hydrocarbon
fuels and unconverted syngas are considered to be by-products
from the F–T reactor. In a typical CTL configuration, a large
portion of these gaseous by-products from the F–T reactor are
combusted to generate electricity.
In the SCL–CTL configuration shown in Fig. 5, the gaseous
fuels and unconverted syngas from the Fischer–Tropsch reac-
tor are introduced into the reducer of the SCL process. These
gaseous fuels are converted to carbon dioxide and water through
the following reaction.
Cx Hy Oz + (2x + y/2 − z)MO
→ (2x + y/2 − z)M + xCO2 + y/2H2 O (8)
Here MO and M refer to the different iron oxide phases.
Reaction (8) reduces the iron oxide from higher oxidation
states to lower oxidation states. The reduced iron particles are
then introduced into the oxidizer where they are reacted with
steam to produce pure hydrogen and regenerate the iron oxide
 L.S. Fan et al. / Particuology 6 (2008) 131–142
(reaction (9)).
M + H2 O → MO + H2
As can be seen, the major feedstock for the SCL reducer
is the by-products from the F–T reactor. Meanwhile, the large
amount of medium pressure (∼25 atm) steam generated by the
waste heat from the F–T reactor provides ample supply for the
steam required in the SCL oxidizer. Therefore, through the uti-
lization of the SCL process, hydrogen, an essential feedstock
for the CTL process, is generated from the by-products of the
F–T synthesis. The liquid fuel yield of the CTL process is thus
improved. Furthermore, the integrated carbon capture capabil-
ity of the SCL process makes the SCL–CTL configuration even
more attractive under a carbon constrained scenario.
The SCL–CTL process has been independently evaluated
by Noblis System under the contract with National Energy
Technology Laboratory (NETL), USDOE. The analysis report
(Tomlinson & Gray, 2007) states that “the (syngas) chemical
looping systems such as that proposed by OSU have the potential
to significantly (∼10%) increase the yield of the conventional
cobalt based F–T process and allow more efficient heat recovery
and much lower (∼19%) carbon emissions”.
To generalize, the syngas chemical looping process has been
successfully demonstrated in a 2.5 kWth bench scale unit. The
demonstration results show that the SCL process can distinc-
tively improve the energy conversion efficiency and product
yield of the state-of-the-art coal gasification processes. Although
no significant impediment for the industrial applications of the
SCL process has been identified to date, high temperature solid
handling is recognized as the major challenge for SCL com-
mercialization. This issue can be addressed through scale up
demonstrations of the process. A 25 kWth sub-pilot scale unit
Fig. 6. Simplified schematic of the coal direct chemical looping (CDCL) system.
137
that operates all three major SCL units is currently under con-
struction.
(9)
3. Iron based chemical looping process for direct coal
gasification—coal direct chemical looping (CDCL)
process
Unlike the SCL process which employs a conventional gasi-
fication system to generate syngas feedstock, the iron based
coal direct chemical looping (CDCL) process takes coal directly
as feedstock rather than syngas. This offers several advantages
such as the reduction in O2 consumption and process intensifi-
cation.
Fig. 6 shows a simplified flow diagram of the CDCL process.
The CDCL process has three main reactors, i.e., the coal reactor,
the hydrogen reactor, and a combustion reactor. The coal reactor
converts the coal into CO2 and H2 O while reducing Fe2 O3 to
a mixture of Fe and FeO, the hydrogen reactor oxidizes the
reduced Fe/FeO particle to Fe3 O4 using steam while producing
a H2 rich gas stream. The combustion reactor pneumatically
transports the Fe3 O4 particles from the H2 reactor outlet to the
fuel reactor inlet using air, the Fe3 O4 particles are reoxidized to
Fe2 O3 during the conveying process.
3.1. Fuel reactor
The fuel reactor is a moving bed reactor operating at
750–900 ◦ C, 1–30 atm. The desirable reaction in the fuel reactor
is:
C11 H10 O(coal) + 26/3Fe2 O3 → 11CO2 + 5H2 O + 52/3Fe
(10)
138 L.S. Fan et al. / Particuology 6 (2008) 131–142
Fig. 7. Gas–solid contacting pattern of the fuel reactor.
