Experimental validation of packed bed chemical-looping combustion

Chemical-looping combustion has emerged as a promising alternative technology, intrinsically integrating CO₂ capture in power production. A novel reactor concept based on dynamically operated packed beds has been proposed [Noorman, S., van Sint Annaland, M., Kuipers, J.A.M., 2007. Packed bed reactor technology for chemical-looping combustion. Ind. Eng. Chem. Res. 46, 4212-4220] and in this work, packed bed chemical-looping combustion was investigated experimentally to provide an experimental proof-of-principle. Using information obtained from both the reduction and oxidation cycles, the measured maximum temperature rise and front velocities in the packed bed during the oxidation cycle corresponded very well with analytical expressions describing the system, especially when the contribution of the formation of carbon during the reduction cycle was taken into account.     

Comparison of iron-, nickel-, copper- and manganese-based oxygen carriers for chemical-looping combustion

For combustion with CO₂ capture, chemical-looping combustion (CLC) with inherent separation of CO₂ is a promising technology. Two interconnected fluidized beds are used as reactors. In the fuel reactor, a gaseous fuel is oxidized by an oxygen carrier, e.g. metal oxide particles, producing carbon dioxide and water. The reduced oxygen carrier is then transported to the air reactor, where it is oxidized with air back to its original form before it is returned to the fuel reactor. The feasibility of using oxygen carrier based on oxides of iron, nickel, copper and manganese was investigated. Oxygen carrier particles were produced by freeze granulation. They were sintered at 1300 °C for 4 h and sieved to a size range of 125-180 μm. The reactivity of the oxygen carriers was evaluated in a laboratory fluidized bed reactor, simulating a CLC system by exposing the sample to alternating reducing and oxidizing conditions at 950 °C for all carriers except copper, which was tested at 850 °C. Oxygen carriers based on nickel, copper and iron showed high reactivity, enough to be feasible for a suggested CLC system. However, copper oxide particles agglomerated and may not be suitable as an oxygen carrier. Samples of the iron oxide with aluminium oxide showed signs of agglomeration. Nickel oxide showed the highest reduction rate, but displayed limited strength. The reactivity indicates a needed bed mass in the fuel reactor of about 80-330 kg/MW_th and a needed recirculation flow of oxygen carrier of 4-8 kg/s, MW_th.     

Enhanced weathering to capture atmospheric carbon dioxide: Modeling of a trickle-bed reactor

Enhanced weathering (EW) of alkaline minerals can potentially capture CO₂ from the atmosphere at gigaton scale, but the reactor design presents great challenges. We model EW with fresh water in a counter-current trickle flow packed bed batch of 1–10 mm calcite particles. Weathering kinetics are integrated with the mass transfer of CO₂ incorporating transfer enhancement by chemical reaction. To avoid flooding, flow rates must be reduced as the particles shrink due to EW. The capture rate is mainly limited by slow transfer of CO₂ from gas to liquid although slow dissolution of calcite can also play a role in certain circumstances. A bed height of at least 7–8 m is required to provide sufficient residence time. The results highlight the need to improve capture rate and reduce energy and water consumption, possibly through enriching the feed with CO₂ and further chemical acceleration of the mass transfer.     

Carbon deposition characteristics and regenerative ability of oxygen carrier particles for chemical-looping combustion

For gaseous fuel combustion with inherent CO₂ capture and low NO_x emission, chemical-looping combustion (CLC) may yield great advantages for the savings of energy to CO₂ separation and suppressing the effect on the environment. In a chemical-looping combustor, fuel is oxidized by metal oxide medium (oxygen carrier particle) in a reduction reactor. Reduced particles are transported to the oxidation reactor and oxidized by air and recycled to the reduction reactor. The fuel and the air are never mixed, and the gases from the reduction reactor, CO₂ and H₂O, leave the system as separate streams. The H₂O can be easily separated by condensation and pure CO₂ is obtained without any loss of energy for separation. In this study, NiO based particles are examined from the viewpoints of reaction kinetics, carbon deposition, and cyclic use (regenerative ability). The purpose of this study is to find appropriate reaction conditions to avoid carbon deposition and achieve high reaction rate (e.g., temperature and maximum carbon deposition-free conversion) and to certify regenerative ability of NiO/bentonite particles. In this study, 5.04% methane was used as fuel and air was used as oxidation gas. The carbon deposition characteristics, reduction kinetics and regenerative ability of oxygen carrier particles were examined by TGA (Thermal Gravimetrical Analyzer).     

