催化裂化油浆中存在饱和烃的原因综述
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摘要
催化裂化油浆是催化裂化过程中沸点大于350℃的未转化烃类,大部分催化裂化油浆中含有大量的饱和烃,接近或者超过原料油中饱和烃的组成,而且大部分是正构烷烃,因此这部分饱和烃是很好的裂化原料。探讨了部分能继续裂化的饱和烃类在催化裂化过程中未充分转化的原因:正构烷烃难以裂化、催化剂表面酸性中心数量和强度的影响、催化剂孔道扩散的限制,竞争吸附的影响,烃类之间的转化等。其中烃类转化的影响还需要实验和理论分析来证明。
The FCC slurry is the unconverted hydrocarbons with boiling point higher than 350 ℃. Most of FCC slurry contains large amount of saturated hydrocarbons,which are close to or exceed the saturated hydrocarbon compositions in the feedstock. Whereas,most of saturated hydrocarbons are normal alkanes,which are the good feedstock of FCCU. The causes of imcomplete conversion of saturated hydrocarbons in FCC process are studied,i. e. the impact of acid on FCC catalyst surfaces,the limitation of catalyst pore dissipation,impact of competitive absorption,and conversion between hydrocarbons. The impacts of other types of hydrocarbons need to be verified by testing and theoretical analysis.
The FCC slurry is the unconverted hydrocarbons with boiling point higher than 350 ℃. Most of FCC slurry contains large amount of saturated hydrocarbons,which are close to or exceed the saturated hydrocarbon compositions in the feedstock. Whereas,most of saturated hydrocarbons are normal alkanes,which are the good feedstock of FCCU. The causes of imcomplete conversion of saturated hydrocarbons in FCC process are studied,i. e. the impact of acid on FCC catalyst surfaces,the limitation of catalyst pore dissipation,impact of competitive absorption,and conversion between hydrocarbons. The impacts of other types of hydrocarbons need to be verified by testing and theoretical analysis.
引文
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[9]黄风林.酸性助剂对催化裂化催化剂活性的影响[J].炼油设计,2001,31(9):28.
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[14]TABAK S A,KRAMBECK F J,GARWOOD W E.Conversion of propylene and butylene over ZSM-5 catalyst[J].AICh E journal,1986,32(9):1526.
[15]WILLIAMS B A,BABITZ S M,MILLER J T,et al.The roles of acid strength and pore diffusion in the enhanced cracking activity of steamed Y zeolites[J].Applied Catalysis A:General,1999,177(2):161.
[16]刘银东,李泽坤,王刚,等.竞争吸附对催化裂化反应过程的影响[J].化工学报,2008,59(11):2794.
[17]ATKINSON D,CURTHOYS G.Heats and entropies of adsorption of saturated hydrocarbons by zeolites X and Y[J].Journal of the Chemical Society,Faraday Transactions 1:Physical Chemistry in Condensed Phases,1981,77(4):897.
[18]De MOOR B A,REYNIERS M F,GOBIN O C,et al.Adsorption of C2-C8n-Alkanes in Zeolites[J].The Journal of Physical Chemistry C,2010,115(4):1204.
[19]郭爱军,王宗贤.饱和烃热裂化夺氢氢转移能力研究[J].燃料化学学报,2001,29(5):404-407.
[2]SHENDYE R V,RAJADHYAKSHA R A.Cracking of long chain n-paraffins on silica-alumina and rare earth exchanged Y zeolite[J].Chemical Engineering Science,1992,47:653.
[3]HANS C B,JOHN R A,GUY B.Marin.A Fundamental Kinetic Model for the Catalytic Cracking of Alkaneson a USY Zeolite in the Presence of Coke Formation[J].Ind.Eng.Chem.Res.2001,40:1337.
[4]KEN C H,ALLAN L L E.Properties of C-C Bonds in n-Alkanes:Relevance to Cracking Mechanisms[J].J.Phys.Chem.A 2002,106:1346.
[5]LI Q B,KEN C H,ALLAN L L E.A Theoretical Comparison of Lewis Acid vs Bronsted Acid Catalysis for n-Hexane Propane+Propene[J].J.Phys.Chem.A 2005,109:6223.
[6]BLASZKOWSHI S R,NASCIMENTO M A C,VAN S R A.Activation of CH and CC bonds by an acidic zeolite:a density functional study[J].The Journal of Physical Chemistry,1996,100(9):3463.
[7]WANG B,MANOS G.Role of strong zeolitic acid sites on hydrocarbon reactions[J].Industrial&Engineering Chemistry Research,2008,47(9):2948.
[8]陆红军.FCC催化剂中B酸和L酸的作用[J].催化裂化,1998,17(2):13.
[9]黄风林.酸性助剂对催化裂化催化剂活性的影响[J].炼油设计,2001,31(9):28.
[10]陈俊武,曹汉昌.催化裂化工艺与工程,北京:中国石化出版社,1994:236.
[11]罗一斌,舒兴田.提高细晶粒Y型分子筛的结构稳定性及其裂化性能的研究[J].石油炼制与化工,2001,32(2):52.
[12]CORMA A,MARTINEZ A,MARTINEZSORIA V,et al.Hydrocracking of vacuum gasoil on the novel mesoporous MCM-41 aluminosilicate catalyst[J].Journal of Catalysis,1995,153(1):25.
[13]LU Y,HE M Y,SHU X T,et al.Interactions of n-alkanes within a restrictive pore system under fluid catalytic cracking(FCC)conditions[J].Energy&fuels,2003,17(4):1040.
[14]TABAK S A,KRAMBECK F J,GARWOOD W E.Conversion of propylene and butylene over ZSM-5 catalyst[J].AICh E journal,1986,32(9):1526.
[15]WILLIAMS B A,BABITZ S M,MILLER J T,et al.The roles of acid strength and pore diffusion in the enhanced cracking activity of steamed Y zeolites[J].Applied Catalysis A:General,1999,177(2):161.
[16]刘银东,李泽坤,王刚,等.竞争吸附对催化裂化反应过程的影响[J].化工学报,2008,59(11):2794.
[17]ATKINSON D,CURTHOYS G.Heats and entropies of adsorption of saturated hydrocarbons by zeolites X and Y[J].Journal of the Chemical Society,Faraday Transactions 1:Physical Chemistry in Condensed Phases,1981,77(4):897.
[18]De MOOR B A,REYNIERS M F,GOBIN O C,et al.Adsorption of C2-C8n-Alkanes in Zeolites[J].The Journal of Physical Chemistry C,2010,115(4):1204.
[19]郭爱军,王宗贤.饱和烃热裂化夺氢氢转移能力研究[J].燃料化学学报,2001,29(5):404-407.