Chemical Looping with Oxygen Uncoupling (CLOU) Studies at the University of Utah

JoAnn S. Lighty, Professor and Chair (jlighty@utah.edu)

Asad H. Sahir, Ph.D. Candidate
Kevin Whitty, Associate Professor
Chris Clayton, Ph.D. Candidate
Department of Chemical Engineering, Institute for Clean and Secure Energy, University of Utah,
50 S. Central Campus Drive, Room 3290 Salt Lake City, UT 841129203
Tel: (801) 5816915, Fax: (801) 5859291
ABSTRACT:
Chemical-looping with oxygen uncoupling (CLOU) is one of the emergent fuel combustion
technologies being currently investigated which has the potential to assist with CO2 capture from
coal-fired power plants. CLOU involves the combustion of fuel in the presence of gaseousphase oxygen released from the decomposition of an oxygen carrier (OC) metal oxide (e.g.
CuO). Compared to Chemical-looping Combustion (CLC), the CLOU process has the promise
of reducing the fuel reactor volume and the OC inventory.. The CLC process requires slower
pre-gasification reaction of the solid fuel into synthesis gas, which is eventually oxidized by the
circulating oxygen carrier.
The presentation discusses components of the program at the University of Utah including
laboratory-scale fluidized bed experiments, process modelling, and construction of a new 100200 kW process development unit (PDU). The goal of the laboratory-scale experiments is to
derive kinetics for the reduction and oxidation of the OCs. The process model is being used to
explore material and energy balance scenarios. These scenarios are looking at the amount of
OC circulated and, given the kinetics, OC inventories needed. The process model also shows
potential heat recovery. Finally, the PDU design considerations are discussed and updates on
the construction given.
INTRODUCTION:
Coal-fired power plants contribute to significant CO2 emissions, which has encouraged
investigation of processes that can capture CO2 with reduced energy penalty. Lab-scale and
pilot scale chemical-looping combustion (CLC) studies have demonstrated the possibility of
facilitating carbon capture [1,2]. A chemical-looping combustion system typically involves two
interconnected fluidized-bed reactors with a metal oxide circulating between them. One of the
reactors serves as a fuel reactor, in which the fuel is combusted with the help of oxygen
supplied by the circulating metal oxide. After being reduced, the metal oxide is regenerated by
reaction with atmospheric oxygen in the air reactor. Chemical-looping combustion (CLC) for
solid fuels involves the following reactions in the fuel reactor: drying (a rapid reaction),
devolatilization (occurring within a second), gasification (on a time scale of minutes) and the
reduction of oxygen carrier by the gases produced by devolatilization and gasification of coal [3].
The slow gasification reactions limit the rate of fuel conversion, resulting in comparatively large
reactors.
Researchers at Chalmers University of Technology in Sweden recognized the limitation of using
CLC technology for processing coal, and several years ago began developing a new generation
of oxygen carriers (OCs). Specifically, they focused on carriers that could spontaneously
release the oxygen in the fuel reactor as gaseous O2. Through thermodynamic analysis, three
metal oxides were identified which have a suitable oxygen partial pressure at fuel reactor

temperatures: CuO, Mn2O3 and Co3O4 [4]. These materials will release, or uncouple, oxygen
under fuel reactor conditions:
4 CuO 2 Cu2O + O2(g)

(1)

6 Mn2O3 4 Mn3O4 + O2(g)

(2)

2 Co3O4 6 CoO + O2(g)

(3)

Because it is in gaseous form, the oxygen released by these reactions can react with solid coal
(char) in the same manner as in a conventional combustion system; therefore, it is not
necessary to have the solid carbon reaction with CO2 and/or water vapor to form a gaseous fuel
to react with a solid metal oxide. This concept, chemical-looping with oxygen uncoupling, or
CLOU, is schematically illustrated in Figure 1 for the CuO/Cu2O system. Solid coal can be
introduced directly into the fuel reactor.
Thermodynamic analysis indicates that the partial pressure of oxygen over the uncoupling
carriers is sufficient for them to release oxygen at conditions of the fuel reactor (low O2 partial
pressure, temperature 900-1100C), and for them to re-oxidize at conditions in the air reactor
(relatively high O2 partial pressure, temperature 800-950C).

Figure 1. Schematic of the CLOU process for using a copper oxide-based oxygen carrier and coal as the
fuel. Oxygen (O2) is spontaneously released (uncoupled) in the fuel reactor and subsequently reacts
with carbon and hydrogen in the coal. The fuel reactor is fluidized by steam and/or recirculated CO2.

Of the proposed metal oxide systems above, the copper oxides are most promising as the
overall reactions in the fuel reactor are exothermic and the rates of reaction are faster for the
uncoupling reaction. Further, the exothermic nature of the reaction adds flexibility with respect
to recirculation rates of the solid material between the air and fuel reactor since it is not
necessary to provide sensible energy from the air reactor to the fuel reactor. For example,
compared to a CLC process, a 45-60 fold increase in reaction rate, for a petcoke with a CuObased carrier, was found using CLOU at temperatures between 950-985C [4,5].

