The effect of shale ash (SA)-based catalysts (SA as carriers to support several transition metal salts, such as ZnCl2, NiCl2·6H2O, and CuCl2·2H2O) on oil shale (OS) pyrolysis was studied. Results showed that SA promoted OS pyrolysis, and the optimum weight ratio of OS:SA was found to be 2:1. The SA-supported transition metal salt catalyst promoted the OS pyrolysis, and the catalytic effect increased with increasing load of the transition metal salt within 0.1–3.0 wt%. The transition metal salts loaded on the SA not only promoted OS pyrolysis and reduced the activation energy required but also changed the yield of pyrolysis products (reduced shale oil and semi-coke yields and increased gas and loss yield). SA-supported 3 wt% CuCl2·2H2O catalyst not only exhibited the highest ability to reduce the activation energy in OS pyrolysis (32.84 kJ/mol) but also improved the gas and loss yield, which was 4.4% higher than the uncatalyzed reaction. The supporting transition metal salts on the SA also increased the content of short-chain hydrocarbons in aliphatic hydrocarbons in shale oil and catalyzed the aromatization of aliphatic hydrocarbons to form aromatic hydrocarbons. The catalytic activity of the transition metal salt on the SA-based catalyst for OS pyrolysis decreased in the order of CuCl2·2H2O > NiCl2·6H2O > ZnCl2.
Shale ash (SA) as the carrier, the ratio of Cu to Ni in the Cu-Ni transition metal salt being, respectively, 1 : 0, 2 : 1, 1 : 1, 1 : 2, 0 : 1, the double transition metal salt catalyst (CumNin/SA) was prepared to explore the effect of such catalysts on the pyrolysis behavior and characteristics of Fushun OS. The research results show that the temperature (
T
max
) corresponding to the maximum weight loss rate decreased by 12.9°C, 4.0°C, and 3.6°C; and the apparent activation energy decreased by 35.2%, 33.9%, and 29.6%, respectively, after adding catalysts Cu0Ni1/SA in pyrolysis. The addition of Cu0Ni1/SA and Cu2Ni1/SA further improves the shale oil (SO) yield of 3.5% and 3.1%, respectively. Cu0Ni1/SA produces more aromatic hydrocarbons, which, however, weakens the stability of SO and is of toxicity in use. After analyzing the pyrolysis product—semicoke (SC) and SO—with ATR-FTIR and GC-MS methods, CumNin/SA promotes the secondary cracking and aromatization of OS pyrolysis, increasing the content of the compound of olefins and aromatics in SO, and hastening the decomposition of long-chain aliphatic hydrocarbons to short-chain aliphatic hydrocarbons.
This paper briefly describes the research status of oil shale pyrolysis technology and the main factors affecting oil shale pyrolysis, with emphasis on four kinds of commonly used catalysts: The effects of natural minerals, metal compounds, molecular sixes, and supported catalysts on the pyrolysis of oil shale were discussed. The changes of the pyrolysis mechanism and product composition of oil shale with the addition of different catalysts were discussed. Finally, the development direction of preparation of new catalysts was discussed, in order to provide a prospect for the development and utilization of unconventional and strategic alternative energy resources around the world.
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