研究了水/甲苯乳化液中二苯并噻吩(硫芴)在分散型钼酸、磷钼酸和四硫钼酸铵催化剂存在下的加氢脱硫反应.反应在高压釜中于340℃及三种不同的气氛即H2,H2/H2O和CO/H2O(CO和H2O经水煤气转换反应(WGSR)产生原位氢)的存在下进行.用GC和GC-MS鉴定、分析了气体和液体产物的组成.结果表明:对硫芴的加氢脱硫反应,在分散型钼酸和磷钼酸存在下,原位产生的氢比加入的分子氢更为有效.动力学研究结果表明:WGSR反应比硫芴的加氢脱硫反应快5～10倍,说明在原位氢存在下硫芴的加氢脱硫反应是速度控制步骤.总之,试验结果证实,在分散型催化剂和原位氢存在下的加氢过程是重油乳状液改质和破乳的有效方法.%The hydrodesulfurization (HDS) of dibenzothiophene (DBT) in H2O/C6 H5 CH3 emulsion was investigated using dispersed catalyst precursors, such as molybdic acid (MA), phosphomolybdic acid (PMA) and ammonium tetrathiomolybdate (ATTM). The HDS experiments were performed in an autoclave at 340 ℃ using different hydrotreating media: H2, H2/H2O, and in situ generated hydrogen from CO/H2O via water gas shift reaction (WGSR). The results indicated that with MA and PMA, in situ hydrogen is more reactive than the supplied molecular H2 for HDS of DBT. The WGSR was found to be faster by a factor of 5～10 than the HDS of DBT,indicating that the HDS of DBT rather than the WGSR is the rate-determining step in the hydroprocess using in situ hydrogen. In summary, the experimental results confirmed that the hydroprocess using in situ hydrogen in the presence of dispersed catalysts was an effective technique to upgrade and demulsify the heavy oil emulsion.
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