金属改性介孔分子筛的制备及其催化氧化脱硫研究
发布时间：2019-07-04 18:54
【摘要】：为了减缓燃料油给环境造成的污染,各国政府对燃料油中硫含量进行严格的限制,燃料油中以噻吩类化合物及其衍生物形式存在的有机硫化物在加氢脱硫工艺中比较难以脱除,致使生产成本增加。氧化脱硫工艺条件缓和,脱硫成本低,关键是开发既能够深度脱硫又高效经济的催化剂。本文将过渡金属Fe/V掺杂到HMS和MCM-41中,制得负载型Fe-V-HMS和V-MCM-41催化剂,研究了两种催化剂对DBT的氧化脱除效果,并通过NH3-TPD、XRD、H2-TPR、FT-IR以及SEM等表征手段对催化剂进行分析,考察催化剂活性组分的负载方法、负载量、溶液pH值以及焙烧温度对催化性能影响;研究了氧化脱硫反应动力学;通过正交实验确定了氧化脱硫反应最佳工艺条件。研究表明,采用一步合成法制备的Fe-V-HMS催化剂氧化脱硫性能优于等体积浸渍法,在合成溶液pH值为10、焙烧温度为550℃、Si/(Fe+V)摩尔比为14.8、V/Fe摩尔比为1:2条件下制备的Fe-V-HMS催化剂脱硫效果最好;在反应温度60℃,反应时间45min,O/S摩尔比为4.5,催化剂用量8g/L(oil)的条件下,脱硫率可达99%以上;DBT氧化生成的DBTO2吸附在Fe-V-HMS催化剂表面,Fe-V-HMS在氧化脱硫反应过程中同时具有催化和吸附作用;Fe-V-HMS催化氧化脱硫反应属于一级反应,其表观活化能为Ea=38.79kJ/mol、指前因子k0=1.33×105。采用水热法制得的V-MCM-41催化剂在Si/V(摩尔比)=50、pH为10.5条件下,V-MCM-41催化剂脱硫效果最好,V-MCM-41催化剂经过正交试验的优化,在O/S为4.5,反应温度70℃,催化剂用量3g/L(oil),反应时间60min的条件下催化剂的脱硫率达到98%以上。以V-MCM-41为催化剂的氧化脱硫反应属于一级反应,其表观活化能为Ea=52.48kJ/mol、指前因子k0=8.04×106min-1。
文内图片：
图片说明：HMS(a、b)和：Fe-V-HMS(c、d)的扫描电镜（SEM）图谱
[Abstract]:In order to slow down the environmental pollution caused by fuel oil, governments of various countries strictly limit the sulfur content in fuel oil. The organic sulfides in the form of thiophene compounds and their derivatives in fuel oil are difficult to be removed in hydrodesulfurization process, which leads to the increase of production cost. The process conditions of oxidative desulfurization are relaxed and the cost of desulphurization is low. the key is to develop catalysts which can both deep desulphurization and high efficiency and economy. In this paper, supported Fe-V-HMS and V-MCM-41 catalysts were prepared by doping transition metal Fe/V into HMS and MCM-41. The oxidative removal effects of the two catalysts on DBT were studied. The catalysts were characterized by NH3-TPD,XRD,H2-TPR,FT-IR and SEM. The effects of loading method, loading amount, pH value of solution and calcination temperature on the catalytic performance were investigated. The kinetics of oxidative desulfurization was studied, and the optimum technological conditions of oxidative desulfurization were determined by orthogonal experiment. The results show that the oxidative desulfurization performance of Fe-V-HMS catalyst prepared by one-step synthesis method is better than that of equal volume impregnation method. When the pH value of synthesis solution is 10, the calcination temperature is 550 鈩，
本文编号：2510139
文内图片：
图片说明：HMS(a、b)和：Fe-V-HMS(c、d)的扫描电镜（SEM）图谱
[Abstract]:In order to slow down the environmental pollution caused by fuel oil, governments of various countries strictly limit the sulfur content in fuel oil. The organic sulfides in the form of thiophene compounds and their derivatives in fuel oil are difficult to be removed in hydrodesulfurization process, which leads to the increase of production cost. The process conditions of oxidative desulfurization are relaxed and the cost of desulphurization is low. the key is to develop catalysts which can both deep desulphurization and high efficiency and economy. In this paper, supported Fe-V-HMS and V-MCM-41 catalysts were prepared by doping transition metal Fe/V into HMS and MCM-41. The oxidative removal effects of the two catalysts on DBT were studied. The catalysts were characterized by NH3-TPD,XRD,H2-TPR,FT-IR and SEM. The effects of loading method, loading amount, pH value of solution and calcination temperature on the catalytic performance were investigated. The kinetics of oxidative desulfurization was studied, and the optimum technological conditions of oxidative desulfurization were determined by orthogonal experiment. The results show that the oxidative desulfurization performance of Fe-V-HMS catalyst prepared by one-step synthesis method is better than that of equal volume impregnation method. When the pH value of synthesis solution is 10, the calcination temperature is 550 鈩，
本文编号：2510139
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