碱处理工艺对HZSM-5分子筛孔结构及其噻吩烷基化反应能力的影响
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摘要
分别采用Na OH和Na2CO3溶液处理n(SiO2)/n(Al2O3)=50的HZSM-5分子筛,制备了微孔-介孔多级孔HZSM-5分子筛并用于噻吩烷基化反应。结果表明:NaOH溶液处理可以在较低的碱液浓度下迅速得到含有微孔-介孔多级孔HZSM-5分子筛,但NaOH溶液碱性较强,对微孔的破坏较大,且处理速度和深度不易控制,处理后各分子筛的孔径、酸量、热稳定性等变化较大,不利于烷基化反应的进行;Na_2CO_3溶液碱性温和,脱硅速率适中,对微孔的破坏较小,处理后各分子筛的孔径、酸量、热稳定性等变化较小,有利于噻吩烷基化反应的进行,其中4 mol/L的Na_2CO_3溶液处理2 h得到的HZ(CO32-,4-2-80)分子筛因烷基化活性高,热稳定性好而更加适合噻吩烷基化反应。
HZSM-5(n(SiO2)/n(Al2 O3)=50) zeolites were treated in NaOH and Na_2CO_3 solutions, obtaining micropore-mesoporous HZSM-5 zeolites for thiophene alkylation reaction. The results show that the microporous-mesoporous HZSM-5 multi-stage zeolites can be obtained after NaOH solution treatment at low alkali concentrations. However, NaOH solution is more alkaline and has a greater damage to micropores, and the processing speed and depth cannot be readily controlled. Also, the pore size, acidity and thermal stability of the sieves zeolites vary greatly after the treatment, which is unfavorable for the alkylation reaction. The alkaline solution of Na2 CO3 is moderate, leading to the moderate rate of desiliconization and the little destruction of micropores, which is favorable for the thiophene alkylation reaction. The HZ(CO32–, 4-2-80) zeolites obtained in 4 mol/L Na_2CO_3 solution for 2 h have better alkylation activity and thermal stability, which are suitable for thiophene alkylation reaction.
HZSM-5(n(SiO2)/n(Al2 O3)=50) zeolites were treated in NaOH and Na_2CO_3 solutions, obtaining micropore-mesoporous HZSM-5 zeolites for thiophene alkylation reaction. The results show that the microporous-mesoporous HZSM-5 multi-stage zeolites can be obtained after NaOH solution treatment at low alkali concentrations. However, NaOH solution is more alkaline and has a greater damage to micropores, and the processing speed and depth cannot be readily controlled. Also, the pore size, acidity and thermal stability of the sieves zeolites vary greatly after the treatment, which is unfavorable for the alkylation reaction. The alkaline solution of Na2 CO3 is moderate, leading to the moderate rate of desiliconization and the little destruction of micropores, which is favorable for the thiophene alkylation reaction. The HZ(CO32–, 4-2-80) zeolites obtained in 4 mol/L Na_2CO_3 solution for 2 h have better alkylation activity and thermal stability, which are suitable for thiophene alkylation reaction.
引文
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[25]邱小云.差热分析曲线的影响因素[J].理化检验:物理分册,2012,48(12):801-803.QIUXiaoyun.PhysTestChemAnalPartA:PhysTest(inChinese),2012, 48(12):801-803.
[2]SUZUKI T, OKUHARA T. Change in pore structure of MFI zeolite by treatmentwithNaOHaqueoussolution[J].MicroporMesoporMater,2001, 43(1):83-89.
[3]TAOY,KANOHH,KANEKOK.Developmentsandstructuresof mesopores in alkaline-treated ZSM-5 zeolites[J]. Adsorpt J Int Adsorpt Soc, 2006, 12(5/6):309-316.
[4]郭元奇,刘冬,高媛,等.劣质柴油加氢脱硫工艺条件及反应动力学研究[J].辽宁石油化工大学学报, 2016, 36(3):15-19.GUOYuanqi,LIUDong,GAOYuan,etal.JLiaoningShihuaUniv(in Chinese), 2016, 36(3):15-19.
[5]张培青,王祥生,郭洪臣,等.水热处理对纳米HZSM-5沸石酸性质及其降低汽油烯烃性能的影响[J].催化学报,2003,24(12):900-904.ZHANGPeiqing, WANGXiangsheng,GUOHongchen,etal.ChinJ Catal(in Chinese), 2003, 24(12):900-904.
[6]王幸宜.催化剂表征[M].上海:华东理工大学出版社, 2008:32-38.
[7]PEREZ-RAMIREZ J, VERBOELEND D, BONILLA A, et al. Zeolite catalystswithtunablehierarchyfactorbypore-growthmoderators[J].Adv Funct Mater, 2009, 19(24):3972-3979.
[8]BJORGEN M, JOENSEN F, HOLM M S, et al. Methanol to gasoline overzeoliteH-ZSM-5:Improvedcatalystperformancebytreatment with NaOH[J]. Appl Catal A:Gen, 2008, 345(1):43-50.
