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 9 ( 2 0 1 4 ) 5 8 0 4 e5 8 1 7

Available online at www.sciencedirect.com

ScienceDirect
journal homepage: www.elsevier.com/locate/he

Chemical looping gasification for hydrogen

production: A comparison of two unique processes
simulated using ASPEN Plus
Stephen G. Gopaul, Animesh Dutta*, Ryan Clemmer
Mechanical Engineering Program, School of Engineering, University of Guelph, Guelph, Ontario N1G 2W1, Canada

article info

abstract

Article history:

The research compares the simulations of two chemical looping gasification (CLG) types

Received 25 October 2013

using the ASPEN Plus simulation software for the production of H2. The simulated biomass

Received in revised form

type was poultry litter (PL). The first CLG type used in situ CO2 capture utilizing a CaO

17 January 2014

sorbent, coupled with steam utilization for tar reforming, allowing for the production of a

Accepted 26 January 2014

CO2-rich stream for sequestration. Near-total sorbent recovery and recycle was achieved

Available online 18 February 2014

via the CO2 desorption process. The second type utilized iron-based oxygen carriers in
reductioneoxidation cycles to achieve 99.8% Fe3O4 carrier recovery and higher syngas

Keywords:

yields. Temperature and pressure sensitivity analyses were conducted on the main re-

ASPEN Plus

actors to determine optimal operating conditions. The optimal temperatures ranged from

Biomass gasification

500 to 1250
C depending on the simulation and reactor type. Atmospheric pressure proved

Chemical looping gasification

optimal in all cases except for the reducer and oxidizer in the iron-based CLG type, which

Hydrogen

operated at high pressure. This CLG simulation generated the most syngas in absolute

Steam gasification

terms (2.54 versus 0.79 kmol/kmol PL), while the CO2 capture simulation generated much

Tar reforming

more H2-rich syngas (92.45 mol-% compared to 62.94 mol-% H2).

Copyright 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

Introduction
Hydrogen (H2) has the potential to shift the global reliance on
fossil fuel energy sources to cleaner, more efficient forms of
energy as it presents a viable alternative. The issues of global
carbon dioxide (CO2) and other greenhouse gas (GHG) emissions and overall atmospheric concentration can also be
addressed with the utilization of H2 technologies for the
generation of energy. Furthermore, H2 presents an advantage
over other conventional alternative energies such as wind and
solar due to its energy storage and transport capabilities.

Thus, H2 utilization has the potential to become widespread in

the near future.
Current methods of H2 production involve the reforming of
fossil fuels; processes that ultimately contribute to the societal and environmental issues mentioned above. Correspondingly, contemporary H2 energy systems are neither GHGneutral nor sustainable since these non-renewable fossil
fuels are responsible for equivalent CO2 emissions. Thus, it is
essential that H2 be produced from a renewable, carbonneutral energy source. The thermochemical gasificationbased conversion of biomass in the presence of steam presents a viable renewable H2 source and is a strong contender
for the replacement of fossil fuel-based H2 production.

* Corresponding author.
E-mail addresses: sgopaul@uoguelph.ca (S.G. Gopaul), adutta@uoguelph.ca (A. Dutta), rclemmer@uoguelph.ca (R. Clemmer).
0360-3199/$ e see front matter Copyright 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ijhydene.2014.01.178

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 9 ( 2 0 1 4 ) 5 8 0 4 e5 8 1 7

Chemical looping gasification (CLG) using biomass fuel is

an example of such H2 energy technologies as it capitalizes on
renewable, environmentally friendly, and abundant sources
of energy. Biomass is an organic fuel source containing carbon, hydrogen, oxygen, nitrogen, and sulfur, and can come in
the form of agricultural wastes, municipal solid wastes, animal wastes, saw dust, etc. [1]. The gasification of biomass involves thermochemical conversion to H2, as well as various
hydrocarbons, for subsequent use in H2 conversion technologies with the aim of energy production. Furthermore,
biomass gasification is a complex, endothermic process consisting of many chemical reactions. These reactions depend
on the gasification agent being used which is commonly
steam. The reactions are summarized in Table 1 [2].
At the present time, minimal research has been conducted
regarding CLG systems development. Moreover, the major
research focus involves the chemical looping combustion
(CLC) process, with emphasis on oxygen carrier development
for use in CLC. Though widely recognized by many researchers, work conducted on the CLG process developed by
Fan et al. at Ohio State University [3] requires further research
and development to become a fully-implemented, renewable
H2 production technology. Furthermore, other advanced
chemical looping systems exemplar of CLG processes for the
purpose of H2 production include the HyPr-RING (Hydrogen
Production by Reaction-Integrated Novel Gasification), fuelflexible advanced combustionegasification, ALSTOM hybrid
gasificationecombustion,
Advanced
GasificationeCombustion (AGC), and Zero Emission Coal Alliance
(ZECA) processes [3e5].
The mitigation and subsequent elimination of sorbent/
catalyst performance degradation over time is an ongoing
challenge in most chemical looping systems. Successful
operation of chemical looping systems is often jeopardized by
unpredictable sorbent behaviour. Thus, research has been
conducted to identify the mechanisms contributing to sorbent
losses and develop performance improvement methods to
ensure sufficient system operation and longevity. Subsequently, sintering of the chemical looping sorbent particles as
a result of high-temperature operation and cyclic heating/
cooling cycles, in conjunction with char and tar deposition,
significantly reduces sorbent capture and regeneration capabilities. The detrimental effects of these phenomena are most
notably felt in CLG systems. Another challenge presented by
chemical looping systems involves the continuous flow of
solid materials between a multitude of interconnected reactors operating at high temperatures and pressure [6].

