CO2 Capture in Coal Combustion by Chemical Looping

with Oxygen Uncoupling (CLOU)

Iaki Adnez-Rubio, Pilar Gayn, Alberto Abad, Francisco Garca-Labiano, Luis F. de
Diego, Juan Adnez
Instituto de Carboqumica (C.S.I.C.), Dept. of Energy & Environment, Miguel Luesma
Castn, 4, Zaragoza, 50018, Spain
iadanez@icb.csic.es; abad@icb.csic.es

Abstract
Chemical Looping with Oxygen Uncoupling (CLOU) process is a Chemical Looping
Combustion (CLC) technology that allows the combustion of solid fuels using oxygen
carriers with inherent CO2 separation. As in CLC technology, in CLOU process the oxygen
necessary for fuel combustion is supplied by a solid oxygen carrier, which contains a metal
oxide. According to the CLOU process is intended to use the capability of some metallic
oxide to generate gaseous oxygen at high temperature. The oxygen carrier circulates between
two interconnected reactors: the fuel reactor (FR) and the air reactor (AR). In the FR, the
oxygen carrier gives the oxygen necessary for fuel conversion to CO2 and H2O. In this reactor
only CO2 and steam are produced. After steam condensation, a pure CO2 stream is obtained.
The reduced oxygen carrier is regenerated to the initial metal oxide in the AR, and it is ready
to start a new cycle. The exit flow contain N2 and unreacted O2. Thus, the CO2 capture is
inherent to the process, being low the energy penalty and economical costs for the CO2
capture. This work shows the main characteristics of the CLOU process when different types
of solid fuels are used. The oxygen carrier was a Cu-based material selected from a previous
screening process with a 60 wt.% of CuO and a 40 wt.% of MgAl2O4 as inert prepared by
spray drying. As solid fuels, coals of different rank (a lignite, two bituminous and an
anthracite) and biomass were used. The CLOU process was carried out in a continuous unit
consisting in two interconnected fluidized bed reactors with a thermal power of 1.5 kWth,
where the proof of the concept for CLOU process was demonstrated. Combustion and CO2
capture efficiencies were analyzed, as well as the oxygen carrier inventory needed to carry
out the process. The results obtained show that CLOU technology has great possibilities for
the use of solids fuels in the CLC process, allowing full combustion and high CO2 capture
efficiencies using low solid inventories.

1. Introduction
The Chemical Looping with Oxygen Uncoupling (CLOU) process is a Chemical Looping
Combustion (CLC) technology that allows the combustion of solid fuels with inherent CO2
separation using oxygen carriers [1]. This technology has low energy penalty and thus low
CO2 capture costs. Figure 1 shows scheme of the CLOU process design. The CLOU
technology takes advantage of the property of some metal oxides which can generate gaseous
oxygen at high temperatures. The oxygen generated by the oxygen carrier reacts directly with
the solid fuel, which is mixed with the oxygen carrier in the fuel reactor. Thus, the need of

solid fuel gasification, that it is a limiting step in conventional CLC process with solid fuels,
is avoided.

N2 (+O2)

CO2 + H2O

CO2

CO2

H2 O

Condenser

MexOy

Fuel
Reactor

Air
Reactor

CO2
H2O

Char

Volatiles

H2O(l)

Coal

O2

MexOy-1

Oxygen
Carrier

Coal
CO2

CO2

Ash

Air

CO2

Figure 1: Scheme of the CLOU process, with the main processes happening in the fuel
reactor for coal combustion.
Three metal oxide systems have been identified to be used as oxygen carrier in CLOU
process: CuO/Cu2O, Mn2O3/Mn3O4, and Co3O4/CoO [1]. After a thermodynamic and kinetic
study, it was found that Cu-based oxygen carriers fulfill all the requirements of the process.
Reaction taking place in the fuel reactor with copper oxide as oxygen carrier are the
following:
4CuO 2Cu 2 O + O2
Coal Volatile Matter + Char
Volatile Matter +O2 CO2 + H 2O

(1)
(2)
(3)

Char + O2 CO2 + H 2O

(4)

4CuO + Coal 2Cu2O + CO2 + H 2O

(5)

