Four different ZSM 5 zeolites are tested for the gas phase Beckmann rearrangement of cyclohexanone oxime (CHO) into lactam. B ZSM 5 derived titanosilicalite (Ti ZSM 5) exhibits catalytic performances comparabl...Four different ZSM 5 zeolites are tested for the gas phase Beckmann rearrangement of cyclohexanone oxime (CHO) into lactam. B ZSM 5 derived titanosilicalite (Ti ZSM 5) exhibits catalytic performances comparable to hydrothermally synthesized titanosilicalite (TS 1), much better than B ZSM 5 and Al ZSM 5. The effect of reaction conditions (solvent, feed space velocity, and water) on the catalytic performance of Ti ZSM 5 is studied. It is found that a quantitative relationship exists among the feed space velocity, the reaction time, and the CHO constant conversion. Ethanol or methanol as solvent shows higher activity, lactam selectivity, and stability than benzene and n hexanol. The addition of water to the rearrangement with a maximum amount of 1.0 mole per mole CHO results in the increase of CHO conversion while no meaningful changes in lactam selectivity and stability are observed.展开更多
运用密度泛函理论研究了B和Ga改性的ZSM-5分子筛催化基于芳烃侧链机理的MTO(methanol to olefin)反应,并与未改性的ZSM-5催化反应的结果进行了比较。结果表明:在三个分子筛(ZSM-5,B-ZSM-5和Ga-ZSM-5)中,对于整个基于芳烃的侧链机理,决...运用密度泛函理论研究了B和Ga改性的ZSM-5分子筛催化基于芳烃侧链机理的MTO(methanol to olefin)反应,并与未改性的ZSM-5催化反应的结果进行了比较。结果表明:在三个分子筛(ZSM-5,B-ZSM-5和Ga-ZSM-5)中,对于整个基于芳烃的侧链机理,决速步骤是对二甲苯的甲基化。从中间体M5开始,生成乙烯的决速步骤都是乙烯的消除;而对于生成丙烯,其决速步骤都是3,3-二甲基-6-亚乙基-1,4-环己二烯的甲基化。与未改性的ZSM-5相比,B改性的ZSM-5分子筛尽管反应活性降低了,但使得甲醇制乙烯的选择性高于制丙烯的选择性,而Ga改性的ZSM-5分子筛对甲醇制乙烯和丙烯的选择性和活性影响都不大。展开更多
Continuous and perfect single-layer B-Al-ZSM-5 zeolite membranes with c-axis orientation, self-transformation from B-containing porous gla ss disks w ith rough and uneven surfaces full of pits, have been in-situ prepa...Continuous and perfect single-layer B-Al-ZSM-5 zeolite membranes with c-axis orientation, self-transformation from B-containing porous gla ss disks w ith rough and uneven surfaces full of pits, have been in-situ prepared on the su bstrates surfaces in a mixed vapor of ethylenediamine, tri-n-propylamine a nd H 2O . The thickness of the membranes is ca. 60 μm. Under the conditions of 20 ℃ and 0.1 MPa pressure difference, the permeabilities of H 2, O 2 and N 2 thro ugh the calcined B-Al-ZSM-5 zeolite membranes are 2 298×10 -8 , 1 176 ×10 -8 and 1 368×10 -9 mol/(m 2·s·Pa), respectively. The calculated values of ideal se lectivities of H 2 an d O 2 over N 2 are 16 8 and 8 60, respectively. The data indicate that the c alcin ed zeolite membranes are non-pinhole, non-crack, continuous and perfect.展开更多