The reaction of NiO/NiAl2O4 particles with alternating methane and oxygen

The reduction and oxidation behaviour of oxygen carrier particles of NiO and NiAl₂O₄ has been investigated in a fluidized bed reactor as well as a thermogravimetric analyzer (TGA). The particles showed high reactivity and gas yield to CO₂ with methane in the temperature interval 750–950°C. In the fluidized bed the yield to CO₂ was between 90 and 99% using bed masses corresponding to 16–57 kg/MW_fuel. Complementary experiments in a TGA at 750 and 950°C showed a clear reaction of the NiAl₂O₄ with CH₄ at the higher temperature. There was methane released from the reactor at high degrees of solid oxidation, which is likely associated with the lack of Ni‐sites on the particles which can reform the methane. There was some carbon formation during the reduction, although the amount was minor when the gas yield to carbon dioxide and degree of oxidation of the solid was high. A simple reactor model using kinetic data from a previous study predicted the gas yield during the reduction in the fluidized bed experiments with reasonable accuracy. The oxygen carrier system investigated in this work shows high promise for use in a real CLC system, provided that the particle manufacturing process can be scaled up with reasonable cost.     

Gas leakage measurements in a cold model of an interconnected fluidized bed for chemical-looping combustion

In chemical-looping combustion (CLC) a gaseous fuel is burnt with inherent separation of the greenhouse gas carbon dioxide. The oxygen is transported from the combustion air to the fuel by means of metal oxide particles acting as oxygen carriers. A CLC system can be designed similar to a circulating fluidized bed, but with the addition of a bubbling fluidized bed on the return side. Thus, the system consists of a riser (fast fluidized bed) acting as the air reactor. This is connected to a cyclone, where the particles and the gas from the air reactor are separated. The particles fall down into a second fluidized bed, the fuel reactor, and are via a fluidized pot-seal transported back into the riser. The gas leaving the air reactor consists of nitrogen and unreacted oxygen, while the reaction products, carbon dioxide and water, come out from the fuel reactor. The water can easily be condensed and removed, and the remaining carbon dioxide can be liquefied for subsequent sequestration.The gas leakage between the reactors must be minimized to prevent the carbon dioxide from being diluted with nitrogen, or to prevent carbon dioxide from leaking to the air reactor decreasing the efficiency of carbon dioxide capture. In this system, the possible gas leakages are: (i) from the fuel reactor to the cyclone and to the pot-seal, (ii) from the cyclone down to the fuel reactor, (iii) from the pot-seal to the fuel reactor. These gas leakages were investigated in a scaled cold model. A typical leakage from the fuel reactor was 2%, i.e. a CO₂ capture efficiency of 98%. No leakage was detected from the cyclone to the fuel reactor. Thus, all product gas from the air reactor leaves the system from the cyclone. A typical leakage from the pot-seal into the fuel reactor was 6%, which corresponds to 0.3% of the total air added to the system, and would give a dilution of the CO₂ produced by approximately 6% air. However, this gas leakage can be avoided by using steam, instead of air, to fluidize the whole, or part of, the pot-seal. The disadvantages of diluting the CO₂ are likely to motivate the use of steam.     

Reactivity of a CaSO<Subscript>4</Subscript>-oxygen carrier in chemical-looping combustion of methane in a fixed bed reactor

