Fuel Processing Technology 150 (2016) 30–40

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Fuel Processing Technology

journal homepage: www.elsevier.com/locate/fuproc

Investigation of Cu–Fe and Mn–Ni oxides as oxygen carriers for

chemical-looping combustion
Volkmar Frick a,⁎, Magnus Rydén b, Henrik Leion a
a
Department of Chemistry and Chemical Engineering, Division of Environmental Inorganic Chemistry, Chalmers University of Technology, 412 96 Gothenburg, Sweden
b
Department of Energy and Environment, Division of Energy Technology, Chalmers University of Technology, 412 96 Gothenburg, Sweden

a r t i c l e i n f o a b s t r a c t

Article history: Combined Cu–Fe and Mn–Ni oxygen carriers were investigated as bed materials for chemical-looping combus-
Received 29 November 2015 tion. The aim was to identify material combinations which yield oxygen carriers with a high reactivity towards
Received in revised form 16 April 2016 gaseous fuels, such as CO, H2 and CH4, as well as sufficient mechanical durability. For this purpose, 18 different
Accepted 25 April 2016
oxygen carriers were spray-dried and calcined at defined temperatures.
Available online 15 May 2016
Gas conversion as well as release of gaseous oxygen was investigated in a batch fluidized bed reactor setup at
Keywords:
temperatures between 850 and 1050 °C. For testing the mechanical durability, a jet-cup attrition rig was used.
Chemical-looping combustion (CLC) Moreover, properties like specific surface area, oxygen transfer capacity and crystalline phase composition
Chemical-looping with oxygen uncoupling were examined to physically and chemically characterize the oxygen carrier particles.
(CLOU) For both the Cu–Fe and Mn–Ni-based materials, oxygen carriers could be produced which showed a high
Combined oxides oxygen carrier reactivity with gaseous fuels like CO or CH4 while having a sufficiently high mechanical strength. These properties
Copper-iron oxides make them interesting candidates for application in chemical-looping combustion.
Manganese-nickel oxides © 2016 Elsevier B.V. All rights reserved.

1. Introduction chemical-looping combustion is largely compatible with conventional

For mitigation of CO2 emissions from combustion of fossil fuels,
chemical-looping combustion (CLC) has been proposed as a promising
process for CO2 sequestration. It has the advantage of low cost and
energy penalties for CO2-capture as no gas separation or scrubber unit
is needed [1,2].
In most CLC related publications, fossil fuel power plants are the
target application for this technology. Nevertheless, it might also be
applied to industrial combustion processes as they represent large
point sources of anthropogenic CO2 emissions and account for about
40% of total global carbon dioxide emissions [3].
1.1. Chemical-looping combustion
Chemical-looping combustion is a process for efficient utilization of
hydrocarbon fuels with inherent CO2 separation [1]. Compared to pre-
or post-combustion carbon capture techniques it has the advantage of
lower energy demand and lower cost penalty, as CO2 is obtained in a
separate stream without any active gas separation. In addition,
⁎ Corresponding author.
E-mail address: volkmar.frick@chalmers.se (V. Frick).
circulating fluidized bed boilers (CFB's) [2,4,5].
To date, chemical-looping combustion has been developed for gas-
eous, liquid and solid fuels and has been implemented in pilot plants
of sizes up to 3 MW [6]. The capability of CLC technology has been dem-
onstrated by research groups around the world and 6700 h of pilot plant
operation has been achieved. Reviews by Fan et al. [7], Adánez et al. [8],
and Lyngfelt [4,9] give an overview over recent developments.
In chemical-looping combustion the fuel gets converted to carbon
dioxide and steam by oxygen provided from a solid metal oxide. In a
subsequent process step, this oxygen carrier is reoxidized to its initial
state with air. To achieve high rates of heat and mass transfer, the pro-
cess is typically implemented as an interconnected dual fluidized bed
reactor system with the oxygen carrier as bed material, as can be seen
in Fig. 1. The oxygen carrying material is oxidized in a separate air reac-
tor, while fuel is converted in a fuel reactor. In this way chemical-
looping combustion enables oxidation of the fuel while avoiding mixing
of CO2 and N2/O2 in the exhaust gas streams.
Usually, the operating temperatures of the fuel reactor are in the
range of 800–1000 °C. The air reactor is typically around 50 °C warmer
than the fuel reactor due to the exothermic nature of the reactions tak-
ing place here. Too high temperatures may cause agglomeration of the
oxygen carrier particles whereas too low temperatures lead to insuffi-
cient fuel conversion. The sum of reactions in fuel and air reactor is

