Different methods of manufacturing FE-based oxygen carrier particles for reforming via chemical looping, and their effect on performance

Chemical looping combustion (CLC) is a means of combusting carbonaceous fuels, which inherently separates the greenhouse gas carbon dioxide from the remaining combustion products, and has the potential to be used for the production of high-purity hydrogen. Iron-based oxygen carriers for CLC have been subject to considerable work; however, there are issues regarding the lifespan of iron-based oxygen carriers over repeated cycles. In this work, haematite (Fe2O3) was reduced in an N2+CO+CO2 mixture within a fluidised bed at 850°C, and oxidised back to magnetite (Fe3O4) in a H2O+N2 mixture, with the subsequent yield of hydrogen during oxidation being of interest. Subsequent cycles started from Fe3O4 and two transition regimes were studied; Fe3O4↔Fe0.947O and Fe 3O4↔Fe. Particles were produced by mechanical mixing and co-precipitation. In the case of co-precipitated particles, Al was added such that the ratio of Fe:Al by weight was 9:1, and the final pH of the particles during precipitation was investigated for its subsequent effect on reactivity. This paper shows that co-precipitated particles containing additives such as Al may be able to achieve consistently high H2 yields when cycling between Fe3O4 and Fe, and that these yields are a function of the ratio of [CO2] to [CO] during reduction, where thermodynamic arguments suggest that the yield should be independent of this ratio. A striking feature with our materials was that particles made by mechanical mixing performed much better than those made by co-precipitation when cycling between Fe3O4 and Fe0.947O, but much worse than co-precipitated particles when cycling between Fe3O 4 and Fe.

A high performance oxygen storage material for chemical looping processes with CO2 capture

Chemical looping combustion (CLC) is a novel combustion technology that involves cyclic reduction and oxidation of oxygen storage materials to provide oxygen for the combustion of fuels to CO2 and H2O, whilst giving a pure stream of CO2 suitable for sequestration or utilisation. Here, we report a method for preparing of oxygen storage materials from layered double hydroxides (LDHs) precursors and demonstrate their applications in the CLC process. The LDHs precursor enables homogeneous mixing of elements at the molecular level, giving a high degree of dispersion and high-loading of active metal oxide in the support after calcination. Using a Cu-Al LDH precursor as a prototype, we demonstrate that rational design of oxygen storage materials by material chemistry significantly improved the reactivity and stability in the high temperature redox cycles. We discovered that the presence of sodium-containing species were effective in inhibiting the formation of copper aluminates (CuAl2O4 or CuAlO 2) and stabilising the copper phase in an amorphous support over multiple redox cycles. A representative nanostructured Cu-based oxygen storage material derived from the LDH precursor showed stable gaseous O2 release capacity (∼5 wt%), stable oxygen storage capacity (∼12 wt%), and stable reaction rates during reversible phase changes between CuO-Cu 2O-Cu at high temperatures (800-1000 °C). We anticipate that the strategy can be extended to manufacture a variety of metal oxide composites for applications in novel high temperature looping cycles for clean energy production and CO2 capture. © The Royal Society of Chemistry 2013.

Interaction between Fe-based oxygen carriers and n-heptane during chemical looping combustion

Chemical looping combustion (CLC) uses a metal oxide (the oxygen carrier) to provide oxygen for the combustion of a fuel and gives an inherent separation of pure CO2 with minimal energy penalty. In solid-fuel CLC, volatile matter will interact with oxygen carriers. Here, the interaction between iron-based oxygen carriers and a volatile hydrocarbon (n-heptane) was investigated in both a laboratory-scale fluidised bed and a thermogravimetric analyser (TGA). Experiments were undertaken to characterise the thermal decomposition of the n-heptane occurring in the presence and in the absence of the oxygen carrier. In a bed of inert particles, carbon deposition increased with temperature and acetylene appeared as a possible precursor. For a bed of carrier consisting of pure Fe2O3, carbon deposition occurred once the Fe2O3 was fully reduced to Fe. When the Fe2O3 was doped with 10 mol % Al2O3 (Fe90Al), deposition started when the carrier was reduced to a mixture of Fe and FeAl2O4, the latter being very unreactive. Furthermore, when pure Fe2O3 was fully reduced to Fe, agglomeration of the fluidised bed occurred. However, Fe90Al did not give agglomeration even after extended reduction. The results suggest that Fe90Al is promising for the CLC of solid fuels. © 2012 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Oxygen carrier dispersion in inert packed beds to improve performance in chemical looping combustion

Various packed beds of copper-based oxygen carriers (CuO on Al2O3) were tested over 100 cycles of low temperature (673K) Chemical Looping Combustion (CLC) with H2 as the fuel gas. The oxygen carriers were uniformly mixed with alumina (Al2O3) in order to investigate the level of separation necessary to prevent agglomeration. It was found that a mass ratio of 1:6 oxygen carrier to alumina gave the best performance in terms of stable, repeating hydrogen breakthrough curves over 100 cycles. In order to quantify the average separation achieved in the mixed packed beds, two sphere-packing models were developed. The hexagonal close-packing model assumed a uniform spherical packing structure, and based the separation calculations on a hypergeometric probability distribution. The more computationally intensive full-scale model used discrete element modelling to simulate random packing arrangements governed by gravity and contact dynamics. Both models predicted that average 'nearest neighbour' particle separation drops to near zero for oxygen carrier mass fractions of x≥0.25. For the packed bed systems studied, agglomeration was observed when the mass fraction of oxygen carrier was above this threshold. © 2013 Elsevier B.V.

CO2-gasification of a lignite coal in the presence of an iron-based oxygen carrier for chemical-looping combustion

Chemical-looping combustion (CLC) has the inherent property of separating the product CO2 from flue gases. Instead of air, it uses an oxygen carrier, usually in the form of a metal oxide, to provide oxygen for combustion. All techniques so far proposed for chemical looping with solid fuels involve initially the gasification of the solid fuel in order for the gaseous products to react with the oxygen carrier. Here, the rates of gasification of coal were compared when gasification was undertaken in a fluidised bed of either (i) an active Fe-based oxygen carrier used for chemical looping or (ii) inert sand. This enabled an examination of the ability of chemical looping materials to enhance the rate of gasification of solid fuels. Batch gasification and chemical-looping combustion experiments with a German lignite and its char are reported, using an electrically-heated fluidised bed reactor at temperatures from 1073 to 1223 K. The fluidising gas was CO2 in nitrogen. The kinetics of the gasification were found to be significantly faster in the presence of the oxygen carrier, especially at temperatures above 1123 K. A numerical model was developed to account for external and internal mass transfer and for the effect of the looping agent. The model also included the effects of the evolution of the pore structure at different conversions. The presence of Fe2O3 led to an increase in the rate of gasification because of the rapid oxidation of CO by the oxygen carrier to CO2. This resulted in the removal of CO and maintained a higher mole fraction of CO2 in the mixture of gas around the particle of char, i.e. within the mass transfer boundary layer surrounding the particle. This effect was most prominent at about 20% conversion when (i) the surface area for reaction was at its maximum and (ii) because of the accompanying increase in porosity and pore size, intraparticle resistance to gas mass transfer within the particle of char had fallen, compared with that in the initial particle. Excellent agreement was observed between the rates predicted by the numerical model and those observed experimentally. ©2013 Elsevier Ltd. All rights reserved.