02638762/06/$30.00+0.

00
# 2006 Institution of Chemical Engineers
Trans IChemE, Part A, September 2006
Chemical Engineering Research and Design, 84(A9): 795 806

www.icheme.org/cherd
doi: 10.1205/cherd05020

THERMAL ANALYSIS OF CHEMICAL-LOOPING

COMBUSTION
E. JERNDAL1! , T. MATTISSON2 and A. LYNGFELT2
1

Department of Chemical and Biological Engineering, Chalmers University of Technology, Goteborg, Sweden
2
Department of Energy and Environment, Chalmers University of Technology, Goteborg, Sweden

n chemical-looping combustion, a gaseous fuel is burnt with inherent separation of the

greenhouse gas CO2. Oxygen is transferred from the combustion air to the fuel by an
oxygen carrier, which is usually a metal oxide, and therefore direct contact between
the fuel and the combustion air is avoided. Thus, the products of combustion, i.e., CO2 and
H2O, are not mixed with the rest of the flue gases and after condensation almost pure CO2
is obtained, without any energy lost for the separation. A thermal analysis of the process
using a large number of possible oxygen carriers was performed by simulating reactions
using the HSC Chemistry 5.0 software. Three fuels were used in the investigation, CH4,
CO and H2. Based on the ability of the oxygen carriers to convert the fuel to the combustion
products CO2 and H2O, stability in air and the melting temperatures of the solid material some
metal oxides based on Ni, Cu, Fe, Mn, Co, W and sulphates of Ba and Sr showed good thermodynamic properties and could be feasible oxygen carriers. Only a few of these possible
oxygen carrier systems, based on Cu, Fe and Mn, showed complete conversion of the fuel
gas, but still the other systems had limited equilibrium restrictions, with only small and acceptable amounts of unreacted CO and H2 released from the fuel reactor. The promising systems
were investigated further with respect to temperature changes in the fuel reactor as well as
possible carbon, sulphide and sulphate formation in the fuel reactor. For some systems the
reactions in the fuel reactor were endothermic, resulting in a temperature drop in the fuel reactor. However, this drop can be limited by applying a sufficient circulation of particles from the
air reactor to the fuel reactor. When Ni or Co is used as oxygen carrier the fuel may need to be
desulphurized prior to combustion to avoid formation of solid or liquid sulphides or sulphates.
On the other hand, to prevent decomposition of the sulphates BaSO4 and SrSO4, in the fuel
reactor, to sulphur-containing gases and metal oxides, it is necessary that some sulphur is
present in the fuel and that high temperatures are avoided. Formation of carbon should not
be a problem as long as the process is run under conditions of high fuel conversion.
Keywords: chemical-looping combustion; CO2 capture; oxygen carriers; thermodynamics.

INTRODUCTION

the other fuel gases, i.e., N2 and unused O2 (Mattisson

et al., 2001).

CO2 is the primary greenhouse gas and it is generally

accepted that CO2 formed by combustion of fossil fuels
contribute to an increased global average temperature.
One way to achieve combustion without CO2 emissions
and still use fossil fuels is separation and sequestration of
CO2 (Kaarstad, 1992). Separation can be made by a
number of different techniques, but most of them have
the disadvantage of requiring a large amount of energy
(Mattisson et al., 2001).
With chemical-looping combustion, no energy is needed
for the separation since CO2 is inherently separated from

Chemical-Looping Combustion
Chemical-looping combustion is a method where a gaseous fuel, such as natural gas or synthesis gas, is burnt
with oxygen transported from the combustion air to the
fuel by an oxygen carrier. This gives the advantage of an
exiting gas stream containing only CO2 and H2O. After
H2O is condensed, almost pure CO2 is obtained for storage.
The chemical-looping combustion system consists of
two separate reactors, an air reactor and a fuel reactor.
An oxygen carrier, which is usually a metal oxide, transports oxygen from the air reactor to the fuel reactor, see
Figure 1. The oxygen carrier is circulating between the
reactors and is oxidized in the air reactor, according to

!
Correspondence to: E. Jerndal, Department of Chemical and Biological
Engineering, Chalmers University of Technology, SE 41296 Goteborg,
Sweden. E-mail: erik.jerndal@chalmers.se

795

796

JERNDAL et al.

the overall reaction (1), and reduced back to its initial state
by the fuel, according to the overall reaction (2).
2n mMex Oy%1 n 1=2mO2 %!

2n mMex Oy
2n mMex Oy Cn H2m %! (2n m)Mex Oy%1
mH2 O nCO2

(1)
(2)

The total amount of heat evolved from reaction (1) and

(2) is equal to the heat released from conventional combustion, where the oxygen is in direct contact with the fuel
(Lyngfelt et al., 2001).
The process has been successfully demonstrated using
gaseous fuel in several prototype units, for instance in a
10-kW unit at Chalmers University of Technology, using
oxygen carriers based on both Ni and Fe (Lyngfelt and
Thunman, 2004).
Oxygen Carriers
The rate of reaction and the oxygen transfer capacity of
the oxygen carrier are important for the amount of bed
material in the reactors and the needed recirculation flow
of oxygen carriers (Lyngfelt et al., 2001). Thus, it is important to find an oxygen carrier with sufficient reduction and
oxidation rates. Also, it has been established that some
metal oxide/metal systems are unable to fully convert the
fuel to carbon dioxide and water, resulting in formation of
the combustible gases hydrogen and carbon monoxide
(Cho, 2005; Mattisson et al., 2005). If the concentrations
of these combustible gases are high, the metal oxides are
not suitable as oxygen carriers, since a large part of the
heating value of the fuel would be lost in the exit stream
from the fuel reactor. Further, the particle needs to be resistant to attrition and fragmentation as well as to deactivation
by carbon and sulphur species in the reactors. It is also an
advantage if the oxygen carrier is cheap and environmentally
sound (Cho et al., 2002). In addition to the above mentioned
criteria, the following aspects need consideration:
. melting temperatures of the compounds used;
. oxygen ratios, which is the maximum transported mass
of oxygen for a given mass flow of metal oxide;
. heat balances of the fuel reactions for the cases where
reaction (2) is endothermic;
. side reactions in the fuel reactor where carbon and
different sulphur-containing compounds may form.
A number of papers have been presented where some of
these aspects are studied for different oxygen carriers. Overviews of the previous work done on different oxides of transition state metals as oxygen carrier particles were made by
Cho (2005) and Brandvoll (2005). Most of the work done on
oxygen carriers focuses on oxides of iron, nickel and copper.
Only a limited amount of work has been performed on the
thermodynamic and thermal aspects of the process. Among
those thermodynamic studies, Lyngfelt et al. (2001) have
studied heat balances and temperature alterations for iron
oxides and nickel oxide, Mattisson and Lyngfelt (2001)
have studied the feasibility of using several different metal
oxides based on Ni, Cu, Co, Fe and Mn, but also different
aspects of NiO as oxygen carrier, including formation of
sulphur-containing compounds (Mattisson et al., 2005) and