The oxygen release reaction (r.1) is endothermic but the global reaction (r.5) in fuel reactor is
exothermic due to the coal combustion (r.3 and r.4). This is an advantageous characteristic of
using this metal oxide, as there can be a temperature increase in the fuel reactor.
The reduced oxygen carrier from the fuel reactor is regenerated in the air reactor:

2Cu 2 O + O2 4CuO

(6)

Figure 2 shows the equilibrium concentration of O2 versus temperature for copper oxide,
calculated using the HSC Chemistry 6.1 software [2]. The oxygen concentration at
equilibrium conditions greatly depends on the temperature. Thus, an equilibrium
concentration of 1.5 vol% O2 can be reached in the fuel reactor at 900 C, whereas the
equilibrium concentration increases up to 12.4 vol% at 1000 C. Nevertheless it could be not
needed to reach the equilibrium concentration in the fuel reactor. Indeed it should be
desirable to get low concentration of oxygen from the fuel reactor in order to obtain a high
purity CO2 stream. In the air reactor, the metal oxide is stable below 950 C if the maximum
oxygen concentration from the air reactor is higher than 4.5 vol%.

20

Oxygen equilibrium (vol%)

CuO
15

Cu2O

10

0
850

900

950
1000
T (C)

1050

1100

Figure 2: Equilibrium oxygen concentrations over the CuO/Cu2O system as a function of

temperature, [2].
An analysis about the suitability of Cu-based materials was carried out previously at ICBCSIC [3]. Particles prepared by several methods with different supporting materials and
different metal oxide contents were tested. From this work, it was shown that particles
containing 60 wt% CuO and using MgAl2O4 as supporting material are adequate for its use as
oxygen carrier for the CLOU process. On the whole, this material shows adequate values of
reactivity and oxygen transport capacity, high attrition resistance and does not have tendency
to agglomerate during operation in a fluidized bed reactor.
The aim of this work was to investigate the performance of a CLOU system using a Cu-based
oxygen carrier. The combustion of coal was carried out in a continuously operated 1.5 kWth
CLOU unit. The effect of operating conditions such as temperature of the fuel reactor,
residence time and the rate of coal feeding on the combustion efficiency were investigated.
The experiments were carried out at 900-960 C in the fuel reactor. The effect of coal rank
was studied in with four coals with different reactivity (a lignite, two bituminous and an
anthracite). A renewable fuel, pine sawdust, was also used in the CLOU unit. The results
obtained are analyzed and discussed in order to be useful for the scale-up of a CLOU process
fuelled with coal.

2. Experimental section
2.1 The Cu-based oxygen carrier
The material used was a Cu-based oxygen carrier prepared by spray drying. Oxygen carrier
particles were manufactured by VITO (Flemish Institute for Technological Research,
Belgium) using MgAl2O4 as inert material. The CuO content was 60 wt%. Particles were
calcined for 24 h at 1100C and sieved (100200 m). From now on the oxygen carrier was
named as Cu60MgAl. Table 1 shows the main properties of this oxygen carrier. It has a low
porosity and superficial area. The mechanical strength of the particles after 24 h of
calcination was adequate for its use in a fluidized bed. The compounds found by XRD
analysis were CuO and MgAl2O4.

Table 1. Properties of the oxygen carrier Cu60MgAl (after 24 h of calcination).

CuO content (wt.%)

60

Oxygen transport capacity, Ro (wt.%)

Crushing strength (N)

2.4
3

Skeletal density (kg/m )

4600

Porosity (%)

16.1
2

Specific surface area, BET (m /g)

< 0.5

XRD main phases

CuO, MgAl2O4

2.2 Fuels
Different solid fuels have been used during the experimental work. Five coals of different
rank have been used: a Spanish anthracite from El Bierzo, three bituminous coals from
Colombia, South African and Czech Republic, together with one Spanish lignite from Teruel.
According to ASTM characterization, Czech Republic coal is a low volatile bituminous coal
(LV), South African coal is a medium volatile bituminous coal (MV) and Colombian coal is a
high volatile bituminous coal (HV). Besides, a pine biomass, from Ans (Huesca, Spain), was
used. The main properties of selected fuels (proximate and ultimate analysis and LHV) are
showed in Table 2. The coal particle size used was +0.2-0.3 mm and the particle size used
was +0.5-2.0 mm for the biomass.
Table 2. Properties of the fuels used in this work.
Anthracite

HV Bitum.

HV Bitum.

