重芳烃制取BTX技术研究进展
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摘要
随着石油化工行业的快速发展,市场上轻芳烃供不应求,而C_9、C_(10)重芳烃的产量却在不断增长,因此,重芳烃脱烷基制取轻芳烃技术越来越引起人们的重视,成为国内外生产轻芳烃的重要手段之一。重芳烃制取BTX技术的研究主要包括催化剂和工艺技术路线两方面。重芳烃轻质化技术路线包括热加氢脱烷基、催化加氢脱烷基、催化加氢裂解、催化非临氢裂解和烷基苯水蒸气脱烷基等方法,涉及脱烷基、歧化和烷基转移等反应。比较有代表性的国外重芳烃轻质化反应工艺技术包括HAD、Detol、Transplus等,国内技术以中国石化石油化工科学研究院(RIPP)、中国石化上海石油化工研究院(SRIPT)的重芳烃轻质化技术为主,各工艺都有其优缺点。重芳烃制取BTX技术发生的反应所用催化剂多属于酸性,未来开发小颗粒、大孔径以及抗积炭能力良好的固体酸催化剂,尤其是催化加氢脱烷基反应和烷基转移反应催化剂,对提高C_9+重芳烃利用价值和增产附加值高的BTX具有重要意义。
With the rapid development of the petrochemical industry, the market demand for light aromatics exceeds the supply,while the production of C_9 and C_(10)heavy aromatics is growing.Therefore,the hydrodealkylation technology of heavy aromatics to light aromatics has attracted more and more attention and become an important means to produce light aromatics at home and abroad.The study on the conversion technology of heavy aromatics to BTX mainly focuses on catalyst and process technology.The technologies include hot hy-drodealkylation,catalytic hydrodealkylation,catalytic hydrocracking,catalytic non-hydrocracking and steam dealkylation of alkylbenzene.Dealkylation,disproportionation and transalkylation reactions are involved.Some representa-tive foreign technologies include HAD,Detol and Transplus,while the domestic market is dominated by the technologies of RIPP and SCRIPT,each has its advantages and disadvantages.Because most of the catalysts used in these technologies are acid,the development of solid acid catalysts with small particle size,large pore diameter and good inhibition of coke formation,especially the catalysts for hydrodealkylation and transalkylation,is of great significance to improve the value of C_9+heavy aromatics in use and to increase the production of high value-added BTX.
With the rapid development of the petrochemical industry, the market demand for light aromatics exceeds the supply,while the production of C_9 and C_(10)heavy aromatics is growing.Therefore,the hydrodealkylation technology of heavy aromatics to light aromatics has attracted more and more attention and become an important means to produce light aromatics at home and abroad.The study on the conversion technology of heavy aromatics to BTX mainly focuses on catalyst and process technology.The technologies include hot hy-drodealkylation,catalytic hydrodealkylation,catalytic hydrocracking,catalytic non-hydrocracking and steam dealkylation of alkylbenzene.Dealkylation,disproportionation and transalkylation reactions are involved.Some representa-tive foreign technologies include HAD,Detol and Transplus,while the domestic market is dominated by the technologies of RIPP and SCRIPT,each has its advantages and disadvantages.Because most of the catalysts used in these technologies are acid,the development of solid acid catalysts with small particle size,large pore diameter and good inhibition of coke formation,especially the catalysts for hydrodealkylation and transalkylation,is of great significance to improve the value of C_9+heavy aromatics in use and to increase the production of high value-added BTX.
引文
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[22]董娇娇,朱瑾,申群兵,等.Mo O3/HZSM-5催化剂上重芳烃加氢脱烷基反应[J].石油化工,2008,37(3):232-237.
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[24]中国石油化工股份有限公司.重质芳烃催化脱烷基催化剂及制备方法:中国,1472182 A[P].2004-02-04.
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[26]KNATTAB S A,ROUSHDY M I,AYOUB S M.Conversion of Hydrocarbons[J].Egypt J Chem,1980,21(4):287-294.
[27]VIKTOR S S,VLADIMIR M G,VALENTINA I L,et al.Method of Dehydrogenation,Dehydrocyclization and Hydrodealkylation:US,4064188[P].1977-12-20.
[28]MARCILLY C R.Where and How Shape Selectivity of Molecular Sieves Operates in Refining and Petrochemistry Catalytic Processes[J].Topics Catal,2000,13(4):357-366.
[29]XIN X,JAMES R,BUTLER W.Method of Conversion of Heavy Aromatics:US,2003/0092950 A1[P].2003-05-15.
[30]中国石油化工集团公司.重质芳烃轻质化催化剂及轻质化产物的分离方法:中国,99105789.9[P].2000-10-25.
[31]中国石油化工集团公司.用于重质芳烃加氢脱烷基与烷基转移的催化剂:中国,1217371 A[P].1999-05-26.
[32]中国石油化工集团公司.重质芳烃加氢脱烷基与烷基转移工艺:中国,97106718[P].1999-05-26.
[2]VITTORIO A,GHIOGGIA V,ANGELO B,et al.Process for the Catalytic Hydrodealkylation of Alkylaromatic Hydrocarbons:US,2007/0203377 A1[P].2007-08-30.