Kronberger et al. (2005) have simulated energy balances

for the process with oxides of Fe, Cu, Ni and Mn. In
patent applications oxides of silver, tungsten and molybdenum and sulphates of barium and strontium are also
suggested as potential oxygen carriers (Cole, 2003).
Cerium has not been proposed as an oxygen carrier in
chemical-looping combustion but for oxygen storage in
catalysts for car exhaust (Holmgren, 1998).
The purpose of the present work is to make a comprehensive
thermal investigation of different possible oxygen carriers.
THEORY
Gas Yield
In chemical-looping combustion, it is important to be able
to convert a high fraction of the incoming fuel to CO2 and
H2O. The fuels studied here are CH4, H2 and CO. To
gauge the degree of fuel conversion to carbon dioxide and
water, the gas yield was defined as the fraction of the fuel
which is oxidized to CO2 or H2O, and is given by equations
(3)(5) below for the different fuels investigated.
pCO2
( pCH4 pCO2 pCO )
pH 2 O
For H2 : gH2
(pH2 pH2 O )
pCO2
For CO: gCO
(pCO pCO2 )
For CH4 : gCH4

(3)
(4)
(5)

Here, pi is the partial pressure of gaseous species in the

product gas. Since the gas yield does not account for the formation of H2 when CH4 is used as fuel, a gas yield based on
the fuels heating values was also calculated as

gheat

pCH4 ,in HCH4 % (pH2 HH2 pCO HCO pCH4 HCH4 )

pCH4 , in HCH4
(6)

The results presented for CH4 are highly relevant for

common gaseous fuels such as natural gas and refinery gas
because of their high fraction of CH4 H2 and CO are relevant
when synthesis gas is used in the process.
Air Ratio
The air ratio, l, is given by the volume fraction of
oxygen in the air leaving the air reactor, xO2,ex, and is
defined as

0:21(1 % xO2 , ex )
0:21 % xO2 , ex

(7)

The conversion of the gas in the air reactor is simply

gox

1
l

(8)
Oxygen Ratio, R0

The oxygen ratio, R0, shows the maximum mass flow of

oxygen that can be transferred between the air and the fuel
reactor for a given mass flow of circulating oxygen carrier

Trans IChemE, Part A, Chemical Engineering Research and Design, 2006, 84(A9): 795 806

THERMAL ANALYSIS OF CHEMICAL-LOOPING COMBUSTION

particles, and is defined as
R0

(mox % mred )
mox

(9)

Since the overall heat released in the two reactors is

equal to that released in conventional combustion, the
heat released or consumed in the fuel reactor may be
obtained by comparing the heat released in the air reactor
to that released in conventional combustion. The temperature difference in the fuel reactor depends on the oxygen
carrier mass flow. A high mass flow gives a small mass
difference in the mass conversion between the two reactors
and results in a small temperature difference between the
reactors. Here, the mass conversion, v, of the oxygen
carrier was defined as

m
mox

(10)

The temperature change in the fuel reactor can be calculated from a heat and mass balance over the fuel reactor,
i.e., the enthalpy of the incoming particles and fuel to the
reactor is equal to the enthalpy of the exiting particles
and gas, which can be expressed as
X
X
ni ' hi Hprod
yi ' hi
(11)
Hreac

where ni is the moles of reactants, yi the moles of products

and hi is the enthalpy of component i calculated from
hi h0i

cpi (T)dt

(12)

298

where h0i is the heat of formation of substance i at 298 K.

Thus, from a molar balance of the incoming and exiting
gas and solids to the reactor the temperature difference can
be calculated for different changes in solid conversion. A
mathematical correlation was adopted for fitting experimental heat capacities. The Kelley equation was used
throughout the calculations in the following form
cpi A B ' 10%3 ' T C ' 105 ' T %2 D ' 10%6 ' T 2

(13)

Carbon Deposition
In the fuel reactor, solid carbon may form on the particles under certain conditions through methane decomposition:
CH4 ! C 2H2 ;

DH 90:29 kJ at 10008C

(14)

or through the Boudouard reaction:

2CO ! C CO2 ;

is defined as the actual amount of O, added with the

oxide and/or with steam, over the stoichiometric amount
needed for full conversion of the fuel:

Heat Balance

DH %167:74 kJ at 10008C
(15)

Carbon formation in the fuel reactor depends on temperature, pressure and the amount of oxygen added to the
reactor with the metal oxide. The oxygen added ratio, 6,

797

nO, added
nO, stoich

(16)

Although steam will likely not be added to the fuel reactor of a real system, the addition of steam is often performed in laboratory experiments in order to suppress
carbon formation. The reason for this is that laboratory
experiments are usually performed with incomplete conversion of the fuel in order to study the reaction rates,
especially at the end of the cycle when the reactivity is
low. Thus, laboratory tests are often associated with thermodynamic conditions that are significantly more favourable for carbon formation, as compared to industrial
processes, where full conversion of the fuel is desired.
Formation of Metal Sulphides and Sulphates
The fuel could contain compounds including sulphur,
such as H2S or COS. The fate of these species in the fuel
reactor may be different and depend upon the oxygen
carrier used. They may be oxidized in the fuel reactor forming SO2 or SO3, or they may react with the metal/metal
oxide to form sulphides or sulphates. Formation of solid
sulphur compounds depends on sulphur compound concentrations as well as temperature and pressure.
METHOD
To simulate chemical reactions and perform equilibrium
calculations, the HSC Chemistry 5.0 software was used.
The equilibrium composition is calculated using the
Gibbs energy minimization method and a routine described
by White et al. (1958). The program finds the most stable
phase combination and seeks the phase composition
where the Gibbs energy of the system reaches its minimum
at a fixed mass balance, constant pressure and temperature
(HSC Chemistryw, 2002).
One assumption made is that all substances in the solid
phase are in pure form and not mixtures. Further, it is
assumed that CH4 can be converted to the gaseous components CO2, CO, H2O and H2 in the fuel reactor. H2 can
be converted to H2O and CO to CO2. O2 is also included
in the equilibrium calculations.
Most of the systems investigated were based on metal
oxides of the metals Ni, Cu, Fe, Cd, Mn, Co, Zn, Ce, W,
Mo and Ag. Furthermore, two systems based on the transition between metal sulphate to metal sulphide were investigated, i.e., Ba and Sr.
RESULTS
Reduction
Table 1 shows the gas yields for all the investigated
metal oxide/reduced metal oxide systems at 10008C and
8008C at atmospheric pressure. Of the 27 systems studied,
only eight have complete fuel conversion, although roughly
half of the systems have conversion above 0.98. Investigations showed that all oxides of silver will decompose