Fresh

Pretreated

4.2
25.5
55.9
14.4

7.5
34.0
49.9
8.6

69.3
3.9
1.9
0.9
5.4
25500

70.8
3.9
1.7
0.5
7.0
25900

LV Bitum.

MV Bitum.

2.0
17.1
68.8
12.1
75.8
3.7
1.9
0.4
4.1
28950

Proximate Analysis (wt.%)

1.0
Moisture
7.5
Volatile matter
59.9
Fixed carbon
31.6
Ash
Ultimate Analysis (wt.%)
60.7
C
2.1
H
0.9
N
1.3
S
2.4
O(1)
21900
LHV (kJ/kg)
(1)
Oxygen to balance

Lignite

Biomass

2.3
33.0
55.9
8.8

12.6
28.6
33.6
25.2

4.2
81.0
14.4
0.4

65.8
3.3
1.6
0.6
17.6
21900

45.4
2.5
0.6
5.2
8.5
16250

51.4
6.5
0.3
0.0
37.2
19200

Agglomeration problems with pipes clogging were found when Colombian coal El
Cerrejn was fed into the fluidized bed because this coal showed an important swelling
behaviour. In order to avoid coal swelling and bed agglomeration, the coal was subjected to a
thermal pre-treatment by pre-oxidation. Coal was heated at 180 C in air atmosphere for 28
hours [4]. Proximate and ultimate analyses of the pre-treated coal are also shown in Table 2.

2.2 Experimental set-up

A schematic view of the CLOU unit is shown in Figure 3. The set-up was basically composed
of two interconnected fluidized bed reactors the air and fuel reactors joined by a loop seal,
and a riser for solids transport from the air reactor to the fuel reactor.

12

Torch
Gas Analysis
O2, CO2, CO, SO2

5
6
4

Tar Analysis

8
Torch

Fuel
Reactor
Air
Reactor
Sec.
Air

12

Gas Analysis
O2, CO2, CO, H2, CH4,SO2

11

Fuel

10

3
11

Air

N2

N2 CO2

1.- Fuel Reactor, FR

7.- Solids reservoir

2.- Loop Seal

8.- Solids control valve

3.- Air Reactor, AR

9.- Fuel feeding system

4.- Riser

10.- Screw feeders

5.- Cyclone

11.- Furnace

6.- Diverting solids valve 12.- Filter

Figure 3. Schematic view of the 1.5 kWth CLOU rig fuelled with coal.
Because of heat losses, the system is not auto-thermal and it is heated up by means of various
independent ovens to get independent temperature control of the air reactor, fuel reactor, and
freeboard above the bed in the fuel reactor, which is actually kept constant at about 900 C in
all the experiments. During operation, temperatures in the bed and freeboard of the fuel
reactor, air reactor and riser were monitored as well as the pressure drops in important
locations of the system, such as the fuel reactor bed, the air reactor bed and the loop seal.
The fuel reactor consisted of a bubbling fluidized bed with 50 mm of inner diameter and 200
mm bed height. N2 was used as fluidizing gas. The gas flow was 186 LN/h. Coal is fed by a
screw feeder at the bottom of the bed right above the fuel reactor distributor plate in order to
maximize the time that the fuel and volatile matter are in contact with the bed material.
The oxygen carrier is reduced in the fuel reactor, evolving gaseous oxygen to the
surroundings. The oxygen burns the volatiles and char proceeding from coal pyrolysis in the
fuel reactor. Reduced oxygen carrier particles overflowed into the air reactor through a Ushaped fluidized bed loop seal with 5 cm of inner diameter, to avoid gas mixing between fuel
and air. A N2 flow of 60 LN/h was introduced in the loop seal.
The oxidation of the oxygen carrier took place in the air reactor, consisting of a bubbling
fluidized bed with 8 cm of inner diameter and 10 cm bed height, and followed by a riser. The
air flow was 1740 LN/h. In addition, a secondary air flow (240 LN/h) was introduced at the
top of the bubbling bed to help particle entrainment through the riser. N2 and unreacted O2
left the air reactor passing through a high-efficiency cyclone and a filter before the stack. The
oxidized solid particles recovered by the cyclone were sent to a solids reservoir, setting the
oxygen carrier ready to start a new cycle. In addition, these particles avoid the leakage of gas
between the fuel reactor and the riser. The regenerated oxygen carrier particles returned to the
fuel reactor by gravity from the solids reservoir through a solids valve which controlled the
flow rates of solids entering the fuel reactor. A diverting solids valve located below the
cyclone allowed the measurement of the solids flow rates at any time. Therefore, this design