Table 1 e Chemical reactions in the steam gasification of

biomass. Adapted from Ref. [2].
Reaction
Wateregas shift
Methane reforming
Wateregas (i)
Wateregas (ii)
Oxidation (i)
Oxidation (ii)
Boudouard
Methanation

Chemical equation
CO H2O / CO2 H2
CH4 H2O / CO 3H2
C H2O / CO H2
C 2H2O / CO2 2H2
C O2 / CO2
C 0.5 O2 / CO
C CO2 / 2CO
C 2H2 / CH4

DH

923

(kJ mol1)

35.6 (exothermic)
225 (endothermic)
136 (endothermic)
100 (endothermic)
394 (exothermic)
112 (exothermic)
171 (endothermic)
89.0 (exothermic)

5805

The CLG of biomass is advantageous in that it is a clean,

renewable source of H2; however some disadvantages remain
prominent. For example, product syngas streams resulting
from the CLG of biomass contain many impurities. Consequently, much research has been conducted regarding syngas
impurity removal, whether it be the end-of-pipe or in situ
approaches. Therefore, the research compares two different
CLG processes under similar feed and operating conditions for
the purpose of H2 production using a computer simulation.
The novelty of the conducted research lies in the development
of the two CLG processes using the ASPEN Plus simulation
software and subsequent comparison of the results using the
same biomass feedstock in both cases.
The paper also includes temperature and pressure sensitivity analyses conducted on all relevant reactors and the results compared between the CLG 1 and CLG 2 processes.
Relevant parameters included optimal operating temperature
and pressure for each reactor and product syngas molar yield
and composition. Comparison of the H2 production and purity
capabilities of the two processes is emphasized upon.

Simulated processes
Two CLG mechanisms were simulated and analysed using the
ASPEN Plus V7.3 software. The simulation results were
compiled for poultry litter (PL), a nonconventional biomass type.

Chemical looping gasification type 1

The first CLG simulation (CLG 1) incorporated in situ product
CO2 capture in the absorbing reactor with the use of a CaO
sorbent. A representative block diagram can be seen in Fig. 1.
CO2 absorption occurs according to the following chemical
reaction [7]:
CaOs CO2g /CaCO3s
This reaction is exothermic with a heat of reaction of
178.3 kJ/mol [7]. In addition, near-total CaO sorbent recovery
and recycle was inherent to the simulation setup. CO2
desorption is the reverse of CO2 absorption and is therefore an
endothermic reaction. The energy required for the reaction to
occur is provided by the higher operating temperature of the
desorbing reactor. The resulting theoretical product stream is
pure CO2 which can be sent for sequestration. Furthermore,
the overall reaction prior to sorbent regeneration is as follows:
Cn Hm Op 2n  pH2 O n CaO/n CaCO3 m=2 2n  pH2
This overall reaction is endothermic with a heat of reaction
of 107.5 kJ/mol [6]. The constants n, m, and p represent the
respective carbon, hydrogen, and oxygen contents in the
biomass being gasified.
Another key aspect of the CLG 1 simulation is the use of
steam (H2O(g)) to address the issue of tar and char formation.
Tar and char were modelled as pure carbon and the reforming
reactions correspond to wateregas (i) and wateregas (ii) from
Table 1 as follows:
Cs H2 Og /COg H2g

Cs 2H2 Og /CO2g 2H2g

5806

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 9 ( 2 0 1 4 ) 5 8 0 4 e5 8 1 7

Fig. 1 e CLG 1 simulation block diagram.

These reactions were assumed to reform all tar compounds exiting the desorbing reactor. Furthermore, the use of
steam is preferable to conventional air since the thermooxidative reforming of pure carbon in air results in a nitrogen (N2) stream which must be subsequently separated from
the CO2 product stream. This process is energy-intensive and
therefore costly [8], however the condensation of steam from
an exit gas stream can also be a costly process. A more practical process schematic illustrating an overview of the CLG 1
process can be seen in Fig. 2.

Chemical looping gasification type 2

Subsequently, syngas chemical looping is another H2-production process involving the gasification of biomass. This
process separates the gasification and looping stages and
produces H2 via reduction, oxidation, and combustion cycles
involving iron (Fe), haematite (Fe2O3), and magnetite (Fe3O4)
[6]. This process was also simulated using ASPEN Plus V7.3
using poultry litter as the chosen biomass type (CLG 2). The
block diagram for the CLG 2 process can be seen in Fig. 3.
Similarly to CLG 1, CLG 2 is comprised of many chemical
reactions involving a multitude of reactors. These reactions
and corresponding reactors are outlined in Table 2 [3]. The
reactions persist under theoretical conditions. In actuality,
tar formation in the reducer is unavoidable. Tar reforming
in the CLG 2 simulation is carried out in the oxidizer, where
large amounts of steam are introduced. Here, tar is
completely reformed by the steam to CO, CO2, and H2 via the
aforementioned wateregas reactions presented in Table 1.
Additionally, pure O2 is utilized in the combustor as
opposed to air for the same reasons explained for the CLG 1
simulation [8].

Feedstock used
Composition of biomass types
The characteristics of three biomass types were compared to
identify a suitable feedstock for utilization in the two simulations. The types are: poultry litter, wood pellets, and oak
pellets. The biomass types vary in their chemical composition
and are thus representative of a spectrum of biomass types,
with poultry litter representing a nonconventional type. Table
3 summarizes ultimate analyses of poultry litter while Table 4
summarizes its proximate analysis.

Chemical equations for gasification of biomass types

Each biomass type was assumed to gasify according to the
following chemical formula [9]:
Cn Hm Op n  pH2 O/n CO m=2 n  pH2
The ultimate analysis of each biomass type assuming an
absence of both sulfur and nitrogen was used to calculate the
n, m, and p values in the equation above. Moreover, the
chemical composition of each biomass type varied in terms of
hydrogen and oxygen content, and was calculated relative to
carbon molar content. The corresponding chemical formulas
for each of the biomass types were found to be CH0.01286O0.1831,
CH0.00973O0.6331, and CH0.01061O0.8667 for poultry litter, willow
pellets, and oak pellets, respectively. Poultry litter can be seen
to contain the greatest hydrogen and lowest oxygen content
per mole of biomass. Consequently, the chemical equation for
the steam gasification of poultry litter is as follows:

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 9 ( 2 0 1 4 ) 5 8 0 4 e5 8 1 7

Fig. 2 e CLG 1 process schematic [6].