UNIVERISTY OF UTAH WORK

The University of Utah has been researching the CLOU process since 2007 with support from
the U.S. Department of Energy. Efforts have focused on the CuO/Cu2O system (Figure 2),
since the copper-based carriers offer the best reactivity and economics. In this case the
reactions are:
4CuO 2 Cu2O + O2 and C + O2 CO2 in the fuel reactor

(4)

2 Cu2O + O2 4 CuO in the air reactor

(5)

To date, we have focused on OC kinetics, lab-scale studies, and process modeling.

Oxygen Carrier Kinetics and Lab-Scale Studies
The work on OC kinetics has been completed in both TGA studies and lab-scale fluidized bed
reactors. The kinetics of both uncoupling oxygen (reduction) and oxidation are of importance.
To avoid agglomeration of the OC, copper oxide must be on a support material. A variety of
supports and copper concentrations have been studied. Recently a copper-oxide on silicon
carbide has been studied and has been shown to be stable. Materials from Chalmers have also
been investigated.
Experimental data from these studies, and lab-scale fluidized bed, work have resulted in the
determination of kinetic parameters. This is shown in Figure 2.

-110 kJ/mol

Figure 2. Kinetics for a variety of materials in TGA, fluidized bed, and fixed bed.
Other values have ranged from 280-300 kJ/mol. These data are important to determine the
times required for reduction, carbon oxidation, and copper oxide oxidation. Figure 4 illustrates
the case for a PRB coal. As seen in this figure, for the fuel reactor, the limiting reaction is the
reduction of the copper oxide. Interestingly, the rate for the copper oxide oxidation decreases
with increasing temperature, resulting in an increase in residence time. This is currently under
further investigation but it has been shown that diffusion versus kinetics might be controlling at
these higher temperatures.

Figure 3. Residence times for 40% CuO/60% ZrO2 particles in a batch fluidized bed
[Size= 125-180 m]. Times are based on 60% and 64% conversion for reduction and oxidation,
respectively.

Process Modeling
The results above determine the amount of material needed to recycle between the two reactors
and the amount in the reactor at any given time. It was desired to keep the residence times
below 100 seconds, which determine the temperatures of the reactors. Table 1 lists the
parameters that were used in an ASPEN Plus model of the process for a feed rate of 100 kg/hr
of a PRB coal.
Table 1. Parameters in the ASPEN Plus Simulation
Air Flow Rate
Temperature of Fuel Reactor investigated
Temperature of Air Reactor investigated
Amount of Cu circulating in the system
(represents 40% CuO on ZrO2)
Amount of ZrO2 circulating in the system
Fraction of flue gas stream recycled for
fluidization for fuel reactor particles
Particle density
Design superficial velocity for fuel reactor
calculated based on particle properties
Design superficial velocity for air reactor
calculated based on particle properties

895 kg/h
950C
935C
3262
kg/h
4579
kg/h
0.69
2140
kg/m3
2.1 m/s
2.4 m/s

The ASPEN Plus process model results in various heat resources. These are individually listed
in Table 2. The entire process, assuming no heat losses, releases approximately 510 kW of

energy. The process model can now be used to investigate different kinetics, conversion rates,
and scenarios.
Table 2. Results from ASPEN Plus Modeling, Energy Sources/Sinks
ENERGY
Fuel reactor
Air reactor
Cool air reactor exhaust from 935C to 150C
Cool flue gas from 950C to 150C
Cool OC for air reactor operation
Reheat OC for fuel reactor operation
Reheat recycle gas from 150C to 950C
Heat air from 25C to 935C
PUMPING/COMPRESSION
Fluidize particles in fuel reactor
Fluidize particles in air reactor

109 kW
394 kW
174 kW
272 kW
22 kW
-23 kW
-185 kW
-241 kW
-3 kW
-6 kW

Future Work
A final step is the construction of a 100-200 kW process development unit (PDU). The PDU is
comprised of two circulating fluidized beds. This unit can further develop the material and
energy balances and begin to investigate operating conditions such as attrition and fluid
dynamics.
REFERENCES:
[1] Adanez J. et al. (2012), Progress in Chemical-Looping Combustion and Reforming
technologies, Progress in Energy and Combustion Science 38(2), pp. 215-282.
[2] Fan L.S. et al. (2012), Chemical looping processes for CO2 capture and carbonaceous fuel
conversion prospect and opportunity, Energy Environ. Sci. 5, pp. 7254-7280.
[3] Linderholm C. et al. (2012), Chemical-looping combustion of solid fuels Operation in a
10kW th unit with two fuels, above-bed and in-bed fuel feed and two oxygen carriers, manganese
ore and ilmenite, Fuel, DOI:10.1016/j.fuel.2012.05.010.
[4] Mattison, T., Lynfelt, A., Leion, H., (2009), Chemical-Looping with Oxygen Uncoupling Using
CuO/ZeO2 with Petroleum Coke, Fuel 88: 683-690.
[5] Abad, A., et al., Demonstration of Chemical Looping with Oxygen Uncoupling Process in a
1.5 kWth Continuously Operating Unit using a Cu-Based Oxygen Carrier, International Journal
of Greenhouse Gas Control, 6:189-200 (2012).