裂解C9芳烃烷基化脱硫反应动力学研究
发布时间：2018-08-11 16:31
【摘要】：C9芳烃作为催化重整和乙烯裂解的主要副产物,它通常作为一种合成树脂的主要原料。但是这种处理方式,极大的降低了C9芳烃的经济价值。近年来,研究者为了提高C9芳烃经济效益,提出将其作为一种汽油添加剂来利用。但是C9芳烃含有较高的含硫量,大约为250mg.L-1。因此,C9芳烃的脱硫就显得很具有必要性。加氢脱硫作为传统的脱硫方法,它会造成辛烷值的大量流失以及高氢量的消耗。因此,很多的深度脱硫方法被提出,包括:烷基化,萃取,沉淀,吸附,氧化脱硫等。在这些非加氢脱硫技术中,烷基化硫转移是指利用C9芳烃中的烯烃与噻吩类硫化物发生烷基化反应而提高含硫化合物的沸点,并通过精馏作用将反应生成的高沸点烷基化产物转移到重馏分中,从而使轻馏分中的噻吩类硫化物得到有效脱除的技术。该技术可在常压下操作,并且采用固体催化剂,具有绿色环保的特点。本文以2-乙基噻吩、2,5-二甲基噻吩和2-正丙基噻吩为硫模型化合物,分别考察了大孔磺酸树脂NKC-9、Amberlyst 35和Amberlyst 36在模拟C9芳烃和真实C9芳烃体系中的烷基化硫转移催化活性,并研究了反应温度的影响和反应前后含硫化合物的分布。结果表明:大孔磺酸树脂Amberlyst 36的烷基化硫转移催化活性优于其余两种树脂催化剂,其中,Amberlyst 36在70~100℃温度范围内反应1h,催化剂和原料剂油质量比为1:30的条件下,噻吩类含硫物的转移率达到93%以上。在催化剂活性评价的基础上,考察了两种活性烯烃(异戊烯作为传统的烯烃添加剂,而甲基苯乙烯作为C9芳烃本身的烯烃)对烷基化脱硫的影响效果。结果表明:甲基苯乙烯能在更短的时间内以更快的速率完成烷基化的硫转移,同时还能提升C9芳烃的辛烷值。本文对他们在Amberlyst 36催化下的动力学进行了研究,并关联了反应动力学参数。研究结果表明:两种条件下2-乙基噻吩、2,5-二甲基噻吩以及2-正丙基噻吩的烷基化反应均遵循一级反应动力学方程,各硫化物活化能和指前因子的大小顺序均为:2-正丙基噻吩2-乙基噻吩2,5-二甲基噻吩。
[Abstract]:C _ 9 aromatics, as the main by-products of catalytic reforming and ethylene cracking, are usually used as the main feedstock of a synthetic resin. However, this treatment greatly reduces the economic value of C 9 aromatics. In recent years, in order to improve the economic efficiency of C 9 aromatics, researchers proposed to use C 9 aromatic hydrocarbons as a gasoline additive. However, C _ 9 aromatics contain a higher sulphur content, about 250 mg 路L ~ (-1). Therefore, the desulfurization of C 9 aromatics is very necessary. Hydrodesulfurization (HDS), as a traditional desulfurization method, will lead to the loss of octane number and the consumption of high hydrogen content. Therefore, many deep desulfurization methods have been proposed, including alkylation, extraction, precipitation, adsorption, oxidation desulfurization and so on. In these non-hydrodesulfurization technologies, the transfer of alkylated sulfur refers to the alkylation of olefins in C 9 aromatics with thiophene sulfides in order to increase the boiling point of sulfur compounds. The high boiling point alkylation products from the reaction were transferred to the heavy fractions by distillation, thus the thiophene sulfides in the light fractions were effectively removed. The technology can be operated under atmospheric pressure and solid catalyst, which has the characteristics of green and environmental protection. Using 2-ethylthiophene (2-ethylthiophene) and 2-propylthiophene (2-propylthiophene) as sulfur model compounds, the alkylation sulfur transfer catalytic activity of macroporous sulfonic resin NKC-9 Amberlyst 35 and Amberlyst 36 in the system of simulated C 9 aromatics and real C 9 aromatics was investigated, respectively. The influence of reaction temperature and the distribution of sulfur compounds before and after reaction were studied. The results showed that the catalytic activity of macroporous sulfonic acid resin Amberlyst 36 was superior to that of the other two kinds of resin catalysts. Amberlyst 36 reacted at 70 鈩，
本文编号：2177586
[Abstract]:C _ 9 aromatics, as the main by-products of catalytic reforming and ethylene cracking, are usually used as the main feedstock of a synthetic resin. However, this treatment greatly reduces the economic value of C 9 aromatics. In recent years, in order to improve the economic efficiency of C 9 aromatics, researchers proposed to use C 9 aromatic hydrocarbons as a gasoline additive. However, C _ 9 aromatics contain a higher sulphur content, about 250 mg 路L ~ (-1). Therefore, the desulfurization of C 9 aromatics is very necessary. Hydrodesulfurization (HDS), as a traditional desulfurization method, will lead to the loss of octane number and the consumption of high hydrogen content. Therefore, many deep desulfurization methods have been proposed, including alkylation, extraction, precipitation, adsorption, oxidation desulfurization and so on. In these non-hydrodesulfurization technologies, the transfer of alkylated sulfur refers to the alkylation of olefins in C 9 aromatics with thiophene sulfides in order to increase the boiling point of sulfur compounds. The high boiling point alkylation products from the reaction were transferred to the heavy fractions by distillation, thus the thiophene sulfides in the light fractions were effectively removed. The technology can be operated under atmospheric pressure and solid catalyst, which has the characteristics of green and environmental protection. Using 2-ethylthiophene (2-ethylthiophene) and 2-propylthiophene (2-propylthiophene) as sulfur model compounds, the alkylation sulfur transfer catalytic activity of macroporous sulfonic resin NKC-9 Amberlyst 35 and Amberlyst 36 in the system of simulated C 9 aromatics and real C 9 aromatics was investigated, respectively. The influence of reaction temperature and the distribution of sulfur compounds before and after reaction were studied. The results showed that the catalytic activity of macroporous sulfonic acid resin Amberlyst 36 was superior to that of the other two kinds of resin catalysts. Amberlyst 36 reacted at 70 鈩，
本文编号：2177586
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