Fig. 3 e CLG 2 simulation block diagram [3].

5807

5808

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 9 ( 2 0 1 4 ) 5 8 0 4 e5 8 1 7

Table 2 e Chemical reactions in syngas chemical looping

[3].
Reactor

Chemical equation

Description

Biomass H2O / H2 CO Steam gasification

of biomass.
Combustor 4Fe3O4 O2 / 6Fe2O3
Forms Fe2O3 for reducer.
Reducer
3CO Fe2O3 / 3CO2 Fe Forms Fe for oxidizer
3H2 Fe2O3 / 3H2O 2Fe and CO and H2O to be
separated.
Oxidizer
3Fe 4H2O / Fe3O4 H2
Forms product H2 and
Fe3O4 for recycle to
combustor.
Gasifier

Table 4 e Proximate analysis of poultry litter.

Parameter
Moisture Content
Fixed Carbon
Volatile Matter
Ash

Mass composition (wt.-%)

20.10
3.33
54.29
22.28

thus phase equilibrium calculations were conducted using

Raoults Law, Henrys Law, ideal gas law, etc.

Component definition and input

CH0:01286 O0:1831s 0:8169 H2 Og /COg 0:8234H2g
It is evident that the steam gasification equations for willow and oak pellets would be of the same form as poultry litter
but rather with different molar coefficients for steam consumption and lesser values for H2 generation. Poultry litter
generated the greatest theoretical H2 yield as roughly 0.82 mol
were generated per mole of biomass and was therefore chosen
as the biomass type to be used for both the CLG 1 and CLG 2
simulations.

Simulation input parameters and description

The following sections outline the input data to the ASPEN
Plus simulation engine as well as the chosen calculation
methods. Moreover, detailed descriptions of the utilized
flowsheets are provided.

Setup and calculation methods

The flowsheet type was chosen as Solids with metric units,
allowing for the analysis and results presentation for solidstate input and output streams. The setup of the flowsheet
involved assigning the MIXCINC stream class to the simulation. This allowed fluid and aqueous streams (MIXED), conventional solid streams (CISOLID), and non-conventional solid
streams (NC) to be input and analysed during simulation runs
and calculations.
Subsequently, the process type was chosen as COMMON.
This allotted a generic industry type to the simulation, as
opposed to chemical, petrochemical, pharmaceutical, etc. The
IDEAL base calculation method was selected for simplicity and

Table 3 e Ultimate analysis of poultry litter in both the

presence and absence of sulfur and nitrogen.
Element

Carbon
Hydrogen
Oxygen
Nitrogen
Sulfur
Ash

Mass composition (wt.-%)

Sulfur and
nitrogen present

Sulfur and
nitrogen absent

43.30
6.62
5.95
5.72
1.15
37.26

46.49
7.11
6.39
e
e
40.01

Solid biomass was modelled using a user-defined, non-conventional solid based on ultimate, proximate, and sulfur analyses. Thus, the input for the poultry litter biomass type was
based on these parameters. Sulfur analyses e including pyritic, sulfate, and organic e were set to zero. Furthermore, the
enthalpy and density of biomass were approximated using
coal properties. The methods used by ASPEN Plus for these
calculations are HCOALGEN and DCOALIGT, respectively.
Fluid streams were modelled using conventional components which have thermophysical data stored in ASPEN Plus
databanks. Therefore, no data input were required for these
components. The components include: hydrogen (H2), water
(H2O), carbon monoxide (CO), carbon dioxide (CO2), methane
(CH4), and oxygen (O2).
Additionally, solid components were modelled using conventional solids which also have necessary thermophysical
data stored in the databanks. Tar formation was approximated as solid carbon (i.e. graphite) in the simulation. The
components include: tar (C), calcium oxide (CaO), calcium
carbonate (CaCO3), iron (Fe), haematite (Fe2O3), and magnetite
(Fe3O4). Calcium-based components were exclusive to the CLG
1 simulation while iron-based components were exclusive to
the CLG 2 simulation, with fluid components being involved in
both.

CLG 1 flowsheet description

The CLG 1 simulation flowsheet can be seen in Fig. 4. The input
and operating conditions for all feed streams and block units
are summarized in Tables 5 and 6, respectively.
Biomass and water at ambient conditions were fed to the
gasifier after being heated to the reactor temperature. This
block gasified the biomass based on user-defined output for H2
and CO. The output from the gasifier was then fed to the
reforming reactor where further gasification reactions
occurred, resulting in H2, CO, CO2, CH4, tar, and steam formation. Subsequently, the output from the reformer was fed
to the absorbing reactor in conjunction with a CaO feed
stream used for CO2 absorption and capture. The solid and
gaseous products from the absorber were then separated with
a gasesolid separator with an efficiency of 99.9%. The product
gases were heated to the WGS reactor temperature and
further gasified to convert the majority of the remaining CO to
H2. Tar products contained in the WGS reactor exit stream
were removed at a removal efficiency of 99.9%, and sent to the
desorbing reactor for steam reforming. The gaseous products

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 9 ( 2 0 1 4 ) 5 8 0 4 e5 8 1 7

5809

Fig. 4 e CLG 1 simulation flowsheet.

of this stream were subsequently condensed to remove most
of the remaining steam and small amounts of tar from the
syngas, consequently increasing H2 purity in the product gas.
It is important to note that the gasification process was
modelled with the combined use of the gasifying, reforming,
absorbing, and WGS reactor blocks rather than in a single
reactor step. This was a result of limitations inherent to
standard ASPEN Plus block unit input options and capabilities.
Furthermore, the solids stream exiting the initial gasesolid
separator containing CaCO3, tar, and unused CaO was fed to
the desorbing reactor, along with tar products from the WGS
reactor exit. Here, CaCO3 was thermally dissociated into CaO
and CO2, whereas all of the present tar was reformed to CO,
CO2, and H2 with the use of steam. An additional gasesolid
separator was utilized to separate the resulting solids (CaO
and remaining tar) and desorber gases. The unused and regenerated CaO stream was cooled to ambient temperature
and sent for re-use in the absorber. Further, the resulting CO2rich stream was also cooled to ambient temperature and sent
for sequestration.

