醇添加剂对Fe-ZSM-5分子筛表面性能的影响及在快速催化裂解甘蔗渣中的应用
|
摘要
以乙醇(EA)和乙二醇为添加剂,采用水热合成法制备了Fe-ZSM-5分子筛,利用XRD,SEM,BET,XPS,FTIR,NH_3-TPD等手段对制备的催化剂进行表征,考察了催化剂催化裂解甘蔗渣制备2,3-二氢苯并呋喃的性能。表征结果显示,醇添加剂可以大幅提高Fe-ZSM-5分子筛的结晶度,增加催化剂的介孔体积、比表面积和表面酸量,且具有表面微观形貌调控能力。实验结果表明,EA-Fe-ZSM-5催化剂催化甘蔗渣具有较高的催化活性和选择性,液相产物中目标产物2,3-二氢苯并呋喃的选择性高达30.28%。
Fe-ZSM-5 zeolite was synthesized by a hydro-thermal method with ethanol(EA) and glycol as additives;the prepared catalyst was characterized by XRD,SEM,BET,XPS,FTIR,NH_3-TPD,and the performance of the catalyst in the preparation of 2,3-dihydrobenzofuran by catalytic cracking of bagasse was studied. The characterization results have shown that the alcohol additive could significantly increase the crystallinity,mesoporous volume,specific surface area and surface acid content of Fe-ZSM-5 zeolite,and has the capability of controlling the surface microtopography.Experimental results show that EA-Fe-ZSM-5 catalyst has high catalytic activity and selectivity for catalytic cracking of bagasse,and the selectivity of a target product 2,3-dihydrobenzofuran in liquid phase products is as high as 30.28%.
Fe-ZSM-5 zeolite was synthesized by a hydro-thermal method with ethanol(EA) and glycol as additives;the prepared catalyst was characterized by XRD,SEM,BET,XPS,FTIR,NH_3-TPD,and the performance of the catalyst in the preparation of 2,3-dihydrobenzofuran by catalytic cracking of bagasse was studied. The characterization results have shown that the alcohol additive could significantly increase the crystallinity,mesoporous volume,specific surface area and surface acid content of Fe-ZSM-5 zeolite,and has the capability of controlling the surface microtopography.Experimental results show that EA-Fe-ZSM-5 catalyst has high catalytic activity and selectivity for catalytic cracking of bagasse,and the selectivity of a target product 2,3-dihydrobenzofuran in liquid phase products is as high as 30.28%.
引文
[1]Stram B N.Key challenges to expanding renewable energy[J].Energy Policy,2016,96:728-734.
[2]马昊.促进我国农村生物质能源发展的财税政策研究[J].生态经济:中文版,2010(5):59-63.
[3]Dauenhauer P J,Huber G W.Biomass at the shale gas crossroads[J].Green Chem,2014,16(2):382-383.
[4]Kaygusuz K,Kele?S.Use of biomass as a transitional strategy to a sustainable and clean energy system[J].Energy Sources Part B,2008,31(1):86-97.
[5]Saxena R C,Adhikari D K,Goyal H B.Biomass-based energy fuel through biochemical routes:A review[J].Renew Sust Energy Rev,2009,13(1):167-178.
[6]Alonso D M,Wettstein S G,Dumesic J A.Gamma-valerolactone,a sustainable platform molecule derived from lignocellulosic biomass[J].Green Chem,2013,15(3):584.
[7]Fan Yongsheng,Cai Yixi,Li Xiaohua,et al.Regeneration of the HZSM-5 zeolite deactivated in the upgrading of bio-oil via non-thermal plasma injection(NTPI)technology[J].J Anal Appl Pyrolysis,2015,111:209-215.
[8]祁亚楠.2,3-二氢苯并呋喃天然产物中间体的合成研究[D].哈尔滨:哈尔滨理工大学,2017.
[9]Li Jian,Li Xiangyu,Zhou Guoqiang,et al.Catalytic fast pyrolysis of biomass with mesoporous ZSM-5 zeolites prepared by desilication with Na OH solutions[J].Appl Catal,A,2014,470(2):115-122.
[10]Hernando H,Moreno I,Fermoso J,et al.Biomass catalytic fast pyrolysis over hierarchical ZSM-5 and Beta zeolites modified with Mg and Zn oxides[J].Biomass Convers Bior,2017,7(3):1-16.
[11]范素兵,车艳盈,吕俊敏,等.TEOS水解对ZSM-5分子筛性质及MTP催化性能的影响[J].天然气化工:C1化学与化工,2017,42(5):10-17.
[12]姚金松,孟明,罗金勇,等.高分散锰氧化物催化剂的结构、性能及载体效应[J].分子催化,2006,20(4):300-305.
[13]Prakash C.Effect of aluminium substitution on electrical conductivity and physical properties of zinc ferrite[J].Mater Lett,1987,6(6):651-652.
[14]苏克新,郭孝天,詹红菊,等.含铁分子筛催化剂合成、表征及应用述评[J].石油化工,2004,33(s1):1711-1713.
[15]高敏,刘春燕,王刃,等.在含乙醇的硅铝凝胶中合成ZSM-5沸石[J].化学通报,2009,72(12):1097-1103.
