Effect of Shale Ash-Based Catalyst on the Pyrolysis of Fushun Oil Shale

Abstract

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.

Progress in Catalytic Pyrolysis of Oil Shale

“…The addition of 0.20 mm shale ash is the best for improving shale oil production rate and kerogen conversion to volatile products [33]. Lu et al [34] studied the effect of Fushun oil shale and shale ash loaded with different transition metal salts (ZnCl 2 , NiCl After hydrodesulfurization, the calorific value and viscosity of shale oil are improved obviously. Catalysts used for modification are always inactivated by coke deposition, but in situ high-temperature treatment in the air effectively removes the coke from the catalyst surface to make it highly active after the devulcanization operation.…”

“…The addition of 0.20 mm shale ash is the best for improving shale oil production rate and kerogen conversion to volatile products [ 33 ]. Lu et al [ 34 ] studied the effect of Fushun oil shale and shale ash loaded with different transition metal salts (ZnCl 2 , NiCl 2 ·6H 2 O, and CuCl 2 ·2H 2 O) on pyrolysis. The transition metal salt catalyst supported by shale ash can reduce the initial pyrolysis temperature of oil shale, and the catalytic effect is enhanced with the increase of transition metal salt loading in the range of 0.1-3.0 wt%.…”

Evaluation of the possibility of use of coal-ash residues of oil shales as a sorbent

“…Образование отходов объясняется тем, что минеральная часть в сланце часто не уступает в количестве органической, и, следовательно, в ходе переработки органической части образуется значительное количество золы. Большое количество исследований направлено на изучение использования золы сланцев в качестве добавок в бетон, дорожные покрытия и в качестве каталитической добавки при переработке горючих сланцев [2][3][4]. Другим перспективным направлением использования золы горючих сланцев является применение их в качестве сорбентов, что позволило бы уменьшить выброс других отходов в окружающую среду.…”

Constrain on Oil Recovery Stage during Oil Shale Subcritical Water Extraction Process Based on Carbon Isotope Fractionation Character

“…Oil shale has become an important backup energy of conventional fossil energy in the world, and its pyrolysis exploitation mode has changed from aboveground (ex situ) to underground (in situ) [1][2][3][4][5][6][7][8], as the former technology encounters significant challenges, such as environmental pollution and inefficiencies [2]. The in situ technology underground could be further divided into [3] (a) in situ artificial crushing and retorting and (b) real underground in situ retorting.…”

“…The in situ technology underground could be further divided into [3] (a) in situ artificial crushing and retorting and (b) real underground in situ retorting. Subcritical water extraction of oil shale is one of the in situ retorting technologies, and the oil generation process can be optimized through altering the heating time, type, and amount of catalyst and maximum temperature [4][5][6][7][8][9]. The quality of oil shale pyrolysis products mainly relates to the heating temperature and time [4], overheating or insufficient heating temperature will lead to a high mining cost with a low resource utilization rate; thus, precise heat transfer and adequate heating conditions are important to maximize oil yield [10].…”