The production of separate streams of pure hydrogen and carbon dioxide from coal via an iron-oxide redox cycle

A chemical looping process using the redox reactions of iron oxide has been used to produce separate streams of pure H2 and CO2 from a solid fuel. An iron oxide carrier prepared using a mechanical mixing technique and comprised of 100wt.% Fe2O3 was used. It was demonstrated that hydrogen can be produced from three representative coals - a Russian bituminous, a German lignite and a UK sub-bituminous coal. Depending on the fuel, pure H2 with [CO] ≲50vol.ppm can be obtained from the proposed process. The cyclic stability of the iron oxide carrier was not adversely affected by contaminants found in syngas which are gaseous above 273K. Stable quantities of H2 were produced over five cycles for all three coals investigated. Independent of the fuel, SO2 was not formed during the oxidation with steam, i.e. the produced H2 was not contaminated with SO2. Since oxidation with air removes contaminants and generates useful heat and pure N2 for purging, it should be included in the operating cycle. Overall, it was demonstrated that the proposed process may be an attractive approach to upgrade crude syngas produced by the gasification of low-rank coals to pure H2, representing a substantial increase in calorific value, whilst simultaneous capturing CO2, a greenhouse gas. © 2010 Elsevier B.V.

Kinetics of the chemical looping oxidation of H2 by a co-precipitated mixture of CuO and Al2O3

Chemical-looping combustion (CLC) has the inherent property of separating 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. When used for the combustion of gaseous fuels, such as natural gas, or synthesis gas from the gasification of coal, the technique gives a stream of CO2 which, on an industrial scale, would be sufficiently pure for geological sequestration. An important issue is the form of the metal oxide, since it must retain its reactivity through many cycles of complete reduction and oxidation. Here, we report on the rates of oxidation of one constituent of synthesis gas, H2, by co-precipitated mixtures of CuO+Al2O3 using a laboratory-scale fluidised bed. To minimise the influence of external mass transfer, and also of errors in the measurement of [H2], particles sized to 355-500μm were used at low [H2], with the temperature ranging from 450 to 900°C. Under such conditions, the reaction was slow enough for meaningful measurements of the intrinsic kinetics to be made. The reaction was found to be first order with respect to H2. Above ∼800°C, the reaction of CuO was fast and conformed to the shrinking core mechanism, proceeding via the intermediate, Cu2O, in: 2CuO+H2→Cu2O+H2O, ΔH1073 K0=- 116.8 kJ/mol; Cu2O+H2→2Cu+H2O, ΔH1073 K0-80.9 kJ/mol. After oxidation of the products Cu and Cu2O back to CuO, the kinetics in subsequent cycles of chemical looping oxidation of H2 could be approximated by those in the first. Interestingly, the carrier was found to react at temperatures as low as 300°C. The influence of the number of cycles of reduction and oxidation is explored. Comparisons are drawn with previous work using reduction by CO. Finally, these results indicate that the kinetics of reaction of the oxygen carrier with gasifier synthesis gases is very much faster than rates of gasification of the original fuel. © 2010 The Institution of Chemical Engineers.

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.