i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 1 0 3 4 6 e1 0 3 5 3

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Thermodynamic analysis of syngas generation

from biomass using chemical looping gasification
method

Kun Wang*, Qingbo Yu**, Qin Qin, Limin Hou, Wenjun Duan
State Environmental Protection Key Laboratory of Eco-Industry, Institute of Thermal Energy and Environmental
Engineering, Northeastern University, No. 11, Lane 3, WenHua Road, HePing District, Shenyang, 110819, Liaoning,
PR China

article info abstract

Article history: Chemical looping gasification (CLG) is a novel technology to convert carbon-containing
Received 8 July 2015 feedstock into syngas. In the technology, lattice oxygen of oxygen carrier is used as oxy-
Received in revised form gen source for char gasification, and then the reduced oxygen carrier is regenerated in air
11 September 2015 atmosphere. In this paper, the mechanism of CLG of biomass using Mn2O3 as oxygen
Accepted 12 September 2015 carrier was discussed firstly and then thermodynamic analysis of syngas generation from
Available online 6 November 2015 biomass was performed by Gibbs free energy minimization method. Chemical equilibrium
calculations were carried out to study the effects of Mn2O3/biomass, operation tempera-
Keywords: ture, pressure, and steam/Mn2O3 on the gasification characteristics. The optimal thermo-
Chemical looping gasification dynamic conditions were determined to improve H2 and CO concentrations as high as
Biomass gasification possible. The optimal Mn2O3/corn cob is 0.18 to obtain the highest CO and H2 yields. The
Syngas results suggest that the preferential conditions are achieved at 1000
C and atmospheric
Mn2O3 pressure, under these conditions, the total dry concentration of CO and H2 is 98.8% in the
Thermodynamic analysis syngas. Steam can be used in the CLG to modify the H2/CO in the syngas. The carbon
conversion also increases under oxidizing atmosphere of steam.
Crown Copyright 2015 Published by Elsevier Ltd on behalf of Hydrogen Energy Publica-
tions LLC. All rights reserved.

to produce biofuels, energy and other chemicals from

Introduction
Biomass, the third largest source of energy in the world, is
dominant choice for replacement of fossil fuels because of its
renewability and carbon neutrality [1,2]. Biomass gasification
is one of the prominent thermochemical conversion methods
biomass, and it has attracted a lot of researchers' interest in
recent years [3]. During biomass gasification process, gasifying
agents such as air, oxygen, steam, carbon dioxide etc. are
required. Comparing with other agents, the heating value of
synthesis gas produced by pure oxygen gasification is the
highest. Moreover, when steam or carbon dioxide is used as

