【摘要】：C9芳烴作為催化重整和乙烯裂解的主要副產(chǎn)物,它通常作為一種合成樹脂的主要原料。但是這種處理方式,極大的降低了C9芳烴的經(jīng)濟(jì)價(jià)值。近年來,研究者為了提高C9芳烴經(jīng)濟(jì)效益,提出將其作為一種汽油添加劑來利用。但是C9芳烴含有較高的含硫量,大約為250mg.L-1。因此,C9芳烴的脫硫就顯得很具有必要性。加氫脫硫作為傳統(tǒng)的脫硫方法,它會造成辛烷值的大量流失以及高氫量的消耗。因此,很多的深度脫硫方法被提出,包括:烷基化,萃取,沉淀,吸附,氧化脫硫等。在這些非加氫脫硫技術(shù)中,烷基化硫轉(zhuǎn)移是指利用C9芳烴中的烯烴與噻吩類硫化物發(fā)生烷基化反應(yīng)而提高含硫化合物的沸點(diǎn),并通過精餾作用將反應(yīng)生成的高沸點(diǎn)烷基化產(chǎn)物轉(zhuǎn)移到重餾分中,從而使輕餾分中的噻吩類硫化物得到有效脫除的技術(shù)。該技術(shù)可在常壓下操作,并且采用固體催化劑,具有綠色環(huán)保的特點(diǎn)。本文以2-乙基噻吩、2,5-二甲基噻吩和2-正丙基噻吩為硫模型化合物,分別考察了大孔磺酸樹脂NKC-9、Amberlyst 35和Amberlyst 36在模擬C9芳烴和真實(shí)C9芳烴體系中的烷基化硫轉(zhuǎn)移催化活性,并研究了反應(yīng)溫度的影響和反應(yīng)前后含硫化合物的分布。結(jié)果表明:大孔磺酸樹脂Amberlyst 36的烷基化硫轉(zhuǎn)移催化活性優(yōu)于其余兩種樹脂催化劑,其中,Amberlyst 36在70~100℃溫度范圍內(nèi)反應(yīng)1h,催化劑和原料劑油質(zhì)量比為1:30的條件下,噻吩類含硫物的轉(zhuǎn)移率達(dá)到93%以上。在催化劑活性評價(jià)的基礎(chǔ)上,考察了兩種活性烯烴(異戊烯作為傳統(tǒng)的烯烴添加劑,而甲基苯乙烯作為C9芳烴本身的烯烴)對烷基化脫硫的影響效果。結(jié)果表明:甲基苯乙烯能在更短的時(shí)間內(nèi)以更快的速率完成烷基化的硫轉(zhuǎn)移,同時(shí)還能提升C9芳烴的辛烷值。本文對他們在Amberlyst 36催化下的動(dòng)力學(xué)進(jìn)行了研究,并關(guān)聯(lián)了反應(yīng)動(dòng)力學(xué)參數(shù)。研究結(jié)果表明:兩種條件下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應(yīng)均遵循一級反應(yīng)動(dòng)力學(xué)方程,各硫化物活化能和指前因子的大小順序均為: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，

本文編號：2177586