Catalytic Conversion of Oil Shale over Fe or Ni Catalysts under Sub-Critical Water

Abstract

Sub-critical water is an environment-friendly solvent. It is widely used for the extraction of various organic compounds. It can be used to dissolve and transport organic matter in oil shale. In this study, the conversion of oil shale was synergistically catalyzed by the addition of Fe or Ni to the Fe inherent in samples under sub-critical water conditions. Oil shale can be converted to gas, oil and residues of oil. Thermogravimetric (TG) analysis results presented that the weight loss of raw oil shale was up to 15.85%. After sub-critical water extraction, the weight loss rate of the residues was reduced to 8.41%. With the application of a metal catalyst, Fe or Ni, the weight loss of residues was further reduced to 7.43% and 6.57%, respectively. According to DTG curves, it was found that there were two weight-loss rate peaks. The decomposition process of kerogen in oil shale could be divided into two cracking processes. One is decomposed at a high velocity at around 420 °C, and another is decomposed at a low velocity at around 515 °C. Gas chromatography (GC) results of gas products indicated that Fe or Ni could contribute to producing normal alkanes, such as methane, ethane, propane, etc., which are produced by the hydrogenation of alkenes via hydrogen transfer during the conversion process of kerogen. Gas chromatography-mass spectrometry (GC–MS) was conducted to analyze the components of the liquid products. The results showed that n-alkanes, iso-alkane, oxygenated hydrocarbons and aromatic compounds were the major components of the kerogen cracking products. When Ni was introduced as a catalyst, the contents of aromatic compounds and oxygenated hydrocarbons in the liquid products were increased from 19.55% and 6.87% to 22.38% and 13.77%, respectively. This is due to the synergistic effect of the addition of Ni with the inherent Fe in oil shale under sub-critical water which ensures kerogen is more easily cracked to produce aromatic compounds and oxygenated hydrocarbons.