【摘要】：原油的重質(zhì)化、劣質(zhì)化程度在不斷加劇,焦化蠟油(CGO)與頁巖油成為FCC擴(kuò)大原料、增加效益的新途徑。然而,CGO與頁巖油中的氮化物會導(dǎo)致產(chǎn)物焦炭收率升高,催化劑失活嚴(yán)重。傳統(tǒng)的氮化物中毒機(jī)理側(cè)重于氮化物與酸性位的作用,但氮化物在催化裂化過程對生焦所起的作用認(rèn)識不夠深刻,氮化物對FCC催化劑中毒機(jī)理仍需補(bǔ)充與完善。本文以模型化合物為原料,著重考察了不同堿性氮化物對模型化合物催化裂化生焦反應(yīng)的影響。當(dāng)N元素的添加量為500 ug/g時(shí),吡啶對鄰二甲苯的生焦起到抑制作用,這與吡啶易與酸性位結(jié)合而難以發(fā)生親電取代反應(yīng)有關(guān)。大分子氮化物(喹啉、吖啶)對鄰二甲苯的生焦具有促進(jìn)作用。當(dāng)N元素的添加量為2000 ug/g時(shí),喹啉促進(jìn)鄰二甲苯生焦的作用因B酸損失增多而被掩蓋。喹啉對甲基環(huán)己烷、1-己烯的生焦具有促進(jìn)作用,然而與鄰二甲苯為原料相比,這種促進(jìn)作用并不明顯。大分子堿性氮化物對焦炭的貢獻(xiàn)不僅與其自身的吸附有關(guān)。在催化裂化反應(yīng)的過程中,氮化物首先吸附到L酸位上,形成“結(jié)焦點(diǎn)”,誘導(dǎo)芳烴化合物快速吸附到“結(jié)焦點(diǎn)”上,然后發(fā)生縮合生焦的反應(yīng),從而導(dǎo)致焦炭產(chǎn)率的增加。該機(jī)理的提出改變了傳統(tǒng)的氮化物對催化劑毒害作用的認(rèn)識,為新型抗氮催化劑的制備提供了重要的理論基礎(chǔ)。結(jié)焦劑的紅外表征與X射線光電子能譜證明了焦炭多層結(jié)構(gòu)的存在,與普通芳烴化合物相比,由于氮化物在催化劑表面具有較強(qiáng)的吸附作用,所以氮化物主要位于焦炭多層結(jié)構(gòu)的最內(nèi)層。結(jié)焦劑的再生行為表明,焦炭的多層結(jié)構(gòu)與NOX的生成密不可分,位于焦炭多層結(jié)構(gòu)內(nèi)層的N原子是NOX的主要貢獻(xiàn)者,這為催化裂化再生如何控制NOX的排放提供了重要的理論基礎(chǔ)。
[Abstract]:The heavy and inferior degree of crude oil is getting worse and worse. (CGO) and shale oil have become a new way to expand the raw material and increase the benefit of FCC. However, CGO and nitride in shale oil can increase the coke yield and deactivate the catalyst seriously. The traditional mechanism of nitride poisoning is focused on the effect of nitride and acid site, but the role of nitride on coke generation in FCC process is not deep enough, and the poisoning mechanism of nitride to FCC catalyst still needs to be supplemented and perfected. In this paper, the effects of different basic nitrides on the catalytic cracking coking of model compounds were investigated. When the addition amount of N is 500 ug/g, pyridine inhibits the coking of o-xylene, which is related to the easy binding of pyridine with acid site and the difficulty of electrophilic substitution reaction. Macromolecular nitrides (quinoline, acridine) promote coke production of o-xylene. When the addition amount of N was 2000 ug/g, the effect of quinoline on coke production of o-xylene was masked by increasing the loss of B acid. Quinoline can promote the coking of methylcyclohexane and 1-hexene, but this effect is not obvious compared with that of o-xylene. The contribution of macromolecular basic nitride to coke is not only related to its own adsorption. In the process of catalytic cracking reaction, nitrides are first adsorbed to L acid sites to form a "junction focus", which induces the aromatics to rapidly adsorb to the "junction focus", and then the reaction of condensation and coking takes place, which leads to the increase of coke yield. This mechanism has changed the understanding of the toxic effect of the traditional nitride on the catalyst and provided an important theoretical basis for the preparation of the new nitrogen-resistant catalyst. Infrared characterization of coking agent and X-ray photoelectron spectroscopy (XPS) proved the existence of multi-layer structure of coke. Compared with ordinary aromatic compounds, nitride has strong adsorption on the surface of catalyst. So the nitride is mainly located in the innermost layer of the multi-layer structure of coke. The regeneration behavior of coking agent shows that the multilayer structure of coke is closely related to the formation of NOX. The N atom located in the inner layer of coke multilayer structure is the main contributor of NOX. This provides an important theoretical basis for how to control the emission of NOX in FCC regeneration.
【學(xué)位授予單位】：中國石油大學(xué)(華東)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2015
【分類號】：TE624.91

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