H2O for H2 production. As such, the Fe2O3 resulting from

combustion was combined with the gasification products in
the reducer. Here, Fe2O3 was reduced to Fe and the gasification
products underwent the various gasification reactions,
resulting in H2, CO, CO2, CH4, tar, and steam. The solid-state
and gaseous products were separated in the cyclone at a
solids removal efficiency of 99.9%. The gases were then fed to
the reforming reactor while the Fe and tar were fed to the
oxidizing reactor for Fe3O4 regeneration. Furthermore, CH4
completely reformed to CO and H2 in the oxidizer. The
oxidizer exit gases and solids were then separated in a secondary cyclone, with over 99.8% regenerated Fe3O4 to be
recycled to the combustor and gases fed to the reformer.
Consequently, the reducer and oxidizer exit gases were
further reformed to H2 and CO2 in the reformer to increase the
H2 yield of the system. Small amounts of CH4 were regenerated in the reformer. The reformer exit gases were next fed to
a condenser to remove most of the remaining steam and residual solids from the resulting syngas. This increased H2
purity in the syngas. CO2 capture was not inherent to CLG 2 as
was the case with CLG 1.

CLG 2 flowsheet description

The CLG 2 simulation flowsheet can be seen in Fig. 5. The input
and operating conditions for all feed streams and block units
are summarized in Tables 7 and 8, respectively.
Biomass and water at ambient conditions were fed to the
gasifier after being heated to the reactor temperature. This
block gasified the biomass based on user-defined output for H2
and CO. The output from the gasifier was then fed to the
reducer. Conversion of Fe3O4 to Fe2O3 via combustion using
pure O2 was carried out to facilitate Fe-generating reduction
reactions, of which the product Fe was further oxidized using

Results and discussion

Important assumptions were initially applied to the simulation to ensure that it ran smoothly and produced results.
These included:
1. Chosen biomass types contained no nitrogen or sulfur.
2. Biomass and steam reacted completely in the first gasification reactor (i.e. the gasifier) and the only products were
H2 and CO.

5810

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 9 ( 2 0 1 4 ) 5 8 0 4 e5 8 1 7

Table 5 e Feed stream input conditions for CLG 1 simulation.

Feed stream

Input conditions
Temperature (
C)

Biomass
H2O-feed
CaO-feed
Steam
a
b

Pressure (atm)

25
25
25
240

Flowrate (kmol/h)

Component

1
1
1
1

1
1
6b
85b

Biomass (Non-conventional)
H2O (Conventional)
CaO (Conventional Solid)
H2O (Conventional)

Input as mass flowrate (kg/h) using biomass molecular weight.

Fed in excess of required stoichiometric amount.

3. Tar by-products formed in the various reactors were pure

carbon.
4. Tar reforming using steam in the CLG 1 simulation was
100% efficient.
5. CO2 desorption from CaCO3 in the CLG 1 simulation was
100% efficient.
6. Gas-solid separators were 99.9% efficient.
The following sections detail the results obtained from
both simulations using poultry litter. Temperature and
pressure sensitivity analyses were conducted for each of the
main reactors to determine the optimal operating conditions for those reactors. The outputs to the gasifier were
specified as part of the simulation in both cases, and thus no
sensitivity analysis could be carried out on those block
units.
Furthermore, the reactor type utilized for the absorber,
WGS reactor, desorber, combustor, reducer, oxidizer, and both
reformers was RGibbs. This reactor is an ASPEN Plus block unit
which calculates its output using the Gibbs free energy minimization method. The calculations are based on the chemical
equilibrium reactions of the components being input to the
reactor under the specified operating conditions.

Determining the optimal operating conditions

CLG 1 results
The reformer in the CLG 1 simulation aimed to produce more
H2 following the gasifier via CO conversion. The aforementioned gasification equations occurred simultaneously,
resulting in by-product formation in the output stream. The
results of the reformer temperature sensitivity analysis can be
seen in Fig. 6, which shows that H2 and CO yield at the
reformer exit increased with increasing operating temperature. Further, by-product formation, aside from CO, tended to
decrease with temperature, and sharply so at the higher end
of the temperature scale. These phenomena are the result of
the gasification equations proceeding in the reformer. The
forward reactions favour H2 and CO production and are
endothermic. Thus, increasing temperature favoured the
formation of these species. As a result, the optimal operating
temperature was subject to debate based on the criterion of
higher H2 yield versus greater H2 purity. The temperature of
750
C was chosen as optimal since H2 yield was relatively
high at this point while CO yield had not yet reached its
highest value. Moreover, by-product yield was relatively low
at this temperature. The trends observed for the reformer

Table 6 e Block unit operating conditions for CLG 1 simulation.

Block information

Operating conditions

Type

Temperature ( C)

Pressure (atm)

Other

Gasifier
Reformer
Absorber
WGS-RCTR
Desorber
Heater
Heat-gas
Cool-CaO
Cool-gas
G-S-SEP1

RYield
RGibbs
RGibbs
RGibbs
RGibbs
Heater
Heater
Heater
Heater
Sep

750
750a
500b
750c
650
750
750e
25
25
e

1
1d
1d
1d
1
1
1
1
1
e

G-S-SEP2
G-S-SEP3
Condense

Sep
Sep
Flash2

e
e
20

e
e
5

Output based on set values for H2 and CO (units of kg/kg total feed)
e
e
e
e
e
e
e
e
Separated gaseous components (H2, CO, CO2, CH4, and H2O) from 99.9%
of solid components (C, CaO, and CaCO3).
Separated DESORBER gases from 99.9% of CaO.
Separated syngas products from 99.9% of tar (C).
e

Name

a
b
c
d
e

Represents optimal operating temperature. Reformer temperature was varied from 500 to 900
C.
Represents optimal operating temperature. Absorber temperature was varied from 300 to 800
C.
Represents optimal operating temperature. WGS reactor temperature was varied from 400 to 1000
C.
Represents optimal operating pressure. Pressure was varied from 1 to 20 atm.
HEAT-GAS heater temperature was set to the WGS reactor temperature being simulated.