[3]TAKATSU K,SUGIMOTO M.Production of Hydrocarbon Oil:Japan,63156889[P].1988.
[4]KAEDING W W,LEE C S.ZSM-5/ZSM-12 Catalyst Mixture for Cracking Alkylbenzenes:US,4577050[P].1986.
[5]KAEDING W W,LEE C S.ZSM-5/ZSM-12 Catalyst Mixture for Cracking Alkylbenzenes:US,4593136[P].1986.
[6]DOELP L C,BRENNER W,WEISS A H.Production of Xylenes by Hydrodealkylation[J].Ind Eng Chem Proc Des Dev,1965,4(1):92-96.
[7]SONG Y,SEO G,KIZHM S.Hydrodealkylation Reaction o f Ethylbenzene Over a Supported Nickel-Tungsten Catalyst[J].Appl Catal A,1992,83(1):75-86.
[8]季静,柴忠义.重质芳烃轻质化技术研究进展[J].化学工业,2013,31(4):25-27.
[9]孙宗海,瞿国华,张溱芳.石油芳烃生产工艺与技术[M].北京:化学工业出版社,1986:151-246.
[10]王士文,秦永宁,廖巧丽,等.含稀土C9-C10芳烃脱烷基的含土催化剂及其制备方法:中国,94118235.5[P].1995.
[11]王士文,秦永宁,李炎生.临氢脱烷基制苯Cr2O3/Al2O3催化剂的失活原因分析[J].石油化工,1989,18(10):661-665.
[12]范景新,臧甲忠,于海斌,等.重芳烃轻质化研究进展[J].工业催化,2015,23(9):666-673.
[13]王士文,秦永宁,李炎生,等.新型临氢脱烷基制苯催化剂的研制[J].石油化工.1990,19(5):283-287.
[14]RABINOVICH G L,CHIZHOV V B.Transformations of C9Aromatic Hydrocarbons in the Presence of Hydrogen on a Polyfunctional Molybdenum-Mordenite Catalyst[J].Neftekhimiya,1983,23(3):353-360.
[15]中国石油化工股份有限公司.重质芳烃催化脱烷基催化剂及制备方法,中国:02125843[P].2004.
[16]任春晓,吴培,李振昊,等.加氢催化剂预硫化技术现状[J].化工进展,2013,32(5):1060-1064.
[17]祁晓岚,左煜,陈雪梅,等.HAT-plus重芳烃轻质化技术[J].石油学报(石油加工),2008,24(增):338-341.
[18]祁晓岚,左煜,孔德金,等.超细β沸石的合成及其催化重芳烃轻质化性能[J].石油化工,2004,33(增):1499-1500.
[19]WU A,DRAKE C A.Hydrodealkylation Catalyst Composition and Process:US,5698757[P].1997-01-16.
[20]VITTORIO A,CHIOGGIA V,ANGELO B,et al.Process for the Catalytic Hydrodealkylation of alkylaromatic Hydrocarbons:US,2007/0203377 A1[P].2007-08-30.
[21]SERRA J,GUILLON E,CORMA A.A Rational Design of Alkyl-Aromatics Dealkylation-Transalkylation Catalysts Using C8and C9Alky1-Aromatics As Reactants[J].J Catal,2004:459-469.
[22]董娇娇,朱瑾,申群兵,等.Mo O3/HZSM-5催化剂上重芳烃加氢脱烷基反应[J].石油化工,2008,37(3):232-237.
[23]SHEN Qunbing,ZHU Xuedong,DONG Jiaojiao,et al.Hydrodealkylation of C9+Heavy Aromatics to BTX over Zeolite-Supported Nickel Oxide and Molybdenum Oxide Catalysts[J].Catal Lett,2009,129:170-180.
[24]中国石油化工股份有限公司.重质芳烃催化脱烷基催化剂及制备方法:中国,1472182 A[P].2004-02-04.
[25]GENDLER J L.以重芳烃为原料增产苯的热加氢脱烷基技术[J].石油炼制译丛,1989(7):6-13.
[26]KNATTAB S A,ROUSHDY M I,AYOUB S M.Conversion of Hydrocarbons[J].Egypt J Chem,1980,21(4):287-294.
[27]VIKTOR S S,VLADIMIR M G,VALENTINA I L,et al.Method of Dehydrogenation,Dehydrocyclization and Hydrodealkylation:US,4064188[P].1977-12-20.
[28]MARCILLY C R.Where and How Shape Selectivity of Molecular Sieves Operates in Refining and Petrochemistry Catalytic Processes[J].Topics Catal,2000,13(4):357-366.
[29]XIN X,JAMES R,BUTLER W.Method of Conversion of Heavy Aromatics:US,2003/0092950 A1[P].2003-05-15.
[30]中国石油化工集团公司.重质芳烃轻质化催化剂及轻质化产物的分离方法:中国,99105789.9[P].2000-10-25.
[31]中国石油化工集团公司.用于重质芳烃加氢脱烷基与烷基转移的催化剂:中国,1217371 A[P].1999-05-26.
[32]中国石油化工集团公司.重质芳烃加氢脱烷基与烷基转移工艺:中国,97106718[P].1999-05-26.