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.

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.