ZnSO_4/Al_2O_3催化剂上异丁烯齐聚反应的研究
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摘要
利用等体积浸渍法制备负载型ZnSO_4/Al_2O_3催化剂并用于异丁烯齐聚催化反应研究,采用XRD、NH_3-TPD、Py-IR、N_2吸附-脱附、SEM等表征方法对催化剂进行表征,考察了催化剂的焙烧温度、硫酸盐负载量对催化剂的表面酸性、催化反应活性及产物分布的影响。实验结果表明,在Al_2O_3载体表面,当ZnSO_4负载量低于15%(w)时具有良好的分散度,表面酸中心主要是以L酸为主,B酸数量较少,且B酸中心数量随着焙烧温度降低而逐渐减少;当焙烧温度低于350℃时,催化剂表面B酸中心消失,较高的硫酸盐分散度和L酸中心数量有利于提高催化活性和二聚体产物的选择性。
Supported ZnSO_4/Al_2O_3 catalyst was prepared by equivalent-volume impregnation,and it was tested in the oligomerization reaction of isobutene. The catalysts were characterized by XRD,NH_3-TPD,Py-IR,N_2 adsorption-desorption and SEM. The influences of calcination temperatures of the catalysts and ZnSO_4 loadings on surface acidity,catalytic reaction activity and product distributions of the catalysts were studied. It was found that crystalline grain of ZnSO_4 was highly dispersed on Al_2O_3 surface with the presence of L acid and a small number of B acid when ZnSO_4 loadings were below 15%(w). The amounts of B acid decreased with the decreasing calcination temperature of the catalysts and it vanished at a temperature below 350 ℃. The results indicated that the highly dispersed ZnSO4 and L acid are in favour of catalytic activity and C_8~= selectivity.
Supported ZnSO_4/Al_2O_3 catalyst was prepared by equivalent-volume impregnation,and it was tested in the oligomerization reaction of isobutene. The catalysts were characterized by XRD,NH_3-TPD,Py-IR,N_2 adsorption-desorption and SEM. The influences of calcination temperatures of the catalysts and ZnSO_4 loadings on surface acidity,catalytic reaction activity and product distributions of the catalysts were studied. It was found that crystalline grain of ZnSO_4 was highly dispersed on Al_2O_3 surface with the presence of L acid and a small number of B acid when ZnSO_4 loadings were below 15%(w). The amounts of B acid decreased with the decreasing calcination temperature of the catalysts and it vanished at a temperature below 350 ℃. The results indicated that the highly dispersed ZnSO4 and L acid are in favour of catalytic activity and C_8~= selectivity.
引文
[1]Jan D Y Y,Barger P T.Processes on industrial C-C bond formation[J].Doi:10.1002/9783527629565.ch15.
[2]Antunes B M,Rodrigues A E,Lin Z,et al.Alkenes oligomerization with resin catalysts[J].Fuel Process Technol,2015,138:86-99.
[3]Tzompantzi F J,Manríquez M E,Padilla J M,et al.One pot preparation of NiO/ZrO2 sulfated catalysts and its evaluation for the isobutene oligomerization[J].Catal Today,2008,133/135:154-159.
[4]Kondo J N,Domen K.IR observation of adsorption and reactions of olefins on H-form zeolites[J].J Mol Catal A:Chem,2003,199(1):27-38.
[5]EniTecnologie SpA.Process for catalytic dimerization of isobutene:US 5324878[P].1994-06-28.
[6]Yoon J W,Chang J S,Lee H D,et al.Trimerization of isobutene over a zeolite beta catalyst[J].J Catal,2007,245(1):253-256.
[7]Tzompantzi F,Valverde-Herrera M,Rodríguez-González J,et al.Improved selectivity to C8-olefins for isobutene oligomerization on NiO-W2O3/Al2O3 catalysts[J].Chem Eng Commun,2009,196(10):1198-1205.
[8]Tzompantzi F,Mantilla A,Del A G.et al.NiO-W2O3/Al2O3catalysts for the production of ecological gasoline:Effect of both NiO and the preparation method on the isobutene oligomerization selectivity[J].Catal Today,2009,143(1):132-136.