5811

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 9 ( 2 0 1 4 ) 5 8 0 4 e5 8 1 7

Fig. 5 e CLG 2 simulation flowsheet.

temperature sensitivity analysis closely reflected those found
by Mahisi et al. [8]. However, ethanol (C2H5OH) was used as the
source biomass in that case.
Next, the results of the pressure sensitivity analysis on the
reformer can be seen in Fig. 7, which illustrates that the
opposite phenomenon from temperature sensitivity occurred.
Both H2 and CO yield began to decrease rapidly with
increasing pressure, especially within the first five atmospheres of pressure increase. Correspondingly, other byproduct formation increased rapidly within the first five atmospheres. Due to the relatively large reduction in H2 yield
and rapid rise of by-product formation at higher pressures,
atmospheric pressure was determined to be optimal for the
reforming reactor. The trends observed for the pressure
sensitivity analysis also closely reflected those observed by
Mahisi et al. [8].
Furthermore, the main goal of the absorber was to capture
generated CO2 using CaO as the sorbent. As previously
mentioned, this is an exothermic equilibrium reaction which
typically occurs at temperatures from 600 to 650
C. Absorber
exit yield, CO2 capture efficiency, and CO2 product yield (i.e.
CO2 sent for sequestration) were parameters of consideration.
It was noted that H2 yield tended to decrease at the absorber
exit relative to H2 in the feed to the reactor. This phenomenon

was deemed a necessary sacrifice to ensure total CO2 capture,

and was compensated for further downstream with the use of
the WGS reactor.
A temperature sensitivity analysis was also conducted on
the absorbing reactor. The analysis showed that H2 production
increased with increasing absorber temperature. Conversely,
CO2 production decreased until reaching a local minimum at
750
C. Accordingly, CO2 capture efficiency slowly decreased
with temperature before being rendered totally ineffective at
750
C. Approximately 500
C was concluded as the optimal
operating temperature for the absorber, based on H2 and CO2
production and CO2 capture efficiency. Higher CO2 production,
relatively high H2 yield, and a CO2 capture efficiency of over
99% were all present at this temperature, which occurred prior
to the rapid decline in CO2 capture. Moreover, the pressure
sensitivity analysis conducted on the absorber yielded similar
results to that of the reformer, and thus atmospheric pressure
was deemed optimal for the absorber. Both CO2 production
and capture efficiency slightly increased with pressure; however minimal gains, on the order of 0.01%, were observed and
were insufficiently beneficial to merit operating the absorber
at higher pressures.
In addition, CO2 desorption was totally effective in the
simulation. CaO sorbent recovery was not, since 0.01% of the

Table 7 e Feed stream input conditions for CLG 2 simulation.

Feed stream

Input conditions

Biomass
H2O-in
Fe3O4-in
O2
Steam
a
b

Temperature ( C)

Pressure (atm)

Flowrate (kmol/h)

Component

25
25
25
25
240

1
1
1
1
32

1a
1
0.0370b
0.10b
20

Biomass (Non-conventional)
H2O (Conventional)
Fe3O4 (Conventional Solid)
O2 (Conventional)
H2O (Conventional)

Input as mass flowrate (kg/h) using biomass molecular weight.

Required stoichiometric amount for down-stream reducer reactions to occur.

5812

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 9 ( 2 0 1 4 ) 5 8 0 4 e5 8 1 7

Table 8 e Block unit operating conditions for CLG 2 simulation.

Block information
Name

Type

Operating conditions
Temperature (
C)

Pressure (atm)

Other
Output based on set values for H2 and CO (units of kg/kg total feed)
e
e
e
e
e
Separated 99.9% of Fe and tar (C) from reducer exit gases (H2, CO, CO2,
H2O, and CH4).
Separated 99.9% of Fe3O4 from oxidizer exit gases (H2, CO, CO2, and H2O)
e

Gasifier
Combust
Reducer
Oxidizer
Reformer
Heater
Cyclone

RYield
RGibbs
RGibbs
RGibbs
RGibbs
Heater
Sep

750
1250
870
720
500
750
e

1
1
30
30
1
1
e

Cyclone2
Condense

Sep
Flash2

e
20

e
1

sorbent feed was lost due to inefficiencies in the gasesolid

separators throughout the process. In an experimental
setting, however, greater amounts of sorbent would be
rendered ineffective as a result of calcium sulfate (CaSO4)
formation from any sulfur components present in the
biomass feedstock [8], which was not considered in the conducted research. Thus, greater amounts of sorbent regeneration would be required in experimental and real-life scenarios
than what is implied by the CLG 1 simulation.
Subsequently, the purpose of the WGS reactor was to
provide a final block unit for H2 production as well as to regain
H2 that was lost as a result of CO2 absorption in the absorbing
reactor. The lowered temperature required for CO2 absorption
to proceed was unfavourable to H2 production and retention
in the absorbing reactor. Both H2 yield and content significantly increased as a result of the gasification reactions that
occurred within the WGS reactor. Furthermore, H2 content in
the syngas product stream was further upgraded with
condenser utilization in the following step. This block unit
effectively liquefied the majority of the steam present in the
WGS reactor exit stream, thereby altering the syngas composition in favour of H2.
The results of the temperature sensitivity analysis conducted on the WGS reactor can be seen in Fig. 8. Both H2 and
CO yield increased significantly after 500
C with increasing

