Clean Coal Technology: A Novel Process for the Combustion of Coal Using an Oxygen Carrier

Lead Research Organisation: University of Cambridge
Department Name: Chemical Engineering and Biotechnology

Abstract

The global supply of electricity accounts for ~38% of total anthropogenic carbon emissions to the atmosphere or ~2,400 Mte/y (carbon basis), a figure projected to exceed 4,000 Mte/y by 2020. Globally, coal generates the largest share of world electricity production (39% of total delivered energy) followed by renewables (principally hydroelectricity) (20%), nuclear (17%), gas (15%) and oil (10%). Electricity production will increase by ~80% over the period 2000 to 2020, with the fraction generated from coal remaining at ~39%, due to increased exploitation of coal in India and China and steady growth in the USA. In the U.K., the most recent White Paper only envisages a future for coal provided ways can be found materially to reduce its carbon emissions , which therfore requires the sequestration of the CO2 arising from the combustion of the coal, or fuels derived from it, in the earth. The cost of sequestration is small (~ $4-8/ te C) compared to the costs of separation of CO2 from typical flue gases (~ $100 - 200/te C)so that such disposal only approaches viability if the CO2 is available in almost pure form, largely free of nitrogen and other inert gases.We wish to use chemical looping for the in situ gasification and combustion of coal in a process to produce CO2 and steam as pure products, without significant contamination by N2. In our proposed scheme, there would be one reactor, containing a bubbling fluidised bed of oxygen carrier, most likely a Cu-based oxide on a titania or alumina support, the durability of which has been demonstrated by other workers. The reactor would be operated in a cycle of three consecutive periods, t1, t2 and t3. During t1, the bed would be fluidised by steam, (or steam and CO2) and coal would be fed steadily to the bed, the temperature of which would be ~ 800 - 1000 C. Two events would occur:(1) the coal would undergo gasification (endothermic) by the steam to yield a synthesis gas containing CO and H2 (plus smaller amounts of CH4 and higher hydrocarbons): C(s) + H2O(g) = CO(g) + H2(g) (enthalpy of reaction: +131 kJ/mol),(2) the syngas would react with the surrounding CuO particles to give CO2 and steam by: CuO(s) + H2(g) = Cu(s) + H2O(g) and CuO(s) + CO(g) = CO2(g) + Cu(s) (enthalpies of reaction -86 kJ/mol and -127 kJ/mol, respectively).Copper has the only oxides which give exothermic reactions in (2); the heat produced exceeds that needed for the endothermic gasification reaction in (1). In effect, the metal oxide has been used in place of air, or cryogenically-produced O2, so that the products of combustion do not contain N2. Of course, this system can only function down to a certain degree of reduction of the metal oxide. Thus, after time t1, the feed of coal ceases and the remaining inventory of bed carbon is allowed to gasify and combust for a further period of time, t2, until the inventory is sufficiently small. At the end of t2, the bed is fluidised by air instead of steam for a period of time, t3, during which the reduced metal oxide carrier is regenerated in Cu + 0.5O2 = CuO (enthalpy of reaction -156 kJ/mol Cu). During t3 some carbon will be burnt off, originating either from coked metal oxide or from residual carbon inventory remaining after t2, so that there would be a small release of CO2 with the regenerating air, but this would be very much less than that emitted by direct combustion of the coal in air. Once the metal oxide has been regenerated, the cycle starts again at t1. Thus, the concept enables coal to be burnt cleanly with a rather smaller reduction in thermal efficiency than is obtained with other schemes for isolating the CO2, using e.g. cryogenically-separated oxygen from air.
 
Description In basic chemical looping (CL), gaseous fuel is oxidised by a metal oxide, MeO, in one reactor: (2n+m)MeO+CnH2m=(2n+m)Me+mH2O+nCO2. The exit gas yields pure CO2 after the steam is condensed. The reduced oxide, Me, is transferred to an oxidation reactor and regenerated: Me+air=MeO. Hence, the fuel is combusted, but the CO2 is separated from the nitrogen in air. This is much more efficient than current methods being considered for separating CO2 from flue gases in power stations. Nothing had previously been published on CL with solid fuels directly, because fuel and reduced oxide cannot be separated during oxidation. Using funding under this award, we were first to publish a technique for this an important achievement - and to demonstrate it. Much work was undertaken on the development of durable particles of oxide, particularly of iron and copper, because the material must be durable (for economic reasons) over many cycles of reduction and oxidation in harsh conditions at high temperature, and a range of successful candidates was found. One spin-off is that coprecipitated mixtures of CuO and Al2O3 are sufficiently reactive to oxidise CO at temperatures as low as 250C, a fact being exploited by a spin-out company, Gas Recovery and Recycle Ltd. (http://gr2l.co.uk/), in the clean-up of expensive noble gases used in silicon wafer manufacture. We later extended CL in an exciting innovation using iron oxides to produce clean hydrogen from biomass, uncontaminated with COx and so suitable for direct fuel cell use. This process is much less scale-dependent than, e.g. the reforming of natural gas for H2, and so is a leading contender for local hydrogen production (the "hydrogen economy").



This project has led to further research on chemical looping and to significant international collaborations, e.g. with Chinese and Swedish researchers.
Exploitation Route The potential lies in energy generation and carbon capture, as well as the use of the oxide materials in other areas, e.g. gas cleaning and selective catalytic oxidation. The techniques and materials discovered have demonstrated the feasibility of CL for use with solid fuels. Some materials have been exploited (as described above) for other chemical processes.
Sectors Chemicals

Energy

Environment

 
Description This grant underpinned all of our subsequent work on chemical looping and formed the basis for extending chemical looping to selective oxidation reactions. The basis results have been exploited by a company for inert gas clean-up
First Year Of Impact 2008
Sector Chemicals
Impact Types Economic