http://dx.doi.org/10.1016/j.fuproc.2016.04.032
0378-3820/© 2016 Elsevier B.V. All rights reserved.
 V. Frick et al. / Fuel Processing Technology 150 (2016) 30–40
Fig. 1. Schematic description of the CLC process.
exothermic and equal to the combustion of the fuel with oxygen. De-
pending on the oxygen carrier material and fuel used, the reaction in
the fuel reactor might be exothermic or endothermic, the latter lowers
the reactor temperature compared to the air reactor [9].
1.2. Oxygen carriers for chemical-looping combustion
Bed materials for CLC are required to exhibit a high fuel conversion
while showing neither substantial fragmentation and abrasion nor
agglomeration at relevant operating temperatures. Moreover, the cost
for raw materials and manufacturing of the oxygen carriers should be
low. If more expensive materials or production methods are used a
longer lifetime is required. Besides, risks with respect to health, environ-
ment and safety have to be considered.
For combustion of ash-containing fuels, low-cost oxygen carriers are
preferred as ash components might have a negative influence on
oxygen carrier life time [10]. In contrast, more expensive and reactive
oxygen carriers could be viable for gaseous fuels [9], from which unde-
sired impurities can be removed at reasonable cost. In CLC, oxides of Mn,
Fe, Ni and Cu are commonly used as oxygen carrier materials. The metal
oxide MexOy reacts with the fuel according to Eq. (1).
ð2n þ mÞMex Oy þ C n H 2m ↔ð2n þ mÞMex Oy−1 þ mH 2 O þ nCO2
The reduced metal oxide MexOy − 1 is reoxidized in the air reactor as
described by Eq. (2).
1
Mex Oy−1 þ O2 ↔Mex Oy
2
The total heat released by a chemical-looping combustor is the same
as for normal combustion [11].
Some metal oxide systems such as Mn2O3/Mn3O4 and CuO/Cu2O are
known to spontaneously release gaseous oxygen when exposed to inert
atmosphere. When applied in CLC, this is referred to as “chemical-
looping with oxygen uncoupling” (CLOU). CLOU has been shown to
improve conversion of solid fuels and it is expected that it will also en-
hance combustion of liquid or gaseous fuels [12–14]. Furthermore, it has
been found that the fuel reactor inventory can be significantly reduced if
materials with CLOU capability are used [15]. For CLOU, several material
combinations have been investigated as bed materials and the suitabil-
ity of the process has been demonstrated in continuous operation [8,9,
16].
An important group of oxygen carriers is Mn-based materials as they
have comparatively high reactivity with CO, H2 and CH4, low material
31
costs as well as low environmental impact. In CLC, Mn2O3 is reduced
in the fuel reactor to MnO whereas for CLOU, oxygen is released via con-
version of Mn2O3 to Mn3O4. Mn-based materials have a low tendency to
agglomerate as metallic Mn never forms. This is because oxides usually
have higher melting points than metals [9]. A disadvantage of pure Mn-
oxide materials is that oxidation in the air reactor has to be performed at
temperatures b 800 °C as the chemical equilibrium doesn't allow oxida-
tion of Mn3O4 at higher temperatures which is required for CLOU. Any-
how, it has been shown that conversion of gaseous fuels is also possible
if just oxidized to Mn2O3 [17,18]. As a solution to incomplete oxidation,
new materials have been produced which consist of Mn in combination
with other oxides like Cu, Fe, Mg, Ca, Ni and Si [19–21].
Another intensely studied group of materials is the one based on the
CuO‐Cu2O system which has been shown to be suitable for the CLC and
CLOU process. Drawbacks are the high raw material price and low me-
chanical strength [9,22].
When using copper-based materials, high temperatures and high
degree of reduction should be avoided as reduction all the way to
metallic Cu can cause agglomeration of the bed material due to the
low melting temperature of elemental copper [23]. To prevent ag-
glomerations, CuO has been combined with Al2O3 as support materi-
al and no defluidization was observed up to a bed temperature of
925 °C [24]. Likewise, it has been shown that impregnated particles
(Cu on alumina) exhibited no agglomeration after 100 oxidation-
reduction cycles [25] and spray-dried CuO–MgAl2O4 could be oper-
ated up to 960 °C in continuous operation [16]. Nevertheless, it has
been shown that material integrity can be a problem when operating
continuously for a longer time [26]. This is confirmed by an extensive
study on supported CuO-based materials performed by Rydén et al.
[22] Improvements in mechanical properties can possibly be
achieved by combining with a suitable support material as has
been investigated by Gayán et al. for an Al2O3-supported Cu-based
oxygen carrier with addition of NiO [27]. Cu–Fe-based oxygen car-
riers have been investigated by TGA for combustion of coal [28]
and coal-derived syngas [29] and operation temperatures up to
900 °C are suggested.
In the past, much research on oxygen carriers for chemical-looping
combustion was done on Ni-based materials as they have high reactiv-
ity with methane, a phenomenon most likely associated with the cata-
lytic properties of metallic Ni. NiO supported on alumina is well
researched and has been successfully tested in long-term operation
ð1Þ [30].
For pure NiO, the fuel conversion to CO2 and H2O is limited by chem-
ical equilibrium to 99–99.5%, depending on temperature [11]. In the
publication by Shulman et al. [20], fuel conversion and oxygen release
of three particles produced from 80 wt.% Mn3O4 and 20 wt.% NiO are
presented. Interestingly, low formation of CO was detected during com-
bustion of methane which implies nearly complete conversion of the
ð2Þ methane.
A drawback of nickel-based materials is that they are sensitive to
sulphur poisoning which limits their application to sulphur-free fuels
[31]. Furthermore, the fuel should be ash-free or even gaseous, as ash-
rich fuels make frequent replacement of the oxygen carrier material
necessary which is not economically feasible for materials with a high
raw material price such as nickel. Besides, for Ni-based particles, health
and environmental aspects have to be considered [9,32].
Synthetic oxygen carriers are commonly produced by spray-drying,
impregnation or freeze-granulation. Spray-drying is often applied be-
cause it is suitable for production of large quantities of materials. The
mechanical strength of the particles can be increased by calcination
and sintering [9]. The time and temperature required vary between dif-
ferent material compositions.
The cost of synthetically produced oxygen carriers has been thor-
oughly discussed by Lyngfelt. The author estimated the cost for
spray-drying to be 500–5000 €/t and raw material prices of copper,
manganese and nickel to be 5400 €/t, 150–400 €/t and 13,000 €/t,
32 V. Frick et al. / Fuel Processing Technology 150 (2016) 30–40

respectively. These material costs are significantly higher than those 2.2. Material characterization
of natural ores such as ilmenite (100 €/t) but might be justified if the
overall process cost can be reduced by higher reactivity and material For engineering of fluidized bed reactor systems, the particles' den-
lifetime [9]. sity strongly affects the minimum fluidization velocity needed to fluid-
ize the particles [34]. Here, the density was measured by weighing a
defined volume of the material. Another important property of bed ma-
1.3. Aim of this study terial is the mechanical durability, which in this study was characterized
by measurement of the crushing strength and the attrition resistance.
This study focuses on investigation of Cu–Fe and Mn–Ni oxygen car- The crushing strength was determined by measuring the force to
riers to be used in chemical-looping combustion. Materials based on Cu, break 30 individual particles in the size range of 180–250 μm using a
Mn or Ni have attracted attention in CLC-related research in the past and digital force gauge (Shimpo FGN-5) and calculating the average value.
are likely to also yield good results when used as combined oxides. The To measure the attrition resistance, a jet cup attrition rig was used
Cu-system has been shown to have remarkable oxygen release proper- where the particles were exposed to a high velocity gas jet. The fines
ties whereas the Ni-system is promising with respect to gas conversion. produced are collected in a filter which is weighed after specific time in-
Combining both systems with other metal oxides might yield bed mate- tervals. To compare the attrition behavior of different particles, the attri-
rials with a lower price and similar or better properties e.g. by formation tion index Ai is calculated according to Eq. (3).
of solid solutions.