Here, the coal considered is Pittsburgh #8 and is represented
by C11 H10 O given the elemental composition (Stultz & Kitto,
1992). This reaction is highly endothermic with a heat of reaction
of 1794 kJ at 900 ◦ C. Therefore, heat needs to be provided to
the first reactor. In order to balance the heat, coal is partially
combusted in situ by sending substoichiometric amounts of O2
(according to coal) into the fuel reactor. The overall reaction,
with negligible heat of reaction, is given as
C11 H10 O + 6.44Fe2 O3 + 3.34O2
→ 11CO2 + 5H2 O + 12.88Fe
Since the amount of oxygen required for reaction (11) is sig-
nificantly less than that for the coal gasification reactions, the
size of the air separation unit is smaller than those used in tradi-
tional gasification processes. This corresponds to savings in both
operation cost and capital investment of the coal to hydrogen
plant.
Fig. 7 shows the gas–solid contacting pattern inside the fuel
reactor. Fresh Fe2 O3 composite particles are fed from the top of
the fuel reactor while coal is introduced in the middle section
of the reactor. This configuration allows the volatiles from the
coal to react with Fe2 O3 particles to form CO2 and H2 O as
they move upward. The devolatilized coal char, however, move
downwards along with the partially reduced Fe2 O3 particles.
The coal char is gradually gasified by the CO2 and H2 O formed
at the lower part of the reactor. Provided enough residence time,
which is estimated to be 30–90 min depending on the operating
temperature and pressure, coal char can be converted fully, while
the Fe2 O3 reduces to a mixture of metallic iron and FeO. Coal ash
will come out along with the particles. Thus, the product from
the fuel reactor is a solid stream with Fe, FeO, and coal–ash
and a gas stream with mainly CO2 and H2 O. By condensing out
the H2 O in the gas stream, a ready-to-sequester CO2 stream is
obtained from the fuel reactor without the inherent separation
costs.
In order to promote the reaction rate between solids, a small
quantity of hydrogen gas (<5%) produced from the hydrogen
reactor is recycled to the bottom of the fuel reactor. By doing
this, the steam formed from the reaction between hydrogen and
FeO at the bottom of the fuel reactor would enhance char gasi-
fication. As opposed to other chemical looping processes which
utilize fluidized bed reactor to convert fuels (Andrus et al., 2006;
Mattisson, Lyngfelt, & Cho, 2001; Rizeq et al., 2002), the SCL
and CDCL processes use countercurrent moving bed to increase
gas–solid conversion. Such gas–solid contacting pattern is ther-
modynamically advantageous. The utilization of such patented
countercurrent moving bed configuration represents a key
enabling factor that makes the SCL and CDCL processes techni-
cally and economically attractive (Fan, Gupta, Velazquez-Vargas
et al., 2007; Thomas, Fan, Gupta, and Velazquez-Vargas (2004)).
3.2. Hydrogen reactor
The hydrogen reactor is a moving bed reactor that operates
at 700–900 ◦ C, and 1–30 atm. In the hydrogen reactor, the Fe
and FeO mixture from the fuel reactor reacts with steam in a
countercurrent mode to achieve maximum solid–gas conversion.
The product of the reactor is Fe3 O4 particles as well as H2 . The
reactions in the hydrogen reactor are the same as those in the
oxidizer in the SCL process (reactions (5) and (6)). This reaction
is slightly exothermic and therefore, steam with a lower temper-
ature is introduced into the reactor to moderate the temperature
of the reactor.
3.3. Combustion reactor
(11) In order to fully convert the CO and H2 from the char gasifica-
tion into CO2 and H2 O, Fe2 O3 have to be used as the feedstock
for the fuel reactor. Therefore, the Fe3 O4 from the hydrogen
reactor needs to be oxidized. This regeneration step is done in
the combustion reactor. The combustion reactor is a fluidized
bed reactor operated at a pressure similar to that of both the
fuel reactor and the hydrogen reactor in an adiabatic mode.
Air is used to pneumatically convey the Fe3 O4 particles from
the outlet of the hydrogen reactor to the fuel reactor inlet. The
Fe3 O4 particles are oxidized to Fe2 O3 in this step (reaction (7)).
This highly exothermic reaction will heat up the solid as well
as the gas. The hot solid would be subsequently fed into the
fuel reactor to partially compensate for the heat needed to con-
vert the coal. The coal ash, with significantly smaller size than
the Fe2 O3 composite particles, will be separated out from the
cyclone on the top of the fuel reactor; makeup particles will
also be introduced to the fuel reactor along with the regenerated
particles.
The CDCL process is currently under demonstration in a
2.5 kWth moving bed unit with encouraging results. ASPEN®
simulation studies (Gupta et al., 2006) showed that a maximum
coal to hydrogen conversion efficiency of above 80% (or 0.18 kg
H2 /kg coal) can be achieved in the CDCL process. Potential
challenges regarding this process include demonstration of high
temperature solid handling and minimization of reactor volumes
through further enhancement of reaction rates. Such challenges
will be addressed through particle optimization and larger scale
demonstrations.
