Papers - Handling and Utilization - Low Temperature Reactions of Oxygen on Bituminous Coal (T.P. 2233, Coal Tech., Aug. 1947)

Reaction of oxygen and bituminous coal starts as soon as the coal bed is exposed to air and, with some coals, proceeds with significant velocity even at normal temperatures and at normal oxygen partial pressures of one-fifth of an atmosphere. At higher temperatures, the reaction is greatly accelerated and ultimately a condition is reached where the process is very rapid and we then speak of combustion. It is the purpose of the present paper to discuss the reactions of oxygen and coal at temperatures below those of active combustion. It is these low temperature oxidation reactions which are responsible for heating in storage and for marked changes in agglutinating proper-ties. These reactions may also be employed for the preparation of organic acids, which are of direct interest to the chemical industry. For convenience in discussion, the low temperature reactions of oxygen and bituminous coal can be roughly divided into three stages though there is, of course, overlapping. Stage I is a surface oxidation stage, characterized by the addition of oxygen, with the formation of oxygen containing groups some of which have acidic properties. Carbon dioxide, carbon monoxide and water may be formed con-comitantly and are always liberated at higher temperatures, and in cases where the oxidation is prolonged. Superficially, the coal is little affected by this primary stage of oxidation and usually only minor changes in ultimate composition result. There may be definite changes in coking and coking properties, and heat of combustion susceptibility to further oxidation. The presence of acidic groups can be demonstrated by specific reactions. These groups may show cation exchange properties like the mineral zeolites. The formation of oxalic acid has been reported. If the oxidation is continued, a large fraction of the organic material of the coal is converted ultimately into alkali soluble, acid insoluble products, which have been given the name "regenerated humic acids" and which are the characteristic products of Stage 2. These humic acids, in the solid stage, do not differ greatly in appearance from the original coal, but show large differences in chemical composition and chemical and physical properties. Along with the humic acids, carbon dioxide and some of the water soluble types of Stage 3, are also formed. If the oxidation is carried still further, the humic acids may be degraded completely to the simpler, lower molecular weight acids of Stage 3 which are characterized by solubility in acid as well as in alkaline media, and by their orange, yellow or white colors. Additional carbon dioxide is formed in the transformation from Stage 2 to Stage 3 and, for a number of American coals, a maximum yield of the water soluble types of acids is reached when about 50 pct of the carbon of the coal is converted to carbon dioxide. Primary Oxidation The initial step in the reaction of gaseous oxygen on coal, like that on carbon,