吲哚在NiW/γ-Al_2O_3催化剂上加氢脱氮的研究
摘要
随着世界范围内原油的日渐枯竭和现代社会对清洁燃料油的需求量不断增加,开发和利用新的替代能源逐渐成为人们研究的热点。页岩油作为一种重要的石油补充能源,由于其杂原子含量和组成不同于原油,因此其加工提质也不同于原油的加工,本论文主要围绕含氮化合物吲哚(IND)的加氢脱氮及其与喹啉(Q)、萘的相互影响展开了详细的研究。
本论文在固定床微反应器中研究了吲哚及其中间产物在NiW／γ-Al203催化剂上的加氢脱氮反应和影响因素。结果表明：提高反应温度、压力、氢油比、以及降低液时空速均可以提高吲哚加氢脱氮的转化率。过高的H2S分压对吲哚的转化率并无明显促进作用,却使脱氮率略有降低。H2S能够促进1,2-二氢吲哚的C(sp3)-N断裂,但抑制了邻乙基苯胺(OEA)的C(sp2)-N断裂。吲哚分子中的氮杂环和芳香环与烯烃是在同一活性位进行加氢反应的。
同时研究了吲哚、喹啉加氢脱氮过程中的相互影响。发现吲哚的添加几乎对喹啉的转化率没有任何影响,但脱氮率略有下降。吲哚抑制了喹啉→5,6,7,8-四氢喹啉(THQ5)和1,2,3,4-四氢喹啉(THQ1)→临丙基苯胺(OPA)反应的进行,并且吲哚分子的吸附性能强于喹啉分子中芳香环而弱于氮杂环的吸附性能。喹啉的添加明显降低了吲哚的转化率和脱氮率,喹啉对吲哚加氢反应和C-N键断裂反应均产生明显的抑制作用。这种抑制作用主要源于Q、THQ1、THQ5对IND及其中间产物的竞争吸附。OEA加氢脱氮反应主要是通过OEA→ECH路径进行的,即使少量的喹啉也会对OEA加氢脱氮反应产生较为严重的抑制作用。
本文还研究了吲哚、喹啉加氢脱氮反应和萘加氢饱和反应的相互影响。发现IND、1,2-二氢吲哚(HIN)、Q、THQ5的加入严重抑制了萘加氢反应的进行。喹啉主要依靠氮杂环的大派键吸附在催化剂的活性中心上,而吲哚吸附主要靠氮原子上的孤对电子。Q和THQ5在加氢活性位上的吸附常数相差不多,且均大于HIN和IND的吸附常数。虽然没有检测到八氢吲哚(OHIN),但可推测出吲哚的HDN确有反应路径HIN→OHIN。萘的加入由于竞争吸附导致HIN→IND的脱氢反应速率降低,严重的抑制了OEA→邻乙基环己基胺(OECHA)的加氢反应,并且OEA在加氢活性位上的吸附常数与萘的吸附常数相差不多。
The more and more requirement of clean fuel oil by the developing of modern society, interest in the development of new substitute energy has been spurred because of the drying up of petroleum feedstock in the range of world day by day. Oil shale has been identified as an alternative source for production of crude oil substitutes. The upgrading process of shale oil is difficult from that of crude oil for the higher content of hetero-atoms. We studied the hydrodenitrogenation (HDN) of indole and mutual influence with quinoline and naphthalene.
The HDN of indole and its intermediates were studied over NiW/y-Al2O3 catalyst in a continuous fixed-bed reactor. The results show that:The HDN of indole increased drastically with the increase of reaction temperature, reaction pressure and hydrogen/oil ratio. Excessively partial pressure of H2S doesn't promote much more for conversion of the HDN of indole, but inhibits the hydrodenitrification conversion. H2S can promote C(sp3)-N bond cleavage in 1,2-dihydroindole, inhibit slightly the hydrogenation reaction and C(sp2)-N bond cleavage in o-ethylaniline due to their competitive adsorption. Hydrogenation of aromatic heterocyclic rings, benzenic rings and olefin group takes place at the same active site.
The mutual influence of HDN of indole and quinoline was also studied in the simultaneous hydroprocessing of feedstock. The results show that:the presence of indole has almost no effect for the quinoline conversion, but leads to denitrogenation conversion dropped. Indole inhibits the hydrogenation of in the Q to THQ5 and the pathway of THQ1 hydrogenolysis to OPA. Indole adsorption constant is bigger than that of benzenic rings, smaller than that of aromatic heterocyclic rings. Adding quinoline into indole decrease seriously the indole conversion and denitrogenationconversion, indicating that quinoline inhibits the hydrogenation reaction pathway and C-N bond cleavage. This can be atributed to the stronger adsorption of quinoline and its intermediates such as 1,2,3,4-tetrahydro-quinoline and 5,6,7,8-tetrahydro-quinoline than indole. Even of the presence of small amount of quinline lead to a drastic inhibiting effect in the HDN of OEA, Which is via OEA-ECH the pathway mainly.
The mutual influence of HDN of indole or quinoline and hydrogenation of naphthalene were also studied in the simultaneous hydroprocessing of feedstock. The results show that:the present of IND, HIN, Q, and THQ5 leads to a drastic inhibiting effect for the hydrogenation of naphthalene. Adsorption of quinoline is via greatπbonds in aromatic heterocyclic rings, but that of indole is via the lone pair electrons of the nitrogen atom. Adsorption constants of quinoline and THQ5 have no obvious difference, which are both bigger than that of HIN and IND. HIN-OHIN pathway can be indicated to present in the HDN of indole from the data, although OHIN is not detected. The present of naphthalene leads to inhibit HIN-IND and OEA-OECHA pathway reactions. Also, OEA adsorption constant is similar as naphthalene on hydrogenation sites.
