Kinetics study on supercritical water conversion of low-maturity shale for hydrogen-rich hydrocarbon gas generation

Supercritical water (SCW) has gained substantial interest for shale exploitation due to its high conversion efficiency. To quantify the generated gases and the mutual conversion of gases on reaction of shale in SCW, experiments were carried out in batch reactor at 400–600°C and residence time up to 480 min. The products are classified as residual solids, liquid intermediates and gases. Experimental results show that the generated gases are mainly C₁, C₂, C₃ alkanes, H₂ and CO₂. The concentrations of C₁ and C₂ alkanes decrease with temperature and residence time but the other three are the opposite. A kinetic model of shale-intermediates-gases reaction is developed. This model can characterize the gas generation features of shale and SCW resulting from chemical reactions, and can quantitatively describe the mutual conversion between gases. The calculated results demonstrate well applicative for predicting gas concentration at various residence time within an acceptable deviation. The reaction process can be divided into three stages: pyrolysis of organic matter to generate intermediates, hydrolysis reaction and alkyl thermal cracking of intermediates to generate gases, mutual conversion between the generated gases. Reactions among gases involve methanation reaction, water-gas shift reaction and hydrocarbon gas decomposition. This study provides a potential kinetic model for the gas generation characteristics of reaction with shale and supercritical water.