过渡金属盐催化剂对抚顺油页岩热解的影响

利用FTIR、XRD研究了抚顺油页岩（OS）的组成结构，TG?MS分析了过渡金属盐催化剂（页岩灰作为载体负载NiCl2?6H2O、CuCl2?2H2O、ZnCl2）对OS热解的催化作用和挥发分析出的影响规律，采用Coats?Redfern模型分析过渡金属盐催化剂对OS热解活化能的影响。结果表明，OS中矿物质主要由石英、硅铝酸盐和少量的碳酸盐组成，有机质主要是脂肪族化合物。三种过渡金属盐催化剂对OS热解均有促进作用，且OS单独热解时，在390.1~581.8 ℃快速热解，占总失重的76.19%。动力学分析结果表明，过渡金属盐催化剂能降低OS热解所需的活化能，其中NiCl2?6H2O降低OS热解活化能的能力最高（18.7 kJ/mol），比OS单独热解活化能降低了23.55%。过渡金属盐催化剂的催化活性由高到低排序为NiCl2?6H2O>CuCl2?2H2O>ZnCl2。此外，过渡金属盐催化剂还能促使OS热解发生挥发分的裂化、芳构化和焦化等反应，从而提高挥发分中脂肪烃（以烷烃、烯烃为代表）和芳香烃浓度。

Effect of Transition Metal Salt Catalysts on Pyrolysis of Fushun Oil Shale

The composition of Fushun oil shale (OS) was analyzed by Fourier transform infrared spectroscopy (FTIR) and X?Ray Diffractomer(XRD).The effects of transition metal salt catalysts (shale ash as a carriers on NiCl₂·6H₂O, CuCl₂·2H₂O, ZnCl₂) on the catalytic effect of pyrolysis of OS and precipitation of volatilization were investigated by TG?MS. Coats?Redfern model was used to analyze the effect of transition metal salt catalyst on the activation energy of OS pyrolysis. The results show that the minerals in OS are mainly composed of quartz, aluminosilicate and a small amount of carbonate, and the organic matter is mainly aliphatic compound. Three transition metal salt catalysts can all promote the pyrolysis of OS. The OS can be rapidly pyrolyzed at 390.1~581.8 ℃ when it is pyrolyzed alone, accounting for 76.19% of the total weight loss. According to the kinetic analysis, the activation energy required by OS pyrolysis can be reduced by the transition metal salt catalysts. NiCl₂·6H₂O has the highest capacity (18.7 kJ/mol) to reduce the activation energy of OS pyrolysis, which is 23.55% lower than that of OS pyrolysis alone. The catalytic activity of the transition metal salt catalysts are in a sequence of NiCl₂·6H₂O>CuCl₂·2H₂O>ZnCl₂. In addition, the transition metal salt catalysts can also promote the cracking, aromatization and coking of volatiles in the pyrolysis of the OS, Thereby increasing the content of aliphatic hydrocarbons (represented by alkanes and alkenes) and aromatic hydrocarbons in volatiles.