[16]常贵环,曹吉林,郭宏飞.聚乙二醇对合成ZSM-5分子筛形貌影响的研究[J].人工晶体学报,2012,41(5):1357-1375.
[17]王亓祥.多级孔道ZSM-5分子筛负载Pt及Pt-Sn催化肉桂醛的选择加氢性能研究[D].上海:华东师范大学,2016.
[18]Borade R B.Synthesis and characterization of ferrisilicate zeolite of pentasil group[J].Zeolites,1987,7(5):398-403.
[19]Li Changlin,Wang Yanqin,Shi Bianfang,et al.Synthesis of hierarchical MFI zeolite microspheres with stacking nanocrystals[J].Microporous Mesoporous Mater,2009,117(1):104-110.
[20]鞠雅娜,沈志虹,赵佳,等.杂原子(B,Ti,Fe)进入Y型分子筛骨架的表征[J].物理化学学报,2006,22(1):36-40.
[21]杭春燕.乙醇和聚乙二醇作有机辅助剂对MCM-22分子筛织构及催化性能的影响[D].北京:北京化工大学,2008.
[22]Shi Yangchun,Xing Enhui,Wu Kejing,et al.Recent progress on upgrading of bio-oil to hydrocarbons over metal/zeolite bifunctional catalysts[J].Catal Sci Technol,2017,7(12):2385-2415.
[2]马昊.促进我国农村生物质能源发展的财税政策研究[J].生态经济:中文版,2010(5):59-63.
[3]Dauenhauer P J,Huber G W.Biomass at the shale gas crossroads[J].Green Chem,2014,16(2):382-383.
[4]Kaygusuz K,Kele?S.Use of biomass as a transitional strategy to a sustainable and clean energy system[J].Energy Sources Part B,2008,31(1):86-97.
[5]Saxena R C,Adhikari D K,Goyal H B.Biomass-based energy fuel through biochemical routes:A review[J].Renew Sust Energy Rev,2009,13(1):167-178.
[6]Alonso D M,Wettstein S G,Dumesic J A.Gamma-valerolactone,a sustainable platform molecule derived from lignocellulosic biomass[J].Green Chem,2013,15(3):584.
[7]Fan Yongsheng,Cai Yixi,Li Xiaohua,et al.Regeneration of the HZSM-5 zeolite deactivated in the upgrading of bio-oil via non-thermal plasma injection(NTPI)technology[J].J Anal Appl Pyrolysis,2015,111:209-215.
[8]祁亚楠.2,3-二氢苯并呋喃天然产物中间体的合成研究[D].哈尔滨:哈尔滨理工大学,2017.
[9]Li Jian,Li Xiangyu,Zhou Guoqiang,et al.Catalytic fast pyrolysis of biomass with mesoporous ZSM-5 zeolites prepared by desilication with Na OH solutions[J].Appl Catal,A,2014,470(2):115-122.
[10]Hernando H,Moreno I,Fermoso J,et al.Biomass catalytic fast pyrolysis over hierarchical ZSM-5 and Beta zeolites modified with Mg and Zn oxides[J].Biomass Convers Bior,2017,7(3):1-16.
[11]范素兵,车艳盈,吕俊敏,等.TEOS水解对ZSM-5分子筛性质及MTP催化性能的影响[J].天然气化工:C1化学与化工,2017,42(5):10-17.
[12]姚金松,孟明,罗金勇,等.高分散锰氧化物催化剂的结构、性能及载体效应[J].分子催化,2006,20(4):300-305.
[13]Prakash C.Effect of aluminium substitution on electrical conductivity and physical properties of zinc ferrite[J].Mater Lett,1987,6(6):651-652.
[14]苏克新,郭孝天,詹红菊,等.含铁分子筛催化剂合成、表征及应用述评[J].石油化工,2004,33(s1):1711-1713.
[15]高敏,刘春燕,王刃,等.在含乙醇的硅铝凝胶中合成ZSM-5沸石[J].化学通报,2009,72(12):1097-1103.
[16]常贵环,曹吉林,郭宏飞.聚乙二醇对合成ZSM-5分子筛形貌影响的研究[J].人工晶体学报,2012,41(5):1357-1375.
[17]王亓祥.多级孔道ZSM-5分子筛负载Pt及Pt-Sn催化肉桂醛的选择加氢性能研究[D].上海:华东师范大学,2016.
[18]Borade R B.Synthesis and characterization of ferrisilicate zeolite of pentasil group[J].Zeolites,1987,7(5):398-403.
[19]Li Changlin,Wang Yanqin,Shi Bianfang,et al.Synthesis of hierarchical MFI zeolite microspheres with stacking nanocrystals[J].Microporous Mesoporous Mater,2009,117(1):104-110.
[20]鞠雅娜,沈志虹,赵佳,等.杂原子(B,Ti,Fe)进入Y型分子筛骨架的表征[J].物理化学学报,2006,22(1):36-40.
[21]杭春燕.乙醇和聚乙二醇作有机辅助剂对MCM-22分子筛织构及催化性能的影响[D].北京:北京化工大学,2008.
[22]Shi Yangchun,Xing Enhui,Wu Kejing,et al.Recent progress on upgrading of bio-oil to hydrocarbons over metal/zeolite bifunctional catalysts[J].Catal Sci Technol,2017,7(12):2385-2415.