Les Rencontres Scientifiques de l'IFP - 1st International Conference on Chemical Looping - 17-19 March 2010 - Proceedings

Copyright 2009, IFP

Reduction performance of ilmenite and hematite oxygen
carriers in the context of a new CLC reactor concept
Georg L. Schwebel
*
, Florian Wiedenmann, Wolfgang Krumm
Institut fr Energietechnik, Paul-Bonatz-Str. 9-11, Universitt Siegen, D-57068 Siegen, Germany
e-mail : g.schwebel@et.mb.uni-siegen.de
* Corresponding author
Abstract Reduction performance of ilmenite and hematite oxygen carriers in the context
of a new CLC reactor concept The research activities at the University of Siegen aim towards the
implementation of a novel technical approach to realize a feasible CLC of fossil and biogenic solid
fuels, characterized by the parallel arrangement of a fixed bed acting as fuel reactor and a fluidized
bed operating as air reactor. In the face of environmental and economical concerns, the use of
natural oxygen carriers is preferred. In this contribution the reduction performance of the natural
minerals ilmenite and hematite is determined. In context of the new reactor conception, three different
particle size fractions are exposed to a gaseous fuel in a laboratory reactor. Apart from the reduction
rate, the oxygen consumption and the release of impurities are measured during heat up operation.
The results are obtained by off-gas analyses. Low costs and an already existing infrastructure for the
acquisition of natural mineral oxygen carriers will enhance their implementation. Both minerals are
already being used as a raw material in e.g. the iron and steel production as well as in the pigment
industry. Integrating CLC into extractive industry will accelerate the development of CLC itself and
will also contribute to the mitigation of greenhouse gas production in industrial processes.


INTRODUCTION
Chemical-looping combustion (CLC) is one of the most
promising methods to lower costs and to prevent a
substantial efficiency decrease compared to common
carbon capture technologies. In contrast to conventional
combustion, the required oxygen is transferred via a
solid oxygen carrier from air to fuel. Hence, the
atmospheric nitrogen does not dilute the combustion
gases resulting in a flue gas consisting of mainly carbon
dioxide (CO
2
) and water (H
2
O). Although there is a
patent on a process to produce pure carbon dioxide [1],
the principle of CLC was first introduced by [2], later
published in English language [3]. During the theoretical
investigations therein, the prime intention was to reduce
exergy losses in combustion and to increase fuel
exploitation by splitting the combustion reaction.
1 NEW CLC REACTOR CONCEPT
The most popular arrangement for purposes concerning
the implementation of CLC using metal oxide based
oxygen carriers technologies are interconnected
fluidised beds [48]. A very different concept is given by
[9], where a donut shaped fixed bed rotates through
different sectors fed with gaseous fuel, steam or air. A
new reactor concept for implementing CLC has been
suggested by [10], Figure 1.

Figure 1: Basic sketch of suggested reactor concept
Based on the IPV-Verfahren

[11], the new concept is

characterised by the parallel arrangement of a fixed bed
acting as fuel reactor and a fluidised bed operating as air
reactor. Especially in connection with the utilisation of
solid fuels, integrating a fixed bed reactor for the
reduction step seems to be very promising. The most
significant advantages are avoiding fuel segregation
connected with less char at the reactor exit, adjustable
residence time and less power demand for fluidisation.
Due to the fixed bed approach, the thermal power per
unit seems to be restricted to approximately 20 MW
th
.
Les Rencontres Scientifiques de l'IFP - 1st International Conference on Chemical Looping - 17-19 March 2010 - Proceedings


2 OXYGEN CARRIERS USED
Regarding environmental and economical concerns, the
use of natural oxygen carriers is preferred. Hence, the
two natural oxygen carriers ilmenite and hematite are
investigated. Both minerals have already been used for
iron and steel production. An overview of ilmenite as a
raw material for pigment industry can be found in [12].
While it is assumed here, that hematite used is in a very
pure state, the ilmenite ore exists in its natural hemo-
ilmenite state. Due to the hematite in the hemo-ilmenite,
the available oxygen content can be expected to be
higher than assumed before [10]. With the oxygen ratios
of ilmenite (R
O,ilm
=0.05) and hematite (R
O,hem
=0.1), the
theoretically available oxygen in the ilmenite ore can be
calculated from its raw mass, assuming an ilmenite
content of 60 % and a hematite content of 20 % in the
raw material.
|
|
.
|

\
|
+
|
|
.
|

\
|

+ =
hem O
ilm O
raw red ox
R 2 0
R 1
1
1 6 0 m m m
,
,
. .