本论文在固定床微反应器中研究了吲哚及其中间产物在NiW／γ-Al203催化剂上的加氢脱氮反应和影响因素。结果表明：提高反应温度、压力、氢油比、以及降低液时空速均可以提高吲哚加氢脱氮的转化率。过高的H2S分压对吲哚的转化率并无明显促进作用,却使脱氮率略有降低。H2S能够促进1,2-二氢吲哚的C(sp3)-N断裂,但抑制了邻乙基苯胺(OEA)的C(sp2)-N断裂。吲哚分子中的氮杂环和芳香环与烯烃是在同一活性位进行加氢反应的。
同时研究了吲哚、喹啉加氢脱氮过程中的相互影响。发现吲哚的添加几乎对喹啉的转化率没有任何影响,但脱氮率略有下降。吲哚抑制了喹啉→5,6,7,8-四氢喹啉(THQ5)和1,2,3,4-四氢喹啉(THQ1)→临丙基苯胺(OPA)反应的进行,并且吲哚分子的吸附性能强于喹啉分子中芳香环而弱于氮杂环的吸附性能。喹啉的添加明显降低了吲哚的转化率和脱氮率,喹啉对吲哚加氢反应和C-N键断裂反应均产生明显的抑制作用。这种抑制作用主要源于Q、THQ1、THQ5对IND及其中间产物的竞争吸附。OEA加氢脱氮反应主要是通过OEA→ECH路径进行的,即使少量的喹啉也会对OEA加氢脱氮反应产生较为严重的抑制作用。
本文还研究了吲哚、喹啉加氢脱氮反应和萘加氢饱和反应的相互影响。发现IND、1,2-二氢吲哚(HIN)、Q、THQ5的加入严重抑制了萘加氢反应的进行。喹啉主要依靠氮杂环的大派键吸附在催化剂的活性中心上,而吲哚吸附主要靠氮原子上的孤对电子。Q和THQ5在加氢活性位上的吸附常数相差不多,且均大于HIN和IND的吸附常数。虽然没有检测到八氢吲哚(OHIN),但可推测出吲哚的HDN确有反应路径HIN→OHIN。萘的加入由于竞争吸附导致HIN→IND的脱氢反应速率降低,严重的抑制了OEA→邻乙基环己基胺(OECHA)的加氢反应,并且OEA在加氢活性位上的吸附常数与萘的吸附常数相差不多。
The more and more requirement of clean fuel oil by the developing of modern society, interest in the development of new substitute energy has been spurred because of the drying up of petroleum feedstock in the range of world day by day. Oil shale has been identified as an alternative source for production of crude oil substitutes. The upgrading process of shale oil is difficult from that of crude oil for the higher content of hetero-atoms. We studied the hydrodenitrogenation (HDN) of indole and mutual influence with quinoline and naphthalene.
The HDN of indole and its intermediates were studied over NiW/y-Al2O3 catalyst in a continuous fixed-bed reactor. The results show that:The HDN of indole increased drastically with the increase of reaction temperature, reaction pressure and hydrogen/oil ratio. Excessively partial pressure of H2S doesn't promote much more for conversion of the HDN of indole, but inhibits the hydrodenitrification conversion. H2S can promote C(sp3)-N bond cleavage in 1,2-dihydroindole, inhibit slightly the hydrogenation reaction and C(sp2)-N bond cleavage in o-ethylaniline due to their competitive adsorption. Hydrogenation of aromatic heterocyclic rings, benzenic rings and olefin group takes place at the same active site.
The mutual influence of HDN of indole and quinoline was also studied in the simultaneous hydroprocessing of feedstock. The results show that:the presence of indole has almost no effect for the quinoline conversion, but leads to denitrogenation conversion dropped. Indole inhibits the hydrogenation of in the Q to THQ5 and the pathway of THQ1 hydrogenolysis to OPA. Indole adsorption constant is bigger than that of benzenic rings, smaller than that of aromatic heterocyclic rings. Adding quinoline into indole decrease seriously the indole conversion and denitrogenationconversion, indicating that quinoline inhibits the hydrogenation reaction pathway and C-N bond cleavage. This can be atributed to the stronger adsorption of quinoline and its intermediates such as 1,2,3,4-tetrahydro-quinoline and 5,6,7,8-tetrahydro-quinoline than indole. Even of the presence of small amount of quinline lead to a drastic inhibiting effect in the HDN of OEA, Which is via OEA-ECH the pathway mainly.
The mutual influence of HDN of indole or quinoline and hydrogenation of naphthalene were also studied in the simultaneous hydroprocessing of feedstock. The results show that:the present of IND, HIN, Q, and THQ5 leads to a drastic inhibiting effect for the hydrogenation of naphthalene. Adsorption of quinoline is via greatπbonds in aromatic heterocyclic rings, but that of indole is via the lone pair electrons of the nitrogen atom. Adsorption constants of quinoline and THQ5 have no obvious difference, which are both bigger than that of HIN and IND. HIN-OHIN pathway can be indicated to present in the HDN of indole from the data, although OHIN is not detected. The present of naphthalene leads to inhibit HIN-IND and OEA-OECHA pathway reactions. Also, OEA adsorption constant is similar as naphthalene on hydrogenation sites.
引文
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