 L.S. Fan et al. / Particuology 6 (2008) 131–142 139

4. Calcium looping process (CLP)

Commercially high-purity hydrogen is produced from

syngas obtained by coal gasification by the water gas shift
reaction (WGSR) in high- and low-temperature shift reactors
using iron oxide and copper catalysts respectively. However
for hydrogen production at high temperatures, the WGSR is
thermodynamically limited which necessitates the addition of
excess steam. Further, the commercial iron oxide and copper
catalysts have a low tolerance to sulfur and chloride impurities
and are prone to deactivation. Hence syngas clean up is required
upstream of the shift reactors, which is conventionally achieved
by using low-temperature scrubbing, which requires additional
equipment and is highly energy-intensive due to the cooling
and heating of the gas streams.
In contrast, the calcium looping technology obviates the
need for a catalyst and achieves simultaneous removal of carbon Fig. 9. Calcium looping process for the production of hydrogen.
dioxide, sulfur, and chloride impurities at high temperatures
during the production of high-purity hydrogen and yields
a sequestration-ready CO2 stream during the regeneration
phase. Thus, the calcium looping process not only improves that it is versatile and is capable of producing hydrogen for
the hydrogen yield and purity but also integrates a CO2 fuel cells, liquid fuel synthesis by Fisher–Tropsch reaction and
management scheme in the hydrogen production process. electricity generation in a gas turbine.
In addition to the production of hydrogen from syngas, the As shown in Fig. 9, the calcium looping process com-
calcium looping process can also be applied to the production prises of two reactors; the carbonation reactor where high-purity
of liquid fuels. It is capable of producing a stream with a 2:1 hydrogen is produced while contaminant removal is achieved
ratio of H2 to CO while removing sulfur and chloride impurities and the calciner where the calcium sorbent is regenerated
to ppb levels which is required for liquid fuel synthesis by the and a sequestration-ready CO2 stream is produced. A detailed
Fischer–Tropsch reaction. explanation of the hydrogen production and sorbent regener-
Fig. 8 illustrates the schematic integration of the calcium ation sections of the calcium looping process are provided
looping process in a typical coal gasification system and shows below.

Fig. 8. Schematic flow diagram of the calcium looping process.

140 L.S. Fan et al. / Particuology 6 (2008) 131–142
4.1. Carbonation reactor
The carbonation reactor comprises of either a fixed fluidized
bed or an entrained flow reactor that operates at high pressures
ranging from 20 to 30 atm and temperatures of 550–650 ◦ C. The
exothermic heat released from the carbonation reactor can be
used to generate electricity in order to meet the parasitic energy
requirement of the overall process.
In the carbonation reactor, the thermodynamic constraint
of the water–gas-shift reaction is overcome by the inces-
sant removal of the CO2 product from the reaction mixture
which enhances H2 production. This is achieved by concurrent
water–gas-shift reaction and carbonation reaction of calcium
oxide to form calcium carbonate thereby removing the CO2
product from the reaction mixture. In order to attain high CO2
capture capacity, the morphological properties of the calcium
sorbent are tailored using surface modifiers (Agnihotri, Chauk,
Mahuli, & Fan, 1999) The calcium oxide obtained from the Ohio
State University patented mesoporous high reactivity precipi-
tated calcium carbonate (PCC) sorbent attains an initial capture
capacity of 70% by weight and a capture capacity of 40–36 wt.%
over 50–100 cycles, which is significantly higher than most of
the high temperature sorbents reported in literature (Iyer, 2006;
Iyer, Gupta, Sakadjian, & Fan, 2004). In addition, the PCC-CaO
sorbent is also capable of reducing the concentration of sulfur
and halides in the outlet stream to ppb levels. Favorable con-
ditions are maintained within the carbonation reactor for the
reaction between the calcium sorbent and the sulfide and halide
impurity. Since the water–gas-shift reaction is conducted in the
presence of the PCC-CaO sorbent, equilibrium favors the forma-
tion of H2 . Hence, stoichiometric quantity of steam is sufficient
to produce high-purity hydrogen. Thermodynamics predicts that
the removal of H2 S and HCl impurities using calcium oxide is
inhibited by the presence of steam and the removal of COS is
inhibited by the presence of CO2 . Since almost all the steam is
consumed in the enhanced WGSR and all the CO2 is removed by
the sorbent, the removal of H2 S, HCl, and COS is also favored
in the system. In addition to the production of hydrogen from
syngas, it is also possible to reform hydrocarbons in the same
system, thus making the system fuel flexible.
