研究了无有机胺醇水体系低硅铝比ZSM-5沸石的绿色合成方法。在无有机胺模板剂和不加晶种的醇水体系中,一步合成了形貌均一的小晶粒聚集体低硅铝比ZSM-5沸石,考察了合成体系中各配料的含量以及晶化温度对合成低硅铝比ZSM-5沸石的影响。利...研究了无有机胺醇水体系低硅铝比ZSM-5沸石的绿色合成方法。在无有机胺模板剂和不加晶种的醇水体系中,一步合成了形貌均一的小晶粒聚集体低硅铝比ZSM-5沸石,考察了合成体系中各配料的含量以及晶化温度对合成低硅铝比ZSM-5沸石的影响。利用XRD、FTIR、SEM、N_(2)吸附-脱附、^(27)Al MAS NMR和^(29)Si MAS NMR等方法对合成的ZSM-5沸石进行表征。实验结果表明,当n(Si)∶n(Al)=20,n(Na_(2)O)∶n(SiO_(2))=0.071,n(C_(2)H_(5)OH)∶n(SiO_(2))=1.77,晶化温度为160℃时,可合成具有高结晶度的纯相ZSM-5沸石。^(27)Al MAS NMR表征结果显示,合成的ZSM-5沸石主要含有骨架四配位铝,无非骨架铝。合成的ZSM-5沸石的比表面积和微孔孔体积分别为384 m^(2)/g和0.14 cm^(3)/g,总酸量达到789μmol/g,骨架n(Si)∶n(Al)=14.4。展开更多
Synthesis of ZSM-5 zeolite typically utilizes small molecule polyamines or quaternary ammonium salts as organic structure guiding agent(OSDA).By contrast,the OSDA-free hydrothermal synthesis system eliminates the use ...Synthesis of ZSM-5 zeolite typically utilizes small molecule polyamines or quaternary ammonium salts as organic structure guiding agent(OSDA).By contrast,the OSDA-free hydrothermal synthesis system eliminates the use of organic templates and the subsequent calcination procedure.This not only reduces the cost of synthesis,but also prevents environmental pollution from the combustion of organic templates,representing an eco-friendly approach.Despite this,literature suggests that even so-called template-free synthesis systems often involve trace amount of organic substances like alcohol.In the present work,a calcined commercial ZSM-5 zeolite was served as seed,with sodium aluminate as aluminum source and silica sol as silicon source,ensuring an entirely template-free synthesis system.Polycrystalline ZSM-5 aggregates consisted of rod-like nanocrystals were successfully prepared in the completely OSDA-free system.Effects of the Si/Al ratio in ZSM-5 seed,dosage and crystallization conditions such as crystallization temperature and crystallization time on ZSM-5 synthesis were investigated.The results show that a highly crystallinity ZSM-5 aggregate consisting of primary nano-sized crystals less than 100 nm is produced from a gel precursor with 5.6%(in mass)seed after hydrothermal treatment for 48 h.Furthermore,the Si/Al ratio in ZSM-5 seed has little effect on the topological structure and pore structure of the synthesized samples.However,the seeds with a low Si/Al ratio facilitate faster crystallization of zeolite and enhance the acidity,especially the strong acid centers,of the catalyst.The catalytic performance of the synthesized polycrystalline ZSM-5 was evaluated during dehydration of methanol and compared with a commercial reference ZSM-5r.The results exhibit that as compared with the reference catalyst,the fabricated sample has a longer catalytic lifetime(16 h vs 8 h)attributed to its hierarchical pores derived from the loosely packed primary nanoparticles.Additionally,the prepared polycrystalline catalyst also exhibits a higher aromatics selectivity(28.1%-29.8%vs 26.5%).展开更多
文摘研究了无有机胺醇水体系低硅铝比ZSM-5沸石的绿色合成方法。在无有机胺模板剂和不加晶种的醇水体系中,一步合成了形貌均一的小晶粒聚集体低硅铝比ZSM-5沸石,考察了合成体系中各配料的含量以及晶化温度对合成低硅铝比ZSM-5沸石的影响。利用XRD、FTIR、SEM、N_(2)吸附-脱附、^(27)Al MAS NMR和^(29)Si MAS NMR等方法对合成的ZSM-5沸石进行表征。实验结果表明,当n(Si)∶n(Al)=20,n(Na_(2)O)∶n(SiO_(2))=0.071,n(C_(2)H_(5)OH)∶n(SiO_(2))=1.77,晶化温度为160℃时,可合成具有高结晶度的纯相ZSM-5沸石。^(27)Al MAS NMR表征结果显示,合成的ZSM-5沸石主要含有骨架四配位铝,无非骨架铝。合成的ZSM-5沸石的比表面积和微孔孔体积分别为384 m^(2)/g和0.14 cm^(3)/g,总酸量达到789μmol/g,骨架n(Si)∶n(Al)=14.4。
基金National Natural Science Foundation of China(U19B2003,21706177,21975174)Foundation Supported by China Petroleum&Chemical Corporation(121014-2)。
文摘Synthesis of ZSM-5 zeolite typically utilizes small molecule polyamines or quaternary ammonium salts as organic structure guiding agent(OSDA).By contrast,the OSDA-free hydrothermal synthesis system eliminates the use of organic templates and the subsequent calcination procedure.This not only reduces the cost of synthesis,but also prevents environmental pollution from the combustion of organic templates,representing an eco-friendly approach.Despite this,literature suggests that even so-called template-free synthesis systems often involve trace amount of organic substances like alcohol.In the present work,a calcined commercial ZSM-5 zeolite was served as seed,with sodium aluminate as aluminum source and silica sol as silicon source,ensuring an entirely template-free synthesis system.Polycrystalline ZSM-5 aggregates consisted of rod-like nanocrystals were successfully prepared in the completely OSDA-free system.Effects of the Si/Al ratio in ZSM-5 seed,dosage and crystallization conditions such as crystallization temperature and crystallization time on ZSM-5 synthesis were investigated.The results show that a highly crystallinity ZSM-5 aggregate consisting of primary nano-sized crystals less than 100 nm is produced from a gel precursor with 5.6%(in mass)seed after hydrothermal treatment for 48 h.Furthermore,the Si/Al ratio in ZSM-5 seed has little effect on the topological structure and pore structure of the synthesized samples.However,the seeds with a low Si/Al ratio facilitate faster crystallization of zeolite and enhance the acidity,especially the strong acid centers,of the catalyst.The catalytic performance of the synthesized polycrystalline ZSM-5 was evaluated during dehydration of methanol and compared with a commercial reference ZSM-5r.The results exhibit that as compared with the reference catalyst,the fabricated sample has a longer catalytic lifetime(16 h vs 8 h)attributed to its hierarchical pores derived from the loosely packed primary nanoparticles.Additionally,the prepared polycrystalline catalyst also exhibits a higher aromatics selectivity(28.1%-29.8%vs 26.5%).