Chemical-looping combustion (CLC) is a promising technology for the combustion of gas or solid fuel with efficient use of energy and inherent separation of CO₂. A reactivity study of CaSO₄ oxygen carrier in CLC of methane was conducted in a laboratory scale fixed bed reactor. The oxygen carrier particles were exposed in six cycles of alternating reduction methane and oxidation air. A majority of CH₄ reacted with CaSO₄ to form CO₂ and H₂O. The oxidation was incomplete, possibly due to the CaSO₄ product layer. The reactivity of CaSO₄ oxygen carrier increased for the initial cycles but slightly decreased after four cycles. The product gas yields of CO₂, CH₄, and CO with cycles were analyzed. Carbon deposition during the reduction period was confirmed with the combustible gas (CO+H₂) in the product gas and slight CO₂ formed during the early stage of oxidation. The mechanism of carbon deposition and effect was also discussed. SO₂ release behavior during reduction and oxidation was investigated, and the possible formation mechanism and mitigation method was discussed. The oxygen carrier conversion after the reduction decreased gradually in the cyclic test while it could not restore its oxygen capacity after the oxidation. The mass-based reaction rates during the reduction and oxidation also demonstrated the variation of reactivity of CaSO₄ oxygen carrier. XRD analysis illustrated the phase change of CaSO₄ oxygen carrier. CaS was the main reduction product, while a slight amount of CaO also formed in the cyclic test. ESEM analysis demonstrated the surface change of particles during the cyclic test. The reacted particles tested in the fixed bed reactor were not uniform in porosity. EDS analysis demonstrated the transfer of oxygen from CaSO₄ to fuel gas while leaving CaS as the dominant reduced product. The results show that CaSO₄ oxygen carrier may be an interesting candidate for oxygen carrier in CLC. This work was presented at the 7 ^th China-Korea Workshop on Clean Energy Technology held at Taiyuan, China, June 26–28, 2008.     

Multiphase CFD Modeling for a Chemical Looping Combustion Process (Fuel Reactor)

There are growing concerns about increasing emissions of greenhouse gases and a looming global warming crisis. CO₂ is a greenhouse gas that affects the climate of the earth. Fossil fuel consumption is the major source of anthropogenic CO₂ emissions. Chemical looping combustion (CLC) has been suggested as an energy‐efficient method for the capture of carbon dioxide from combustion. A chemical‐looping combustion system consists of a fuel reactor and an air reactor. The air reactor consists of a conventional circulating fluidized bed and the fuel reactor is a bubbling fluidized bed. The basic principle involves avoiding direct contact of air and fuel during the combustion. The oxygen is transferred by the oxygen carrier from the air to the fuel. The water in combustion products can be easily removed by condensation and pure carbon dioxide is obtained without any loss of energy for separation. With the improvement of numerical methods and more advanced hardware technology, the time required to run CFD (computational fluid dynamic) codes is decreasing. Hence, multiphase CFD‐based models for dealing with complex gas‐solid hydrodynamics and chemical reactions are becoming more accessible. To date, there are no reports in the literature concerning mathematical modeling of chemical‐looping combustion using FLUENT. In this work, the reaction kinetics models of the (CaSO₄ + H₂) fuel reactor is developed by means of the commercial code FLUENT. The effects of particle diameter, gas flow rate and bed temperature on chemical looping combustion performance are also studied. The results show that the high bed temperature, low gas flow rate and small particle size could enhance the CLC performance.     

Effect of fuel particle size on reaction rate in chemical looping combustion

Chemical looping combustion (CLC) uses an oxygen carrier circulating between an air and a fuel reactor to replace direct burning of fuels in air. The very low energy penalty for CO₂ separation in CLC gives it the potential to become an important technology on the way to a CO₂ neutral energy supply. In this work, the influence of the particle size of coal on the rate of reaction of the coal was investigated in a bed of oxygen carrier. In order to do this, a method to quench the reaction of coal with oxygen carriers at a specified time and measure the particle size distribution of the remaining coal was developed. Three size fractions of coal were used in the experiments: 90–125, 180–212 and 250–355 μm. Particle size distributions of the fuel show a decrease in particle size with time. The influence of devolatilisation of the coal on the coal particle size was measured, showing that coal particles do not break in the fluidized bed reactor used for the experiments. Reaction rates based on measurements of gas phase concentrations of CO₂, CO and CH₄ showed that the reaction rate is independent of the particle size. These results are in line with literature findings, as studies have shown that carbon gasification is size-independent at conditions similar to those in the performed CLC experiments.     

CO2 reduction with Zn particles in a packed‐bed reactor

A two‐step solar thermochemical cycle for splitting CO₂ with Zn/ZnO redox reactions is considered, consisting of: (1) the endothermic dissociation of ZnO with concentrated solar radiation as the heat source and (2) the non‐solar, exothermic, reduction of CO₂ to CO by oxidizing Zn to ZnO; the latter is recycled to the first step. The second step of the cycle is investigated using a packed‐bed reactor where micron‐sized Zn particles were immobilized in mixtures with submicron‐sized ZnO particles. Experimental runs were performed for Zn mass fractions in the range 67–100 wt % and CO₂ concentration in the range 25–100%, yielding Zn‐to‐ZnO conversions up to 71% because of sintering prevention, as corroborated by SEM analysis. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Mathematical modeling and simulation of steady state plug flow for lactose-lactase hydrolysis in fixed bed