Important factors to be assessed in this study are reactivity towards m f ;t¼60 min −m f ;t¼30 min 60
gaseous fuels such as H2, CO and CH4, CLOU oxygen release and mechan- Ai ¼ ∙ ∙100 ½wt:%=h ð3Þ
ms 30
ical durability. The aim is to identify robust oxygen carriers while taking
advantage of the high O2 release and gas conversion.
mf,t is the cumulative elutriated mass at time t and ms is the initial
mass of the sample. The attrition index shall not be interpreted as an es-
2. Experimental timation of the expected life-time of oxygen carrier materials in practi-
cal operation, but only as a measure of the relative mechanical
2.1. Assessed oxygen carriers durability of the particles. A detailed overview of the set-up and proce-
dure for attrition measurements is given by Rydén et al. [35].
In this study, oxygen carriers consisting of different ratios of Cu/Fe Furthermore, the specific surface area (BET) of the particles was
and Mn/Ni were studied. The oxygen carriers were manufactured by measured before (fresh state) and after (used state) testing in the fluid-
VITO in Belgium by means of spray-drying. They were produced from ized bed reactor. This was done by N2 adsorption in a Micromeritics
commercial raw materials (CuO: Sigma-Aldrich, Fe2O3: Alfa Aesar, NiO TriStar 3000 apparatus.
(Green grade F): Novamet, Mn3O4 (Trimanox): Chemalloy). First, To determine the phase composition of the materials, they were ana-
these raw materials were milled to powder and dispersed in deionized lyzed before and after fluidized bed reactor testing by powder X-ray dif-
water together with polyvinyl alcohol (PVA) as organic binder. This sus- fractometry (Siemens D5000, Cu Kα1 radiation). Thereby it was possible
pension was then pumped through a nozzle into the spray-drying appa- to draw conclusions about the mechanism responsible for oxygen release.
ratus where the water evaporated. The particles obtained were calcined For quantification of CLOU oxygen release, measurements with a Q500
in air for 4 h. Table 1 gives an overview of the particles and production TA-Instruments thermogravimetric analyzer (TGA) were performed. Dur-
conditions being used. This production method has been used before ing these tests the feed gas volume flows and the sample mass have been
and is further explained elsewhere [33]. varied to minimize mass transfer limitations. A sample of 7 mg oxygen
The Cu–Fe sample with the highest Cu content calcined at 1100 °C carriers, which has already experienced reducing and oxidizing conditions
(Cu30Fe_1100) could not be tested as production of particles failed in a batch fluidized bed reactor, was placed on an alumina crucible and ex-
due to the high calcination temperatures. posed to alternating oxidizing (5 vol.% O2 in N2) and inert conditions. The
material was oxidized for 60 min and exposed to pure N2 for 15 min. To
ensure stable oxygen release, at least five oxidation-reduction cycles
were performed. The oxygen transfer capacity RO was calculated accord-
Table 1
ing to Eq. (4) by relating the difference between the sample mass in oxi-
Properties of oxygen carriers assessed in this study.
dized state mox and the mass in reduced state mred (at the end of the
Oxygen carrier Synthesis composition [wt.%] Calcination temperature [°C] inert period) to the sample mass in oxidized state mox.
Cu5Fe_950 950
Cu5Fe_1025 5% CuO, 95% Fe2O3 1025 mox −mred
Cu5Fe_1100 1100 RO ¼ 100 ½wt:% ð4Þ
mox
Cu15Fe_950 950
Cu15Fe_1025 15% CuO, 85% Fe2O3 1025
Cu15Fe_1100 1100 The maximum absolute rate in weight change of the oxygen carrier
was taken as a measure for the maximum CLOU reaction rate.
Cu30Fe_950 950
Cu30Fe_1025 30% CuO, 70% Fe2O3 1025
Cu30Fe_1100a 1100 2.3. Experimental method and setup for batch reactor testing
Ni5Mn_1000 1000
Ni5Mn_1100 5% NiO, 95% Mn3O4 1100 A batch fluidized bed reactor made of quartz glass with an inner di-
Ni5Mn_1200 1200 ameter of 22 mm and a height of 820 mm has been used to determine
Ni10Mn_1000 1000 the materials' capability to release gaseous oxygen and to convert syn-
Ni10Mn_1100 11% NiO, 89% Mn3O4 1100 gas (50 vol.% H2 in CO) as well as methane. At a height of 370 mm (mea-
Ni10Mn_1200 1200 sured from the bottom), a porous quartz plate was placed to support the
Ni33Mn_1000 1000 bed material. The temperatures of inflowing gas and of the fluidized bed
Ni33Mn_1100 34% NiO, 66% Mn3O4 1100 were measured by thermocouples (Type K) just under the porous plate
Ni33Mn_1200 1200 and in the actual bed. The condition of the fluidized bed was monitored
a
Material formed a solid block during calcination. by measuring the pressure drop over the reactor.
 V. Frick et al. / Fuel Processing Technology 150 (2016) 30–40 33

