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The best catalysts for promoting char gasification are Group I metals, particularly lithium and potassium, although other metals are active to a lesser extent. The most prevalent metal naturally in biomass char is potassium, which is not only inherently active, but volatilises to become finely distributed throughout the char mass. The formation of an active carbon/potassium complex is frequently proposed. Calcium is the other most common active metal found in biomass, but is far less effective and less volatile. In a gasification system the metals remain as carbonate due to the action of carbon dioxide. The alkali metals can react with silica to form silicates, which prevents catalytic action. Transition metals can also participate in catalysis of gasification; iron accelerates gasification and nickel prevents carbon deposition, which helps in conditioning biomass-derived syngas. Volatile iron pentacarbonyl has been identified as a promoter of the char gasification step, with catalytic activity related to the finely dispersed low-valency metal atoms generated during the thermo-decomposition of biomass.

The literature on the presence of heavy metals in contaminated wastes is reviewed. Various categories of materials produced from domestic and industrial activities are included, but municipal solid waste, which is a more complex material, is excluded. This review considers among the most abundant the following materials - wood waste including demolition wood, phytoremediation scavengers and chromated copper arsenate (CCA) timber, sludges including de-inking sludge and sewage sludge, chicken litter and spent pot liner. The partitioning of the metals in the ashes after combustion or gasification follows conventional behaviour, with most metals retained, and higher concentrations in the finer sizes due to vaporisation and recondensation. The alkali metals have been shown to catalyse the biomass conversion, particularly lithium and potassium, although other metals are active to a lesser extent. The most prevalent in biomass is potassium, which is not only inherently active, but volatilises to become finely distributed throughout the char mass. Because the metals are predominantly found in the ash, the effectiveness of their removal depends on the efficiency of the collection of particulates. The potential for disposal into soil depends on the initial concentration in the feed material.

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A range of pulverized coals were combusted in a laboratory drop-tube furnace at temperatures of 1573, 1723, and 1873 K under oxidizing and reducing conditions to determine the effect of combustion stoichiometry on ash formation mechanisms. As iron mineral transformations were expected to be most affected by combustion stoichiometry, two of the test coals chosen were of high pyrite (FeS2) content and two of high siderite (FeCO3) content. It was found that the ash formation mechanisms of excluded quartz, koalinite, and calcite were not affected by oxidizing or reducing combustion conditions. Excluded pyrite was found to decompose to pyrrhotite, which oxidized to produce an FeO−FeS melt phase which was stable under reducing conditions. Under oxidizing conditions oxidation continued, producing magnetite and hematite. Excluded siderite was found to decompose to wustite, which was stable under reducing conditions, but oxidized to produce magnetite under oxidizing conditions. Included pyrite and siderite were determined to behave as for excluded pyrite and siderite if there was no contact with alumino-silicates. Included pyrite that contacted alumino-silicate minerals was observed to form two-phase FeS/Fe-glass ash particles, with incorporation of iron into the glass proceeding as the FeS phase was oxidized. Included siderite that contacted alumino-silicate minerals was determined to directly form iron alumino-silicate glass ash particles. Iron alumino-silicate glass ash was determined to form with iron in the Fe2+ state, much of which subsequently transformed to the Fe3+ state in oxidizing conditions, but remained primarily as in the Fe2+ state under reducing conditions.

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