Hydrous pyrolysis: a tool for the study of organic acid synthesis

Abstract

Hydrous pyrolysis, commonly used for the simulation of liquid hydrocarbon generation, is a potentially useful technique for the study of dissolved organic acid synthesis if modifications to conventional methods are made. Simple experiments demonstrate the thermal origin of formic, acetic, proprionic, and butyric acids. The use of stainless steel reactors at high temperatures ( ca. 300°C), however, results in short chain aliphatic acid yields and distributions that are a function of experimental conditions. Once generated, propionate is destroyed more rapidly than acetate during the experiments. Experimental artifacts can be reduced by using lower temperatures and less catalytically active reactor materials. With present methodology, hydrous pyrolysis provides a useful semi-quantitative method for assessing the organic acid generating capacities of different rocks and organic matter types. As much as 1.2 wt% of the organic C in low thermal rank kerogen can be converted to short chain aliphatic acids. However, carbon dioxide is the dominant oxygen-containing product, exceeding organic acid yields by roughly 10 times. Relative organic acid generating capacities can vary by a factor of two or more in narrow stratigraphic intervals (<3 m). Bulk geochemical parameters, like oxygen indices, and gross organic petrography (organic matter type) only partly explain the observed variations in organic acid yields between samples.