[9]GROEN J C, PEFFER L A A, JACOB A, et al. On the introduction of intracrystallinemesoporosityinzeolitesupondesilieationinalkaline medium[J]. Mieropor Mesopor Mater, 2004, 69(l/2):29-34.
[10]张彦禹.多级孔HZSM-5催化剂上甲醇合成燃料油的催化性能研究[D].太原:太原理工大学, 2011.ZHANG Yanshu. Study on catalytic performance of methanol for fuel oilsynthesisovermulti-poreHZSM-5catalysts(inChinese,dissertation). Taiyuan:Taiyuan University of Technology, 2011.
[11]刘冬梅,王海彦,孔飞飞,等.TPAOH处理制备的微介孔催化剂物化性质与噻吩烷基化性能研究[J].燃料化学学报,2016,44(11):1370-1379.LIUDongmei,WANGHaiyan,KONGFeifei,etal.JFuelChem Technol(in Chinese), 2016, 44(11):1370-1379.
[12]刘冬梅,铁大兴,高晨义,等.混合碱处理制备微介孔催化剂及其噻吩烷基化催化性能[J].燃料化学学报, 2017, 45(2):200-212.LIU Dongmei, TIE Daxing, GAO Chenyi, et al. J Fuel Chem Technol(in Chinese), 2017, 45(2):200-212.
[13]康蕾,王海彦,关纵弛,等.Mn-Zn复合氧化物的结构及其负载Ni脱硫催化剂的脱硫性能[J].石油学报(石油加工), 2017, 33(1):49-55.KANG Lei, WNGHaiyan, GUANZongchi, et al. JPet(Pet Process)(in Chinese), 2017, 33(1):49-55.
[14]汪树军,梁娟,郭文,等. ZSM-5沸石骨架铝迁移规律的研究I水热处理条件及沸石硅铝比的影响[J].催化学报, 1992, 13(1):38-43.WAG Shujun, LIAN Juan, GUO Wen, et al. Chin J Catal(in Chinese).1992, 13(1):38-43.
[15]MCQUEEND,CHICHEBH,FAJULAF,etal.AMultitechnique characterizationoftheacidityofdealuminatedmazzite[J].JCatal,1996, 161(2):587-596.
[16]ALINEAuroux,YOUNESBenTaarit.Calorimetricstudyofthe acidity of Y-zeolites treated with silicon tetrachloride[J]. Can J Chem,2011, 66(4):1013-1017.
[17]申宝剑,黄海燕,徐春明,等.双组元Y/MCM-41中微孔复合分子筛的合成和表征[J].化学学报, 2003, 12(61):1904-1910.SHENGBaojian,HUANGHaiyan,XUChunming,etal.ActaChim Sin(in Chinese), 2003, 12(61):1904-1910.
[18]ZHAOL,XUCM,GAOS,etal.Effectsofconcentrationonthe alkali-treatmentofZSM-5zeolite:Astudyondividingpoints[J].J Mater Sci, 2010, 45(19):5406-5441.
[19]孙超,杨依苏,杜俊明,等.碱处理法制备微介孔ZSM-5催化剂及其在甲醇制丙烯(MTP)反应中的应用[J].复旦学报:自然科学版,2012, 51(5):565-569.SUNChao,YANGYisu,DUJunming,etal.JFudan:NatSci(in Chinese), 2012, 51(5):565-569.
[20]SHETTI V N, KIM J, SRIVASTAVA R, et al. Assessment of the mesopore wallcatalyticactivitiesofMFIzeolitewithmesoporous/microporous hierarchical structures[J]. J Catal, 2008, 254(2):296-303.
[21]金丛,沈健.USY分子筛催化噻吩十二烯烷基化工艺条件的考察[J].辽宁石油化工大学学报, 2014, 34(2):29-32.JINCong,SHENGJian.JLiaoningShihuaUniv(inChinese),2014,34(2):29-32.
[22]赵燕,杨兴斌.铵离子交换后脱胺对β沸石脱铝及酸性和结构的影响[J].化学工程, 2000, 28(6):46-49.ZHAO Yan, YANG Xingbing. J Chem Eng(in Chinese), 2000, 28(6):46-49.
[23]康承琳,周震寰,冯小兵,等.ZSM-5分子筛酸性质对二甲苯异构化反应的影响[J].石油炼制与化工, 2013, 44(12):35-40.KANG Chenglin, ZHOU Zhenhuan, FENG Xiaobing, et al. J Pet Refin Chem Eng(in Chinese), 2013, 44(12):35-40.
[24]徐晨瑀,张海燕,马宇彤,等.分子筛改性研究综述[J].能源化工,2017, 38(1):51-55.XUChenyu, ZHANG Haiyan, MAYutong, et al. JEnergy Chem Ind(in Chinese), 2017, 38(1):51-55.
[25]邱小云.差热分析曲线的影响因素[J].理化检验:物理分册,2012,48(12):801-803.QIUXiaoyun.PhysTestChemAnalPartA:PhysTest(inChinese),2012, 48(12):801-803.