allowed us to control and measure the solids circulation flow rate between both reactors. The
total oxygen carrier inventory in the system was between 2 to 3 kg, being about 0.5-0.8 kg in
the fuel reactor. CO, CO2, H2, CH4, and O2 were analyzed in the outlet stream from fuel
reactor, whereas CO2, CO and O2 were analyzed from the flue gases of the air reactor.
Data evaluation
In the continuous CLOU unit, to analyze the confidence of the results, mass balances to
oxygen, carbon and sulphur were carried out using the measurements of the gas stream
coming from the air and fuel reactors. The CO2 capture efficiency, CC , was defined as the
fraction of carbon present in the coal which is at the outlet of the fuel reactor. This is the real
carbon captured in the CLOU system, as the remaining carbon exits as CO2 together with
nitrogen at the air reactor outlet.
FCO2 ,outAR
(7)
fC
m SF
MC
The CO2 capture efficiency depends on the conversion of char in the fuel reactor, Xchar. Its
value was calculated considering that the carbon contained in the fuel reactor comes from the
carbon in volatiles (FC,vol) and carbon in char converted.
CC = 1

X char =

FCO2 ,outFR + FCO,outFR + FCH 4 ,outFR FC,vol

FCO2 ,outFR + FCO,outFR + FCH 4 ,outFR + FCO2 ,outAR FC,vol

(8)

The combustion efficiency in the fuel reactor, comb,FR, evaluates the combustion degree
considering only the fraction of coal converted in the fuel reactor. Thus, the combustion
efficiency in the fuel reactor was calculated through the quotient between the oxygen
required to fully burn unconverted gases (CH4, CO and H2) and the oxygen demanded for full
combustion of the coal converted in the fuel reactor.

comb,FR = 1

2FCH 4 ,outFR + 0.5 ( FCO,outFR + FH 2 ,outFR )

2O m SF
-2FCO2 ,outAR -2FC,elut
M O2

(9)

The results obtained were evaluated considering the fuel reactor temperature, the solids
circulation flow rate and the coal feeding rate. In this sense, the oxygen carrier to fuel ratio
was defined as the ratio of the oxygen transported by the oxygen carrier to the oxygen
demanded by coal for complete combustion. A value of = 1 corresponds to the
stoichiometric flow of CuO needed to fully convert coal to CO2 and H2O, being CuO reduced
to Cu2O. Thus, was calculated with the following equation:
ROC m OC
(10)
O m SF
m OC being the solids circulation flow rate in the completely oxidized state and m SF the massbased flow of coal fed in to the reactor; O is the stoichiometric kg of oxygen to convert 1 kg
of coal to CO2 and H2O. This value was calculated from the proximate and ultimate analysis
of coal, see Table 1.2, by using the following equation:
=

 f
f
f
f
O = C + 0.25 H + S O M O2
MC
M H M S M O2

fi being the mass fraction of the element i in coal.

(11)

3. Result and discussion

3.1 Proof of the concept of the CLOU process in a 1.5 kWth continuous
unit using coal
In this section the results obtained during coal combustion in a CLOU unit composed of two
interconnected fluidized beds are described. Until this work only experiments in batch
fluidized bed reactor for the combustion of solid fuels at small scale were carried out [1, 5, 6]
in the literature. Therefore, this extensive experimental campaign carried out in this work was
fundamental to understand the CLOU process, its flexibility depending on the type of fuel
and the effect of operating conditions, as well as its possible operational problems.
The effect of the operating conditions on the performance of the CLOU process was analyzed
using pre-treated Colombian coal El Cerrejn as fuel. Table 3 shows a compilation of the
main variables used in each test. 30 h of hot fluidization conditions, whereof 18 h
corresponded to coal combustion were done.
Table 3. Main data for experimental tests in the continuous CLOU unit of 1.5 kWth with El
Cerrejn coal.
SF
m FR
TFR
OC (kg/h) m
m
Power (W) mOC (kg)
Test

