焦化粗苯加氢脱硫催化剂的研究-化学工艺专业论文.docxVIP

焦化粗苯加氢脱硫催化剂的研究 摘要 山西省是全国最大的炼焦工业基地，也是全国最大的粗苯生产基地。粗苯成分复 杂，主要通过加氢精制来获得苯、甲苯和二甲苯(合称 BTX)等化工原料，因此研究焦 化粗苯加氢催化剂具有重要的意义。 本论文重点研究了负载型 CoMo 催化剂在粗苯加氢脱硫(HDS)反应中的活性，以 反应产物中噻吩脱除率作为主要评价指标，同时尽可能地提高 BTX 总收率。考察了不 同成型载体对催化剂活性的影响，确定了介孔丰富的 Al2O3 作为后续实验的载体；考 察了 CoMo 浸渍顺序、负载量和 n(Co)/n(Co+Mo)对催化剂在 HDS 反应中活性的影响。 研究结果表明：采用共浸渍法，CoO 和 MoO3 相对于载体的负载量分别为 2%和 8%且 n(Co)/n(Co+Mo)=0.3 时制备的催化剂活性最高，完成了催化剂的开发。模拟工业粗苯 加氢精制过程确定工艺窗口为：主加氢温度 300℃、反应压力 3.0 MPa、液时空速 2 h-1、氢油比 600:1。 考察了乙二胺四乙酸(EDTA)、柠檬酸(CA)和草酸(OA)三种螯合剂及其添加量对催 化剂 在 HDS 反应中 活性的影响，研究 结果表明： 当 n(Co):n(EDTA)=1:0.5 、 n(Co):n(CA)=1:1 和 n(Co):n(OA)=1:1.5 时，催化剂的 HDS 活性分别达到各自添加比例 的最大值。其中 Co-Mo-CA/Al2O3 在最佳工艺条件下对噻吩的脱除率达到 99.9%以上， 并且在 100 h 的寿命实验中表现出良好的稳定性，完成了催化剂的优化。 关键词：焦化粗苯；催化剂；加氢脱硫；噻吩；Co；Mo；螯合剂 Study on the Hydrodesulfurization Catalyst in Coking Crude Benzene ABSTRACT Shanxi province is the countrys largest coking industrial and crude benzene production base. Crude benzene composition is complex, mainly through hydrofiging for benzene, toluene and xylene (called the BTX) and other chemical raw materials. So it’s significant to research the hydrogenation catalyst of the coking crude benzene. This paper focuses on the study of supported CoMo catalysts in benzene hydrogenation desulfurization (HDS) reaction activity. The thiophene conversion as the main evaluation index and as much as possible to improve BTX recovery. The experimental results showed that when nCo/n(Co+Mo) ratio was 0.3, the mass fractions of CoO and MoO3 relative to the alumina were 2% and 8%, the hydrodesulfurization activity of the catalyst prepared by Co-Mo co-impregnation method was the highest, meanwhile BTX retention rate maintained a high level. HDS reaction of the real-feedstock was studied by using a down-flow tubular reactor with the first-stage temperature of 220℃, second-stage temperature of 300℃, LHSV of 2 h?1, H2 pressure of 3 MPa and hydrogen-oil volume ratio of 600, the catalytic activity of HDS has the best performance . The chelating agents of ethylenediamine tetraacetic