A detailed mathematical model for evaluating lactose hydrolysis with immobilized enzyme in a packed bed tubular reactor is presented. The model accounts for axial and radial dispersion effects, chemical reaction and external mass transfer resistances but is void of significant internal diffusion resistances of the particles. The comprehensive model was then simplified to a plug flow model for lactose-lactose hydrolysis in fixed bed. The resulting plug flow model was solved by using Runge-Kutta-Gill method via employing different kinetics for lactose hydrolysis. The reliability of model simulations was tested using experimental data from a laboratory packed bed column, where the β-galactosidase of Kluyveromyces fragilis was immobilized on spherical chitosan beads. Comparison of the simulated results with experimental exit conversion show that the plug flow model incorporating Michaelis-Menten kinetics with competitive product (galactose) inhibition are appropriate to interpret the experimental results and simulate the process of lactose hydrolysis in a fixed bed when the mass transfer resistance was reduced by a factor of 34.5.     

Electrochemical treatment of human wastes in a packed bed reactor

There is an increasing interest in the use of electrochemical methods for dealing with pollution problems. This paper deals with the mass balance and the use of a packed bed reactor for the electrochemical incineration of human wastes. Parametric studies were carried out to determine the effect of: (i) anodic particle size, (ii) flow rate of faeces/urine mixture, (iii) height of packed bed, (iv) current density and (v) cathode to anode spacing arrangement, on the rate of oxidation of human waste. It is shown that particles of Ebonex (0.5–1.0 mm diam.) coated with a catalyst layer, comprising SnO₂/Sb₂O₃, a solution flow rate of 0.9–1.4 cm s^–1 through the packed bed based on the cross sectional area of the reactor, a bed height of 5–8 cm and a current density based on the geometric area of the particles of 5 mA cm^–2 comprise an optimum set of parameters for the scale-up of a packed-bed electrochemical reactor system. A preliminary design for the further scale up of the process is also described.     

Mass transfer characteristics of wire-mesh honeycomb reactors

The mass transfer characteristics in honeycombs made of catalyst-deposited metal wire meshes (wire-mesh honeycomb; WMH) were studied to test the prediction that WMH has better flow distribution and a higher rate of interphase mass transfer than the conventional ceramic type of honeycomb module. The WMH module was constructed from alternating layers of flat and corrugated wire-mesh sheets packed within a frame. Wire-mesh sheets were coated with aluminum particles using electrophoretic method. Thermal sintering at 800°C and then calcinations at 500°C yielded a porous layer of Al/Al₂O₃ composite particles that were firmly attached on the wire surface. The alumina-protected wire meshes were further deposited with Pt/TiO₂ catalyst powder by washcoating method. The oxidation of ethyl acetate was monitored as model reaction. A one-dimensional model was established and the parameters of intrinsic first-order kinetics were regressed from the reaction results obtained in the region controlled by chemical reaction, after which interphase mass transfer coefficients were regressed in other region. Three expressions for the Sherwood number that are typically used for honeycomb, wire-mesh gauze and packed bed reactors were examined to determine the optimal expression for WMHs. The mass transfer coefficient in the WMH was found to be quite different from that in the conventional ceramic honeycomb reactor and much higher than that in the wire-mesh gauze reactor. The best-fit results were obtained with packed-bed expression, Sh=1.06Re^0.50Sc^1/3, indicating the mechanism of reaction in the WMH is most similar to that in a packed bed. The optimal Sh expression was then used to predict the behavior of systems with a larger channel size or longer bed; the model predictions showed good agreement with experimental results from real WMH reactors.     

Multiphase CFD-based models for chemical looping combustion process: Fuel reactor modeling