Presumed that the impurities act totally inert, the
theoretical oxygen ratio is R
O,hemo-ilm
=0.05.
3 EXPERIMENTAL SECTION
3.1 Equipment
The experimental plant used can be seen from Figure 2.
Its geometry is similar to the reactor utilised in a former
study [10].

Figure 2: Experimental plant
The core component is an electrically heated tube
reactor with an inner diameter of 0.0531 m. The
fluidisation and fuel gases are supplied via mass flow
controllers (mfc). A fixed bed of incombustible material,
leads to a homogenous and preheated mass flow into
the tube reactor. Off-gas is analysed to determine the
main gas components like O
2
, H
2
, CH
4
, C
2
H
4
, CO, CO
2
,
SO
2
and optional organic carbon.
3.2 Procedure
A total mass of 0.4 kg of oxygen carrier is placed in the
laboratory plant at ambient temperature. While heating
up in air, the oxygen consumption and release of
impurities are measured. After reaching the target
temperature, the reduction-oxidation experiments are
performed. For reduction, a fuel gas consisting of 50 %
H
2
, 25 % CO, and 25 % CH
4
, diluted with nitrogen, is
used. The oxidation takes place by injecting air. Three
different particle size fractions of oxygen carrier are
used: the small fraction with particles in the range of
0.18 to 0.25 mm, the medium fraction in the range of 0.5
to 0.71 mm and the coarse fraction in the range of 1.0 to
1.4 mm.
3.3 Data evaluation
The reaction rate r

is calculated as the time derivative

of the mass conversion during reduction according to
the following equation:
dt
) t ( d
) t ( r
e
=
e

Therefore, a water flow evolving during the reduction
period is calculated by a hydrogen balance.
3.4 Results
During the first heat up in air, hematite only releases
impurities. As obvious from Figure 3 ilmenite also
consumes oxygen. The oxygen gathered in the
displayed experiment accounts for a difference in
oxygen conversion of X=0.07.

Figure 3: mole fraction of measured components in the offgas
The reduction performance is indicated by the maximum
reduction rates (max r

.). For ilmenite, the difference

between the small and medium sized particles is
negligible at higher temperatures, Figure 4. Compared to
this, the coarse fraction shows lower reduction rates,
possibly pointing out a strong influence of pore diffusion.
For hematite, the particle size seems to be of less
importance, Figure 5. For both minerals, the impact of
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the number of cycles is obvious. While max r

is
increasing during the first cycles utilizing ilmenite, it is
decreasing using hematite, Figure 6.
0 2 4 6 8 10
0
1
2
3
4
5
x 10
-5 max r
e
in 1/s
number of cycles


coarse ilm
medium ilm
small ilm

Figure 4: ilmenite at 900C
0 2 4 6 8 10
0
1
2
3
4
5
x 10
-5 max r
e
in 1/s
number of cycles


coarse hem
medium hem
small hem

Figure 5: hematite at 900C
0 2 4 6 8 10
0
1
2
3
4
5
x 10
-5 max r
e
in 1/s
number of cycles

medium hem
medium ilm

Figure 6: Comparison of ilmenite and hematite at 900C
The influence of temperature is lower for hematite.
Regarding the CO
2
-yield, the performance of ilmenite is
below of that for hematite at lower temperatures, but it is
increasing stronger with higher temperatures resulting in
maximum CO
2
-yields of above 0.9 for ilmenite and only
up to 0.85 for hematite.
In the first experiments of this series, strong
agglomeration occurred during oxidation after a
reduction period of ten minutes, most probably initiated
by carbon burning during oxidation, with ilmenite at
900 C. To lower the risk of agglomeration, the reduction
time was limited to five minutes. Throughout all
experiments, carbon formation on the particle surface
during reduction occurred, visible after reactor cooling
down.
ACKNOWLEDGMENTS
The present work was subsidised by the doctoral
scholarship programme of the DBU (www.dbu.de). The
used samples of ilmenite and hematite were gratefully
provided by ArcelorMittal Eisenhttenstadt GmbH as
well as by Pontax GmbH.

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