* Corresponding author. P.O. Box 345, Northeastern University, No. 11, Lane 3, Wenhua Road, Heping District, Shenyang, Liaoning, PR
China. Tel./fax: 86 024 83672216.
** Corresponding author. P.O. Box 345, Northeastern University, No. 11, Lane 3, Wenhua Road, Heping District, Shenyang, Liaoning, PR
China. Tel./fax: 86 024 83672216.
E-mail addresses: wangk_neu@126.com (K. Wang), yuqb@smm.neu.edu.cn (Q. Yu).
http://dx.doi.org/10.1016/j.ijhydene.2015.09.155
0360-3199/Crown Copyright 2015 Published by Elsevier Ltd on behalf of Hydrogen Energy Publications LLC. All rights reserved.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 1 0 3 4 6 e1 0 3 5 3
gasifying agent, a lot of external heat is required because the
gasification reaction is strong endothermic. Unfortunately,
the high cost of oxygen increases the operating cost of pure
oxygen gasification [4e7].
Chemical looping gasification (CLG) is a novel technology to
convert carbon-containing feedstock into syngas. In this
technology, lattice oxygen of oxygen carrier is used to replace
pure oxygen to gasify, and the concept is derived from
chemical looping combustion (CLC) [8]. The schematic of CLG
of biomass is illustrated in Fig. 1. In the fuel reactor, biomass is
pyrolyzed into three phase products of gas, tar, and char first
and then the products of pyrolysis react with oxygen carrier.
Oxygen carrier provides oxygen and the tar and char are
broken down into syngas. In the air reactor, the reduced ox-
ygen carrier is regenerated in air atmosphere. The principle of
CLG is similar to the production of hydrogen via hydrolysis of
hydrides [9e11]. Because the oxidation reaction is strong
exothermic, the required heat of biomass gasification can be
provided by the circulating oxygen carrier from the air reactor.
Works have been done to investigate the feasibility and
adaptability of CLG technology. Huang et al. investigated the
CLG of biomass process with natural hematite as oxygen
carrier in a fluidized bed reactor. Comparing with biomass
steam gasification, carbon conversion and gas yield increased
by 7.47% and 11.02%, respectively, and tar content lowered by
51.53% [12]. Acharya et al. studied CLG of biomass for
hydrogen-enriched gas production with in-process carbon
dioxide capture. Experimental results show that the use of
calcium oxide not only helps to reduce the concentration of
carbon dioxide to nearly zero but also increases the hydrogen
concentration [13]. The NiO modified iron ore as an oxygen
carrier in the CLG of biomass process was also investigated by
Huang et al. Results show that the presence of spinel-type
nickel iron oxide NiFe2O4 apparently improved the reaction
rate of char gasification [14].
Oxygen carrier is the key issue for achieving CLG process.
Cu-, Mn-, Co-, Ni-, Fe-, Ce-based oxygen carriers are greatly
applied and proved to be fitted candidates in the CLC [15e18].
Among the oxygen carriers, Cu-, Mn-, Co-based oxygen car-
riers can release oxygen when temperatures are high [19e21].
When the three oxygen carriers are used in the CLG, the
gasification rate of char can increase because the reaction
between oxygen carrier and char is changed from solidesolid
reaction to gasesolid reaction. Due to the low melting point of
Syngas N2
Fuel reactor MexOy-2 Air reactor
Pyrolysis Oxidation
Gasification
MexOy
Biomass Air
Fig. 1 e The schematic of CLG of biomass.
10347
copper oxides, agglomeration may be the biggest issue of Cu-
based oxygen carrier in high temperature. Comparing with
cobalt oxides, the price of manganese oxides are much low.
Moreover, the performances of high conversion of fuel, high
temperature stability, and high oxygen transfer capacity of
Mn-based oxygen carrier or manganese ore as an oxygen
carrier are presented in the CLC. Additionally, some Mn-based
materials show low rate of attrition, making them very
promising oxygen carrier materials for applications related to
CLC [22e24]. The CLC and CLG processes all refer to the con-
version of fuel. The only difference is a low oxygen carrier/fuel
is used in the CLG because its target product is synthesis gas
rather than heat. Hence, the use of cheap Mn-based materials
for CLG technology seems to be very appropriate.
In the present study, the feasibility of Mn2O3 as oxygen
carrier for CLG was investigated by thermodynamic method.
An optimal mol ratio of biomass to Mn2O3 was determined to
obtain the highest H2 and CO yields. Besides, the equilibrium
calculations employing the Gibbs free energy were used to
evaluate the influence of operation temperature, pressure on
gasification products. Moreover, the effect of steam on
composition adjustment of the products was also analyzed.
Mechanism
Gasification is a thermochemical process in which the solid
fuels are converted to combustible gases by partial oxi-
dization. Similar to the coal gasification, the biomass gasifi-
cation process is divided into two-step: pyrolysis and
gasification [25]. The first step mainly produces tars and
noncondensable gases at 200
C~500
C. The gasification pro-
cess takes place at 500
C~1200
C. In the gasifier, the pyrolysis
and gasification occur simultaneously. The chemical re-
actions which occur in CLG of biomass with Mn2O3 as oxygen
carrier are presented as follows:
In the fuel reactor:
Pyrolysis: CnHmOy 4 syngas (H2, CO, CH4, CO2)
tar char (1)
During gasification process, the products of pyrolysis react
with Mn2O3 (assuming the gasification temperature 1000
C):
CO 3Mn2O3 4 CO2 2Mn3O4 DH 192.2 kJ/mol (2)
CO Mn2O3 4 CO2 2MnO DH 101.9 kJ/mol (3)
H2 3Mn2O3 4 H2O 2Mn3O4 DH 160.0 kJ/mol (4)
H2 Mn2O3 4 H2O 2MnO DH 69.7 kJ/mol (5)
CH4 3Mn2O3 4 2H2 CO 2Mn3O4 DH 65.8 kJ/mol (6)
10348 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 1 0 3 4 6 e1 0 3 5 3