采用水热合成法辅加磁场成功制备了b、c复合轴向型ZSM-5分子筛,考察了磁感线分布、磁场强度和作用时间对ZSM-5分子筛结构和甲醇芳构化反应催化性能的影响。结果表明,磁场强度和作用时间可以精密调控材料的孔径分布;磁场强度47.1 m T,平...采用水热合成法辅加磁场成功制备了b、c复合轴向型ZSM-5分子筛,考察了磁感线分布、磁场强度和作用时间对ZSM-5分子筛结构和甲醇芳构化反应催化性能的影响。结果表明,磁场强度和作用时间可以精密调控材料的孔径分布;磁场强度47.1 m T,平行磁感线位置下作用5 h,合成材料具有b、c-复合轴取向结构,介孔的比表面积和孔容比分别达到67%和78%。相比常规ZSM-5,新材料具有更高的催化稳定性,反应20 h后的甲醇转化率和芳烃收率保持在98%和36%以上。展开更多
基金the Foundations for Basic Research ofTsinghua U niversity and of China Petrochem icalCompany
文摘Four different ZSM 5 zeolites are tested for the gas phase Beckmann rearrangement of cyclohexanone oxime (CHO) into lactam. B ZSM 5 derived titanosilicalite (Ti ZSM 5) exhibits catalytic performances comparable to hydrothermally synthesized titanosilicalite (TS 1), much better than B ZSM 5 and Al ZSM 5. The effect of reaction conditions (solvent, feed space velocity, and water) on the catalytic performance of Ti ZSM 5 is studied. It is found that a quantitative relationship exists among the feed space velocity, the reaction time, and the CHO constant conversion. Ethanol or methanol as solvent shows higher activity, lactam selectivity, and stability than benzene and n hexanol. The addition of water to the rearrangement with a maximum amount of 1.0 mole per mole CHO results in the increase of CHO conversion while no meaningful changes in lactam selectivity and stability are observed.
文摘运用密度泛函理论研究了B和Ga改性的ZSM-5分子筛催化基于芳烃侧链机理的MTO(methanol to olefin)反应,并与未改性的ZSM-5催化反应的结果进行了比较。结果表明:在三个分子筛(ZSM-5,B-ZSM-5和Ga-ZSM-5)中,对于整个基于芳烃的侧链机理,决速步骤是对二甲苯的甲基化。从中间体M5开始,生成乙烯的决速步骤都是乙烯的消除;而对于生成丙烯,其决速步骤都是3,3-二甲基-6-亚乙基-1,4-环己二烯的甲基化。与未改性的ZSM-5相比,B改性的ZSM-5分子筛尽管反应活性降低了,但使得甲醇制乙烯的选择性高于制丙烯的选择性,而Ga改性的ZSM-5分子筛对甲醇制乙烯和丙烯的选择性和活性影响都不大。
文摘Continuous and perfect single-layer B-Al-ZSM-5 zeolite membranes with c-axis orientation, self-transformation from B-containing porous gla ss disks w ith rough and uneven surfaces full of pits, have been in-situ prepared on the su bstrates surfaces in a mixed vapor of ethylenediamine, tri-n-propylamine a nd H 2O . The thickness of the membranes is ca. 60 μm. Under the conditions of 20 ℃ and 0.1 MPa pressure difference, the permeabilities of H 2, O 2 and N 2 thro ugh the calcined B-Al-ZSM-5 zeolite membranes are 2 298×10 -8 , 1 176 ×10 -8 and 1 368×10 -9 mol/(m 2·s·Pa), respectively. The calculated values of ideal se lectivities of H 2 an d O 2 over N 2 are 16 8 and 8 60, respectively. The data indicate that the c alcin ed zeolite membranes are non-pinhole, non-crack, continuous and perfect.
文摘采用水热合成法辅加磁场成功制备了b、c复合轴向型ZSM-5分子筛,考察了磁感线分布、磁场强度和作用时间对ZSM-5分子筛结构和甲醇芳构化反应催化性能的影响。结果表明,磁场强度和作用时间可以精密调控材料的孔径分布;磁场强度47.1 m T,平行磁感线位置下作用5 h,合成材料具有b、c-复合轴取向结构,介孔的比表面积和孔容比分别达到67%和78%。相比常规ZSM-5,新材料具有更高的催化稳定性,反应20 h后的甲醇转化率和芳烃收率保持在98%和36%以上。