Chemical looping combustion (CLC) is a flameless two-step fuel combustion that produces a pure CO₂ stream, ready for compression and sequestration. The process is composed of two interconnected fluidized bed reactors. The air reactor which is a conventional circulating fluidized bed and the fuel reactor which is a bubbling fluidized bed. The basic principle is to avoid the direct contact of air and fuel during the combustion by introducing a highly-reactive metal particle, referred to as oxygen carrier, to transport oxygen from the air to the fuel. In the process, the products from combustion are kept separated from the rest of the flue gases namely nitrogen and excess oxygen. This process eliminates the energy intensive step to separate the CO₂ from nitrogen-rich flue gas that reduce the thermal efficiency.Fundamental knowledge of multiphase reactive fluid dynamic behavior of the gas-solid flow is essential for the optimization and operation of a chemical looping combustor.Our recent thorough literature review shows that multiphase CFD-based models have not been adapted to chemical looping combustion processes in the open literature. In this study, we have developed the reaction kinetics model of the fuel reactor and implemented the kinetic model into a multiphase hydrodynamic model, MFIX, developed earlier at the National Energy Technology Laboratory. Simulated fuel reactor flows revealed high weight fraction of unburned methane fuel in the flue gas along with CO₂ and H₂O. This behavior implies high fuel loss at the exit of the reactor and indicates the necessity to increase the residence time, say by decreasing the fuel flow rate, or to recirculate the unburned methane after condensing and removing CO₂.     

Effective methane reforming with CO2 and O2 under pressurized condition using NiO–MgO and fluidized bed reactor

Circulation of Ni_0.15Mg_0.85O catalyst particles in the fluidized bed reactor gave much higher CH₄ conversion in methane reforming with CO₂ and O₂ under pressurized condition than the case of the catalyst without moving in the fixed bed reactor. In addition, circulation of the catalyst particles in the fluidized bed reactor inhibited carbon deposition which is the serious problem in methane reforming.     

Reactivity of a spray-dried NiO/NiAl2O4 oxygen carrier for chemical-looping combustion

Kinetic data of a promising oxygen carrier of NiO/NiAl₂O₄ have been established from experiments in a small fluidized bed batch reactor using methane. The particles were prepared by spray-drying using commercially available raw material and selected as the best candidates from an earlier screening study. The particles clearly showed high reactivity, with a maximum gas yield between 86% and 93% in the temperature interval 750 °C to 950 °C when using a bed mass and a gas flow corresponding to only 6 kg/MW_fuel. A comparison of the reactivity with data from TGA experiments showed that the reactivity generally was faster in the batch fluidized bed in the investigated temperature interval. A simple reactor model using kinetic data from the batch fluidized bed reactor and the TGA predicted a minimum mass of 9–24 kg/MW_fuel of oxygen carrier particles for full gas yield of methane to carbon dioxide in the fuel reactor. Comparison with experiments performed in a 10 and 120 kW CLC reactor with the same type of oxygen carrier showed that even when employing 13 to 50 times the amount of oxygen carrier theoretically needed for complete gas conversion, full gas yield was not obtained in the circulating systems. Hence it is of great importance to consider the fluid dynamics and gas-solid contact when modeling the fuel reactor of a chemical-looping combustor.     

Particle-resolved simulation of packed beds by non-body conforming locally refined orthogonal hexahedral mesh

The traditional fixed-bed reactor design is usually not suitable for the low tube-to-particle diameter ratios (N=D/d < 8) where the local phenomena of channeling near the wall and backflow in the bed are dominant. The recent "solid particle" meshing method is too complicated for mesh generation, especially for non-spherical particles in large random packed beds, which seriously hinders its development. In this work, a novel high-fidelity mesh model is proposed for simulation of fixed bed reactors by combining the immersed boundary and adaptive meshing methods. This method is suitable for different shapes of particles, which ingeniously avoids handling the complex "contact point" problem. Several packed beds with two different shapes of particles are investigated with this model, and the local flow in the bed is simulated without geometrical simplification. The predicted pressure drop across the fixed bed and heat transfer of the single particle are in good agreement with the corresponding empirical relations. Compared with spherical particles, the packed bed packing with pentaphyllous particles has lower pressure drop and better heat/mass transfer performance, and it shows that this method can be used for the screening of particle shapes in a fixed bed.     

