负载型固体杂多酸的制备及其脱硫性能研究

发布时间：2018-06-12 11:29

  本文选题：固体杂多酸 + 多孔载体　； 参考：《山东大学》2017年硕士论文

【摘要】：燃油中硫的燃烧能形成SO_x,是酸尘降(雾、雨、雪等)形成的主要因素,其中危害最大的当属酸雨,不仅腐蚀建筑物、树木,恶化生态环境,而且会导致水质酸化、土壤品质、粮食大量减产,给经济带来巨大损失。近年来随着人民环保理念逐渐加强,世界各主要国家纷纷颁布法令限定油中的硫含量,2017年1月1日,我国开始全面实行国五排放标准,当务之急是如何高效脱除燃料油中的难溶含硫化物。氧化脱硫操作条件温和,对噻吩等杂环类有机硫化物脱除效率高,且不需要消耗氢气,是替代加氢脱硫最有希望的深度脱硫技术之一。Keggin结构杂多酸具有脱硫活性高、酸性可调节、操作条件温和等优势而得到广泛应用。鉴于杂多酸以上诸多优势,本文主要将活性组分固体杂多酸咪唑磷钨酸负载在多孔载体上,并考察催化剂对油品脱硫效果。研究内容如下:首先,采用共沉淀、机械混合、溶胶-凝胶法负载活性组分1-丁基-3甲基咪唑磷钨酸盐([BMIM]_3HPW)并考察了对DBT(二苯并噻吩)的脱硫性能。结果表明,最佳反应条件是以共沉淀法负载的30wt%[BMIM]_3HPW/介孔SiO_2为催化剂,催化剂与油质量比0.22%,O/S=6,75℃下搅拌反应120min,反应完成后水洗,DBT脱除率达到99%以上。对反应后的催化剂进行重复再利用,共沉淀及溶胶凝胶法负载的[BMIM]_3HPW/SiO_2催化剂具备良好的再生活性,且[BMIM]_3HPW/介孔 SiO_2 的稳定性要高于[BMIM]_3HPW/SiO_2。其次,分别采用共沉淀和机械混合法将[Bmim]_3PW_(12)O_(40)负载在H_2O、HC_1、HNO_3、NaOH处理过的活性炭上,并探究上述催化剂对DBT的催化性能。实验结果表明,最佳反应条件为以HNO_3-C作为载体,O:S=10:1,DMF与模拟油体积比 1:5,60℃下反应 2h,[Bmim]_3PW_(12)O_(40)/HNO_3-C 负载量为 50wt%时,DBT脱除率最高,达到了 86.95%,表明该催化剂催化活性高,工业应用前景广阔。再次,主要研究了[Bmim]_3PW_(12)O_(40)/SiO_2、[Bmim]_3PW_(12)O_(40)/C、[Bmim]_3PW_(12)O_(40)/SiO_2、[Bmim]_3PW_(12)O_(40)/C几种催化剂对200#溶剂油的脱硫性能。通过以上研究得出,最佳反应条件为O:S=14:1,DMF与200#体积比1:2,催化剂占油品质量的0.263%,70 ℃下反应2h,不加乙酸时,以30wt%[Bmim]_3PW_(12)O_(40)/SiO_2作为催化剂,200#脱硫率可达到82.5%,加入乙酸后,以30wt%[Bmim]_3PW_(12)O_(40)/介孔SiO_2作为催化剂时,200#脱硫率达到了 98.5%,可满足工业生产需要,并证实了前言中猜测催化剂对于轻质油品如200#溶剂油应同样具有高的催化活性的正确性。最后,鉴于工程硕士需要实习一年,总结了专业实践一年的主要实习内容,实习心得及初步具备的工程思想,为科学研究转化成工业生产力做了铺垫。
[Abstract]:The combustion of sulfur in fuel oil can form SOS x, which is the main factor of acid dust falling (fog, rain, snow, etc.). The most harmful factor is acid rain, which not only corrodes buildings, trees, and deteriorates the ecological environment, but also leads to water quality acidification and soil quality. A large reduction in grain production has brought huge losses to the economy. In recent years, as the people's concept of environmental protection has gradually strengthened, major countries in the world have promulgated laws to limit the sulfur content in oil. On January 1, 2017, China began to implement the national five emission standards. The urgent task is how to efficiently remove insoluble sulfides from fuel oil. The oxidation desulfurization has the advantages of mild operating conditions, high removal efficiency for thiophene and other heterocyclic organic sulfides, and no need for hydrogen consumption. It is one of the most promising deep desulfurization technologies for hydrodesulfurization. Keggin structure heteropoly acids have high desulfurization activity. Acid adjustable, mild operating conditions and other advantages and widely used. In view of the advantages of heteropoly acids, solid heteropoly acid imidazophos tungstic acid was supported on porous carrier and the desulfurization effect of catalyst on oil was investigated. The main contents are as follows: firstly, coprecipitation, mechanical mixing and sol-gel method were used to support the active component 1- Ding Ji-3 methyl imidazophos tungstate ([BMIM] 3H PWC) and the desulfurization performance of p-DBT (dibenzothiophene) was investigated. The results show that the optimum reaction conditions are as follows: 30wt% [BMIM] / mesoporous SiO-2 as catalyst supported by coprecipitation method, and the ratio of catalyst to oil is 0.22o / Sn 675 鈩，

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