temperature, and then began to plateau at higher temperatures. Although the CO yield increase with temperature was
pronounced, the H2 to CO yield ratio remained very high due
to low concentrations of CO. Other by-product formation
generally declined with increasing temperature and was even
negligible in the case of CO2. Accordingly, the optimal operating temperature for the WGS reactor was found to be 750
C,
which provided relatively high H2 yield while maintaining a
lower total by-product yield. This temperature is considerably
higher than the 300
C value observed by Mahisi et al. [8].
However, H2 yield increased following WGS reactor utilization
in both CLG 1 and the simulation conducted by Mahisi et al.
The reactor in that simulation accounted for an 8% increase in
H2 yield, while the CLG 1 simulation exhibited an approximate
170% increase. The substantially larger increase in CLG 1 can
be attributed to the requirement for the regeneration of
reduced amounts of H2 following the CO2 absorption step.
Additionally, the pressure sensitivity analysis conducted on
the WGS reactor demonstrated that atmospheric pressure
was optimal. H2 production decreased and by-product formation increased with pressure, similarly to trends observed
for the previous reactors.
Overall, the optimal reactor temperatures for the CLG 1
simulation were 750
C, 500
C, and 750
C for the reformer,
absorber, and WGS reactors, respectively. Therefore, a value

Fig. 6 e CLG 1 reformer temperature sensitivity analysis.

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 9 ( 2 0 1 4 ) 5 8 0 4 e5 8 1 7

5813

Fig. 7 e CLG 1 reformer pressure sensitivity analysis.

of 750
C was chosen for the gasifier as a conservative estimate. Moreover, this value is in agreement with some gasifier
temperatures utilized in coal-type or wood-type biomass
gasification studies outlined in the literature [10e20], and is
80
C warmer than the value of 670
C reported by Acharya [6].

CLG 2 results
Combustor operating conditions were chosen as 1250
C and
1 atm based on data presented by Fan [3]. These conditions
proved sufficient to fully convert Fe3O4 to Fe2O3 via thermooxidation given a stoichiometric excess of pure O2.
The CLG 2 simulation reducer aimed to generate Fe by
reacting Fe2O3 with the H2 and CO gasification products. Byproduct formation was evident in the simulation. These
phenomena are better illustrated in the temperature sensitivity analysis of Fig. 9. The analysis was conducted at 30 atm
rather than atmospheric pressure as this was the recommended pressure proposed by Fan [3]. Also, Fe formation was
determined to be undesirably low at atmospheric pressure.
Fig. 9 displays that minimal increases in H2 and CO yield were
initially observed before slowly decreasing at the critical point

of roughly 875
C. Conversely, at this critical point, by-product

formation (CO2, H2O, CH4, and tar) tended to increase with
temperature. Fe formation was virtually unaffected by temperature variation for the tested range. Therefore, 870
C was
chosen as the optimal reducer temperature. This value was
chosen due to its slightly lower cost implications when
compared to the critical point of 875
C which was too proximate to the decreasing portion of the H2 yield curve. Moreover,
the optimal operating pressure of 30 atm was confirmed via a
pressure sensitivity analysis on the reducer, ranging from 30
to 37 atm, conducted at the optimal temperature of 870
C. H2
and CO production decreased with increasing pressure while
by-product formation increased, similar to the trends of the
CLG 1 pressure sensitivity analyses.
In addition, the general purpose of the CLG 2 oxidizer was
both to produce H2 in greater quantities than the gasifier and
to regenerate spent Fe3O4. The temperature sensitivity analysis for the oxidizer was again conducted at 30 atm rather
than atmospheric pressure as this was the recommended
pressure proposed by Fan [3]. The analysis demonstrated that
temperature variation only had a significant effect on CO and

Fig. 8 e CLG 1 WGS reactor temperature sensitivity analysis.

5814

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 9 ( 2 0 1 4 ) 5 8 0 4 e5 8 1 7

Fig. 9 e CLG 2 reducer temperature sensitivity analysis.

CH4 yield. CO increased relatively quickly with temperature

and quantities of CH4 were negligible below about 680
C.
Thus, 720
C was chosen as the optimal oxidizer temperature
as only trace amounts CH4 were present, and negligible
changes in H2 yield were observed. Oxidizer pressure was
incrementally increased to 40 atm to determine pressure effects. However, minimal changes in component yield were
observed in any case, and 30 atm was confirmed as the
optimal operating pressure. Finally 20 kmol/h was chosen as
the design feed steam flowrate to the oxidizer after flowrate
variation analysis was conducted from 5 to 25 kmol/h to
determine the effects on component yields. The analysis was
carried out under steam conditions of 240
C and 32 atm. Byproduct CO yield tended to decrease with increasing flowrate, with other component species virtually unaffected, and
so a higher flowrate was chosen to minimize CO yield.
Subsequently, the CLG 2 reformer was meant to further
increase H2 yield and content via reforming of the remaining
by-products. The temperature sensitivity analysis was conducted and the optimal operating temperature chosen based

on H2 yield and by-product levels present in the syngas stream

exiting the condenser unit at the process termination. The
observed results from the analysis can be seen in Fig. 10. It can
be seen that H2 and CO2 yield in the syngas begin to decrease
after reformer temperatures reach roughly 500
C. CO yield
increased rapidly over the simulated range, albeit at lower
concentrations throughout. CH4 yield rapidly decreased between 400 and 500
C. H2 yield tended to peak at approximately 1.60 kmol/kmol PL. In addition, syngas composition
was closely examined under varying temperature conditions.
The respective component curves had roughly the same
shape as the syngas yield curves which are illustrated in
Fig. 10. H2 and CO2 comprised the majority of the syngas with
CO, H2O, and CH4 by-products accounting for smaller percentages. Again, H2 composition peaked in the 450e500
C
range and began to decrease with further temperature
increase.
Based on the aforementioned trends, 500
C was chosen as
the optimal operating temperature for the CLG 2 reforming
reactor. This is due to both higher H2 yield and content in the

Fig. 10 e CLG 2 reformer syngas yield temperature sensitivity analysis.

