清洁油品升级背景下加氢脱硫技术研究进展
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摘要
为满足"史上最严"的国Ⅵ汽油质量标准,发展"低硫、控烯、保辛烷值"的清洁汽油生产新技术成为当前研究热点。当前清洁汽油生产的主流技术是选择性催化加氢脱硫技术,本文首先从催化裂化(FCC)汽油中汽油辛烷值损失与汽油中不同碳数和结构烯烃加氢饱和规律的研究开始,详细分析了当前国Ⅵ升级背景下的加氢脱硫技术发展现状,特别针对提高加氢脱硫催化剂脱硫选择性及辛烷值恢复性能的研究进展进行了综述。基于现有的炼油发展现状及难题,建议了未来清洁油品的发展方向:秉承"分子炼油"理念,进一步完善分子层次的汽油组成认知,不断实现汽油组成中各类烃的精准分离和高效转化,可满足清洁油品的升级需求,还可应对未来油品结构调整。
To meet the"strictest in history"national Ⅵ gasoline quality standards, the development of low sulfur, olefin, and octane number clean gasoline production technology has become a hot researchtopic. The mainstream technology of clean gasoline production is selective hydrodesulfurizationtechnology. This article expounded the research on the relationship between the octane number loss ofFCC gasoline and the hydrogenation saturation law of olefins with different carbon numbers and structuresin FCC gasoline. And the status of hydrodesulfurization technology under the background of Ⅵ upgradingin China was also analyzed in detail. The research progress of the hydrodesulfurization catalysts about thedesulfurization selectivity and octane number recovery performance was reviewed. Based on the currentstatus and problems of refinery development, the future development of the clean oil was suggested.Adhering to the concept of "molecular refining", the knowledges of the gasoline composition need to be improved so the continuous separation and efficient conversion of various hydrocarbons in gasoline composition will be realized, which can meet the upgrading requirements of clean oil products and the structural adjustment of future oil products.
To meet the"strictest in history"national Ⅵ gasoline quality standards, the development of low sulfur, olefin, and octane number clean gasoline production technology has become a hot researchtopic. The mainstream technology of clean gasoline production is selective hydrodesulfurizationtechnology. This article expounded the research on the relationship between the octane number loss ofFCC gasoline and the hydrogenation saturation law of olefins with different carbon numbers and structuresin FCC gasoline. And the status of hydrodesulfurization technology under the background of Ⅵ upgradingin China was also analyzed in detail. The research progress of the hydrodesulfurization catalysts about thedesulfurization selectivity and octane number recovery performance was reviewed. Based on the currentstatus and problems of refinery development, the future development of the clean oil was suggested.Adhering to the concept of "molecular refining", the knowledges of the gasoline composition need to be improved so the continuous separation and efficient conversion of various hydrocarbons in gasoline composition will be realized, which can meet the upgrading requirements of clean oil products and the structural adjustment of future oil products.
引文
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[2]中华人民共和国国家质量监督检验检疫总局,环境保护部.车用汽油有害物质控制标准(第四、五阶段):GWKB1.1—2011[S].北京:中国标准出版社,2011.General Administration of Quality Supervision,Inspection andQuarantine of the People's Republic of China,Ministry of Ecologyand Environment of the People's Republic of China. Hazardousmaterials control standard for motor vehicle gasoline(Ⅳ,Ⅴ):GWKB1.1—2011[S]. Beijing:Standards Press of China, 2011.
[3]申兴海. FCC汽油萃取蒸馏脱硫制取欧Ⅳ清洁汽油的研究[D].上海:华东理工大学, 2011.SHEN X H. Removing sulfur Compounds from fluid catalyticcracking gasoline by extractive distillation for producing EuropeⅣgasoline[D]. Shanghai:East China University of Science andTechnology, 2011.
[4]娄永峰.满足国Ⅴ汽油标准的汽油加氢脱硫工艺最新进展[J].山东化工, 2016, 45(18):38-43.LOU Y F. Latest advances of gasoline hydrodesulfurizationprocess for gasoline meeting National StandardⅤ[J]. ShandongChemical Industry, 2016, 45(18):38-43.
[5] BACO F, DEBUISSCHE Q, MARCHAL N. Prime G+processdesulfurization of FCC gasoline with minimized octane loss[C]//Proceedings of the Fifth International Conference on RefineryProcessing, AIChE 2002 Spring National Meeting. March11-14,New Orleans, LA. 2002.
[6] BRIGNAC B G. The SCAN fining hydrotreatment process[J].World Refining, 2000, 10(7):14-18.
[7] GARDNER R, EA SCHWARZ K R. Start-up of the first CDHydro/CDHDS Unit at Irving Oil's Saint John, New Brunswick Refinery[C]//NPRA Annual Meeting. 2001.