content measured does not represent oxygen released from the materi-
al but rather oxygen from the previous oxidation period.
After operation at 1050 °C, reactivity with methane and CLOU oxy-
gen release have been assessed again at 950 °C to check if the material
suffered damage due to high process temperatures.
The values for the gas flowrates were chosen significantly above the
minimum fluidization velocity Umf to ensure sufficient fluidization of
the particles. For oxidizing conditions, a flowrate of 900 ml/min was
chosen which corresponds to a fluidization velocity 10–14 times higher
than the minimum fluidization velocity (0.014 m/s b Umf,oxidizing b
0.016 m/s, depending on operating temperature). For the inert period
and fuel period (syngas/methane), flow rates of 600 ml/min and
Fig. 2. Scheme of the experimental setup for batch reactor testing. 450 ml/min were chosen which correspond to 7–9 and 4–5 times the
minimum fluidization velocity (0.014 m/s b Umf,inert b 0.016 m/s,
0.019 m/s b Umf,fuel b 0.023 m/s) [34].
The feed gas flows were regulated by mass flow controllers. Comput- Characteristic numbers for comparison of oxygen carriers are the
er controlled electric valves were switched according to a pre-defined fuel conversion which is expressed by the CO2 yield γCO2 and the degree
sequence to provide oxidizing, inert or reducing gas atmospheres. The of oxygen carrier conversion ω which are calculated according to
product gases were cooled after leaving the reactor and steam was con- Eqs. (5) and (6).
densed. The dry gas composition together with the gas flow was mea-
sured by a Rosemount NGA-2000 analyzer. Nondispersive infrared
yCO2
detectors (NDIR) were used for measurement of CO, CO2 and CH4, γCO2 ¼ ½− ð5Þ
yCO2 þ yCO þ yCH4
whereas a thermal conductivity detector (TCD) and a paramagnetic
sensor were used for H2 and O2, respectively. A sketch of the experimen-
tal setup is given in Fig. 2.
yi is the molar fraction of component i in the off-gas stream.
Of each oxygen carrier material, 15 g particles of size 125–180 μm
were placed on the porous plate inside the reactor. The particles were
fluidized in oxidizing conditions (5 vol.% O2 in N2) while the reactor m
ω¼ ½−  ð6Þ
was heated to the operating temperature (850–1050 °C). This specific mox
oxygen concentration was chosen because it resembles the target con-
centration at the outlet of a continuous CLC air reactor. In a commercial
unit, higher oxygen partial pressures would cause larger exhaust gas m is the current mass and mox the mass of the oxygen carrier in its
flows along with a decreased thermal efficiency [9]. fully oxidized condition.
The particles were exposed to oxidizing, inert and reducing condi- The oxygen carrier conversion ω can't directly be measured in a fluid-
tions after having reached a specific bed temperature according to the ized bed but it can be calculated as a function of time from the effluent
procedure given in Table 2. A sequence of reducing conditions followed concentrations by applying an oxygen mass balance over the reactor.
by oxidizing conditions is referred to as a cycle. All cycles were conduct- Eq. (7) is valid for combustion of syngas and Eq. (8) for combustion of
ed at least twice to guarantee a steady cyclical behavior. Before and after methane.
combustible gases were fed into the reactor, it was flushed for 60 s with
nitrogen to avoid measurement errors due to combustion of fuel with
t n_ M O
remaining oxygen. For re-oxidation, the particles were exposed to oxi- ωt ¼ ωt−1 −∫ t−1 ∙ð2yCO2 þ yCO −yH2 þ 2yO2 Þdt ð7Þ
mox
dizing conditions until the oxygen concentration in the product gas
was stable and reached again 5 vol.%.
Pure methane and a mixture of 50 vol.% CO in H2 (syngas) were ap- t n_ M O
plied for investigation of the oxygen carriers' reactivity with gaseous ωt ¼ ωt−1 −∫ t−1 ∙ð4yCO2 þ 3yCO −yH2 þ 2yO2 Þdt ð8Þ
mox
fuels. The period for feeding syngas was chosen 4 times longer than
the period for feeding of methane since CH4 consumes four times
more oxygen per mole of gas. MO is the molar mass of oxygen and n_ the molar flow rate at the re-
Assessment of the CLOU oxygen release was done by exposing the actor outlet.
oxygen carrier particles to N2 for 360 s. The oxygen content in the off- For comparison of different oxygen carriers at different operating
gas was recorded and the average value during the last 300 s was conditions, average values for the CO2 yield have been calculated for ω
used for comparison. The first 60 s were neglected because the oxygen ranging from 1 to 0.99.

Table 2
Experimental procedure used to investigate oxygen release and gas conversion.

Gas composition Bed No. of cycles Duration Duration Duration

temperature [°C] inert period (CLOU) [s] N2-purge [s] reduction period [s]

50 vol.% CO in H2 950 2 – 60 80
100 vol.% CH4 850 2 – 60 20
100 vol.% N2 850 2 360 – –
100 vol.% CH4 950 2 – 60 20
100 vol.% N2 950 2 360 – –
100 vol.% CH4 1050 2 – 60 20
100 vol.% N2 1050 2 360 – –
100 vol.% CH4 950 2 – 60 20
100 vol.% N2 950 2 360 – –
34 V. Frick et al. / Fuel Processing Technology 150 (2016) 30–40

Table 3 Table 4
Bulk density (tapped) and specific surface area (BET) for investigated particles. Oxygen transfer capacity (CLOU) and maximum absolute weight change (=max. oxygen
release rate) for Cu–Fe and Mn–Ni particles at 950 °C.
Oxygen carrier Bulk density [g/cm3] Specific surface area
(BET) [m2/g] Oxygen O2 transfer capacity at Max. abs. weight change at 950 °C
carrier 950 °C [wt.%] [wt.%/min]
Fresh Used Fresh Used
Cu5Fe_950 0.4 0.3
Cu5Fe_950 1.9 2.0 0.8 0.3
Cu5Fe_1025 0.4 0.2
Cu5Fe_1025 2.1 2.0 0.1 0.2
Cu5Fe_1100 0.4 0.2
Cu5Fe_1100 2.1 1.9 0.1 0.2
Cu15Fe_950 1.2 0.6
Cu15Fe_950 1.5 1.4 0.8 0.5
Cu15Fe_1025 1.3 0.7
Cu15Fe_1025 1.8 1.5 0.4 0.4
Cu15Fe_1100 1.2 0.6
Cu15Fe_1100 2.0 1.8 0.1 0.2
Cu30Fe_950 2.6 3.3
Cu30Fe_950 1.4 1.6 0.6 0.2
Cu30Fe_1025 2.1 1.0
Cu30Fe_1025 2.0 1.7 0.1 0.1
Ni33Mn_1000 1.2 0.9
Ni5Mn_1000 1.5 1.6 0.6 0.4
Ni33Mn_1100 1.2 0.7
Ni5Mn_1100 2.1 2.1 0.1 0.1
Ni33Mn_1200 1.1 0.4
Ni5Mn_1200 2.3 2.2 0.1 0.1
Ni10Mn_1000 1.6 1.7 0.4 0.3
Ni10Mn_1100 2.0 2.0 0.2 0.1
Ni10Mn_1200 2.2 2.2 0.1 0.1 oxidizing to inert atmosphere. In Fig. 3, the average oxygen concentra-
Ni33Mn_1000 1.5 1.7 0.6 0.3 tion during the last 300 s of the inert period is depicted for three differ-
Ni33Mn_1100 2.1 2.1 0.3 0.2 ent bed temperatures. The values for experiments done at 950 °C after
Ni33Mn_1200 2.4 2.4 0.0 0.1
operation at 1050 °C are also included. It can be seen that higher opera-
tion temperatures led to higher oxygen concentrations in the exhaust
3. Results gas.
For Cu–Fe-based materials (Fig. 3, left side), it is clear that those with
3.1. Physical properties the highest copper content, Cu30Fe_950 and Cu30Fe_1025, performed
significantly better than the other six materials. Moreover, it can be
The specific surface area and the bulk density of the Cu–Fe and Mn–Ni seen that the average oxygen concentration was proportional to the
oxygen carrier particles are given in Table 3. It can be seen that for Mn–Ni copper content of the oxygen carrier material. The difference between
based materials the density increased with increasing calcination temper- materials with the same material composition but different calcination
ature. For Cu–Fe based materials, this trend was more pronounced at temperature was marginal.
higher copper content. During reactivity testing in the batch fluidized bed When looking at the data for Mn–Ni materials (Fig. 3, right side), it
reactor, the bulk density changed just for Cu–Fe and there seems to be a becomes obvious that just the materials produced from 34 wt.% NiO
trend towards a similar density for all particles with a specific Cu–Fe ratio. showed a noteworthy oxygen release. With respect to calcination tem-
Regarding the specific surface area, it can be noted that it decreased perature during manufacturing of the oxygen carriers, it can be said that
for both material groups with increasing calcination temperature which lower calcination temperatures led to higher oxygen concentrations.
may indicate a decreasing porosity. Comparing the fresh and used state, This effect was more pronounced at lower fluidized bed temperatures.
particles with low calcination temperature underwent a decrease in To measure the maximum oxygen release rate as well as the oxygen
specific surface area whereas those with higher calcination temperature transfer capacity RO, CLOU cycles were performed in a thermogravimet-
tended to remain rather constant. ric analyzer (TGA) at 950 °C as explained in Section 2.2. The correspond-
With respect to different copper contents, no major effect on surface ing results are summarized in Table 4 and TGA curves of selected
area could be observed for particles calcined at the same temperature. carriers (one for each synthesis composition) are shown Fig. 4. For
The same is valid for the nickel content which neither had a strong influ- Mn–Ni-based materials, just those who showed significant oxygen re-
ence on surface area nor bulk density. lease in the fluidized bed experiment were investigated by TGA.
It can be seen that the oxygen transfer capacity and the maximum
3.2. CLOU oxygen release release rate increased with increasing copper content. For
Cu30Fe_950, RO was 6.5 times higher than for the material produced
The spontaneous oxygen release due to chemical-looping with oxy- from 5 wt.% CuO, e.g. Cu5Fe_950. Regarding the max. O2 uncoupling
gen uncoupling has been assessed by switching the reactor from rate, a value 11 times higher could be achieved for Cu30Fe_950

