Study of sulfur transfer reaction on Ni-Mo/Al2O3 catalyst
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摘要: 制备了以γ-Al2O3为载体的Ni-Mo催化剂,并用于FCC汽油的加氢硫转移反应。对Ni-Mo/Al2O3催化剂上的硫转移反应机理进行了研究,考察了不同反应条件对硫转移反应的影响。实验结果表明,硫醇与烯烃的反应在催化剂表面的加氢活性位上进行,小分子的硫醇发生加氢脱硫,生成吸附态H2S,吸附态的H2S与烯烃反应,生成大分子硫醇和硫醚;另外小分子硫醇还可直接与烯烃发生反应,生成硫醚。提高反应温度、压力、氢油比或降低空速,均可提高催化剂的硫转移反应活性,轻质硫转化率得到明显提高,且单烯选择性还能维持在98%左右。Abstract: The bimetal Ni-Mo catalysts supported on γ-Al2O3 were prepared and used for the selective hydrogenation of FCC gasoline for sulfur transfer. The reaction mechanism of sulfur transfer on Ni-Mo/Al2O3 catalyst was studied and the influence of reaction conditions on sulfur transfer was investigated. The results showed that the reaction of thiol and olefin happened on the active sites of hydrogenation on catalyst surface. Hydrodesulfurization of small molecule thiol firstly produced adsorbed hydrogen sulfide, then the adsorbed hydrogen sulfide reacted with adsorbed olefin and formed macromolecular thiol or thioether; Besides, small molecule thiol can also directly reacted with olefins to produce thioether. The activity of sulfur transfer reaction of Ni-Mo/Al2O3 catalyst was improved through the increase of reaction temperature, pressure, and H2/oil ratio or the decrease of LHSV. The conversion of light sulfur compounds was obviously improved, and mono-olefins selectivity was maintained at around 98%.
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Key words:
- sulfur transfer /
- light sulfur /
- mono-olefins selectivity /
- reaction conditions
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高道伟, 段爱军, 赵震, 邓云川. FCC汽油加氢脱硫工艺技术研究进展[J]. 石油与天然气化工, 2013, 42(3): 216-221. (GAO Dao-wei, DUAN Ai-jun, ZHAO Zhen, DENG Yun-chuan. Research development of hydrodesulfurization technology of FCC gasoline[J]. Chemical Engineering of Oil & Gas, 2013, 42(3): 216-221.) 邢金仙, 刘晨光. 催化裂化汽油中硫和族组成及硫化物类型的馏分分布[J]. 炼油技术与工程, 2003, 33(6): 6-9. (XING Jin-xian, LIU Chen-guang. Distribution of sulfur, group composition and types of sulfur compounds in FCC naphtha[J]. Petroleum Refinery Engineering, 2003, 33(6): 6-9.) 马宝利, 徐峰, 刘茉, 董春明, 杨晓东. FCC汽油加氢脱硫提高辛烷值技术研究进展[J]. 炼油与化工, 2013, 24(4): 1-3. (MA Bao-li, XU Feng, LIU Mo, DONG Chun-ming, YANG Xiao-dong. Technical research progress on FCC gasoline hydrodesulfurization for improvement of octane number[J]. Refining and Chemical Industry, 2013, 24(4): 1-3.) 梁咏梅, 史权, 刘旭霞, 何俊辉. 催化裂化汽油选择性加氢脱硫中轻重馏分切割温度的研究[J]. 石油炼制与化工, 2011, 42(5): 40-44. (LIANG Yong-mei, SHI Quan, LIU Xu-xia, HE Jun-hui. Study on the cut points of light and heavy gasoline fractions for selective hydrodesulfurization of FCC gasoline[J]. Petroleum Processing and Petrochemicals, 2011, 42(5): 40-44.) 温广明, 王丹, 赵野, 吴昆鹏. 催化裂化汽油加氢脱硫技术进展[J]. 工业催化, 2008, 16(12): 1-6. (WEN Guang-ming, WANG Dan, ZHAO Ye, WU Kun-peng. Advances in FCC gasoline hydrodesulfurization technologies[J]. Industrial Catalysis, 2008, 16(12): 1-6.) 董海明, 曲云, 孙丽琳. Prime-G+技术在催化裂化汽油加氢脱硫装置上的应用[J]. 石油炼制与化工, 2012, 43(11): 27-30. (DONG Hai-ming, QU Yun, SUN Li-lin. Application of Prime-G+ technology in FCC naphtha hydrodesulfurization unit[J]. Petroleum Processing and Petrochemicals, 2012, 43(11): 27-30.) 周庆水, 郝振歧, 王艳涛, 赵乐平. OCT-M FCC汽油深度加氢脱硫技术的研究及工业应用[J]. 石油炼制与化工, 2007, 38(9): 28-31. (ZHOU Qing-shui, HAO Zhen-qi, WANG Yan-tao, ZHAO Le-ping. Development and commercial application of OCT-M process for FCC naphtha deep hydrodesulfurization[J]. Petroleum Processing and Petrochemicals, 2007, 38(9): 28-31.) BRUNET S, MEY D, PEROT G, BOUCHY C, DIEHL F. On the hydrodesulfurization of FCC gasoline: A review[J]. Appl Catal A: Gen, 2005, 286(2): 143-172. DENNIS H. Process for the removal of mercaptans and hydrogen sulfide from hydrocarbon streams: US, 5510568. 1997-02-04. PODREBARAC G G, GILDERT G R. Process for sulfur reduction in naphtha streams: US, 6444118. 2002-09-03. DENNIS H, GILDERT G R. Process for removal of mercaptans from hydrocarbon streams: US, 6440299. 2002-08-27. ALEXIS A, GRIESBAUM K, WARREN A. Organic sulfur compounds. VIII. Addition of thiol to conjugated diolefins[J]. J Am Chem Soc, 1962, 84(20): 3897-3904. MARVEL C S, MARKHART A H. Polyalkylene sulfides. V. The rate of formation in emulsion[J]. J Am Chem Soc, 1951, 73(3): 1064-1065.
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