Trans IChemE, Part A, Chemical Engineering Research and Design, 2006, 84(A9): 795 806

798

JERNDAL et al.
Table 1. Gas yields for all the investigated oxide systems. Systems with yields below 0.92 are indicated with ! .

gheat

NiO/Ni
CuO/Cu
Cu2O/Cu
Fe2O3/Fe3O4
Fe3O4/Fe0.945O!
Fe0.945O/Fe!
CdO/Cd
Mn2O3/Mn3O4
Mn3O4/MnO
MnO/Mn!
Co3O4/CoO
CoO/Co
ZnO/Zn!
CeO2/CeO1.83!
CeO1.83/CeO1.72!
CeO1.72/Ce2O3!
Ce2O3/Ce!
WO3/WO2.96
WO2.96/WO2.722
WO2.722/WO2!
WO2/W!
MoO3/MoO2.889
MoO2.889/MoO2.75
MoO2.75/MoO2
MoO2/MoO!
BaSO4/BaS
SrSO4/SrS

gCH4

gCO

gH2

8008C

10008C

8008C

10008C

8008C

10008C

8008C

10008C

0.9949
1.0000
1.0000
1.0000
0.5529
0.3884
0.9881
1.0000
1.0000
0.0020
1.0000
0.9695
0.0306
0.4595
0.0556
0.0131
0.0000
0.9998
0.9957
0.5760
0.3075
1.0000
1.0000
1.0000
0.3077
0.9824
0.9877

0.9917
1.0000
0.9999
1.0000
0.7579
0.3936
0.9877
1.0000
0.9999
0.0206
1.0000
0.9496
0.0624
0.7658
0.1145
0.0507
0.0000
0.9989
0.9899
0.5821
0.4143
0.9747
1.0000
0.9999
0.4107
0.9749
0.9814

0.9949
1.0000
1.0000
1.0000
0.5406
0.3676
0.9880
1.0000
1.0000
0.0000
1.0000
0.9691
0.0022
0.4426
0.0167
0.0001
0.0000
0.9998
0.9957
0.5647
0.2819
1.0000
1.0000
1.0000
0.2821
0.9822
0.9875

0.9883
1.0000
0.9999
1.0000
0.6820
0.2898
0.9827
1.0000
0.9999
0.0000
1.0000
0.9299
0.0124
0.6917
0.0516
0.0040
0.0000
0.9984
0.9858
0.4804
0.3095
0.9646
1.0000
0.9999
0.3060
0.9648
0.9738

0.9949
1.0000
1.0000
1.0000
0.5408
0.3681
0.9880
1.0000
1.0000
0.0000
1.0000
0.9691
0.0035
0.4429
0.0190
0.0004
0.0000
0.9998
0.9957
0.5649
0.2827
1.0000
1.0000
1.0000
0.2829
0.9822
0.9875

0.9883
1.0000
0.9999
1.0000
0.6820
0.2898
0.9827
1.0000
0.9999
0.0000
1.0000
0.9299
0.0124
0.6917
0.0517
0.0040
0.0000
0.9984
0.9858
0.4804
0.3095
0.9646
1.0000
0.9999
0.3060
0.9648
0.9738

0.9946
1.0000
1.0000
1.0000
0.5264
0.3548
0.9873
1.0000
1.0000
0.0000
1.0000
0.9674
0.0033
0.4288
0.0179
0.0003
0.0000
0.9998
0.9954
0.5506
0.2711
1.0000
1.0000
1.0000
0.2713
0.9812
0.9868

0.9931
1.0000
0.9999
1.0000
0.7841
0.4086
0.9897
1.0000
0.9999
0.0000
1.0000
0.9574
0.0209
0.7916
0.0844
0.0068
0.0000
0.9991
0.9916
0.6102
0.4316
0.9788
1.0000
1.0000
0.4275
0.9789
0.9844

to silver at all temperatures and pressures studied and therefore silver oxides can not be used in the process. Depending
upon the oxygen carrier system, the yield can both increase
and decrease as the temperature increases. For the systems
with high fuel conversions, i.e., higher than 0.92, the higher
temperature gave a lower gas yield, with the cadmium
system using H2 as the only exception. For systems with
low fuel conversion the higher temperature increased the
yield, since there is unreacted fuel gas leaving these
systems. CH4 and CO reacting with Fe0.945O and WO2.722
were the only exceptions.
The effect of an increased pressure was also investigated.
As there is no gas expansion during the reaction of the
metal oxide with CO and H2, the total pressure will not
have any effect on gas yield. However, for methane there
is a gas expansion, see reaction (2), and thus systems
which do not have complete conversion of the fuel will
be affected adversely by the total pressure. For the
oxygen carriers which have gas yield above 0.92 at atmospheric pressure, the methane conversion was complete but
there was incomplete conversion of H2 and CO. However,
for the systems where the gas yield for methane is below
0.92, there was methane released from the outlet and a
clear negative effect of pressure was seen. All oxide systems with so poor conversion will later be excluded from
further consideration, see oxygen ratio section below.

MoO3, BaSO4 and SrSO4, respectively, in the air reactor

at all temperatures and oxygen partial pressures realistic
for the process. However, as shown in Figure 2, CuO,
Mn2O3 and Co3O4 decompose to Cu2O, Mn3O4 and
CoO respectively, already at relatively low temperatures.
The temperature of decomposition is dependent on the
partial pressure of oxygen. According to Figure 2, the
more oxidized form in the system is favoured at low
temperatures and high oxygen partial pressures. Thus, at
higher temperatures a higher partial pressure of oxygen
would be needed in the air reactor to prevent decomposition. In the air reactor, at atmospheric pressure, the
oxygen partial pressure in incoming combustion air is
0.21 and this is then lowered as oxygen is consumed. It
is essential that the oxygen carrier is able to reduce this
pressure and a limit has been set at 0.04, which corresponds to an air ratio of 1.19 and a gas conversion of
0.84 for an atmospheric process.

