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
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
Solid-state crystallization process and mechanism of B-Al-ZSM-5 zeolite from a dry gel of B2O3. A12O3 ? SiO2 in the mixture of ethylamine and water vapour were studied by11B,27Al,29Si,13C MAS NMR, XRD and IR. The extr...Solid-state crystallization process and mechanism of B-Al-ZSM-5 zeolite from a dry gel of B2O3. A12O3 ? SiO2 in the mixture of ethylamine and water vapour were studied by11B,27Al,29Si,13C MAS NMR, XRD and IR. The extranetwork trigonal BO3 units in the gel play an important role in the process of crystallization. The change of chemical environment around Al atoms is complicated in the process of crystallization. Octahedral Al-O groups existing in the intermediate products do not appear in both the initial gel and final product. Silicon is mainly present as hydroxyl compounds, and the extrastructural Si-O groups detected in the process of crystallization disappear after complete crystallization. Ethylamine plays the role of both template and reactant. It acts with the boron-, aluminum-, and silicon-hydroxyls through hydrogen bonding and promotes the crystallization process. The relative crystallinity of the final & A1-ZSM-5 product is about 93% as measured with11B MAS NMR and IR.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
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。
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Solid-state crystallization process and mechanism of B-Al-ZSM-5 zeolite from a dry gel of B2O3. A12O3 ? SiO2 in the mixture of ethylamine and water vapour were studied by11B,27Al,29Si,13C MAS NMR, XRD and IR. The extranetwork trigonal BO3 units in the gel play an important role in the process of crystallization. The change of chemical environment around Al atoms is complicated in the process of crystallization. Octahedral Al-O groups existing in the intermediate products do not appear in both the initial gel and final product. Silicon is mainly present as hydroxyl compounds, and the extrastructural Si-O groups detected in the process of crystallization disappear after complete crystallization. Ethylamine plays the role of both template and reactant. It acts with the boron-, aluminum-, and silicon-hydroxyls through hydrogen bonding and promotes the crystallization process. The relative crystallinity of the final & A1-ZSM-5 product is about 93% as measured with11B MAS NMR and IR.
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.