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 9 ( 2 0 1 4 ) 5 8 0 4 e5 8 1 7

5815

Fig. 11 e Comparison of simulation syngas yields.

resulting syngas stream, as well as lower by-product yields

and compositions in proximity to this temperature. Increasing
operating pressure above atmospheric conditions tended to
decrease desirable product yield and correspondingly
increased by-product yield and concentration. Thus, a
detailed pressure sensitivity analysis was not further pursued
for the CLG 2 reformer.

Comparison of simulation results

The following section details a comparison between the results of the two biomass gasification simulations. Comparisons are made based on syngas yield and composition.

Syngas yield comparison

A comparison of the absolute syngas yields for the CLG 1 and
CLG 2 simulations can be seen in Fig. 11. It is evident that CLG 2
generated more syngas than CLG 1, at values of roughly 2.54
and 0.79 kmol/kmol PL, respectively. However, it is also

important to note that CO2 removal was not a focal point of

CLG 2, and thus almost 0.87 kmol CO2/kmol PL adds to the
absolute CLG 2 syngas value. Furthermore, H2 can be seen to
be the main constituent in both cases, with the CLG 2 syngas
producing more H2 in absolute terms.
CLG 1 generated 0.73 kmol H2/kmol PL while CLG 2 generated 1.60 kmol H2/kmol PL. These values are less than those
reported in the literature for either case. Processes similar to
CLG 1 reported H2 yields ranging from 1.6 to roughly
5.7 kmol H2/kmol biomass [2,8], while Fan outlined a process
similar to CLG 2 capable of producing approximately
11.73 kmol H2/kmol coal [3]. The latter process, however, used
coal as the solid fuel and greater amounts of iron-based oxygen carriers than CLG 2.
Furthermore, the assumption that all biomass and steam
were completely converted to H2 and CO in the gasifier was
challenged, and its effect on syngas yield in both cases was
determined. This was done in terms of conversion efficiency,
labelled as gasifier efficiency. The analyses showed that the

Fig. 12 e Comparison of simulation syngas compositions.

5816

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 9 ( 2 0 1 4 ) 5 8 0 4 e5 8 1 7

yields of all syngas components linearly decreased with a

decrease in gasifier efficiency. It is also noted that the reduction in H2 yield from 100 to 50% gasifier efficiency is relatively
drastic; 0.73 to 0.36 kmol/kmol PL.

costs. Subsequently, comparing the cost estimates would

provide an idea of the feasibility of the proposed processes
from a practical standpoint.

Syngas composition comparison

Conclusions

A comparison of the syngas compositions in either simulation

can be seen in Fig. 12, which also includes individual
component compositions. It can be seen that H2 is the main
component in either syngas stream, at 92.45 mol-% and
62.94 mol-% for CLG 1 and CLG 2, respectively. The former
value is greater than the 80.94% H2 value reported by Acharya
under similar conditions. Further, the CO2 concentration of
0.01% in CLG 1 syngas is significantly lower than that reported
in the literature 5.71% [6]. Other studies similar to CLG 1 reported lower obtained H2 concentrations, ranging from
roughly 70e90 mol-% [2,7,8].
However, as previously mentioned, CO2 was not removed
from the syngas stream in CLG 2, and thus its relatively large
constituency of 34.11 mol-% is accounted for by that fact. Had
CO2 removal been inherent to the design of CLG 2, and
assuming removal efficiency upwards of 99%, the H2 composition of the CLG 2 syngas would be over 95 mol-%. Further, the
62.94 mol-% value from CLG 2 is similar to the 62.1 mol-%
found in the literature [3].

Future research
Potential for future research stems in-part from the simulation flowsheets and block unit setups themselves. Determining a method to model biomass gasification in a single
gasifying reactor, as opposed to four separate reactors in the
case of the CLG 1 process, is exemplar of this. This would allow
for biomass gasification to occur spontaneously in an
equilibrium-based reactor, i.e. RGibbs, rather than in a reactor
with user-defined outputs, as is the case for both simulations.
Further, this would allow for an investigation of the sensitivity
of the gasifying reactor to steam-to-biomass, calcium-tobiomass, and equivalence ratios.
In addition, the nitrogen and sulfur components of each
biomass type could be included in calculations to further
enhance the accuracy of the simulation. Consequently, this
would require modification of the flowsheet and input parameters to deal with any sulfur dioxide (SO2), hydrogen sulfide (H2S), or nitrogen (N2) streams that may be present from
gasification of biomass containing these elements [21].
Moreover, more detailed design of the gasesolid separators
(e.g. cyclones) utilized in the simulation would further increase its accuracy. For example, cyclones, baghouses, or
electrostatic precipitators (ESPs) could be designed for
gasesolid separation. These process units would be more
representative of an industrial-scale scenario, as opposed to
the generic separator blocks used in this simulation.
Furthermore, the energy requirements of such block units
could be accurately represented as well.
Finally, a cost analysis for each block unit could be conducted to obtain an overall syngas production cost for each
simulated process type. The cost analysis could be based on
energy requirements and feed stream raw materials supply