Oxidation
Calculations showed that several of the reduced metal
oxides or metals could not be oxidized back to their original form. Ni, Fe, Cd, Zn, Ce, W, Mo, BaS and SrS will
be oxidized to NiO, Fe2O3, CdO, ZnO, CeO2, WO3,

Figure 1. Chemical-looping combustion.

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THERMAL ANALYSIS OF CHEMICAL-LOOPING COMBUSTION

799

Table 2. Melting temperatures for the metals and

metal oxides.
Melting point (8C)

Figure 2. The partial pressure of oxygen at which the metal oxides

decompose to their more reduced form as a function of temperature.

If pO2 is 0.04, the temperature where Cu2O is formed is

9448C. A similar behaviour can be seen for the systems
based on manganese and cobalt. If pO2 is 0.04, the temperature where Mn3O4 is formed is 7388C. Formation temperature of CoO is 8458C at the oxygen partial pressure 0.04.
Thus, systems including Mn2O3 or Co3O4 are probably
not realistic at atmospheric conditions. Under pressurized
conditions the partial pressure of O2 is higher and thus
the decomposition temperature would be higher. It should
be noted though that a high turbine inlet temperature is
desired if the process is to be used in a pressurized combined gas and steam turbine cycle.
Melting Points
The most suitable design for a chemical-looping combustion process is interconnected fluidized beds (Lyngfelt et al.,
2001). Here, it is important to avoid melting and agglomeration of the circulating particles. It is well known that
materials become soft at temperatures approaching their
melting points. Thus, it is advantageous to operate the process at temperatures far from this temperature. Table 2
show the melting temperatures of the investigated metals
and metal oxides. Since the process needs a temperature
between 6008C and 12008C, some metals and metal oxides
suggested are unsuitable in chemical-looping combustion.
Cd, Zn, Ce and MoO3 have melting temperatures that are
too low for being used as oxygen carriers.
Cu has a relatively low melting temperature of 10858C
and therefore a chemical-looping combustion process
using copper may need to be conducted at temperatures
below 9008C. Cho et al. (2004) noticed agglomeration of
freeze granulated Cu-based oxygen carriers, but GarcaLabiano et al. (2004a) suggested that agglomeration
problems could be avoided by using Cu-based particles
prepared by impregnation.
Oxygen Ratio, R0
A high oxygen ratio is an advantage for the process since
more oxygen can be transported per mass unit of added
material. The pairs that are not fully reduced to their metallic form in the fuel reactor like Fe2O3/Fe3O4, Mn3O4/
MnO and WO3/WO2.722 have the disadvantage of showing
low oxygen ratios. Table 3 shows the oxygen ratio of the
investigated oxygen carriers. It should be noted that the

Ni
NiO
Cu
Cu2O
CuO
Fe
Fe0.945O
Fe3O4
Fe2O3
Cd
CdO
Mn
MnO
Mn3O4
Mn2O3
Co
CoO
Co3O4
Zn
ZnO
Ce
Ce2O3
CeO1.72
CeO1.83
CeO2
W
WO2
WO2.722
WO2.96
WO3
Mo
MoO2
MoO2.75
MoO2.889
MoO3
BaS
BaSO4
SrS
SrSO4

1455
1955
1085
1235
1446
1538

1597
1565
321

1246
1842
1562
1347
1495
1830

420
1975
798
2230

2400
3407
1724

1472
2623
1927

802
2230
1580
2227
1607

oxygen ratio will decrease when an inert material is used

together with the active oxygen carriers.
In the analysis of the heat balance, carbon deposition and
fate of sulphur species given below, only systems showing
sufficient gas yields, having oxides forming in the air reactor and having sufficiently high melting temperatures will
be investigated. Thus, the oxide systems indicated with !
in Table 1 are excluded because of their low ability to oxidize the fuel and Cd is excluded because of its low melting
Table 3. Oxygen ratio, R0, for the
different pairs of metals/metal
oxides.
R0
NiO/Ni
CuO/Cu
Cu2O/Cu
Fe2O3/Fe3O4
Mn2O3/MnO
Mn3O4/MnO
Co3O4/Co
CoO/Co
WO3/WO2.722
BaSO4/BaS
SrSO4/SrS

Trans IChemE, Part A, Chemical Engineering Research and Design, 2006, 84(A9): 795 806

0.214
0.201
0.112
0.033
0.101
0.070
0.266
0.214
0.019
0.274
0.348

800

JERNDAL et al.
Table 4. Reaction enthalpies at 10008C.
(DH(kJ mol21O2)

O2 1/2CH4 ! 1/2CO2 H2O

O2 2H2 ! 2H2O
O2 2CO ! 2CO2
O2 2Ni ! 2NiO
O2 2Cu ! 2CuO
O2 4Cu ! 2Cu2O
O2 4Fe3O4 ! 6Fe2O3
O2 4MnO ! 2Mn2O3
O2 6MnO ! 2Mn3O4
O2 3/2Co ! 1/2Co3O4
O2 2Co ! 2CoO
O2 0.278/2WO2.722 ! 0.278/2WO3
O2 1/2BaS ! 1/2BaSO4
O2 1/2SrS ! 1/2SrSO4

2401.7
2498.5
2562.8
2468.5
2295.9
2331.7
2478.8
2359.1
2449.4
2446.8
2466.9
2419.6
2481.7
2475.7

temperature. Mo is excluded because MoO3 has too low

melting temperature. Ag is excluded because it can not
be oxidized in the air reactor.