Behavior of ilmenite as oxygen carrier in chemical-looping combustion

For a future scenery where will exist limitation for CO₂ emissions, chemical-looping combustion (CLC) has been identified as a promising technology to reduce the cost related to CO₂ capture from power plants. In CLC a solid oxygen-carrier transfers oxygen from the air to the fuel in a cyclic manner, avoiding direct contact between them. CO₂ is inherently obtained in a separate stream. For this process the oxygen-carrier circulates between two interconnected fluidized-bed reactors. To adapt CLC for solid fuels the oxygen-carrier reacts with the gas proceeding from the solid fuel gasification, which is carried out right in the fuel-reactor. Ilmenite, a natural mineral composed of FeTiO₃, is a low cost and promising material for its use on a large scale in CLC.The aim of this study is to analyze the behavior of ilmenite as oxygen-carrier in CLC. Particular attention was put on the variation of chemical and physical characteristics of ilmenite particles during consecutive redox cycles in a batch fluidized-bed reactor using CH₄, H₂ and CO as reducing gases. Reaction with H₂ was faster than with CO, and near full H₂ conversion was obtained in the fluidized-bed. Lower reactivity was found for CH₄. Ilmenite increased its reactivity with the number of cycles, especially for CH₄. The structural changes of ilmenite, as well as the variations in its behavior with a high number of cycles were also evaluated with a 100 cycle test using a CO + H₂ syngas mixture. Tests with different H₂:CO ratios were also made in order to see the reciprocal influence of both reducing gases and it turned out that the reaction rate is the sum of the individual reaction rates of H₂ and CO. The oxidation reaction of ilmenite was also investigated. An activation process for the oxidation reaction was observed and two steps for the reaction development were differenced. The oxidation reaction was fast and complete oxidation could be reached after every cycle. Low attrition values were found and no defluidization was observed during fluidized-bed operation. During activation process, the porosity of particles increased from low porosity values up to values of 27.5%. The appearance of an external shell in the particle was observed, which is Fe enriched. The segregation of Fe from TiO₂ causes that the oxygen transport capacity, R_OC, decreases from the initial R_OC = 4.0% to 2.1% after 100 redox cycles.     

Solid fuels in chemical-looping combustion using oxide scale and unprocessed iron ore as oxygen carriers

Chemical-looping combustion (CLC) is a novel technology that can be used to meet demands on energy production without CO₂ emissions. The CLC-process includes two reactors, an air and a fuel reactor. Between these two reactors oxygen is transported by an oxygen carrier, which most often is a metal oxide. This arrangement prevents mixing of N₂ from the air with CO₂ from the combustion. The combustion gases consist almost entirely of CO₂ and H₂O. Therefore, the technique reduces the energy penalty that normally arises from the separation of CO₂ from other flue gases, hence, CLC may make capture of CO₂ cheaper.Iron ore and oxide scale from steel production were tested as oxygen carriers in CLC batch experiments with solid fuels. Petroleum coke, charcoal, lignite and two bituminous coals were used as fuels.The experiments were carried out in a laboratory fluidized-bed reactor that was operating cyclically with alternating oxidation and reduction phases. The exhaust gases were led to an analyzer where the contents of CO₂, CO, CH₄ and O₂ were measured. Gas samples collected in bags were used to analyze the content of hydrogen in a gas chromatograph.The results showed that both the iron ore and the oxide scale worked well as oxygen carrier and both oxygen carriers increased their reactivity with time.     

Development of Cu-based oxygen carriers for chemical-looping combustion

In a chemical-looping combustion (CLC) process, gas (natural gas, syngas, etc.) is burnt in two reactors. In the first one, a metallic oxide that is used as oxygen source is reduced by the feeding gas to a lower oxidation state, being CO₂ and steam the reaction products. In the second reactor, the reduced solid is regenerated with air to the fresh oxide, and the process can be repeated for many successive cycles. CO₂ can be easily recovered from the outlet gas coming from the first reactor by simple steam condensation. Consequently, CLC is a clean process for the combustion of carbon containing fuels preventing the CO₂ emissions to the atmosphere. The main drawback of the overall process is that the carriers are subjected to strong chemical and thermal stresses in every cycle and the performance and mechanical strength can decay down to unacceptable levels after enough number of cycles in use.In this paper the behaviour of CuO as an oxygen carrier for a CLC process has been analysed in a thermogravimetric analyser. The effects of carrier composition and preparation method used have been investigated to develop Cu-based carriers exhibiting high reduction and oxidation rates without substantial changes in the chemical, structural and mechanical properties for a high number of oxidation-reduction cycles. It has been observed that the carriers prepared by mechanical mixing or by coprecipitation showed an excellent chemical stability in multicycle tests in thermobalance, however, the mechanical properties of these carriers were highly degraded to unacceptable levels. On the other hand, the carriers prepared by impregnation exhibited excellent chemical stability without substantial decay of the mechanical strength in multicycle testing. These results suggest that copper based carriers prepared by impregnation are good candidates for CLC process.