Fig. 3. Average oxygen concentration during inert period for Cu–Fe (left) and Mn–Ni oxygen carriers (right).
 V. Frick et al. / Fuel Processing Technology 150 (2016) 30–40
Fig. 4. TGA-curves for CLOU oxygen release at 950 °C for selected oxygen carriers.
compared to Cu5Fe_950. With respect to calcination temperature, it can
be seen that differences in transfer capacity and release rate for mate-
rials with low copper content (Cu5Fe, Cu15Fe) were marginal whereas
for materials produced from 30 wt.% CuO, both values decreased for in-
creasing calcination temperature.
For the Mn-Ni-based materials, it can be concluded that there was
just a marginal change in transfer capacity when increasing calcination
temperature. In contrast, the oxygen release rate decreased almost lin-
early for increasing calcination temperature.
Concerning the evolution of CLOU reaction rate with time (s. Fig. 4),
it is apparent that the mass change of the oxygen carriers was highest
within the first minute of exposure to N2 and decreased with time.
However, the materials still showed a measurable weight change even
after 5 min. Whether this behavior limits a chemical-looping process
depends on the specific residence time distribution of the particles in
the fuel reactor.
3.3. Fuel conversion
Research on combustion of gaseous fuels was done to assess the ma-
terials' capability to provide oxygen. In a first stage, combustion of syn-
gas was investigated as H2 and CO are both easy to convert. Fig. 5 shows
the conversion of CO which is expressed by the CO2 yield as a function of
temperature.
It is clear that all materials showed a high degree of syngas conver-
sion at 950 °C. Concerning hydrogen, full conversion to H2O was
achieved for all materials.
In contrast, conversion of methane was more difficult than conver-
sion of syngas. This becomes quite obvious when comparing Fig. 6
with Fig. 5. Interestingly, only Cu–Fe based materials produced from
Fig. 5. CO2 yield as a function of oxygen carrier conversion for combustion of syngas at 950 °C for Cu–Fe oxygen carriers (left) and Mn–Ni oxygen carriers (right).
35
15 wt.% CuO and Mn–Ni based materials produced from 34 wt.% NiO ex-
hibited a high and relatively stable methane conversion. For Mn–Ni, the
reactivity towards methane seems to be related to the nickel content.
With respect to the impact of calcination temperature, it is clear that
lower calcination temperatures promoted reactivity towards methane.
Regarding conversion of methane, the average CO2 yield as a func-
tion of temperature is shown in Fig. 7. In most cases, higher tempera-
tures promoted gas conversion. At a bed temperature of 1050 °C, all
oxygen carriers but Ni5Mn_1200 and Ni10Mn_1000 achieved a CO2
yield above 0.9. Exceptional reactivity was found for Ni33Mn_1000
and Ni33Mn_1100 with an average CO2 yield greater than 0.95 for all
temperatures investigated.
Comparison of methane conversion before and after operation at
1050 °C shows that most materials retained their reactivity. A significant
deviation can be seen for Ni10Mn_1000 which exhibited a lower gas
conversion at 1050 °C and even lower at 950 °C. Reactivity deteriorated
also for Cu5Fe_950, Cu15Fe_1100 and Cu30Fe_950 due to high temper-
ature operation. High reactor temperatures together with strongly re-
ducing conditions are known to cause structural changes especially in
materials based on elements with low melting point such as copper.
During activity testing, most materials tended to form agglomera-
tions. Only Cu5Fe_950 did not show any signs of agglomeration. All ag-
glomerations had in common that they were rather soft and fell apart
when some force was applied.
3.4. Mechanical durability
The mechanical durability was assessed by measuring the crushing
strength of fresh particles and the attrition rate for used particles. A
low attrition rate and high crushing strength are preferred properties
of oxygen carriers in fluidized bed applications. The measurement re-
sults for Cu–Fe-based materials are summarized in Fig. 8.
It is apparent that the crushing strength of the fresh particles in-
creased for increasing calcination temperature indicating a higher me-
chanical durability. Interestingly, only the used particles produced
from 15 wt.% CuO followed this trend i.e. they showed a lower attrition
index for materials with higher calcination temperature. All other used
Cu–Fe-based particles exhibited a fairly low attrition rate which was in-
dependent from calcination temperature. This suggests that their me-
chanical properties must have significantly been altered due to
reactivity testing.
To determine whether an oxygen carrier might be interesting for
further research, the average CO2 yield at 950 °C is plotted versus the at-
trition index for all Cu-Fe-based materials being part of the investigation
(s. Fig. 8, right side). As the attrition rate resembles the mechanical du-
rability after reactivity testing, values for the CO2 yield at 950 °C after
operation at 1050 °C are used likewise. With respect to methane conver-
sion and attrition index, the oxygen carriers Cu30Fe_950 and
Cu30Fe_1025 are highly interesting candidates as they both showed
36 V. Frick et al. / Fuel Processing Technology 150 (2016) 30–40