CH4 4Mn2O3 4 2H2O CO2 8MnO DH 85.2 kJ/mol (7)
C 3Mn2O3 4 CO 2Mn3O4
C 2Mn2O3 4 CO2 4MnO
Water gas shift (WGS):
CO H2O 4 H2 CO2
Primary water gas (PWG):
C H2O 4 H2 CO
Boudouard (BD):
DH 24.4 kJ/mol
DH 36.1 kJ/mol
DH 32.2 kJ/mol
DH 135.5 kJ/mol
likely that the reaction toward positive will proceed [26].
Fig. 2 shows the DG of the above reactions at different tempe
ratures.
(8) Except for reactions of (10)e(14), DG of other reactions al-
ways below zero at different temperatures and these reactions
are spontaneous during the gasification process. DG of re-
(9) actions of (11)e(13) have the tendency of decreasing with
temperature increasing. When temperatures are higher than
700
C, DG of reactions of (11)e(13) are below zero. Because
reactions of (11)e(13) are the main reactions which can
convert CO2 and CH4 in the syngas to CO and H2, the optional
temperatures of the CLG process should be higher than 700
C.
(10) DG of reactions of (10) and (14) increases with temperature
increasing and high temperature can inhibit the formation of
CO2 and CH4.
Comparing (2) and (3), DG of reaction of the former is lower
than that of the latter. The same conclusion can be drawn
from the comparing of (4) and (5), (6) and (7), (8) and (9). Mn2O3
(11) follows the principle of stepwise reduction in the CLG of
biomass process and the final reduction product is MnO. The
final gasification result shows that the effect is the mutual
cooperation of the multiple reactions.

C CO2 4 2CO DH 167.7 kJ/mol (12)

Methodology
Methane reforming (MR):
Corn cob, the biomass used in the paper, was performed in the
thermodynamic equilibrium calculation. The proximate and
ultimate analyses of corn cob are listed in Table 1. The main
CH4 H2O 4 3H2 CO DH 225.8 kJ/mol (13) content of elements in the corn cob is C, H and O and other
content of elements (N, S) is negligibly small. In the thermo-
dynamic equilibrium calculation of feedstock gasification, the
Methane formation (MF):
sample composition is usually simplified as C, H and O. The
results and conclusions obtained when only these three ele-
ments were considered small deviation with those when
C 2H2 4 CH4 DH 90.3 kJ/mol (14) other elements were also included [27,28]. In the present
study, the biomass char is represented by a simplified formula
of CH1.56O0.79.
Oxidation (OD):
During thermodynamic equilibrium calculation, the
approach of the Gibbs free energy minimization was used. A
variety of literature is available that utilize the potential of
C O2 4 CO2 DH 395.2 kJ/mol (15) the free energy minimization for the gasification purpose.
Syed and Isam have performed the thermodynamics anal-
ysis of gasification process using air, air-steam and solar-
Partial oxidation (POD):
steam to convert bituminous coal into syngas by the Gibbs
energy minimization approach [29]. Li et al. developed a non-
stoichiometric equilibrium model based on free energy
2C O2 4 2CO DH 227.4 kJ/mol (16) minimization to predict the performance of gasifiers [30].
Baratieri et al. used the minimization of the Gibbs energy
In the above reactions, reactions of (1),(6),(11)e(13) are method to estimate the theoretical yield and the equilibrium
endothermic and the other are exothermic. Only reactions of composition of the reaction products of biomass thermo-
(10) and (13) are homogeneous and the others are heteroge- chemical conversion processes [31]. This method does not
neous. DG is a measure of the thermodynamic driving force involve specific chemical reaction equation and has a high
that makes the reaction proceed, which can be expressed as: degree of thermodynamic consistency. In the present study,
Lagrange multiplier was used to deal with the optimization
problem.
DG DH  TDS (17)
The total Gibbs free energy of a system can be expressed as
If DG < 0, the chemical reaction can proceed spontane- a linear combination of the chemical potential of each
ously. Moreover, the more negative the value of DG, the more component in the system:
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 1 0 3 4 6 e1 0 3 5 3 10349

