HY分子筛酸密度对催化异丁烷-丁烯烷基化反应性能的影响
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摘要
通过对Y分子筛进行铵交换,获得了分子筛孔道相似、酸密度在2.87～12.99 mmol/g范围内的一系列分子筛。在控制变量的前提下,考察了这一系列分子筛在异丁烷-丁烯烷基化反应中的催化性能,研究了分子筛酸密度对其催化烷基化反应活性的影响规律。结果表明,分子筛总酸密度越大,其相对氢转移活性越高,催化烷基化反应单程寿命越长,越有利于烷基化目标产物的生成。
A series of Y zeolites with similar pore structures and different acid densities in the range of 2.87 to 12.99 mmol/g were prepared by exchanging Na~+ ion with ammonium salts. The effect of acid density on their catalytic performance was studied. The results show that high hydride activity and long single-pass catalyst life are due to the high acid density, which is beneficial for high selectivity of target products.
A series of Y zeolites with similar pore structures and different acid densities in the range of 2.87 to 12.99 mmol/g were prepared by exchanging Na~+ ion with ammonium salts. The effect of acid density on their catalytic performance was studied. The results show that high hydride activity and long single-pass catalyst life are due to the high acid density, which is beneficial for high selectivity of target products.
引文
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[21]FELLER A,ZUAZO I,GUZMAN A,et al.Common mechanistic aspects of liquid and solid acid catalyzed alkylation of isobutane with n-butene[J].Cheminform,2003,34(41):313-323.
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[23]CORMA A,MARTINEZ A,MARTINEZ C.Isobutane/2-Butene alkylation on MCM-22 catalyst.Influence of zeolite structure and acidity on activity and selectivity[J].Catalysis Letters,1994,28(2/3/4):187-201.
[24]鲁玉莹,李永祥,龙军,等.C4烷基化反应机理的分子模拟[J].石油学报(石油加工),2016,32(1):14-20.(LU Yuying,LI Yongxiang,LONG Jun,et al.Molecular simulation of mechanism for C4alkylation[J].Acta Petrolei Sinica(Petroleum Processing of Section),2016,32(1):14-20.)
[25]FELLER A,GUZMAN A,ZUAZO I,et al.On the mechanism of catalyzed isobutane/butene alkylation by zeolites[J].Journal of Catalysis,2004,224(1):80-93.
[2]毛东森,卢文奎,陈庆龄,等.固体酸代替液体酸催化剂的环境友好新工艺[J].石油化工,2001,30(2):152-156.(MAO Dongsen,LU Wenkui,CHENQingling,et al.The environmentally friendly technology of solid catalysts[J].Petrochemical Technology,2001,30(2):152-156.)
[3]WEITKAMP J,TRAA Y.Isobutane/Butene alkylation on solid catalysts:Where do we stand?[J].Catalysis Today,1999,49(1/2/3):193-199.
[4]HOMMELTOFT S I.Isobutane alkylation:Recent developments and future perspectives[J].Applied Catalysis A General,2001,221(1/2):421-428.
[5]FELLER A,BARTH J O,GUZMAN A,et al.Deactivation pathways in zeolite-catalyzed isobutane/butene alkylation[J].Journal of Catalysis,2003,220(1):192-206.
[6]JONG K P D,MESTERS C M A M,PEFEROEN D G R,et al.Paraffin alkylation using zeolite catalysts in a slurry reactor:Chemical engineering principles to extend catalyst lifetime[J].Chemical Engineering Science,2001,51(10):2053-2060.
[7]CORMA A,MARTNEZ A,MARTNEZ C.Isobutane/2-Butene alkylation on ultrastable Y zeolites:Influence of zeolite unit cell size[J].Journal of Catalysis,1994,146(1):185-192.
[8]YOO K,SMIRNIOTIS P G.The influence of Si/Al ratios of synthesized beta zeolites for the alkylation of isobutane with 2-butene[J].Applied Catalysis AGeneral,2002,227(1/2):171-179.
[9]YOO K S,SMIRNIOTIS P G.Zeolites-catalyzed alkylation of isobutane with 2-butene:Influence of acidic properties[J].Catalysis Letters,2005,103(3):249-255.
[10]付强,谢文华,慕旭宏,等.分子筛对异丁烷、丁烯烷基化反应催化性能的影响[J].石油化工,2004,33(增刊1):801-802.(FU Qiang,XIE Wenhua,MUXuhong,et al.The effects of zeolite catalysts on the alkylation of isobutane with butene[J].Petrochemical Technology,2004,33(S1):801-802.)