In conclusion:
1. Poultry litter was the chosen biomass type to be simulated
both because it is a nonconventional biomass type and due
to its greater H2 yield potential when compared with willow pellets and oak pellets.
2. The optimal operating condition estimates determined for
the main reactors in both simulations were in line with
those presented in the literature.
a. CLG 1 simulation:
i. Reformer: 750
C, 1 atm.
ii. Absorber: 500
C, 1 atm.
iii. WGS reactor: 750
C, 1 atm.
b. CLG 2 simulation:
i. Combustor: 1250
C, 1 atm.
ii. Reducer: 870
C, 30 atm.
iii. Oxidizer: 720
C, 30 atm.
iv. Reformer: 500
C, 1 atm.
3. CLG 1 and CLG 2 syngas yields were 0.79 and 2.54 kmol/
kmol PL, respectively. CLG 2 generated the most H2 in the
product syngas stream, 1.60 kmol/kmol PL, based on absolute yield, with CLG 1 producing only 0.73 kmol/kmol PL.
H2 production was significantly less than that outlined in
the literature for both simulations.
4. CLG 1 produced purer syngas with an H2 concentration of
92.45 mol-%, while CLG 2 had 62.94 mol-% H2. The lower
CLG 2 concentration was due to the presence of CO2 in that
syngas stream, as its removal was not a focus of that
simulation. CLG 1 exhibited more H2 rich syngas than other
studies while CLG 2 produced results similar to those found
in the literature.
5. Future research could focus on increasing the accuracy and
scalability of the simulations through assumption mitigation or removal. Examples include modelling biomass
gasification in a single gasifying reactor, detailed design of
gasesolid separators, and inclusion of nitrogen and sulfur
elements in biomass ultimate analyses.

Acknowledgements
The authors would like to acknowledge funding from NSERC
via the Discovery Grant Program. The authors would like to
thank Miss Leanna Harnarain for proofreading the manuscript and for improving its appearance.

Appendix A. Supplementary data

Supplementary data related to this article can be found at
http://dx.doi.org/10.1016/j.ijhydene.2014.01.178.

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 9 ( 2 0 1 4 ) 5 8 0 4 e5 8 1 7

references
[12]
[1] Holladay J, Hu J, King D, Wang Y. An overview of hydrogen
production technologies. Catal Today 2009;139.4:244e60.
[2] Florin N, Harris A. Hydrogen production from biomass
coupled with carbon dioxide capture: the implications of
thermodynamic equilibrium. Int J Hydrogen Energy
2007;32.17:4119e34.
[3] Fan Liang-Shih. Chemical looping systems for fossil energy
conversions. Hoboken, NJ: Wiley-AIChE; 2010 [Print].
[4] Ni M, Leung D, Leung M, Sumathy K. An overview of
hydrogen production from biomass. Fuel Process Technol
2006;87.5:461e72.
[5] Kirtay Elif. Recent advances in production of hydrogen from
biomass. Energ Convers Manage 2011;52:1778e89.
[6] Acharya Bishnu. Chemical looping Gasification of biomass for
hydrogen-enriched Gas production [Thesis]. Halifax, Nova
Scotia: Dalhousie University; 2011 [N.p.: Dalhousie University,
Department of Mechanical Engineering, n.d. Print].
[7] Acharya B, Dutta A, Basu P. Chemical-looping gasification of
biomass for hydrogen-enriched gas production with in-process
carbon dioxide capture. Energy Fuels 2009;23:5077e83.
[8] Mahishi Madhukar R, Sadrameli MS, Vijayaraghavan Sanjay,
Goswami DY. A novel approach to enhance the hydrogen
yield of biomass gasification using CO2 sorbent. J Eng Gas
Turb Power 2008;130:011501-1e011501-8 [Print].
[9] Moghtaderi B. Effects of controlling parameters on
production of hydrogen by catalytic steam gasification of
biomass at low temperatures. Fuel 2007;86.15:2422e30.
[10] Abuadala A, Dincer I, Naterer GF. Exergy analysis of
hydrogen production from biomass gasification. Int J
Hydrogen Energy 2010;35:4981e90.
[11] Gonzalez J, Roman S, Bragado D, Calderon M. Investigation
on the reactions influencing biomass air and air/steam

[13]

[14]

[15]

[16]

[17]

[18]

[19]

[20]

[21]

5817

gasification for hydrogen production. Fuel Process Technol

2008;89.8:764e72.
Shen L, Gao Y, Xiao J. Simulation of hydrogen production
from biomass gasification in interconnected fluidized beds.
Biomass Bioenerg 2008;32.2:120e7.
Franco C, Pinto F, Gulyurtlu I, Cabrita I. The study of
reactions influencing the biomass steam gasification
process. Fuel 2003;82.7:835e42.
Pfeifer C, Puchner B, Hofbauer H. Comparison of dual
fluidized bed steam gasification of biomass with and without
selective transport of CO2. Chem Eng Sci 2009;64.23:5073e83.
Lin Shiying, Harada Michiaki, Suzuki Yoshizo,
Hatano Hiroyuki. Hydrogen production from coal by
separating carbon dioxide during gasification. Fuel
2002;81:2079e85.
Hanaoka T, Yoshida Takahiro, Fujimoto Shinji, Kamei Kenji,
Harada Michiaki, Suzuki Yoshizo, et al. Hydrogen production
from woody biomass by steam gasification using a CO2
sorbent. Biomass Bioenerg 2005;28.1:63e8.
Guoxin Hu, Hao Huang. Hydrogen rich fuel Gas production
by Gasification of wet biomass using a CO2 sorbent. Biomass
Bioenerg 2009;33.5:899e906.
Mahishi M, Goswami D. An experimental study of hydrogen
production by gasification of biomass in the presence of a
CO2 sorbent. Int J Hydrogen Energy 2007;32.14:2803e8.
Acharya Bishnu, Dutta Animesh, Basu Prabir. An
investigation into steam gasification of biomass for hydrogen
enriched Gas production in presence of CaO. Int J Hydrogen
Energy 2010;35.4:1582e9.
Faaij A, van Ree R, Waldheim L, Olsson E, Oudhuis A, van
Wijk A, et al. Gasification of biomass wastes and residues for
electricity production. Biomass Bioenerg 1997;12.6:387e407.
Piroonlerkgul P, Wiyaratn W, Soottitantawat A,
Kiatkittipong W, Arpornwichanop A, Laosiripojana N, et al.
Operation viability and performance of solid oxide fuel cell
fuelled by different feeds. Chem Eng J 2009;155:411e8.