Fig. 2 e The DG of the reactions at different temperatures.

X
N 6MnO O2 4 2Mn3O4 (23)
G n i mi (18)
i1

At the equilibrium state, G is a minimum, subject to, 4Mn3O4 O2 4 6Mn2O3 (24)

X
N
aij ni Aj ; j 1; 2; ; M (19) The regeneration of the oxygen carrier was proved by ex-
i1 periments [33,34]. The combined oxygen carrier is also bene-
ficial to the gasification and oxidation processes and this will
Lagrange multiplier is introduced to remove the
be investigated in the next step [35e37].
constraints:
In order to get the optimal operating parameters of the CLG
!
X
N X
M X
N process, sensitivity analysis of the results were performed.
L mi n i  lj aij ni  Aj (20) Carbon conversion was defined as the ratio of moles of carbon
i1 ji i1
in syngas to moles of carbon in fuel.
In order to find the equilibrium components, Eq. (20) can be
treated as follows:

XM Results and discussion

vL
mi  aji lj 0 (21)
vni j1 Effect of Mn2O3 to biomass
 
ni Fig. 3 shows the gases yield and carbon conversion under
mi DG0fi RT ln (22)
ntotal different Mn2O3 to biomass (0.05e0.5). The gasification tem-
The value of each species present can be obtained by this perature is 1000
C and at the atmospheric pressure. The
method. During the simulation, the gaseous and solid spe- amount of biomass in the calculation is 1 kmol. It can be seen
cies in the products are listed in Table 2. The biomass and that the amount of CO increases firstly and then decreases
oxygen carrier are mixed perfectly. The process occurs at with Mn2O3/biomass increasing. The amount of H2 is almost
steady state and isothermal conditions. The process is the same when Mn2O3/biomass is smaller than 0.18, and then
adiabatic and the temperature distribution uniform [32]. The begins to decrease with Mn2O3/biomass increasing when
regeneration of the reduced oxygen carrier is essential to Mn2O3/biomass is bigger than 0.18. Because the gasification
the feasibility of CLG technology. The reaction of MnO to temperature is high and CH4 is converted to CO and H2, the
Mn2O3 follows the principle of sequential reaction and is amount of CH4 is always little under different Mn2O3/biomass.
divided into two steps: The total amount of CO and H2 at Mn2O3/biomass of 0.18 is the
biggest. The total dry concentration of CO and H2 is 98.8% at
Mn2O3/biomass of 0.18 and begins to decrease with Mn2O3/
biomass increasing. The lattice oxygen provided by Mn2O3
increases with Mn2O3/biomass increasing and biomass can be
completely converted to CO2 and CH4. The amount of CO2 or
Table 1 e The proximate and ultimate analyses of corn
cob (wt.%, dry basis).
Proximate analysis Ultimate analysis Table 2 e The gaseous and solid species in the products.
a
C H O N S Volatile Fixed Ash Species
carbon
C CO CO2 CH CH2 CH3 CH4 C2H C2H2 C2H3
45.28 5.89 47.79 0.83 0.21 79.68 17.78 2.54
C2H5 C3H2 C3H4 C3H8 C4H8 C3H10 H H2 H2O H2O
a
By difference. H2O2 O O2 C4H4O CHO Mn2O3 Mn3O4 MnO Mn3C Cs
10350 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 1 0 3 4 6 e1 0 3 5 3
Fig. 3 e The gases yield and carbon conversion under
different Mn2O3 to biomass.
H2O increases with Mn2O3/biomass increasing. The reactions
of (2)e(16) except for (14) towards positive are all enhanced
with lattice oxygen increasing and the carbon conversion
increases.
Although the carbon conversion increases with Mn2O3/
biomass increasing, the biomass needs be partially oxidized to
