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: 催化裂化汽油超深度加氢脱硫和保护烯烃不被加氢饱和为烷烃,依然是我国汽油质量升级的技术需求。本论文从传质角度出发,设计并制备了蛋壳型加氢脱硫催化剂,创新性的采用调控陈化时间的方法,可控制备了一系列的蛋壳型催化剂。采用SEM-EDX、XRD、H2-TPR、N2吸/脱附、XPS和HRTEM对催化剂进行表征。表征结果表明制备的蛋壳型催化剂具有蛋壳厚度可调、蛋壳分布均匀的优点;蛋壳厚度对层状结构MoS2的片层长度和层数略有影响,但随着蛋壳厚度的增加,催化剂中Edge边位比例(fe)和Rim角位比例(fc)的比值fe/fc略有降低。最后选用模型催化裂化汽油对催化剂的脱硫性能进行考察,蛋壳型催化剂对脱硫活性影响较小,但蛋壳型催化剂具有更低的烯烃饱和活性,这主要归因于蛋壳催化剂具有更高的fe/fc,同时更低的传质阻力使得烯烃分子在含Mo活性相的壳层停留时间更短。

     

    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 Mo12O40P3− complex in the solution. The migration rate of Mo12O40P3− 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.

     

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