V-W-Mo-Cu催化剂作用下生物质醇解重油加氢精制研究

Study on the hydrorefining of heavy oil from biomass alcoholysis in the presence of V-W-Mo-Cu catalyst

生物质醇解产生的重油降低了生物油品质。为此,本文考察了V-W-Mo-Cu催化剂作用下重油的加氢精制。结果表明,在330℃以上该催化剂才表现出加氢反应活性,在450℃时轻油产率最高可到93%。延长加氢反应时间有利于重油低温下的聚合反应和高温下的裂解反应;同时,只有在6 MPa以上的初始氢压下才能饱和裂解片段,从而提高重油加氢所得的轻油产率。轻油的气相色谱-质谱联用仪(GCMS)分析结果表明,催化加氢使重油大分子裂解生成1-甲基-2-乙基苯、丁基苯、1-乙基-3-乙烯基苯和苯酚等小分子的芳烃和酚类物质。然而,加氢后催化剂的红外分析结果表明,重油同时发生了聚合反应,生成含有多种含氧官能团的大分子芳烃或酚类聚合物。经过550℃焙烧后,催化剂重复使用5次,轻油产率仍有70%。

Bio-oil was degraded by the heavy oil from biomass alcoholysis. Therefore,the hydrorefining of heavy oil was studied in the presence of V-W-Mo-Cu catalyst in this paper. The results showed that the catalyst revealed its reactivity only at above 330℃,and achieved the highest light oil yield of 93%at 450℃. The extension of hydrogenation time was beneficial to the polymerization of heavy oil at low reaction temperature and the depolymerization at high reaction temperature. Meanwhile,the saturation of depolymerization fractions can be per-formed,and the yield of light oil from heavy oil hydrogenation can be promoted when the ini-tial hydrogen pressure was increased to 6 MPa. The gas chromatography-mass spectrometry （GC-MS） analysis on light oil indicated that heavy oil could be cracked into micromolecule arene and phenolic compounds after hydrogenation,including 2-ethyl-1-methyl-benzene,butyl-benzene,3-ethenyl-1-ethyl-benzene and phenol. However,the Fourier transform infrared spec-trometer （FTIR） analysis on catalyst after hydrogenation showed that heavy oil also could be po-lymerized into macromolecule arene and phenolic polymer. After being baked at 550℃,the cat-alyst could be reused more than 5 times,and the yield of light oil was still up to 70%.