combustible syngas not to CO2 and H2O in the CLG. The
optimal mol ratio of Mn2O3 to biomass should be 0.18.
Effect of temperature
The effect of temperature on the gasification characteristics
is shown in Fig. 4 for Mn2O3/biomass of 0.18 and the at-
mospheric pressure. The amount of biomass in the calcu-
lation is 1 kmol. From Fig. 4(a), it can be seen that the
temperature has a significant effect on biomass gasification
in the CLG. Temperatures are less than 1000
C, the amount
of H2 increases greatly with temperature increasing and
reaches 0.75 kmol at 1000
C and then increases slowly. At
about 400
C, CO is generated and increases greatly with
temperature increasing. At 1000
C, the amount of CO is
0.91 kmol. The amount of CH4 decreases with increasing of
temperature and reduces to zero at 800
C. The changing
trend of H2O with temperature is the same with that of CH4.
Fig. 4 e The effect of temperature on the gasification characteristics.
At about 1000
C, the amount of H2O reduces to zero. With
the increasing of temperature, the amount of CO2 increases
firstly and then decreases, and its yield reaches to the
maximum 0.27 kmol at 550
C. At about 1000
C, the amount
of CO2 reduces to zero.
The reactions of PWG, BD and MR are all endothermic.
According to the Le Chatelier's principle, high temperature
favors the products in endothermic reaction, resulted favor-
ably in the higher production of CO and H2 as temperature
increases. From Fig. 4(b), it can be seen that the total con-
centration of CO and H2 increases with increasing of tem-
perature. At 1000
C, the total dry concentration of CO and H2
is 98.8% and increases slowly with temperature increasing
from 1000
C. The carbon conversion also increases with
temperature increasing. High temperature restrains the for-
mation of carbon deposition on the surface of Mn2O3.
In the CLG process, when temperatures are higher than
1100
C, there is a small amount of Mn in the reduction pro-
duces and MnO is almost the only reduction product. In
addition, the reduced formation of manganese can prevent
the formation of stable chemical structures in hydrocarbons,
mediate the CeH bond, speed up the degradation of hydro-
carbons, and weaken the CeC bond [38,39]. Thereby MnO can
act as catalysts to promote the gasification of tar and char.
Effect of pressure
The effect of operation pressure on the gasification charac-
teristics is shown in Fig. 5 for Mn2O3/biomass of 0.18 and
temperature of 1000
C. As operation temperature increases,
the gas yields and concentrations of CO and H2 decrease, the
gas yields and concentrations of CO2 and H2O increase. The
carbon conversion decreases and carbon deposition on the
surface of Mn2O3 increases with pressure increasing. Based on
Le Chatelier's principle, reactions of (11)e(13),(16) shift to the
left and H2 and CO are consumed. Reaction of (14) shifts to the
right. The gas yield and concentration of CH4 increase slightly
with the increasing of pressure. High operation pressure is not
conducive to the CLG of biomass.
On the contrary, negative pressure of the reduction process
can increase the yields of CO and H2. However, the negative
pressure brings some problems such as equipment
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 1 0 3 4 6 e1 0 3 5 3 10351

Fig. 5 e The effect of operation pressure on the gasification characteristics.