DH/DHdir

comb CH4

DH/DHdir

comb H2

DH/DHdir

comb CO

1.00
1.00
1.17
0.74
0.83
1.19
0.89
1.12
1.11
1.16
1.04
1.20
1.18

0.94
0.59
0.67
0.96
0.72
0.90
0.90
0.94
0.84
0.97
0.95

1.00
0.83
0.53
0.59
0.85
0.64
0.80
0.79
0.83
0.75
0.86
0.85

The reaction enthalpies for the reaction between the various metals or reduced metal oxides and oxygen at 10008C
can be found in Table 4. The ratio of the reaction enthalpy
of the oxidation to that of conventional combustion for the
three fuels is also shown. Because the overall heat released
from chemical-looping combustion is the same as that from
normal combustion, it is possible to determine whether the
reactions in the fuel reactor are endothermic or exothermic
from this ratio. Thus, a ratio above 1 means that the reaction in the fuel reactor is endothermic and a ratio below
1 indicate an exothermic fuel reactor reaction. Thus, it is
seen in Table 4 that the reaction in the fuel reactor is
always exothermic when H2 or CO is used.
As seen from Table 4, some of the reactions are
endothermic when methane is used. This means that there
will be a temperature decrease in the fuel reactor. It is
important that the temperature drop is not too large, since
this will mean that the reaction between the fuel and the
oxygen carrier will be slower or even stop. The temperature
drop was calculated as a function of v for the endothermic
reactions, and the results are presented in Figures 3 5. If

the reaction is exothermic, heat will need to be removed

from the reactors to avoid excess temperatures. A high
reactor temperature should be avoided because it might
lead to sintering or deactivation of the oxygen carrier.
The exothermic nature of the reaction in the air reactor
may result in temperature gradients within the particles.
This temperature increase depends on several factors such
as size, porosity, composition, reactivity with the reacting
gases and diffusion factors. However, Garca-Labiano
et al. (2004b) showed that under conditions present in a
chemical-looping combustion system and with particle
sizes normally used, the temperature increase was only
about 158C, at most, in the particles. Their conclusion
was that when using small particles, these can be considered to be isothermal for most reactions.
In the calculations of the temperature decrease in Figures
35, the following assumptions were made. Temperature in
the air reactor has been set to 10008C and the incoming
methane is assumed to be preheated to 4008C. Further, the
process is thought to be fully adiabatic, meaning that no
heat is gained to or lost from the fuel reactor. Because the
inlet temperature of methane is 4008C, some of the exothermic reactions may also give a fuel reactor temperature
slightly below 10008C after reaction. This fuel reactor temperature decrease is small and should have a negligible effect
on the process. The temperature in the fuel reactor would, in
some cases, be very low if the metal oxide/sulphate is

Figure 3. Temperature change in the fuel reactor for cobalt and nickel
oxides.

Figure 4. Temperature change in the fuel reactor for manganese, iron and
tungsten oxides.

Heat Balance

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THERMAL ANALYSIS OF CHEMICAL-LOOPING COMBUSTION

Figure 5. Temperature change in the fuel reactor for strontium- and barium
sulphide/sulphate.

entirely reduced. This is of course not viable, since these non

catalytic gas solid reactions require a relatively high temperature to proceed. Therefore, temperature decreases to
below 6008C are not shown. The implication of this is that
the change in solid conversion, Dv, between the fuel and
air reactor should not be too high. This is accomplished in
practice by maintaining a sufficient circulation of solids.
Carbon Deposition
Under certain conditions solid carbon deposition on the
oxygen carrier particles may occur if a carbon-containing
fuel is used. This could have an adverse effect on the process. Formed carbon can be transported back to the air reactor causing CO2 formation, resulting in lower separation
efficiency of CO2 (Cho et al., 2005) Parameters influencing
carbon formation are temperature, pressure and amount of
added oxygen. Normally, low temperatures and small
amounts of added oxygen benefit the formation as seen in
Figure 6. Here, the oxygen added ratio, equation (16),
below which carbon formation is thermodynamically feasible, is shown as a function of the temperature. It is
assumed that the fuel is CH4 and that all of the oxygen is
added to the fuel reactor with the metal oxide. At low temperatures an increased pressure will favour carbon formation
while at high temperatures an increased pressure counteracts carbon formation. This is due to the fact that carbon

Figure 6. The oxygen added ratio, 6, needed to avoid carbon formation

when CH4 is used as fuel.

801

is formed by two reactions, the Boudouard reaction

dominating at low temperatures and the methane decomposition reaction dominating at higher temperatures. In
methane decomposition, less carbon is formed at higher
pressures while in the Boudouard reaction more carbon is
formed at higher pressures. At temperatures above approximately 9508C, no carbon formation should be expected as
long as more than one fourth of the oxygen needed for
complete fuel conversion is supplied.
When CO is used as fuel, the Boudouard reaction is the
only reaction accounting for carbon formation. Therefore,
formation is favoured at low temperatures, small amounts
of added oxygen and high pressures. Figure 7 shows that
at low temperatures more oxygen has to be added to
avoid carbon formation while at high temperatures less
oxygen has to be added when comparing with CH4 as fuel.
Providing oxygen to the fuel by water addition could be
interesting when examining oxygen carriers experimentally. Results of water addition could also be of interest if
the process is to be used in chemical-looping reforming,
where synthesis gas is produced from light hydrocarbons
(Ryden and Lyngfelt, 2004). As seen in Figure 8, the
same amount of oxygen has to be added to avoid carbon
formation if it comes from H2O as if it comes from the
metal oxide at temperatures above approximately 9508C.
Since 6 here is about 0.25, at least 1 mole of H2O has to
be added to avoid carbon formation to every mole of
CH4. At lower temperatures, less oxygen has to be added
to avoid carbon formation when it comes from H2O compared to if the oxygen is added by a metal oxide. With
H2O as oxygen source an increased pressure will counteract
carbon formation indicating that methane decomposition is
the dominating reaction.
Fate of Sulphur Species
Gas phase reactions
Refinery gas and natural gas may contain small amounts
of sulphur-containing species like H2S and COS. The most
likely of these to occur in significant amounts is H2S and
thus its reactions were investigated. H2S in the fuel will
be partially oxidized to SO2 by oxidants such as H2O,
CO2 or the metal oxide when the fuel is burnt. Formation
of COS, SO3 and S2 is generally insignificant.
For CuO/Cu, Cu2O/Cu, Fe2O3/Fe3O4, Mn2O3/MnO
and Mn3O4/MnO, H2S in the fuel is converted to SO2 to

Figure 7. The oxygen added ratio, 6, needed to avoid carbon formation

with CO as fuel.

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802

JERNDAL et al.

