甘油辅助下晶种法合成ZSM-5分子筛
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摘要
以硅溶胶为硅源,甘油为辅助剂,采用晶种替代有机模板剂在水热条件下合成ZSM-5分子筛。考察了晶化温度和甘油对ZSM-5分子筛相对结晶度、晶粒尺寸、比表面积和酸性等性质对其催化性能的影响。利用X射线衍射(XRD)、扫描电镜(SEM)、N_2吸附-脱附(BET)、NH_3-TPD等分析手段对不同甘油含量分子筛样品进行表征。结果表明:在170℃晶化温度下,适量甘油辅助剂的添加,可以提高ZSM-5沸石分子筛的相对结晶度,并在一定程度上抑制α-SiO_2杂晶的产生,从而提高其比表面积。在甲苯歧化反应中,添加甘油合成的ZSM-5催化剂表现出优良的催化性能,与未添加甘油合成的ZSM-5催化剂相比,甲苯转化率提高6~7百分点。
ZSM-5 zeolite was hydrothermally synthesized by glycerin-assisted seed crystallization method with silica sol as the silica resource,in the absence of the organic template.The influences of crystallization temperature and glycerin content on the relative crystallinity,the crystal size,specific surface area and the acidity of ZSM-5 zeolite and its catalytic properties were studied.The samples of zeolite with different glycerol adding content were characterized by XRD,SEM,N_2 adsorption-desorption and NH_3-TPD.The results show that,under the crystallization temperature of 170℃,adding appropriate amount of glycerol not only increases the relative crystallinity of ZSM-5 zeolite,but also inhibits the production ofα-SiO_2 miscellaneous crystallinity to some extent,thus increasing its specific surface area.In toluene disproportionation reaction,the samples synthesized with glycerin perform higher catalytic properties than the samples without adding glycerin.The toluene conversion increases by 6-7 percentage points.
ZSM-5 zeolite was hydrothermally synthesized by glycerin-assisted seed crystallization method with silica sol as the silica resource,in the absence of the organic template.The influences of crystallization temperature and glycerin content on the relative crystallinity,the crystal size,specific surface area and the acidity of ZSM-5 zeolite and its catalytic properties were studied.The samples of zeolite with different glycerol adding content were characterized by XRD,SEM,N_2 adsorption-desorption and NH_3-TPD.The results show that,under the crystallization temperature of 170℃,adding appropriate amount of glycerol not only increases the relative crystallinity of ZSM-5 zeolite,but also inhibits the production ofα-SiO_2 miscellaneous crystallinity to some extent,thus increasing its specific surface area.In toluene disproportionation reaction,the samples synthesized with glycerin perform higher catalytic properties than the samples without adding glycerin.The toluene conversion increases by 6-7 percentage points.
引文
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[15]王岳,李凤艳,赵天波,等.纳米ZSM-5分子筛的合成、表征及甲苯歧化催化性能[J].石油化工高等学校学报,2005,18(4):20-23.(WANG Yue,LI Fengyan,ZHAO Tianbo,et al.Synthesis and characterization of nanoparticle ZSM-5 zeolite and catalytic properties of toluene disproportionation[J].Journal of Petrochemical Universities,2005,18(4):20-23.)
[16]张卿,张兰兰,胡思,等.不同铝源合成ZSM-5分子筛及其MTP催化性能[J].石油学报(石油加工),2012,28(增刊1):39-43.(ZHANG Qing,ZHANG Lanlan,HU Si,et al.Effect of aluminum sources on the synthesis of ZSM-5 and their catalytic properties for MTP reaction[J].Acta Petrolei Sinica(Petroleum Processing Section),2012,28(Suppl 1):39-43.)
[17]谢在库,金国林.合成丝光沸石结晶度测定方法的研究及应用[J].石油化工,1990,19(11):762-768.(XIE Zaiku,JIN Guolin.Study and application of methods for determination of crystallinity of synthetic mordenite catalysts[J].Petrochemical Technology,1990,19(11):762-768.)
[2]张伟,张堃,雍晓静,等.不同硅源合成ZSM-5分子筛及其MTP反应催化性能[J].天然气化工(C1化学与化工),2015,40(1):13-17.(ZHANG Wei,ZHANG Kun,YONG Xiaojing,et al.Effect of silicasources on synthesis of ZSM-5 and their catalytic properties for MTP reaction[J].Natural Gas Chemical Industry(C1Chemistry and Technology),2015,40(1):13-17.)
[3]CHEN Xiaoxin,YAN Wenfu,SHEN Wanling,et al.Morphology control of self-stacked silicalite-1crystals using microwave-assisted solvothermal synthesis[J].Microporous and Mesoporous,2007,104(1):296-304.