When the calcium looping process is applied to the produc-
tion of liquid fuels, as can be seen in Fig. 10, the unreacted syngas
and lighter hydrocarbons at the exit of the Fischer–Tropsch
Fig. 10. Calcium looping process for the production of liquid fuels.
reactor are recycled back to the carbonation reactor where the
reforming of the hydrocarbons and the water–gas-shift reaction
result in the production of a stream with a 2:1 ratio of H2 /CO
which is the optimum feed for the Fisher–Tropsch reaction. The
reactions occurring in the carbonation reactor are as follows:
WGSR : CO + H2 O → H2 + CO2 (12)
Carbonation : CaO + CO2 → CaCO3 (13)
Sulfur capture(H2 S) : CaO + H2 S → CaS + H2 O (14)
Sulfur capture(COS) : CaO + COS → CaS + CO2 (15)
Halide capture(HCl) : CaO + 2HCl → CaCl2 + H2 O (16)
4.2. Calcination reactor
The spent sorbent, consisting mainly of CaCO3 , is regener-
ated back to CaO in the calciner. The calciner is operated at
atmospheric pressure and at a temperature of 800–1000 ◦ C in a
rotary calciner or a fluidized bed system. The regenerated sor-
bent produced from the calciner is then conveyed back into the
high-pressure carbonation reactor through a lock hopper system.
A mixture of CO2 and steam is used as the medium of calcination
with the steam being condensed out at the exit of the calciner
to produce a sequestration-ready CO2 stream. The heat can be
supplied directly or indirectly where a mixture of fuel and oxi-
dant can be supplied to the calciner. The reactions occurring in
the calciner are:
Calcination : CaCO3 → CaO + CO2 (17)
The hydrogen production as well as the sorbent regeneration
steps of the calcium looping process have been studied exten-
sively in an integrated fixed bed reactor to determine the kinetics
as well as the optimum reaction condition of the process. Fig. 11
shows the integrated experimental setup used for the proof of
concept studies of the calcium looping process. The bench scale
reactor is coupled with a set of continuous gas analyzers which
detect concentrations of CO, CO2 , H2 , H2 S, CH4 , and higher
Fig. 11. Integrated fixed bed reactor for proof of concept studies of the calcium
looping process.
 L.S. Fan et al. / Particuology 6 (2008) 131–142
Fig. 12. Process analysis of the calcium looping process using ASPEN® Plus simulator.
hydrocarbons in the product stream. The reactor setup is capa-
ble of handling very high pressures and temperatures of up to
20 atm and 900 ◦ C respectively, which are representative of the
conditions in a commercial coal to hydrogen system. Experi-
mental analyses have shown that very high-purity hydrogen can
be produced by the calcium looping process with simultaneous
removal of CO2 and sulfur impurities to ppm levels (Iyer et al.,
2007; Iyer et al., 2006)
The calcium looping process for the production of hydrogen
from coal has also been modelled using ASPEN® Plus software
(see Fig. 12). The simulations were conducted for the hydro-
gen production process in combination with a pressure swing
adsorption (PSA) system for the production of fuel cell grade
hydrogen. It has found that the over all efficiency of the process
for the production of 99.999% pure hydrogen is 63% (HHV)
when compared to the state-of-the-art process for the production
of hydrogen from coal which has an efficiency of 57% (HHV).
Hence, this technology provides an efficient “one box” mode
of operation for the production of high-purity hydrogen with
CO2 , sulfur and chloride capture that integrates the WGSR,
CO2 capture, sulfur removal and hydrogen separation in one
consolidated unit. This “one box” process depicts the potential
to achieve higher system efficiencies with lower overall footprint
by combining different process units in one stage.
5. Conclusions
The three novel gasification looping strategies discussed in
this paper provide integrated CO2 separation and efficient prod-
uct generation with high energy conversion efficiency. These
advantages make the hydrogen, electricity, and liquid fuel pro-
141
duction from coal more affordable even in a carbon constrained
scenario. Thus, with the rising global energy demand and crude
oil/natural gas prices, coupled with environmental concerns,
the application of the chemical looping technologies presents
a promising option for optimum coal conversion.
Acknowledgement
This work has been supported by the Ohio Coal Development
Office of the Ohio Air Quality Development Authority, U.S.
Department of Energy, Ohio State University and an industrial
consortium.
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