Figure 8. The oxygen added ratio, 6, needed to avoid carbon formation,

when H2O is added as oxygen source to CH4.

somewhere between 99.3 and 100%, for every temperature

studied between 6008C and 12008C. Calculations including
formation of COS, SO3 and S2 showed that these concentrations were very low for all these metal/metal oxide
pairs, with concentrations of SO2 H2S being at least
151 times larger than COS SO3 S2 for all systems independent of pressure and temperature.
For the NiO/Ni and WO3/WO2.722 systems the
conversion of H2S was somewhat lower, as seen in Figures
9 and 10. For NiO/Ni calculations show that the concentration of SO2 H2S is at least 52 times larger than the
concentration of COS SO3 S2 and for WO3/WO2.722
the concentration of SO2 H2S is at least 77 times larger
than the concentration of COS SO3 S2. As seen from
Figures 9 11, the oxidation of H2S is enhanced at high
temperatures and low pressures.
For the two systems including cobalt oxides, i.e., Co3O4/
Co and CoO/Co, H2S is partially oxidized to SO2 according to Figure 11. The figure shows that the Co3O4/Co
system converts H2S to a much greater extent than the
CoO/Co system. For Co3O4/Co, the conversion is almost
complete at all pressures and temperatures above 8008C.
In contrast, CoO/Co never gives a full conversion of
H2S. The concentrations of COS, SO3 and S2 are much
lower in the system with Co3O4/Co than in that with
CoO/Co. Here, the concentration of SO2 H2S is at least
191 times larger than the concentration of COS SO3
S2, while it is at least 23 times larger for CoO/Co.

Figure 9. The degree of conversion from H2S in the fuel to the oxidized
form, SO2, for NiO/Ni.

Figure 10. The degree of conversion from H2S in the fuel to SO2 for
WO3/WO2.722.

Figure 11. The degree of conversion from H2S in the fuel to SO2 for
Co3O4/Co and CoO/Co.

For systems containing BaSO4/BaS and SrSO4/SrS, SO2

may form by decomposition of the sulphate, predominantly
at high temperatures and low total pressures. Figures 12 and
13 show the partial pressure of sulphur-containing gases as
a function of the temperature at which the sulphates start to
decompose. Decomposition results in formation of sulphurcontaining gases and the metal oxides BaO and SrO,
respectively. Thus, to avoid loss of oxygen carrier because
of decomposition, the sulphur content of the added fuel
must not be too low and the temperature should not be
too high.

Figure 12. Decomposition temperature of BaSO4 at different concentrations of sulphur-containing gases.

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THERMAL ANALYSIS OF CHEMICAL-LOOPING COMBUSTION

803

Figure 13. Decomposition temperature of SrSO4 at different concentrations of sulphur-containing gases.

Figure 15. Concentration of sulphur-containing gases needed in the gas

phase for formation of Cu2S in the Cu2O/Cu system.

Solid phase reactions

H2S and SO2 could react with the oxygen carrier, forming sulphides and sulphates. The formation of metal sulphides or sulphates on the oxygen carrier particles could
result in deactivation of the particles. Thus, calculations
were performed to see if this was possible and, if so, at
what partial pressure of sulphur-containing gases. In summary, of all of the investigated systems, only Ni and Co
formed sulphides at SO2 and H2S partial pressures and
temperatures which may be encountered in a chemicallooping combustion fuel reactor. In the system with
Fe2O3/Fe3O4, there is no risk of sulphide or sulphate formation at any concentration of sulphur-containing gases
at any temperature. Below, a more detailed analysis of
the Mn, Ni, Cu, Co and W based systems is given. As
seen in Figures 14 17, formation might take place at
high sulphur-containing gas concentrations. The sulphur
concentration needed for formation of these compounds
increases with temperature and decreases with total
pressure. The fact that formation is enhanced at higher
pressures is explained by the higher partial pressure of
H2S and SO2 when the total pressure is increased.
During the oxidation of CH4, there is a volume expansion by approximately a factor 3 which reduces the concentration of sulphur species. This means that the H2S
concentration in the fuel can be approximately three
times that shown in the figures below before sulphide or
sulphate formation is expected.

With nickel oxide as oxygen carrier, there is a significant

risk of sulphide formation at low temperatures as seen in
Figure 14. There are several different nickel sulphides,
and calculations showed that Ni3S2 is the phase which is
most likely to form.
In the system containing CuO/Cu, the concentration of
sulphur-containing gases, i.e., H2S, SO2, SO3, COS and
S2, needed for formation of Cu2SO4 is at least 2.2 vol%
at 15 bar and 33 vol% at 1 bar. Fractions that high are
not likely to be found in the fuel and therefore the risk of
formation is low. Figure 15 shows that when Cu2O is
used as oxygen carrier, the sulphide first formed is Cu2S.
Formation needs lower concentration of sulphur-containing
gases than formation of Cu2SO4 when CuO is used as
oxygen carrier, but is still quite unlikely. At 1 bar, Cu2S
forms at a sulphur concentration of at least 10 vol%
which is just above the range shown in Figure 15.
For Mn3O4/MnO, there is no formation of sulphides. For
formation of MnSO4, a sulphur concentration of at least
3.1 vol% at 15 bar and 46 vol% at 1 bar is needed at
every temperature investigated. Concentrations that high
are unlikely to occur and thus sulphate formation should
not be a problem. Figure 16 shows that the risk of
MnSO4 formation is somewhat greater for the Mn2O3/
MnO system.
With respect to cobalt oxide, CoS0.89 may form in the
fuel reactor. As shown in Figure 17 there is a significant

Figure 14. Concentration of sulphur-containing gases, i.e., H2S, SO2, SO3,

COS and S2, needed in the gas phase for formation of Ni3S2 in the NiO/Ni
system.

Figure 16. Concentration of sulphur-containing gases needed in the gas

phase for formation of MnSO4 in the Mn2O3/MnO system.

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804

JERNDAL et al.

Figure 17. Concentration of sulphur-containing gases needed in the gas

phase for formation of CoS0.89 in the Co3O4/Co and CoO/Co systems.

risk of formation for both systems, especially at low

temperatures.
For WO3/WO2.722, a sulphur concentration of at least
3.6 vol% at 15 bar and 7.4 vol% at 1 bar is needed for formation of WS2 and therefore sulphide formation should not
be expected.

