[BMIM]Cl-AlCl_3离子液体酸性调变对催化正戊烷异构化性能的影响
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摘要
氯铝酸离子液体具有优良的催化轻质烷烃异构化性能,为研究该类离子液体酸性调变对其催化异构化性能的影响,分别向1-丁基-3-甲基咪唑氯铝酸离子液体([BMIM]Cl-AlCl_3)中添加ZnCl_2(L酸)和氯化(1-甲基-3-羧甲基咪唑)([cmmim]Cl,B酸),并通过紫外-可见吸收光谱和乙腈吸附红外光谱对改性离子液体酸性进行测定,考察了其对离子液体催化正戊烷异构化反应活性的影响。结果表明,改性离子液体的酸性随ZnCl_2质量分数的增加而逐渐减弱,催化正戊烷异构化反应活性也随之减弱,但异构烷烃的选择性增强;而添加少量[cmmim]Cl后的改性离子液体酸性先增加后降低,但随着[cmmim]Cl质量分数的增加,离子液体黏度不断上升,催化正戊烷异构化的活性呈现逐渐降低趋势。
Chlorine aluminate ionic liquid has an excellent catalytic performance on isomerization of light paraffin.In order to investigate the effect of acidity adjustment on the catalytic isomerization performance of chlorine aluminate ionic liquid,ZnCl_2( L acid) and [cmmim]Cl( B acid) are added into [BMIM]Cl-AlCl_3 ionic liquid,respectively.The acidity of the modified [BMIM]Cl-AlCl_3 ionic liquids is characterized by UV-Vis spectra and acetonitrile adsorption FT-IR spectra,while the catalytic performance of the modified [BMIM]Cl-AlCl_3 ionic liquid on n-pentane isomerization is also studied.The results show that with the increasing amount of ZnCl_2,both the acidity and the catalytic activity of the modified ionic liquid decrease while the selectivity of iso-paraffins is improved. The acidity of the ionic liquid adding a few amounts of [cmmim]Cl becomes stronger firstly and then drops.But these two indexes both drop when the amount of[cmmim]Cl increases continuously.
Chlorine aluminate ionic liquid has an excellent catalytic performance on isomerization of light paraffin.In order to investigate the effect of acidity adjustment on the catalytic isomerization performance of chlorine aluminate ionic liquid,ZnCl_2( L acid) and [cmmim]Cl( B acid) are added into [BMIM]Cl-AlCl_3 ionic liquid,respectively.The acidity of the modified [BMIM]Cl-AlCl_3 ionic liquids is characterized by UV-Vis spectra and acetonitrile adsorption FT-IR spectra,while the catalytic performance of the modified [BMIM]Cl-AlCl_3 ionic liquid on n-pentane isomerization is also studied.The results show that with the increasing amount of ZnCl_2,both the acidity and the catalytic activity of the modified ionic liquid decrease while the selectivity of iso-paraffins is improved. The acidity of the ionic liquid adding a few amounts of [cmmim]Cl becomes stronger firstly and then drops.But these two indexes both drop when the amount of[cmmim]Cl increases continuously.
引文
[1]Plechkova N V,Seddon K R.Applications of ionic liquids in the chemical industry[J].Chemical Society Reviews,2008,37(1):123-150.
[2]周建军,刘植昌,张睿,等.室温离子液体催化正戊烷异构化反应[J].燃料化学学报,2008,36(2):156-159.
[3]Meyer C,Wasserscheid P.Effective n-octane isomerization under exceptionally mild conditions using a novel class of superacidic ionic liquids[J].Chemical Communications,2010,46(40):7625-7627.
[4]张振华,赵国英,卢丹,等.醚基复合氯铝酸离子液体催化异丁烷烷基化[J].过程工程学报,2017,(5):1016-1022.
[5]石振民,武晓辉,刘植昌,等.室温离子液体催化正己烷异构化反应的研究[J].燃料化学学报,2008,36(5):594-600.
[6]Zhang R,Meng X,Liu Z,et al.Isomerization of n-pentane catalyzed by acidic chloroaluminate ionic liquids[J].Industrial&Engineering Chemistry Research,2008,47(21):8205-8210.
[7]Liu H,Meng X,Zhang R,et al.Reaction performance and disappearance kinetics of n-pentane isomerization catalyzed by chloroaluminate ionic liquid[J].Catalysis Communications,2010,12(3):180-183.
[8]刘徽.功能化酸性离子液体催化正构烷烃异构化反应性能研究[D].哈尔滨:黑龙江大学,2010.