[9]Mantilla A,Tzompantzi F,Ferrat G,et al.Oligomerization of isobutene on sulfated titania:Effect of reaction conditions on selectivity[J].Catal Today,2005,107/108:707-712.
[10]Abrahamsson P.A method of making a catalyst based on silicon dioxide and phosphoric acid:EP0371938[P].1990-06-06.
[11]Honkela M L,Root A,Lindblad M,et al.Comparison of ion-exchange resin catalysts in the dimerisation of isobutene[J].Appl Catal,A,2005,295(2):216-223.
[12]Cai Tianxi.Studies of a new alkene oligomerization catalyst derived from nickel sulfate[J].Catal Today,1999,51(1):153-160.
[13]唐晓东,严志宇,曹殿学,等.负载型硫酸铁对烯烃齐聚催化作用的研究[J].石油学报:石油加工,1996,12(4):36-43.
[14]苏德香,纪敏,田福平,等.碱性助剂对负载型固体酸催化剂上异丁烯齐聚的影响[J].石油化工,2009,38(6):598-602.
[15]樊宏飞,曹殿学,贺民,等.硫酸铁-硫酸镍复合系列烯烃叠合催化剂的研究[J].石油学报:石油加工,1999,15(3):52-57.
[2]Antunes B M,Rodrigues A E,Lin Z,et al.Alkenes oligomerization with resin catalysts[J].Fuel Process Technol,2015,138:86-99.
[3]Tzompantzi F J,Manríquez M E,Padilla J M,et al.One pot preparation of NiO/ZrO2 sulfated catalysts and its evaluation for the isobutene oligomerization[J].Catal Today,2008,133/135:154-159.
[4]Kondo J N,Domen K.IR observation of adsorption and reactions of olefins on H-form zeolites[J].J Mol Catal A:Chem,2003,199(1):27-38.
[5]EniTecnologie SpA.Process for catalytic dimerization of isobutene:US 5324878[P].1994-06-28.
[6]Yoon J W,Chang J S,Lee H D,et al.Trimerization of isobutene over a zeolite beta catalyst[J].J Catal,2007,245(1):253-256.
[7]Tzompantzi F,Valverde-Herrera M,Rodríguez-González J,et al.Improved selectivity to C8-olefins for isobutene oligomerization on NiO-W2O3/Al2O3 catalysts[J].Chem Eng Commun,2009,196(10):1198-1205.
[8]Tzompantzi F,Mantilla A,Del A G.et al.NiO-W2O3/Al2O3catalysts for the production of ecological gasoline:Effect of both NiO and the preparation method on the isobutene oligomerization selectivity[J].Catal Today,2009,143(1):132-136.
[9]Mantilla A,Tzompantzi F,Ferrat G,et al.Oligomerization of isobutene on sulfated titania:Effect of reaction conditions on selectivity[J].Catal Today,2005,107/108:707-712.
[10]Abrahamsson P.A method of making a catalyst based on silicon dioxide and phosphoric acid:EP0371938[P].1990-06-06.
[11]Honkela M L,Root A,Lindblad M,et al.Comparison of ion-exchange resin catalysts in the dimerisation of isobutene[J].Appl Catal,A,2005,295(2):216-223.
[12]Cai Tianxi.Studies of a new alkene oligomerization catalyst derived from nickel sulfate[J].Catal Today,1999,51(1):153-160.
[13]唐晓东,严志宇,曹殿学,等.负载型硫酸铁对烯烃齐聚催化作用的研究[J].石油学报:石油加工,1996,12(4):36-43.
[14]苏德香,纪敏,田福平,等.碱性助剂对负载型固体酸催化剂上异丁烯齐聚的影响[J].石油化工,2009,38(6):598-602.
[15]樊宏飞,曹殿学,贺民,等.硫酸铁-硫酸镍复合系列烯烃叠合催化剂的研究[J].石油学报:石油加工,1999,15(3):52-57.