DISCUSSION
It is important that the oxygen carrier used in the chemical-looping combustion process can convert the gas almost
completely to CO2 and H2O. Combustible gases, such as
CH4, CO and H2, leaving the fuel reactor, would mean a
loss in combustion efficiency. An oxygen carrier for
which minor amounts of fuel gas is unconverted may be
acceptable, since only a small amount of oxygen would
be needed downstream the fuel reactor to oxidize these
species. Based on the results from the reduction and oxidation calculations, it was found that some oxides of
copper, iron and manganese are suitable as oxygen carriers
since they can fully convert the fuel. Nickel oxide, tungsten
oxide, barium- and strontium sulphate also show high gas
yield, although they are not able to fully convert the fuel.
Cobalt has a somewhat lower gas yield, which is a drawback for this oxide system. More specifically, all iron
oxides except Fe2O3/Fe3O4 are thermodynamically unsuitable oxygen carriers. Further, MnO/Mn, ZnO/Zn and all
oxides of cerium can be excluded. Low melting temperatures indicate that zinc, cerium, cadmium and molybdenum
can not be used in the process. Molybdenum is excluded
because its stable oxide MoO3 melts at a low temperature.
For copper, a low temperature may be required because of
its relatively low melting temperature.
Some oxides do not form in the air reactor at conditions
feasible for the process. Silver could not be used because it
does not form any oxides at the conditions investigated.
Mn2O3, CuO and Co3O4 decompose at high temperatures
and including these oxides in the process would require a
low temperature. If a higher temperature is preferred, the
more reduced forms, Mn3O4, Cu2O and CoO should be
used. However, it should be noted that by running the process under an increased total pressure, the more oxidized
form could be used at a higher temperature without
decomposing.

All the systems investigated, except those with copper

oxides and the Mn2O3/MnO system, gave a temperature
drop in the fuel reactor when methane was burnt. This
temperature decrease was most striking for systems with
a high oxygen ratio and this could be a problem since
the reactions might slow down or even stop at low temperatures. To prevent this temperature decrease from being
too large, a high oxygen carrier mass flow is needed.
This would result in a low degree of conversion difference
between the reactors, and thus a smaller temperature difference. For systems giving an increased fuel reactor temperature, e.g., oxidation of methane with copper oxides, the
reactor may be cooled to achieve desired reaction temperatures. This is also the case for CO and H2 combustion,
where the reaction in the fuel reactor always is exothermic.
Since the chemical-looping combustion process always
should be run with full or high fuel conversion, the
amount of added oxygen is always well over the amount
where carbon formation is possible. Therefore, problems
with carbon formation are not expected in a wellmixed fluidized fuel reactor. However, carbon formation may have to
be considered for applications where the local or total
oxygen supply could be low, e.g., chemical-looping
reforming. Further, some studies have found minor
carbon formation of NiO based carriers, although more
than the thermodynamic amount of oxygen was added.
The authors suggested that carbon may be an intermediary
product in the reduction process (Cho et al., 2005).
H2S in the fuel will be oxidized to SO2 when the fuel is
burnt. For most of the systems studied, this oxidation is
almost complete at all conditions. Exceptions are systems
based on nickel, cobalt and tungsten, where the oxidation
to SO2 is low at low temperatures and increased pressures.
If there are low concentrations of sulphur-containing gases
and a high temperature in the fuel reactor, BaSO4 and
SrSO4 will decompose. This decomposition of the sulphates leads to a loss of the active oxygen carrier and
thus BaSO4 and SrSO4 cannot be used at these conditions.
The three sulphides and sulphates that are most likely to
be formed are Ni3S2, MnSO4 and CoS0.89. All these compounds have low melting points, 7898C, 7008C and
8348C, respectively, and therefore it is imperative to
avoid formation of these in a fluidized bed fuel reactor.
The results are summed up in Table 5 below, where the
different oxide systems feasible for the process can be
compared.
Since this is a theoretical thermodynamic analysis of the
process, it should be noted that all the results refer to equilibrium. However, in a real application the rates of reaction,
i.e., in the fuel and air reactor, are also very important and
have implications with respect to the size of a CLC
system. There have been quite a number of investigations
in the last few years of oxygen carrier reactivities, especially
carriers based on Cu, Mn, Fe and Ni, see for instance Johansson (2005) for a review. The reaction rates vary considerably
and are dependant not only on the type of oxygen carrier, but
also preparation method and type of inert material used.
Abad et al. (2006) point out that there are several resistances
that can affect the reaction rates in the fluidized bed reactors.
An investigation of the kinetics of the reduction and
oxidation reactions with three oxygen carriers based on
Cu, Fe, and Ni reduced by the fuel gases CH4, CO and H2
was performed at atmospheric pressure and showed that

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THERMAL ANALYSIS OF CHEMICAL-LOOPING COMBUSTION

805

Table 5. Comparison between the different systems.

Fuel conversion
NiO/Ni
CuO/Cu
Cu2O/Cu
Fe2O3/Fe3O4
Mn2O3/MnO
Mn3O4/MnO
Co3O4/Co
CoO/Co
WO3/WO2.722
BaSO4/BaS
SrSO4/SrS

Decomposition
temperature
for pO2 0.04

Melting
temperature

I
9448C

Conversion
of H2S to SO2

Sulphide/sulphate
formed

Ni3S2

10858C
10858C
MnSO4!

7388C
L
L
I
I
I

8458C

I
L
I

CoS0.89
CoS0.89

!
Only at lower temperatures.
I incomplete; L low.

the kinetic parameters of the reactions were controlled by

chemical reactions.

present in the fuel and that excessively high temperatures

are avoided.
NOMENCLATURE

CONCLUSIONS
A comprehensive thermal investigation of oxygen carriers for chemical looping combustion has been performed.
Some metal oxides and reduced metal oxide/metal
systems based on Cu, Mn and Fe show excellent characteristics and can be used as oxygen carriers in chemicallooping combustion. Oxides of Ni and W as well as BaS
and SrS are also highly promising, but have somewhat
lower gas yields in comparison to Cu, Mn and Fe. The
metal Co and its corresponding oxide, CoO, give a gas
yield between 0.93 and 0.97 and this may be too low for
practical use.
Oxidation investigations indicate that for oxides of
copper, manganese and cobalt, it is the more reduced
oxide form Cu2O, Mn3O4 and CoO, respectively that
should be used, unless the process is performed at low temperatures or higher total pressures. The use of copper is also
limited to lower temperatures due to its low melting point.
Fe2O3 has the advantages as oxygen carrier of being
cheap and easily available (Mattisson et al., 2001). Disadvantages with the iron oxides, the systems with manganese oxides and the tungsten oxides are their relatively
low oxygen ratios.
Although there was a temperature drop in the fuel reactor
for many systems using methane as fuel, the drop can be
limited by applying a sufficient rate of circulation of
solids between the air and fuel reactor.
The possible formation of solid carbon, sulphides and
sulphates was investigated. Formation of carbon should
not be a problem as long as the process is run under conditions of high fuel conversion, i.e., with a sufficient
amount of oxygen continuously added with the particles.
With respect to sulphur contamination, H2S in the fuel is
converted partially to SO2 as the fuel is burnt. When
nickel, cobalt or manganese is used as oxygen carrier the
fuel may need to be desulphurized prior to combustion to
avoid formation of solid or liquid sulphides or sulphates.
To prevent decomposition of the oxygen carriers BaSO4
and SrSO4 to sulphur-containing gases and metal oxides,
in the fuel reactor, it is necessary that some sulphur is