Fig. 6. CO2 yield as a function of oxygen carrier conversion at 950 °C for combustion of methane.

high gas conversion and a low attrition index. Not equally good but still
remarkable are the oxygen carriers Cu5Fe_950, Cu5Fe_1025 and
Cu15Fe_1100. They had a somewhat higher attrition rate but still fairly
high CO2 yields.
For oxygen carriers based on Ni, mechanical durability was only
assessed by measuring the crushing strength as usage of the attrition
rig is restricted to non-toxic material. In a similar manner as for the
Cu-Fe-based materials, the CO2 yield is plotted versus the mechanical
durability which in this case is represented by the crushing strength in-
stead of the attrition index as can be seen in Fig. 9.
Interestingly, the particles with different Ni content followed deviat-
ing trends for CO2 yield and crushing strength when calcined at differ-
ent temperatures. Those produced from 34 wt.% NiO showed
significant changes in crushing strength but had an almost constant
gas conversion. In contrast, the materials produced from 5 wt.% NiO ex-
hibited an almost inversely proportional relationship between CO2 yield
and crushing strength.
It is apparent that the best candidate with respect to methane con-
version is the material with the highest Ni content sintered at 1200 °C,
Ni33Mn_1200. This oxygen carrier had a fairly high crushing strength
and almost full gas conversion. Also, the other two materials with the
same Ni content might be interesting candidates as mechanical durabil-
ity was just tested for fresh materials and solidification might have oc-
curred due to repeating reduction and oxidation cycles.
3.5. X-ray diffraction results
The crystalline phases have been analyzed by X-ray diffraction to
draw conclusions about the mechanism responsible for CLOU oxygen
release and to check if the material could be reoxidized by 5 vol.% O2
after having been exposed to reducing gases such as CH4 and syngas.
The phases determined from X-ray diffractograms are listed in Table 5.
The predominant phases detected in all Cu–Fe materials were Fe2O3
and the copper–iron spinel phase (CuxFe1 − x)3O4. This spinel phase is a
solid solution of CuFe2O4 and Fe3O4. In some samples, also single Fe3O4
of spinel type has been detected but this result is quite uncertain as peak
overlapping occurs with the other spinel phase. Comparison with the
Cu–Fe–O phase diagram generated by Khvan et al. [36] shows that the
detected crystalline phases in the used samples agree well with chemi-
cal equilibrium at 950 °C and 5 vol.% O2 indicating that reoxidation was
possible under these conditions. From the phase diagram and the XRD
data, it can be concluded that CLOU oxygen release most likely occurred
due to the phase change expressed by Eq. (9).


ðCux Fe1−x Þ3 O4 þ Fe2 O3 ↔ Cux Fe5=3−x 3 O4 þ 3=2O2 ð9Þ
From the phase diagram [36], it can be seen that oxygen release
Cu
should improve with increasing copper content in the range 0≤ CuþFe ≤0

Fig. 7. Average CO2 yield from methane conversion as a function of temperature. Left side: Cu–Fe materials, right side: Mn–Ni materials.
 V. Frick et al. / Fuel Processing Technology 150 (2016) 30–40 37

Fig. 8. Left side: attrition (used particles) and crushing strength (fresh particles) data for investigated materials. Right side: average CO2 yield for methane conversion at 950 °C as a function
of attrition index for Cu–Fe particles.

:45 as the phase boundary approaches lower temperatures. This agrees
well with the results for oxygen uncoupling in Section 3.2.
For the materials based on Mn–Ni, spinel-type (MnxNi1 − x)3O4 has
been found in all samples. Furthermore, Mn3O4 (Hausmannite) and
Mn2O3 were frequently found in the used samples. For materials pro-
duced from 34 wt.% NiO, NiO was found in all fresh as well as used sam-
ples. By comparison with a phase diagram for Mn–Ni in air, published by
Golikov and Balakirev [37], it becomes obvious that the predominant
phases occurred according to chemical equilibrium. For the fresh sam-
ples of Ni5Mn and Ni10Mn, the existence of the phases Mn–Ni-spinel,
Mn2O3 and Mn3O4 can be explained either by the production conditions
or by the fact that they were cooled down in air after calcination. Only
for the Ni33Mn materials, the presence of the phases Mn3O4 and NiO
can't be explained by chemical equilibrium as they are not stable in
the relevant temperature interval. A possible explanation for this is
that the raw materials of these two compounds might not have been
milled and mixed sufficiently to form the common Mn–Ni-spinel
phase. In the used samples, it can be seen that the same phases occurred
as in the fresh samples. With respect to reoxidation of the particles, this
is a good sign because all phases formed during reduction seem to have
been oxidized back to the original phases.
Possible mechanisms for CLOU oxygen release for Ni5Mn and
Ni10Mn can't be formulated from the phase diagram [37] because
phase transformation from the two phases, stable at 900 °C, Mn–Ni-spi-
nel and Hausmannite (Mn3O4) to Mn–Ni-spinel does not yield gaseous
oxygen. This has also been observed during CLOU experiments (s.
Section 3.2). Oxygen release is only possible at strongly reducing condi-
tions. In contrast, for Ni33Mn, oxygen release is possible by converting
the Mn–Ni-spinel to NixMn1 − xO which enables formation of gaseous
oxygen according Eq. (10).
be suitable for CLC with respect to methane conversion and mechanical
durability.
In the overview images, it can be noted that the particles mostly
have a spherical shape and it seems to be quite common that they
have one or more small satellite particles attached to them. Some parti-
cles even exhibit a donut shape and are sometimes filled with smaller
particles. When comparing pre and post-reaction particles, no agglom-
erations can be seen at this scale but some debris can be found in the
used samples. The satellites on the particles are likely to have been
worn off during the attrition test and with an optimized production
method it is likely that more uniform particles can be produced that
have less satellites on them and hence lower attrition.
At 10,000× magnification, it can be noted that for the copper–iron
material the grain size increased and the pore number decreased as a re-
sult of activity testing which indicates a decreased particle porosity. For
the Mn–Ni material, no major change in surface morphology can be ob-
served. The grain size and shape seem to be similar but there might be a
slight increase in pore number. These observations agree well with the
changes in physical properties described in Section 3.1 as a significant
increase in bulk density and a notable decrease in surface area have
been detected for Cu30Fe_950. In contrast, Ni33Mn_1200 showed no
change in bulk density and just a slightly higher specific surface area.