[8]高晓东,张登前,李明丰,等.满足国Ⅴ汽油标准的RSDS-Ⅲ技术的开发及应用[J].石油学报(石油加工), 2015, 31(2):482-486.GAO X D, ZHANG D Q, LI M F, et al. Development andapplication of RSDS-Ⅲtechnology for NationalⅤgasolineproduction[J]. Acta Petrolei Sinica(Petroleum Processing Section),2015, 31(2):482-486.
[9] SHIH S S, OWENS P, PALIT J. Mobil's OCTGAIN Proeess:FCCgasoline desulfurization reaches a new Performance level[C]//NPRA Annual Meeting, San Antonio,Texas. 1999.
[10]李明丰,夏国富,褚阳,等.催化裂化汽油选择性加氢脱硫催化剂RSDS-1的开发[J].石油炼制与化工, 2003,34(7):1-4.LI M F, XIA G F, ZHU Y, et al. Preparation of selectivehydrodesulfurization catalyst RSDS-I for naphtha[J]. PetroleumProcessing and Petrochemicals, 2003,34(7):1-4.
[11]石冈,范煜,鲍晓军,等.催化裂化汽油加氢改质GARDES技术的开发及工业试验[J].石油炼制与化工, 2013, 44(9):66-72.SHI G, FAN Y, BAO X J, et al. Development and application ofGARDES technology for fluid catalytic cracking gasoline hydro-upgrading[J]. Petroleum Processing and Petrochemicals, 2013, 44(9):66-72.
[12]接瑜.催化汽油加氢脱硫装置国Ⅴ升级改造设计[J].石油与天然气化工, 2017(4):11-15.JIE Y. Revamp design of the FCC gasoline hydrodesulfurizationunit to upgrade to NationalⅤgasoline[J]. Chemical Engineering ofOil&Gas, 2017(4):11-15.
[13]乔景辉,李程飞,周雪梅.吉化Prime G+装置国Ⅴ质量升级技术方案及运行分析[J].化工科技, 2017, 25(6):62-66.QIAO J H, LI C F, ZHOU X M. Technical scheme and operationanalysis of ChinaⅤquality upgrading of Jilin PetrochemicalPrime G+unit[J]. Science&Technology in Chemical Industry,2017, 25(6):62-66.
[14]李志超,肖立刚,张晓光,等.燃料型炼油厂国Ⅵ汽油升级路线分析[J].炼油技术与工程, 2017(6):40-43.LI Z C, XIAO L G, ZHANG X G, et al. Analysis of upgradingprocess for GuoⅥgasoline for fuel-type refinery[J]. PetroleumRefinery Engineering, 2017(6):40-43.
[15]曹湘洪.面向未来,我国生产汽油的技术路线选择[J].石油炼制与化工, 2012, 43(8):1-6.CAO X H. The choice of china`s gasoline production process routefor the future[J]. Petroleum Processing and Petrochemicals, 2012,43(8):1-6.
[16] Gilbert W. Formation of thiophenic species in FCC gasoline fromH2S generating sulfur sources in FCC conditions[J]. Fuel, 2014,121:65-71.
[17]魏秀萍,贾黎黎,赵运芳.催化裂化汽油中含硫化物类型及分布规律[J].精细石油化工, 2013(6):70-74.WEI X P, JIA L L, ZHAO Y F. Type and distribution patterns ofsulfur compounds in fluid catalytic cracking gasoline[J]. SpecialtyPetrochemicals, 2013(6):70-74.
[18] LEFLAIVE P, LEMBERTON J, PEROT G, et al. On the origin ofsulfur impurities in fluid catalytic cracking gasoline:reactivity ofthiophene derivatives and of their possible precursors under FCCconditions[J]. Applied Catalysis A:General, 2002, 227(1):201-215.
[19] CIS R, JHOSN J, GODOY J, et al. Characterization of Tungsten-modified ultrastable Y zeolite catalysts and their activity inthiophene hydrodesulfurization[J]. Journal of Catalysis, 1993, 141:206-218.
[20]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(6):6-9.XING J X, LIU C G. Distribution of sulfur, group composition andtypes of sulfur compounds in FCC naphtha[J]. Petroleum RefineryEngineering, 2003(6):6-9.
[21]李凤琪,全瀛寰,朱凌辉,等.哈油FCC汽油硫及烯烃含量分布特征研究[J].炼油技术与工程, 2015(7):18-20.LI F Q, QUAN Y H, ZHU L H, et al. Study on sulfur and olefindistribution of FCC gasoline from Kazakhstan crude oil[J].Petroleum Refinery Engineering, 2015(7):18-20.
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