cpi
Hi
Hprod
Hreac
h0i
hi
m
mox
mred
ni
nO,added
nO,stoich
pCH4,in
pi
R0
T
xO2,ex
yi

specific heat capacity at constant pressure for component i,

J mol21 K21
lower heating value of component i, J
enthalpy of the exiting particles and gas, J
enthalpy of the incoming particles and fuel, J
heat of formation of component i at 298 K, (J mol21)
enthalpy of component i, J mol21
actual mass of oxygen carriers, kg
mass of oxygen carriers in oxidized form, kg
mass of oxygen carriers in reduced form, kg
amount of reactants, mol
actual amount of O added with the oxygen carrier and/or
steam, mol
stoichiometric amount of oxygen needed for full conversion
of the fuel, mol
partial pressure of methane in the reactant gas, Pa
partial pressure of component i in the product gas, Pa
oxygen ratio
temperature, K
volume fraction of oxygen in the air leaving the air reactor
amount of products, mol

Greek symbols
gheat
gas yield for methane based on the fuels heating values
gi
gas yield of component i
gox
conversion of gas in the air reactor
DH
standard heat of reaction, J
l
air ratio
6
oxygen added ratio
v
mass conversion of oxygen carrier

REFERENCES
Abad, A., Adanez, J., Garca-Labiano, F., de Diego, L.F., Gayan, P. and
Celaya, J., 2006, Mapping of the range of operational conditions for
Cu-, Fe-, and Ni-based oxygen carriers in chemical-looping combustion,
Accepted for publication in Chem Eng Sci.
Brandvoll, ., 2005, Chemical looping combustion-fuel conversion with
inherent CO2 capture, Doctoral thesis for the degree of Doktor Ingenir,
Norwegian University of Science and Technology.
Cho, P., 2005, Development and characterisation of oxygen-carrier
materials for chemical-looping combustion, Thesis for the Degree of
Doctor of Philosophy, Chalmers University of Technology.
Cho, P., Mattisson, T. and Lyngfelt, A., 2002, Reactivity of iron oxide with
methane in a laboratory fluidized bed-application of chemical-looping
combustion, Proceedings of the 7th International Conference on Circulating Fluidized Beds, Niagara Falls, Ontario, Canada, 599 606.

Trans IChemE, Part A, Chemical Engineering Research and Design, 2006, 84(A9): 795 806

806

JERNDAL et al.

Cho, P., Mattisson, T. and Lyngfelt, A., 2004, Comparison of iron-, nickel-,
copper- and manganese-based oxygen carriers for chemical-looping
combustion, Fuel, 83: 12151225.
Cho, P., Mattisson, T. and Lyngfelt, A., 2005, Carbon formation on nickel
and iron oxide-containing oxygen carriers for chemical-looping
combustion, Ind Eng Chem Res, 44: 668676.
Cole, J.A., 2003, Process for separating synthesis gas into fuel cell quality
hydrogen and sequestration ready carbon dioxide, Patent Application
Publication, Pub. No.: US 2003/0035770 A1.
Garca-Labiano, F., de Diego, L.F., Adanez, J., Abad, A. and
Gayan, P., 2004a, Reduction and oxidation kinetics of a copper-based
oxygen carrier prepared by impregnation for chemical-looping
combustion, Industrial and Engineering Chemistry Research, 43:
81688177.
Garca-Labiano, F., de Diego, L.F., Adanez, J., Abad, A. and Gayan, P.,
2004b, Temperature variations in the oxygen carrier particles during
their reduction and oxidation in a chemical-looping combustion
system, Chem Eng Sci, 60: 851862.
Holmgren, A., 1998, Catalysts for car exhaust: oxygen storage in
platinum/ceria and mass transfer in monoliths, Thesis for the degree
of Doctor of Philosophy, Chalmers University of Technology.
HSC Chemistryw 5.0 for Windows, 2002, Chemical Reaction and Equilibrium Software with Extensive Thermochemical Database, Outokumpu
Reaearch Oy.
Johansson, M., 2005, Selection of oxygen carriers for chemical-looping
combustion using methane as fuel, Thesis for the degree of Licentiate
of Engineering, Chalmers University of Technology.
Kaarstad, O., 1992, Emission-free fossil energy from norway, Energy
Conversion and Management, 33(58), 781786.

Kronberger, B., Loffler, G. and Hofbauer, H., 2005, Simulation of mass

and energy balances of a chemical-looping combustion system, Clean
Air: International Journal on Energy for a Clean Environment, 6: 1 14.
Lyngfelt, A., Leckner, B. and Mattisson, T., 2001, A fluidized-bed combustion process with inherent CO2 separation; application of chemical-looping combustion, Chemical Eng Sci, 56: 31013113.
Lyngfelt, A., and Thunman, H., 2004, Construction and 100 h of operational
experience of a 10-kW chemical looping combustor, in Thomas, D. (ed.).
The CO2 Capture and Storage Project (CCP) for Climate Change Mitigation, Vol. 1Capture and Separation of Carbon Dioxide From Combustion Sources (Elsevier Science, London, UK).
Mattisson, T. and Lyngfelt, A., 2001, Capture of CO2 using chemicallooping combustion, First Biennial Meeting of the ScandinavianNordic Section of the Combustion Institute, April 18 20, Goteborg,
Sweden.
Mattisson, T., Lyngfelt, A. and Cho, P., 2001, The use of iron oxide as an
oxygen carrier in chemical-looping combustion of methane with
inherent separation of CO2, Fuel, 80: 19531962.
Mattisson, T., Johansson, M. and Lyngfelt, A., 2006, The use of NiO as an
oxygen carrier in chemical-looping combustion, Fuel, 85: 736 747.
Ryden, M. and Lyngfelt, A., 2004, Hydrogen and power production with
integrated carbon dioxide capture by chemical-looping reforming, 7th
International Conference on Greenhouse Gas Control Technologies,
Vancouver, Canada.
White, W.B., Johnson S.M. and Dantzig, G.B., 1958, Chemical equilibrium in complex mixtures. Journal of Chemical Physics, 28: 751 755.
The manuscript was received 30 September 2005 and accepted for
publication after revision 21 April 2006.

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