[11]杜晓辉,高晓云,高雄厚,等.钠对Y型分子筛水热稳定性的影响[J].石化技术与应用,2013,31(4):265-268,279.(DU Xiaohui,GAO Xiaoyun,GAOXionghou,et al.Effects of sodium content on hydrothermal stability of Y zeolite[J].Petrochemical Technology&Application,2013,31(4):265-268,279.)
[12]程时文,兰玲,于彦校,等.Y分子筛改性对其结构和酸性的影响[J].石化技术与应用,2011,29(5):401-405.(CHENG Shiwen,LAN Ling,YU Yanxiao,et al.The effect of different dealumination on Y zeolite[J].Petrochemical Technology&Application,2011,29(5):401-405.)
[13]要旸,肖强,李丽颖,等.不同骨架硅铝比Y分子筛热改性过程的固体NMR表征[J].南开大学学报(自然科学版),2004,37(2):102-106.(YAO Yang,XIAOQiang,LI Liying,et al.The MAS NMR of Y zeolites with different framework Si/Al ratio[J].Acta Scientiarum Naturalium Universitatis Nankaiensis,2004,37(2):102-106.)
[14]DIAZ-MENDOZA F A,PERNETT-BOLAO L,CARDONA-MARTINEZ N.Effect of catalyst deactivation on the acid properties of zeolites used for isobutane/butene alkylation[J].Thermochimica Acta,1998,312(1/2):47-61.
[15]LUKYANOV D B.A test method for quantitative characterization of zeolite hydrogen transfer activity[J].Journal of Catalysis,1994,145(1):54-57.
[16]CORMA A,MARTINEZ A.Chemistry,catalysts and processes for isoparaffin-olefin alkylation-actual situation and future-trends[J].Catalysis Reviews-Science and Engineering,1993,35(4):483-570.
[17]张乐,高雄厚,张艳惠,等.钠含量对超稳Y分子筛物化性能的综合影响[J].人工晶体学报,2014,43(2):454-460.(ZHANG Le,GAO Xionghou,ZHANGYanhui,et al.Effects of sodium content on physicochemical properties of USY zeolite[J].Journal of Synthetic Crystals,2014,43(2):454-460.)
[18]罗杰盛,张志喜,刘璞生,等.NH+4(Na)Y分子筛水热超稳工艺[J].石化技术与应用,2012,30(6):494-496.(LUO Jiesheng,ZHANG Zhixi,LIU Pusheng,et al.The technology of stream treatment on NH+4(Na)Y[J].Petrochemical Technology&Application,2012,30(6):494-496.)
[19]徐如人,庞文琴,霍启升,等.分子筛与多孔材料化学[M].北京:科学出版社,2015.
[20]NIVARTHY G S,SESHAN K,LERCHER J A.The influence of acidity on zeolite H-BEA catalyzed isobutane/n-butene alkylation[J].Microporous&Mesoporous Materials,1998,22(s1/2/3):379-388.
[21]FELLER A,ZUAZO I,GUZMAN A,et al.Common mechanistic aspects of liquid and solid acid catalyzed alkylation of isobutane with n-butene[J].Cheminform,2003,34(41):313-323.
[22]LAVRENOV A V,BOGDANETS E N,DUPLYAKINV K.Solid acid alkylation of isobutane by butenes:The path from the ascertainment of the reasons for fast deactivation to the technological execution of the process[J].Catalysis in Industry,2009,1(1):50-60.
[23]CORMA A,MARTINEZ A,MARTINEZ C.Isobutane/2-Butene alkylation on MCM-22 catalyst.Influence of zeolite structure and acidity on activity and selectivity[J].Catalysis Letters,1994,28(2/3/4):187-201.
[24]鲁玉莹,李永祥,龙军,等.C4烷基化反应机理的分子模拟[J].石油学报(石油加工),2016,32(1):14-20.(LU Yuying,LI Yongxiang,LONG Jun,et al.Molecular simulation of mechanism for C4alkylation[J].Acta Petrolei Sinica(Petroleum Processing of Section),2016,32(1):14-20.)
[25]FELLER A,GUZMAN A,ZUAZO I,et al.On the mechanism of catalyzed isobutane/butene alkylation by zeolites[J].Journal of Catalysis,2004,224(1):80-93.