(C)
CLOU01
CLOU02
CLOU03
CLOU04
CLOU05
CLOU06
CLOU07
CLOU08
CLOU09
CLOU10
CLOU11
CLOU12

903
917
941
960
924
929
917
920
925
901
901
898

1.2
1.2
1.2
1.2
4.3
3.2
2.6
2.1
1.1
1.1
2.0
4.0

2.8
2.8
2.8
2.8
4.7
3.5
2.8
2.3
1.2
2.8
2.8
2.8

4.2
4.2
4.2
4.2
9.0
9.0
9.0
9.0
9.0
3.7
7.0
13.9

(kg/h)
0.112
0.112
0.112
0.112
0.67
0.89
0.112
0.135
0.256
0.112
0.112
0.112

681
681
681
681
410
541
681
821
1560
681
681
681

0.41
0.41
0.37
0.39
0.47
0.45
0.41
0.37
0.37
0.45
0.45
0.49

(kg/MWth)
605
605
547
577
1150
835
605
454
235
663
663
721

The fuel reactor temperature (CLOU01-CLOU04), the coal feeding rate (CLOU05-CLOU09)
and the solid circulation flow rate (CLOU01 and CLOU10-CLOU12) were varied during
experimental work. The CLOU prototype was easy to operate and control, and steady state
for each operating condition was maintained for at least 60 minutes. Agglomeration or
defluidization was never detected with this Cu-based oxygen carrier, even though the fuel
reactor temperature was as high as 960 C.
In all cases, CH4, CO or H2 were not detected in the outlet gas stream of the fuel reactor. The
possible presence of tars or light hydrocarbons (C2-C4) was also analyzed. For some
experiments, tar measurements were done using tar protocol [7] at the fuel reactor outlet
stream. Tar was not detected in the fuel reactor outlet flow, that is, no hydrocarbons heavier
than C5. In addition, gas from the fuel reactor outlet stream was collected in bags and

analysed off line using a gas chromatograph. The analysis showed that there were no C2-C4
hydrocarbons in the gases. Thus, CO2, H2O and O2 were the only gases at the fuel reactor
outlet together with the N2 introduced as fluidizing gas. It must be pointed out that small
amounts of SO2 and NOX were also present at the fuel reactor gas stream. Therefore, volatiles
were fully converted into CO2 and H2O in the fuel reactor by reaction with the oxygen
released from the CuO decomposition. In addition, the oxygen release rate was high enough
to supply an excess of gaseous oxygen (O2) exiting together with the combustion gases. In the
air reactor the CO2 and O2 concentration decreased when the temperature increased in the
fuel reactor.
Figure 4(a), (b) and (c) show the CO2 capture efficiency, char conversion and the combustion
efficiency as a function of the fuel rector temperature, the coal feeding rate and the solids
circulation flow rate. Moreover, Figure 4 shows the variation of solids conversion in every
case. Complete combustion to CO2 and H2O of the coal was observed in the fuel reactor, i. e
comb , FR = 100% . However, the char conversion in the fuel reactor determines the CO2
capture efficiency in the CLOU system by the undesirable CO2 emissions in the air reactor
outlet. It can be seen that high values of CO2 capture were obtained in all cases. It is
noteworthy the positive effect of fuel reactor temperature on the CO2 capture efficiency, see
Figure 4(a). Thus, when the fuel reactor temperature was 960 C, 99 % of carbon in coal is
captured, i.e. only 1 % of carbon is exiting in the air reactor outlet gas stream. The reason for
this high CO2 capture efficiency is the fast conversion of char in the fuel reactor by
combustion with gaseous oxygen. Figure 4(a) also shows values of char conversion above 96
%, which increases with the temperature.
1.00

1.0

98

0.98

0.8

96

0.96

94

0.94

92

0.92

0.2

0.90

0.0

100
(c)

90
900

920

940

Temperature (C)

960

50

100 150 200 250

Coal feeding rate (g/h)

0.6
0.4

XOC (-)

(b)

Xchar (-)

Efficiency (%)

(a)

10 12 14 16

Solids flow rate (kg/h)