1
ðNix Mn1−x Þ3 O4 ↔3 Nix Mn1−x O þ O2 ð10Þ
2

At strongly reducing conditions e.g. very high temperatures,

NixMn1 − xO might even decompose to elemental nickel and depleted
NixMn1 − xO [37].

3.6. Electron imaging (SEM)

Electron images were taken with low (260 ×), intermediate

(~ 2000 ×) and high magnification (10,000 ×) to identify changes in
the particle collective, the morphology of a selected particle and the mi-
crostructure on the particle's surface when comparing fresh and used
samples. From the Cu–Fe and Mn–Ni-based materials, Cu30Fe_950 Fig. 9. Average CO2 yield from methane conversion at 950 °C as a function of crushing
(Table 6) and Ni33Mn_1200 (Table 7) are presented as they proved to strength.
38 V. Frick et al. / Fuel Processing Technology 150 (2016) 30–40

Table 5 min (45 wt.% CuO) according to the definition in Section 2.2. In our
Crystalline phases detected by X-ray diffraction. work, the highest rate measured was 3.3 wt.%/min for Cu30Fe_950
Oxygen carrier fresh sample used sample which is in line with the results from Clayton and Whitty.
Cu5Fe_950 Fe2O3, (CuxFe1 − x)3O4, (Fe3O4) Fe2O3, (CuxFe1 − x)3O4
Moreover, all Cu–Fe materials showed nearly full syngas conversion.
Cu5Fe_1025 Fe2O3, (CuxFe1 − x)3O4, Fe3O4 Fe2O3, (CuxFe1 − x)3O4, Fe3O4 With respect to methane conversion, still 4 materials achieved a CO2
Cu5Fe_1100 Fe2O3, (CuxFe1 − x)3O4 Fe2O3, (CuxFe1 − x)3O4, Fe3O4 yield above 90% for a process temperature as low as 950 °C. If related
Cu15Fe_950 Fe2O3, (CuxFe1 − x)3O4, Fe3O4 Fe2O3, (CuxFe1 − x)3O4, Fe3O4 to the Cu-based oxygen carrier CuAl2O4 investigated previously by
Cu15Fe_1025 Fe2O3, (CuxFe1 − x)3O4, (Fe3O4) Fe2O3, (CuxFe1 − x)3O4, Fe3O4
Arjmand et al. [24], it can be said that the methane conversion is
Cu15Fe_1100 Fe2O3, (CuxFe1 − x)3O4, (Fe3O4) Fe2O3, (CuxFe1 − x)3O4, Fe3O4
Cu30Fe_950 (CuxFe1-x)3O4, Fe2O3 (CuxFe1-x)3O4, Fe2O3, Fe3O4 lower for the materials investigated here. The fact that the oxygen car-
Cu30Fe_1025 (CuxFe1-x)3O4, Fe2O3 (CuxFe1-x)3O4, Fe2O3, Fe3O4 riers with 30 wt.% CuO, Cu30Fe_950 and Cu30Fe_1025, showed lower
Ni5Mn_1000 Mn2O3, (MnxNi1 − x)3O4 Mn3O4, (MnxNi1 − x)3O4, methane conversion than the carriers with 15 wt.% CuO is somewhat
Mn2O3 unexpected especially if taking the oxygen transfer capacities (s.
Ni5Mn_1100 Mn2O3, Mn3O4, (MnxNi1 − x)3O4 Mn3O4, (MnxNi1 − x)3O4,
Mn2O3
Table 4) into account. A possible explanation might be the 60 s inert
Ni5Mn_1200 Mn3O4, (MnxNi1 − x)3O4 Mn3O4, (MnxNi1 − x)3O4, purging period before introducing the fuel as a significant amount of ox-
Mn2O3 ygen could have already been released due to CLOU, especially for ma-
Ni10Mn_1000 Mn2O3, (MnxNi1 − x)3O4 (MnxNi1-x)3O4, Mn3O4, Mn2O3 terials with high oxygen release rate.
Ni10Mn_1100 Mn2O3, (MnxNi1 − x)3O4 (MnxNi1-x)3O4, Mn3O4, Mn2O3
The weaknesses of copper-based materials become obvious when
Ni10Mn_1200 (MnxNi1 − x)3O4, Mn3O4, Mn2O3 (MnxNi1-x)3O4, Mn3O4, Mn2O3
Ni33Mn_1000 (MnxNi1 − x)3O4, Mn3O4, NiO (MnxNi1-x)3O4, NiO turning to the mechanical properties. Low values for crushing strength
Ni33Mn_1100 (MnxNi1 − x)3O4, Mn3O4, NiO (MnxNi1-x)3O4, Mn3O4, NiO were measured before reactivity testing especially for oxygen carriers
Ni33Mn_1200 (MnxNi1 − x)3O4, Mn3O4, NiO (MnxNi1-x)3O4, Mn3O4, NiO with higher copper content. Interestingly, solidification occurred for
the weakest materials with highest copper content when exposing
them to high temperatures and reducing atmosphere so that they
4. Discussion reached the best values for the attrition index (used state). In the exten-
sive attrition study published by Rydén et al. [35], spray-dried CuO/ZrO2
The combined copper iron oxygen carriers, assessed within this particles showed attrition indices between 6.78 and 27 wt.%/h. Com-
work have shown very interesting chemical properties. They exhibited pared to these values, the particles with 5 and 30 wt.% CuO showed sig-
significant oxygen release even at temperatures as low as 850 °C. Both nificantly better attrition behavior.
materials produced from 30 wt.% CuO, Cu30Fe_950 and Cu30Fe_1025, When considering chemical and mechanical performance, it
showed oxygen release superior to the other materials with O2 concen- can be seen that the two materials produced from 30 wt.% CuO
trations above 2 vol.% for a process temperature of 1050 °C. Likewise, showed both a high methane conversion and a substantial me-
they had the highest oxygen transfer capacity and the fastest oxygen re- chanical durability after having been exposed to cyclic oxidation
lease rate which can be explained by the course of the phase boundary and reduction which makes them interesting candidates for fur-
relevant for CLOU oxygen release. In literature, some data on CLOU reac- ther research.
tion kinetics determined by TGA is available. Cu-based oxygen carriers The most striking result for the combined Mn–Ni oxygen carriers is
prepared by wet impregnation and freeze granulation were assessed the CLOU oxygen release: materials with high Ni content released sig-
by Clayton and Whitty [38]. They determined a decomposition rate of nificant amounts of oxygen whereas materials produced from 5 or
about 0.003 gO2/(gCu*s) at 950 °C for the carrier with 45 wt.% CuO on 10 wt.% NiO released only traces. The materials produced from
ZrO2 and a slightly lower rate for 16 wt.% CuO on SiO2 which corre- 34 wt.% NiO also proved to have a high oxygen transfer capacity and
sponds to a rate ranging from 2.3 wt.%/min (16 wt.% CuO) to 6.5 wt.%/ O2 release rate.