[9]沈康文,曾丹林,张崎,等.离子液体在催化中的应用研究进展[J].材料导报,2016,30(5):57-62.
[10]Berenblyum A S,Katsman E A,Karasev Y Z.The nature of catalytic activity and deactivation of chloroaluminate ionic liquid[J].Applied Catalysis A:General,2006,315:128-134.
[11]刘晓飞,包道日娜.环境友好的离子液体催化剂在石油化工中的应用[J].内蒙古石油化工,2012,(23):36-38.
[12]宋兆阳,周文博,张征太,等.[BMIM]Cl-Al Cl3离子液体催化正戊烷异构化反应性能[J].石油炼制与化工,2017,(2):78-82.
[13]Zinurov D R,Zinurov R R,Akhmed Yanova R A,et al.Skeletal isomerization of n-pentane in the presence of an Al Cl3-based ionic liquid[J].Petroleum Chemistry,2010,50(5):376-380.
[14]刘徽,肖林飞,吴伟,等.改性氯铝酸盐酸性离子液体催化正癸烷异构化反应研究[J].化学与粘合,2010,(6):30-33.
[15]张傑.氯铝酸离子液体催化异丁烷和丁烯烷基化反应的研究[D].北京:北京化工大学,2008.
[16]Fei Z,Zhao D,Geldbach T J,et al.Brnsted acidic ionic liquids and their zwitterions:Synthesis,characterization and pKa determination[J].Chemistry-A European Journal,2004,10(19):4886-4893.
[17]吴芹,董斌琦,韩明汉,等.氯铝酸离子液体的酸性及其催化烷基化反应研究[J].光谱学与光谱分析,2007,27(3):460-464.
[2]周建军,刘植昌,张睿,等.室温离子液体催化正戊烷异构化反应[J].燃料化学学报,2008,36(2):156-159.
[3]Meyer C,Wasserscheid P.Effective n-octane isomerization under exceptionally mild conditions using a novel class of superacidic ionic liquids[J].Chemical Communications,2010,46(40):7625-7627.
[4]张振华,赵国英,卢丹,等.醚基复合氯铝酸离子液体催化异丁烷烷基化[J].过程工程学报,2017,(5):1016-1022.
[5]石振民,武晓辉,刘植昌,等.室温离子液体催化正己烷异构化反应的研究[J].燃料化学学报,2008,36(5):594-600.
[6]Zhang R,Meng X,Liu Z,et al.Isomerization of n-pentane catalyzed by acidic chloroaluminate ionic liquids[J].Industrial&Engineering Chemistry Research,2008,47(21):8205-8210.
[7]Liu H,Meng X,Zhang R,et al.Reaction performance and disappearance kinetics of n-pentane isomerization catalyzed by chloroaluminate ionic liquid[J].Catalysis Communications,2010,12(3):180-183.
[8]刘徽.功能化酸性离子液体催化正构烷烃异构化反应性能研究[D].哈尔滨:黑龙江大学,2010.
[9]沈康文,曾丹林,张崎,等.离子液体在催化中的应用研究进展[J].材料导报,2016,30(5):57-62.
[10]Berenblyum A S,Katsman E A,Karasev Y Z.The nature of catalytic activity and deactivation of chloroaluminate ionic liquid[J].Applied Catalysis A:General,2006,315:128-134.
[11]刘晓飞,包道日娜.环境友好的离子液体催化剂在石油化工中的应用[J].内蒙古石油化工,2012,(23):36-38.
[12]宋兆阳,周文博,张征太,等.[BMIM]Cl-Al Cl3离子液体催化正戊烷异构化反应性能[J].石油炼制与化工,2017,(2):78-82.
[13]Zinurov D R,Zinurov R R,Akhmed Yanova R A,et al.Skeletal isomerization of n-pentane in the presence of an Al Cl3-based ionic liquid[J].Petroleum Chemistry,2010,50(5):376-380.
[14]刘徽,肖林飞,吴伟,等.改性氯铝酸盐酸性离子液体催化正癸烷异构化反应研究[J].化学与粘合,2010,(6):30-33.
[15]张傑.氯铝酸离子液体催化异丁烷和丁烯烷基化反应的研究[D].北京:北京化工大学,2008.
[16]Fei Z,Zhao D,Geldbach T J,et al.Brnsted acidic ionic liquids and their zwitterions:Synthesis,characterization and pKa determination[J].Chemistry-A European Journal,2004,10(19):4886-4893.
[17]吴芹,董斌琦,韩明汉,等.氯铝酸离子液体的酸性及其催化烷基化反应研究[J].光谱学与光谱分析,2007,27(3):460-464.