【作者】 陈杰；

【导师】 赫崇衡；

【作者基本信息】 华东理工大学 ， 化学工艺， 2013， 硕士

【摘要】 本论文重点研究了粗苯加氢脱硫主反应催化剂,以反应产物中噻吩残留量作为主要评价指标,同时尽可能地提高三苯保留率。本论文从催化剂的制备方法、第二助剂磷及金属助剂对催化剂加氢脱硫活性的影响等方面进行了研究。考察了不同CO-MO浸渍顺序、n(Co)/n(Co+Mo)原子配比以及钴钼负载量对CoMo/γ-A1203催化剂加氢脱硫活性的影响。研究结果表明,当n(Co)/n(Co+Mo)=0.35, CoO.MoO3相对于载体的负载量分别为4.9%和17.4%,且P/MoO3质量比为0.11时,采用Co-Mo-P共浸渍法所制备的催化剂具有最高的加氢脱硫活性,同时保持了较高的三苯保留率。通过正交实验筛选了浸渍温度、干燥温度和焙烧温度对催化剂加氢脱硫活性的影响。最终得到催化剂的最佳制备工艺条件为：浸渍温度为10℃,干燥温度为110℃,焙烧温度为50℃。本论文在CoMoP/γ-Al2O3催化剂上添加了Fe、Cu、K、Mg、X等金属助剂,制备出了相应的改性催化剂,研究了助剂添加方式和种类对CoMoP/γ-A12O3催化剂加氢脱硫活性的影响。研究结果发现,采用共浸渍法添加助剂X能显著提高CoMoP/γ-A12O3催化剂的加氢脱硫活性。当X氧化物相对于载体的负载量为1.0%时,CoMoP-X/γ-A12O3催化剂具有最佳的加氢脱硫活性和较高的三苯保留率。相比CoMoP/γ-Al2O3催化剂,在低反应条件和高反应条件下,CoMoP-X/γ-A12O3催化剂的反应产物中噻吩残留量分别从0.71ppm和0.50ppm下降至0.45ppm和0.15ppm。实验通过比较工业应用BASF主催化剂和CoMoP-X/γ-A12O3催化剂在相同反应条件下相同反应时间内的积碳情况,发现反应后两种催化剂上的碳物种失重量均为3.22%左右,表明COMoP-X/γ-A12O3催化剂与工业应用BASF主催化剂的抗结焦能力相差不大,表现出较好的抗结焦能力。更多还原

【Abstract】 This paper mainly focused on the development and optimization of the main catalyst for hydrodesulfurization of crude benzene. The preparation methods of catalysts, the effect of phosphor and metal modifiers on the performances of these catalysts for hydrosulfurization of crude benzene were studied.The experimental results showed that when nCo/n(Co+Mo) ratio was0.35, the mass fractions of CoO and MoO3relative to the carrier were4.9%and17.4%, and the mass ratio of P to MoO3was0.11, the hydrodesulfurization activity of the catalyst prepared by Co-Mo-P coimpregnation method was the highest, meanwhile BTX retention rate maintained a high level. The results of orthogonal experiments showed that the optimum preparation conditions of catalysts are as follow:impregnation temperature is10℃, drying temperature is110℃, calcination temperature is500℃.In this paper, CoMoP/γ-Al2O3catalysts modified with the metal modifier such as Fe, Cu, K, Mg, X were prepared. The effect of modifying methods and modifier types on the hydrodesulfurization activity and selectivity of catalysts were studied. The research results showed that CoMoP-X/γ-Al2O3catalyst prepared by co-impregnation can improve the activity for hydrodesulfurization of crude benzene obviously. And CoMoP-X/γ-Al2O3catalyst has the highest activity and the suitable selectivity when the mass capacity of X relative to the carrier is1.0%. Comparison with CoMoP/γ-Al2O3catalyst, thiophene residues of CoMoP-X/γ-Al2O3catalyst went down respectivily from0.71ppm and0.50ppm to0.45ppm and0.15ppm under the low reaction conditions and high reaction conditions.In order to evaluate the carbon deposition on BASF catalyst and CoMoP-X/γ-Al2O3catalyst after reacting under the same reaction conditions and the same time, we made TG analysis for the two different catalysts. The analysis results showed that the lost weight of carbon species on the two catalysts were both around3.22%, which indicated that the CoMoP-X/γ-Al2O3catalyst showed a good ability of resistance to coking as BASF catalyst.更多还原