Table 6
SEM images of Cu30Fe_950 in fresh and used state: overview image, individual particle and microstructure at 10,000× magnification.

Overview Individual particle /10,000× magn.

Cu30Fe_950 (fresh)

Cu30Fe_950 (used)
 V. Frick et al. / Fuel Processing Technology 150 (2016) 30–40
Table 7
SEM images of Ni33Mn_1200 in fresh and used state: overview image, individual particle and microstructure at 10,000× magnification.
Overview
Ni33Mn_1200 (fresh)
Ni33Mn_1200 (used)
Regarding conversion of fuel, all Mn–Ni-based materials showed sig-
nificant gas conversion as additional oxygen release is possible at
strongly reducing conditions. Even though all materials showed almost
full and stable syngas conversion, huge differences for methane conver-
sion could be seen: Ni5Mn and Ni10Mn showed similar CO2 yields be-
tween 40 and 90% but Ni33Mn exhibited a CO2 yield between 90 and
100%. Interestingly, the materials with high Ni content showed almost
full gas conversion (99.6–99.9%) for methane at 1050 °C and a similar
conversion for syngas at 950 °C. In literature, it is reported that the sys-
tem NiO/Ni is not capable of fully converting methane or CO at relevant
temperatures [39]. By combining Ni with Mn, this limitation seems to
have been overcome. A reason for this is possibly the formation of
solid solutions such as Ni–Mn spinel which have significant impact on
oxygen release and possibly also cause changes in chemical equilibrium
for combustion of methane and CO. An intensively tested Ni-based oxy-
gen carrier is NiO on NiAl2O4 produced by spray drying. Jerndal et al.
[40] have investigated different manufacturing parameters for this car-
rier and have determined a crushing strength between 1.2 and 1.9 N
(same NiO quality as used in this manuscript: Novamet Green grade
F) and a CO2 yield for combustion of methane between 0.8 and 0.99.
Ni33Mn_1200, which can be best used for comparison (similar NiO con-
tent and calcination temperature), has an analog crushing strength and
seems to be superior with respect to methane conversion.
With respect to physical properties, it was established that the calci-
nation temperature is decisive for bulk density, specific surface area and
crushing strength i.e. the mechanical durability. Attrition tests on used
Mn–Ni oxygen carriers were not performed because of their toxicity.
Anyhow, it is likely that the Mn–Ni particles retained their mechanical
strength throughout activity testing as their physical properties
remained fairly constant. The same can be concluded when looking at
the electron microscope images as they show a similar particle mor-
phology in fresh and used state.
From a mechanical and reactivity point of view, it can be concluded
that among Mn–Ni-based materials, Ni33Mn_1200 is most suitable for
conversion of gaseous fuels as it fully converted both methane and syn-
gas (CO + H2). Nevertheless, also Ni5Mn_1200 and Ni10Mn_1200 are
interesting candidates as they had a high crushing strength and high
methane as well as full syngas conversion.
39
Individual particle /10,000× magn.
A drawback of all materials assessed in this study is that they formed
agglomerations during testing in the batch fluidized bed reactor at tem-
peratures as high as 1050 °C. Whether this turns out to be relevant for
real application remains to be shown in a continuous unit. This is mainly
because the fluidization conditions present in the batch fluidized bed
reactor are different from those in continuous dual fluidized bed reac-
tors. Especially the reactor temperatures used for investigation of the
materials are higher than those commonly used in continuous CLC
units which are mostly limited to 950 °C. Furthermore, it is likely that
the degree of reduction of the oxygen carrier will be different in a con-
tinuous reactor system which can significantly change the melting point
of the material and thereby its agglomeration tendency.
5. Conclusions
The fuel conversion and physical properties of 17 spray-dried com-
bined Cu–Fe and Mn–Ni oxygen carriers were investigated. Parameters
varied during material production were the material composition and
the calcination temperature.
Regarding conversion of syngas all materials showed an almost full
gas conversion. With respect to conversion of methane, several material
combinations were identified with a CO2 yield of N90% at 950 °C. Excep-
tionally high CO2 yields were measured for the Ni–Mn-based materials
produced from 34 wt.% NiO which is equal or even better than compa-
rable materials presented in literature.
Significant CLOU oxygen release was detected for all Cu-Fe materials
but just for one material combination of Mn–Ni which could be ex-
plained by the corresponding phase diagrams.
By testing mechanical durability and investigation of surface mor-
phology before and after fluidized-bed testing, promising candidates
for application in chemical-looping combustion were identified. Com-
pared to similar materials investigated by other researchers, an im-
proved mechanical strength has been acquired for some of the
copper- and nickel-based materials.
Especially noteworthy with respect to reactivity and mechanical du-
rability are the two oxygen carriers produced from 30 wt.% CuO and
sintered at 950/1025 °C as well as the carrier produced from 34 wt.%
NiO and calcined at 1200 °C.
40 V. Frick et al. / Fuel Processing Technology 150 (2016) 30–40
Acknowledgement
This study has been funded by the Swedish Energy Agency and
Preem AB. The authors gratefully acknowledge the financial support.
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