Periodic density functional theory was applied to investigate the reaction mechanism for the methylation of toluene with methanol over HZSM-5.The results indicated that toluene could be methylated at its para,meta,ort...Periodic density functional theory was applied to investigate the reaction mechanism for the methylation of toluene with methanol over HZSM-5.The results indicated that toluene could be methylated at its para,meta,ortho and geminal positions via a concerted or stepwise pathway.For the concerted pathway,the calculated free energy barriers for the para,meta,ortho and geminal methylation reactions were 167,138,139 and 183 kJ/mol,respectively.For the stepwise pathway,the dehydration of methanol was found to be the rate-determining step with a free energy barrier of145 kj/mol,whereas the free energy barriers for the methylation of toluene at its para,meta,ortho and geminal positions were 127,105,106 and 114 kj/mol,respectively.Both pathways led to the formation of C8H11^＋ species as important intermediates,which could back-donate a proton to the zeolite framework via a reorientation process or form gaseous products through demethylation.Methane was formed via an intramolecular hydrogen transfer reaction from a ring carbon of the C8H11^＋ species to the carbon of the methyl group,with calculated energy barriers of 136,132 and134 kj/mol for the para,meta and ortho C8H11^＋ species,respectively.The calculated free energy barriers for the formation of para-,meta- and ortho-xylene indicated that the formation of the para-xylene had the highest energy barrier for both pathways.展开更多
采用Na AlO2和HCl两步法对ZSM-5分子筛进行改性,运用XRD、SEM、NH3-TPD、N2吸附-脱附、ICP-OES、TG等方法对改性前后的分子筛进行表征。结果表明:经Na Al O2改性后的ZSM-5分子筛中引入了介孔,且分子筛的晶型、酸性、微孔体积等保持较好...采用Na AlO2和HCl两步法对ZSM-5分子筛进行改性,运用XRD、SEM、NH3-TPD、N2吸附-脱附、ICP-OES、TG等方法对改性前后的分子筛进行表征。结果表明:经Na Al O2改性后的ZSM-5分子筛中引入了介孔,且分子筛的晶型、酸性、微孔体积等保持较好,并具有较高的固相收率;酸洗前通过中间焙烧有利于消除孔道覆盖和恢复酸性。将改性后的分子筛应用于甲醇芳构化反应中,在温度400℃、压力0.15 MPa、质量空速1.9h-1的反应条件下,经0.45 mol/L Na Al O2改性的分子筛反应效果最优,产物芳烃收率可达41.9%,BTX收率达32.7%;与原粉分子筛相比,产物芳烃收率提高了3.8百分点,BTX收率提高了4.4百分点;同时,其反应稳定性可达30 h,较原粉延长了1倍多。展开更多
以改良的Stober方法制得的介孔硅球为硅源兼硬模板剂,合成硅铝摩尔比为30的多级孔ZSM-5分子筛。采用XRD、FESEM、N_2吸附-脱附、NH_3-TPD等手段对合成的样品进行表征,研究晶化温度、晶化时间、晶化方法对分子筛形貌和结构性能的影响,并...以改良的Stober方法制得的介孔硅球为硅源兼硬模板剂,合成硅铝摩尔比为30的多级孔ZSM-5分子筛。采用XRD、FESEM、N_2吸附-脱附、NH_3-TPD等手段对合成的样品进行表征,研究晶化温度、晶化时间、晶化方法对分子筛形貌和结构性能的影响,并将其应用于甲醇制芳烃(Methonal to Aromatics,MTA)反应。结果表明,以介孔硅球作为硅源兼硬模板剂,在110℃条件下晶化72 h能够得到结晶度较高的ZSM-5分子筛,该分子筛含有丰富的介孔及大孔,比表面积高达529 m^2/g,且在MTA反应中表现出比较好的催化稳定性。展开更多
基金supported by the National Natural Science Foundation of China(21446003)the Specialized Research Fund for the Doctoral Program of Higher Education(20130074110018)~~
文摘Periodic density functional theory was applied to investigate the reaction mechanism for the methylation of toluene with methanol over HZSM-5.The results indicated that toluene could be methylated at its para,meta,ortho and geminal positions via a concerted or stepwise pathway.For the concerted pathway,the calculated free energy barriers for the para,meta,ortho and geminal methylation reactions were 167,138,139 and 183 kJ/mol,respectively.For the stepwise pathway,the dehydration of methanol was found to be the rate-determining step with a free energy barrier of145 kj/mol,whereas the free energy barriers for the methylation of toluene at its para,meta,ortho and geminal positions were 127,105,106 and 114 kj/mol,respectively.Both pathways led to the formation of C8H11^＋ species as important intermediates,which could back-donate a proton to the zeolite framework via a reorientation process or form gaseous products through demethylation.Methane was formed via an intramolecular hydrogen transfer reaction from a ring carbon of the C8H11^＋ species to the carbon of the methyl group,with calculated energy barriers of 136,132 and134 kj/mol for the para,meta and ortho C8H11^＋ species,respectively.The calculated free energy barriers for the formation of para-,meta- and ortho-xylene indicated that the formation of the para-xylene had the highest energy barrier for both pathways.
文摘采用Na AlO2和HCl两步法对ZSM-5分子筛进行改性,运用XRD、SEM、NH3-TPD、N2吸附-脱附、ICP-OES、TG等方法对改性前后的分子筛进行表征。结果表明:经Na Al O2改性后的ZSM-5分子筛中引入了介孔,且分子筛的晶型、酸性、微孔体积等保持较好,并具有较高的固相收率;酸洗前通过中间焙烧有利于消除孔道覆盖和恢复酸性。将改性后的分子筛应用于甲醇芳构化反应中,在温度400℃、压力0.15 MPa、质量空速1.9h-1的反应条件下,经0.45 mol/L Na Al O2改性的分子筛反应效果最优,产物芳烃收率可达41.9%,BTX收率达32.7%;与原粉分子筛相比,产物芳烃收率提高了3.8百分点,BTX收率提高了4.4百分点;同时,其反应稳定性可达30 h,较原粉延长了1倍多。
文摘以改良的Stober方法制得的介孔硅球为硅源兼硬模板剂,合成硅铝摩尔比为30的多级孔ZSM-5分子筛。采用XRD、FESEM、N_2吸附-脱附、NH_3-TPD等手段对合成的样品进行表征,研究晶化温度、晶化时间、晶化方法对分子筛形貌和结构性能的影响,并将其应用于甲醇制芳烃(Methonal to Aromatics,MTA)反应。结果表明,以介孔硅球作为硅源兼硬模板剂,在110℃条件下晶化72 h能够得到结晶度较高的ZSM-5分子筛,该分子筛含有丰富的介孔及大孔,比表面积高达529 m^2/g,且在MTA反应中表现出比较好的催化稳定性。