Figure 4. CO2 capture efficiency (----), char conversion (----), combustion efficiency ()
and variation of the oxygen carrier conversion (--X--) at different (a) fuel reactor
temperatures; (b) coal feeding rates; and (c) solids circulation flow rate.
The fuel load had no relevant effect on the CO2 capture efficiency; see Figure 4(b). Since the
circulation rate and the temperature are kept constant and there is an oxygen excess in all
cases, the resulting CO2 capture efficiency for the different coal feeding rates does not change
substantially. Thus, at the conditions used in the CLOU system, the oxygen generated in the
fuel reactor was not limited by the reactivity of this oxygen carrier, i.e. the more oxygen is
demanded, more oxygen is supplied. Figure 4(b) also shows that more oxygen is transferred
between the two reactors, as it is indicated by the increase of the variation of solids
conversion between 23 to 90 %. Complete combustion was reached even with the highest
coal feeding rate uses, which corresponded to a solid inventory in the fuel reactor as low as
235 kg/MWth, see Table 3.

Figure 4(c) shows that an increase in the solids circulation flow causes a decrease in the char
conversion and in the CO2 capture efficiency. The negative effect of the solids circulation
rate on the char conversion was due to the decrease in the residence time of solids in the fuel
reactor. A residence time above 300 s is needed to get a char conversion about 97 % at 900
C with this coal.
In short, very good results during El Cerrejn coal combustion have been shown by the
CLOU process. CO2 capture efficiency can be close to 100 % and full combustion of fuel to
CO2 and H2O was obtained.

3.2 Effect of coal rank on the performance of CLOU process

In the previous section, full CO2 capture and combustion efficiencies were obtained working
with a highly reactive bituminous coal with high volatile content. However, it is expected that
coal reactivity, which depends on coal rank, can affect to the efficiency of the process. This
issue is analyzed in this section.
To investigate the performance of the CLOU system in the combustion of different coals,
several tests under continuous operation were carried out in the CLOU unit of 1.5 kWth. The
Cu60MgAl material was used as oxygen carrier. The effect of the coal rank and the fuel
reactor temperature on the combustion efficiency and carbon capture efficiency was
investigated. A total of 40 h of operation were carried out. The temperature in the fuel reactor
was varied from 900 to 950 C. The temperature in the air reactor was maintained at 900 C.
Table 4 shows operational variables used in this work for each coal. The solids circulation
rate was maintained at a mean value of 3-4 kg/h, whereas the coal feeding rate was varied
from 0.08 to 0.13 kg/h depending on the coal type. The oxygen carrier to fuel ratio, , was
around 1.0-1.2. Steady state at constant temperature was maintained for 60 min in each
condition.

Table 4. Operational conditions during experimental work in the CLOU continuous unit of
1.5 kWth with different coals.
SF
OC

m
m
mFR
Coal

Anthracite
LV Bituminous
MV Bituminous
Lignite

(kg/h)
0.10
0.10
0.08
0.13

(kg/h)
3.1
3.7
3.2
3.0

(-)
1.1
1.0
1.1
1.2

Power (W)
583
805
592
582

(kg/MWth)
894
709
1003
845

Figure 5(a) shows the combustion and CO2 capture efficiency obtained for different coals as a
function of the fuel reactor temperature. In all cases, no CH4, CO, H2 or higher hydrocarbons
were detected in the gases exiting from the fuel reactor. Thus, CO2, H2O and O2 were the
only gases, together with N2 introduced as fluidizing gas. The oxygen release rate was high
enough to supply an excess of gaseous oxygen (O2) exiting together with the combustion
gases. Oxygen concentration was at equilibrium conditions for each temperature. Also, small
fractions of SO2 and NO were present in the gases coming from sulphur and nitrogen present
in the coal. Therefore, complete combustion in the fuel reactor of coal to CO2 and H2O was
found for all the operating conditions and coals.

90

80

80

70

50
900

Capture Comb.
Lignite
MV Bituminous
LV Bituminous
Anthracite

70

60

50

910

920

930

940

950

Char Conversion (-)

90

60

1.0

100

Combustion Efficiency (%)

CO2 Capture Efficiency (%)

100

0.9

0.8

0.7

Lignite
MV Bituminous
LV Bituminous
Anthracita

0.6

0.5

960

Temperature (C)

900

920

940

960

Temperature (C)