[4]龙英才.二乙醇胺-甘油-Na2O-SiO2-Al2O3-H2O系统中沸石的生成[J].化学学报,1984,42(6):523-528.(LONG Yingcai.The crystallization of zeolites in diethanolamine-glycerol-Na2O-SiO2-Al2O3-H2O system[J].Acta Chimica Sinica,1984,42(6):523-528.)
[5]DENG Zhongyan,ZHANG Yicheng,ZHENG Jingwei,et al.A hierarchical bulky ZSM-5zeolite synthesized via glycerol-mediated crystallization using a mesoporous steam-treated dry gel as the precursor[J].New Journal of Chemistry,2015,39(10):7777-7780.
[6]徐如人,庞文琴,于吉红,等.分子筛与多孔材料化学[M].北京:科学出版社,2004:295-300.
[7]朱日良.甲苯常压歧化反应工艺研究[D].杭州:浙江大学,2009.
[8]尹建军,邢伟静,李玉波,等.ZSM-5分子筛结晶度及晶粒大小的影响因素[J].分子催化.2012,26(2):162-168.(YIN Jianjun,XING Weijing,LI Yubo,et al.The influence factors of the crystallinity and crystal size of ZSM-5zeolite[J].Journal of Molecular Catalysis,2012,26(2):162-168.)
[9]范素兵,申达,吕俊敏,等.多级孔ZSM-5性质及其对甲醇制丙烯催化性能的影响[J].天然气化工(C1化学与化工),2015,40(1):1-5.(FAN Subing,SHEN Da,LJunmin,et al.Properties of hierarchical ZSM-5and its effect on reaction of methanol to propylene[J].Natural Gas Chemical Industry(C1 Chemistry and Technology),2015,40(1):1-5.)
[10]FAN Fengtang.Preparation and exploration of reaction kinetics model of phosphate modified Na2WO4/SiO2catalyst[J].Hans Journal of Chemical Engineering and Technology,2013,3(4):132-137.
[11]刘文艳,王华,高文桂,等.不同助剂对合成甲醇工业催化剂二氧化碳加氢性能的影响[J].材料导报,2012,26(6):96-99.(LIU Wenyan,WANG Hua,GAO Wengui,et al.Effect of different promoter on industrial methanol synthesis catalyst from CO2hydrogenation[J].Materials Review,2012,26(6):96-99.)
[12]刘通.ZSM-22分子筛的合成及其加氢选择裂化/异构化性能研究[D].大连:大连理工大学,2014.
[13]刘新辉,管冬冬,姜男哲.乙醇对晶种法合成六角板状ZSM-5催化剂的影响[J].石油学报(石油加工),2017,33(4):655-661.(LIU Xinhui,GUAN Dongdong,JIANG Nanzhe.Influence of ethanol on the synthesis of hexagonal platelet ZSM-5 by the seeded method[J].Acta Petrolei Sinica(Petroleum Processing Section),2017,33(4):655-661.)
[14]刘冬梅,翟玉春,马健,等.Na2CO3处理法制备微介孔ZSM-5沸石及其催化硫醚化性能[J].石油学报(石油加工),2015,31(1):38-44.(LIU Dongmei,ZHAI Yuchun,MA Jian,et al.Preparation of micromesoporous ZSM-5modified by Na2CO3and its catalytic performance for sulfur etherification[J].Acta Petrolei Sinica(Petroleum Processing Section),2015,31(1):38-44.)
[15]王岳,李凤艳,赵天波,等.纳米ZSM-5分子筛的合成、表征及甲苯歧化催化性能[J].石油化工高等学校学报,2005,18(4):20-23.(WANG Yue,LI Fengyan,ZHAO Tianbo,et al.Synthesis and characterization of nanoparticle ZSM-5 zeolite and catalytic properties of toluene disproportionation[J].Journal of Petrochemical Universities,2005,18(4):20-23.)
[16]张卿,张兰兰,胡思,等.不同铝源合成ZSM-5分子筛及其MTP催化性能[J].石油学报(石油加工),2012,28(增刊1):39-43.(ZHANG Qing,ZHANG Lanlan,HU Si,et al.Effect of aluminum sources on the synthesis of ZSM-5 and their catalytic properties for MTP reaction[J].Acta Petrolei Sinica(Petroleum Processing Section),2012,28(Suppl 1):39-43.)
[17]谢在库,金国林.合成丝光沸石结晶度测定方法的研究及应用[J].石油化工,1990,19(11):762-768.(XIE Zaiku,JIN Guolin.Study and application of methods for determination of crystallinity of synthetic mordenite catalysts[J].Petrochemical Technology,1990,19(11):762-768.)