燃料化学学报（中英文）2025，Vol.53Issue(5)：725-732,8.DOI:10.3724/2097-213X.2024.JFCT.0037
蛋壳型Co/Mo催化剂的可控制备及其加氢脱硫性能
Controllable preparation and hydrodesulfurization performance of eggshell type Co/Mo catalyst
摘要
Abstract
The catalytic cracking gasoline with high sulfur and high olefin content accounts for about 60%of the gasoline pool in China.Therefore,ultra-deep selective hydrodesulfurization of catalytic cracking gasoline and the protection of olefins from hydrogenation saturation are still the key technical problems to be solved in the production of high octane gasoline for a long time in the future.During the decades of the development of fluid catalytic cracking gasoline hydrodesulfurization,researchers have systematically investigated the distribution of sulfur species and hydrocarbon composition,process technology,active phase structure,promoter effect and mass transfer.From the view of mass transfer,this paper innovatively adopted the method of adjusting aging time,prepared a series of eggshell type catalysts in a controllable way.The performance of these catalysts for ultra-deep selective hydrodesulfurization of fluid catalytic cracking gasoline was investigated.A new concept was provided for the design and development of fluid catalytic cracking gasoline hydrodesulfurization catalysts.The catalysts were characterized by SEM-EDX,XRD,H2-TPR,N2 adsorption-desorption,XPS and HRTEM.The SEM-EDX results showed that the Mo element was an eggshell type distribution in the catalyst while the Co element evenly distributed in the catalyst.The thickness of eggshell increased gradually with the extension of aging time and Mo elements tended to be evenly distributed until the aging time is 95 min.The reason was that the Co element existed as Co2+while the Mo and P element formed[Mo12O40P]3-complex in the solution.The migration rate of[Mo12O40P]3-complex in the catalyst pores was slow during impregnation while the Co2+migrating fast.The SEM-EDX results indicated that the eggshell thickness of catalyst could be adjusted by controlling aging time.The XRD and H2-TPR results showed that the eggshell distribution of Mo did not change the dispersibility of the active metals.The N2 adsorption/desorption results showed that the aging time had little effect on the pore structure of the catalysts.The XPS results showed that the content of Mo4+and Co-Mo-S on catalyst surface decreased with the increasing of eggshell thickness,it may be due to the migration of Mo element into the interior of the catalyst,resulting in a decrease in the concentration of Mo element on the surface of the catalyst.The HRTEM results showed that the eggshell thickness had a slight effect on the length and number of layers of MoS2,but with the increase of eggshell thickness,the proportion of fe/fc in the catalyst decreases slightly.Finally,model catalytic cracking gasoline was used to investigate the desulfurization performance of the catalyst.The results showed that the eggshell type catalyst had little effect on desulfurization activity,but the eggshell type catalyst had lower olefin saturation activity.At different reaction temperatures,with the increase of the eggshell thickness,the desulfurization selectivity of the catalyst gradually decreased which mainly due to the fact that the eggshell catalyst had a higher fe/fc,while the lower mass transfer resistance made the olefin molecules stay in the shell containing the Mo active phase for a shorter time.关键词
催化裂化汽油/加氢脱硫/选择性/蛋壳催化剂Key words
fluid catalytic cracking gasoline/hydrodesulfurization/selectivity/eggshell catalyst分类
化学工程引用本文复制引用
徐景东,李文涛,李慧胜,艾子龙,王廷海,徐人威..蛋壳型Co/Mo催化剂的可控制备及其加氢脱硫性能[J].燃料化学学报（中英文）,2025,53(5):725-732,8.基金项目
The project was supported by National Natural Science Foundation of China(22072019)and Sinochem Quanzhou Energy Technology Co.,Ltd.(ZHQZKJ-XZ-21-F-ZS-0146). 国家自然科学基金(22072019)和中化泉州能源科技有限责任公司(ZHQZKJ-XZ-21-F-ZS-0146)资助 （22072019）