Figure 5. (a) Combustion efficiency in the fuel reactor and CO2 capture efficiency, and (b)
char conversion obtained with different coals, as a function of the fuel reactor temperature.
The type of coal affected to the CO2 capture efficiency. The CO2 capture efficiency decreased
in the order Lignite > Medium Volatile Bituminous > Low Volatile Bituminous > Anthracite.
For all coals, CO2 capture increased with temperature, being this effect more relevant for
coals with low volatile matter content as Anthracite and LV Bituminous coal. Similar CO2
capture efficiencies were obtained for Lignite and Medium Volatile Bituminous coal at
temperatures above 940 C. In these cases, the CO2 capture efficiency was above 99%.
However, these results clearly indicate the need of a carbon separation system to return
unconverted char to the fuel reactor when low reactive coals are used. This system is similar
to the proposed for iG-CLC with solid fuels [8].
CO2 capture efficiencies are dependent on the carbon transferred from the fuel to the air
reactor. As all the carbon in volatiles was captured, the CO2 capture depends on the
unconverted char in the fuel reactor, i.e. the char conversion. Figure 5(b) shows the char
conversion as a function of the fuel reactor temperature for different coals. Similar trends to
that found for the CO2 capture efficiency were found for different coals. Char conversions
increased when temperature increased for all coals and the increase was more relevant for
low rank coals.

3.3 Biomass combustion by CLOU process

If a CO2 capture system is implemented in a biomass combustion process, the global carbon
balance to the atmosphere will be negative, because the carbon dioxide generated was
previously removed from the atmosphere by the biomass. Consequently, biomass is an
interesting fuel for testing in CLOU process, because it would be possible to obtain negative
CO2 emissions. However, biomass has a higher volatile matter content than coals and
different behaviour could be expected during combustion. Therefore, the evaluation of
biomass in a CLOU process must be analyzed.
To investigate the combustion of biomass by a CLOU system, different tests were carried out
with pine wood as fuel under continuous operation in the continuous CLOU unit of 1.5 kWth.
Cu60MgAl material was used as the oxygen carrier. The effect of the fuel reactor temperature
on the combustion efficiency and CO2 capture efficiency was investigated. Thus, the fuel
reactor temperature was varied from 860C to 935C. The temperature in the air reactor was

kept at 900C. A total of 10 h of continuous operation were carried out. The solids circulation
rate was maintained at a mean value of 4.1 kg/h, while the biomass feeding rate was 0.22
kg/h, corresponding to a power of 1.2 kWth. The oxygen carrier to fuel ratio, , was around
1.2.

100

(a)
95

95

90

90

85

85

80

80

75
840

75
860

880

900

920

FR Temperature (C)

940

1.0

(b)
Char conversion (-)

Combustion efficiency (%)

100

Carbon Capture efficiency (%)

Figure 6(a) shows the combustion and CO2 capture efficiencies obtained in the CLOU unit as
a function of the fuel reactor temperature. When the fuel reactor temperature was higher than
900C, no CH4, CO, H2, tars or light hydrocarbons were detected in the gases exiting from the
fuel reactor. Thus, CO2, H2O and O2 were the only gases from biomass combustion by CLOU
and complete combustion of biomass was found in the fuel reactor for the experiments at
temperatures higher than 900C.

0.8

0.6

0.4

0.2
840

860

880

900

920

940

FR Temperature (C)

Figure 6. (a) Combustion efficiency in the fuel reactor and CO2 capture efficiency, and (b)
char conversion, as a function of the fuel reactor temperature
At a lower temperature, i.e. 860C, 82% of combustion efficiency was obtained, and there
were CO and tars presents at the outlet of fuel reactor. Tar compounds were detected at a
concentration of 0.31 g/Nm3 (dry basis). The composition of these tars was mainly
naphthalene (61.7 wt.%), phenantrene (13.1 wt.%), acenaphthylene (12.5 wt.%) indene (7.2
wt.%) and stryrene (5.5 wt.%). The high volatile matter content of the biomass is responsible
for the low combustion efficiency showed at the lowest temperature.
Regarding the CO2 capture efficiency, an increase with the fuel reactor temperature was
measured. Thus, high CO2 capture efficiency values were found at fuel reactor temperatures
higher than 900C because of the high char conversion, reaching 100% at 935C. Figure 6 (b)
shows char conversion increased with the fuel reactor temperature because of the higher char
combustion rates. However, low char conversion can be seen at the lowest temperature, when
only 15 % of char conversion is reached in the fuel reactor. At this temperature, there is no
gaseous O2 in the fuel reactor exiting flow. However, the 80% of CO2 capture efficiency
obtained was due to the high amount of volatiles in the biomass.
To understand the differences on performance at temperatures lower or higher than 900C, it
should be considered the increase in the reaction rate and in the equilibrium O2 concentration.
It is necessary to take into account that O2 generated from CuO increases with temperature. In
this way, at 860C, the O2 generated is very low (equilibrium O2 concentration is 0.5 vol.%).
At this temperature, oxygen carrier reduction to generate gaseous O2 is extremely slow [9].