manufacturing and production safety. So the optimal pressure
should be the atmospheric pressure.
Effect of steam
In the CLG process, oxygen carrier provides oxygen source for
char gasification and we can control the operation tempera-
ture to obtain syngas of different H2/CO. For example, when
the temperature is 650
C, the H2/CO in the syngas is 2 and the
syngas can be used to produce methanol. However, when
temperature is 650
C, the yields of H2 and CO are all very low,
and they are 0.482 kmol and 0.240 kmol, respectively.
Comparing the gases yields at 1000
C, the yield of H2 is
reduced by 37.5% and the yield of CO is reduced by 74.9%.
Steam is widely considered as gasifying agents, which can
provide oxygen source for char gasification facilitating the
carbon converted into carbonaceous gas. When steam is used
in the CLG of biomass process, the reactions of (10),(11),(13) are
facilitated. The H2/CO can be changed by using steam as
gasifying agent in the CLG.

Fig. 6 e The effect of steam on the gasification characteristics.

10352 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 1 ( 2 0 1 6 ) 1 0 3 4 6 e1 0 3 5 3

Acknowledgments

This research was financially supported by National Natural

Science Fund of China (51274066, 51576035) and National
High-tech R&D Program of China (2013BAA03B03).

Nomenclature

DG Gibbs free energy change of reaction, J/mol or kJ/mol

DH enthalpy change of reaction, J/mol or kJ/mol
DS entropy change of reaction, J/mol or kJ/mol
T reaction temperature,
C
R universal gas constant, J mol1K1
G total Gibbs free energy of a system, J/mol or kJ/mol
n specie present in the system
N total number of specie present in the system
Fig. 7 e The changes of the H2/CO with the amount of m chemical potential
steam. a number of atoms in each molecule
A total number of atomic masses of the element
M the total number of atoms present in the system
l Lagrange multiplier

Fig. 6 shows the effect of steam on the gasification Subscript

characteristics. The increase of steam facilitates the water i number of ith specie present in the system
gas shift reaction (10) proceeding toward the right. The H2 j number of jth element in molecular formula of
yield increases and CO yield decreases as the steam/Mn2O3 species
increases. Although the yield of CO2 also increases with the f formation in the system
steam/Mn2O3 increasing, the yield of CO2 is only 31.1% of
yield of H2 at 1000
C. The increase of steam also facilitates Abbreviations
the primary water gas reaction (11) proceeding toward the FR fuel reactor
right. The carbon conversion increases with the steam/ AR air reactor
Mn2O3 increasing. When the amount of steam/Mn2O3 is BD boudouard reaction
bigger than 1, the carbon conversion can reach 100% at MF methane formation reaction
1000
C. Fig. 7 shows the changes of the H2/CO with the MR methane reforming reaction
amount of steam. The H2/CO increases with the amount of OD oxidation reaction
steam increasing. The H2/CO in the syngas can be adjusted PWG primary water gas reaction
by using the steam as gasifying agent in the CLG. At 800
C, WGS water gas shift reaction
the H2/CO is from 1.06 to 2.49 as the steam/Mn2O3 is from POD partial oxidation reaction
0.5 to 9.

references

Conclusions
Thermodynamic analysis of syngas generation from biomass
using CLG method was carried out with the method of Gibbs
free energy minimization. The mechanism of CLG of biomass
was also analyzed. Mn2O3 was used as oxygen carrier in this
study. When the Mn2O3/corn cob is 0.18, the CO and H2 yields
in the syngas are maximum. Temperature has a significant
effect on biomass gasification and the yields of H2 and CO
increase with temperature increasing. Pressure has a negative
effect on the gas production, and atmospheric pressure was
proposed as operating condition. The optimal thermodynamic
conditions were determined as operation temperature of
1000
C and atmospheric pressure. Under these conditions,
the total dry concentration of CO and H2 is 98.8%. Steam can
be used in the CLG to modify the H2/CO in the syngas. Besides
the H2/CO, the carbon conversion increases with the steam/
Mn2O3 increasing.
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