At temperatures 900C, O2 released from the oxygen carrier should be of great relevance
for the conversion of gaseous compounds proceeding from coal devolatilization. Thus,
volatile matter reacts with gaseous O2 from the oxygen uncoupling mechanism in a
homogeneous reaction. In order to obtain complete combustion, an oxygen uncoupling effect
is needed. Thus, it was found that volatiles were fully converted into CO2 and H2O in the fuel
reactor at temperatures higher than 900C by reaction with the oxygen released from CuO
decomposition. Thus, it was concluded that at the lower temperature, 860C, the oxygen
uncoupling effect is low because the O2 equilibrium concentration is low and the oxygen
generation by the oxygen carrier particles is slow. So the conversion rate of char by
combustion reaction should be low. Char conversion is mainly driven at this temperature by
the slower gasification reaction with the low H2O or CO2 concentration present inside the fuel
reactor (since N2 is used as fluidization media in these tests).

4. Conclusions
The proof of the CLOU concept in a continuous 1.5 kWth CLOU unit system was carried out
during 18 h of bituminous coal combustion with the Cu60MgAl oxygen carrier. The effect of
the operating conditions such as temperature of the fuel reactor, solids circulation rate and
the coal feeding rate on the CO2 capture efficiency, and the combustion efficiency were
investigated. In all cases, unburnt compounds were not present in the fuel reactor outlet,
being CO2 and H2O the only products of combustion even if the oxygen carrier particles were
highly converted. Also, high CO2 capture efficiencies were measured.
Moreover, the performance of the CLOU process for combustion of coals of different rank
(one lignite, two bituminous coals and one anthracite) was determined in the 1.5 kWth a
continuous CLOU unit with the Cu60MgAl oxygen carrier. With all the coals used, unburnt
compounds were not present in the fuel reactor outlet. The coal rank showed an important
effect on the CO2 capture efficiency. Very high CO2 capture efficiencies were obtained with
the lignite and the medium volatiles bituminous coals, reaching values of 99% with the
lignite at 950 C. It can be said that with all the coals used, unburnt compounds were not
present in the fuel reactor outlet. CO2, H2O and O2 were the only products present at the fuel
reactor outlet. Coal rank showed an important effect on CO2 capture efficiency. Very high
carbon capture efficiencies were obtained for Lignite and MV Bituminous coals, reaching
values of 99% with Lignite at 950 C. The CO2 capture efficiency increased with fuel reactor
temperature and this increase was more relevant for Anthracite and LV Bituminous. For low
reactivity coals it would be necessary the use of a carbon separation system to reach high CO2
capture efficiencies.
Combustion of biomass by CLOU process to obtain negative CO2 emissions was
demonstrated for the first time in the continuous CLOU unit of 1.5 kWth during 10 h of
operation. A fuel reactor temperature higher than 900C was required to exploit the oxygen
uncoupling benefits and resulting in no unburnt compounds at the fuel reactor outlet.
Complete combustion and 100% CO2 capture efficiency were achieved at a fuel reactor
temperatures higher of 935C using low solids inventory in the fuel reactor.

Acknowledgement
This work was partially supported by the European Commission, under the RFCS program
(ECLAIR Project, Contract RFCP-CT-2008-0008; and ACCLAIM Project, Contract RFCPCT-2012-00006), ALSTOM Power Boilers (France) and by the Spanish Ministry of Science

and Innovation (PN, ENE2010-19550 ENE2011-26354). I. Adnez-Rubio thanks CSIC for

the JAE fellowship.

Additional information
This work was compiled in the Thesis for the degree of Doctor by the Zaragoza University of
Iaki Adnez-Rubio (2015). More information can be found in the bibliography: [3, 9-17]

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