本文研究了H-SAPO-34催化甲醇和丁醇转化反应及其产物分布的差异,结合气相色谱-质谱(GC-MS)联用、^(13)C交叉极化魔角旋转核磁共振(^(13)C CP MAS NMR)技术捕获了反应过程中生成的重要反应中间物种.甲醇转化过程以乙烯、丙烯和丁烯为主...本文研究了H-SAPO-34催化甲醇和丁醇转化反应及其产物分布的差异,结合气相色谱-质谱(GC-MS)联用、^(13)C交叉极化魔角旋转核磁共振(^(13)C CP MAS NMR)技术捕获了反应过程中生成的重要反应中间物种.甲醇转化过程以乙烯、丙烯和丁烯为主要产物;而丁醇转化过程中主要产物是丁醇脱水生成的丁烯,反应初期以丙烯和丁烯作为主要产物.两种醇类转化均以低碳烯烃作为主要产物,且存留物种和^(13)C CP MAS NMR分析均观察到芳烃物种,说明H-SAPO-34催化甲醇和丁醇转化存留在催化剂上的有机物种相近.虽然起始于不同的醇类反应,但H-SAPO-34上限域空间的酸催化环境都能引导甲醇和丁醇制取低碳烯烃的反应过程.展开更多
A convenient and effective procedure was developed for the conversion of alcohol to olefin by tosylation and subsequent β-elimination promoted by silica gel in this study. Treatment of the alcohols with p-toluenesulf...A convenient and effective procedure was developed for the conversion of alcohol to olefin by tosylation and subsequent β-elimination promoted by silica gel in this study. Treatment of the alcohols with p-toluenesulfonyl chloride in pyridine at 0℃ af- fords tosylates which undergo β-elimination with silica gel in dichloromethane or chloroform at room temperature, yielding olefins with high productivity.展开更多
Enhancing the dispersion and dissolution of substrate particles in substrate water suspension is a feasible way to improve steroid bioconversion. The aim of the present study is to investigate the effects of applying ...Enhancing the dispersion and dissolution of substrate particles in substrate water suspension is a feasible way to improve steroid bioconversion. The aim of the present study is to investigate the effects of applying surfactant to microbial conversion system on the dispersion, solubilization and in turn bioconversion of steroid substrate. The model system is hydroxylation of substrate 19α- 17α-epoxy- 4-pregnene- 3.2It-dine by microbial enzymes from Rhizopus nigricanl. The results show that the presence of substrate leads to an increase in critical micelle concentration （ CMC） of surfactant PSE compared with the normal CMC of PSE in aqueous solution. The grinding time during substrate suspension preparation affects the substrate aqueous solubility differently with the varied surfactant concentrations while barely making any difference in substrate solubility in the absence of surfactant. The properly prolonged grinding time can make up for the loss in substrate solubility arising from the reduction in surfactant concentration. The surfactant complexes composed of surfactants PSE and MGE at appropriate ratios are screened out with orthodoxy experiment method. the interaction between PSE and MGE exerts the most prominent effects on substrate bioconversion, and the surfactant complexes show more beneficial effects on steroid bioconversion than the surfactant PSE used alone.展开更多
文摘本文研究了H-SAPO-34催化甲醇和丁醇转化反应及其产物分布的差异,结合气相色谱-质谱(GC-MS)联用、^(13)C交叉极化魔角旋转核磁共振(^(13)C CP MAS NMR)技术捕获了反应过程中生成的重要反应中间物种.甲醇转化过程以乙烯、丙烯和丁烯为主要产物;而丁醇转化过程中主要产物是丁醇脱水生成的丁烯,反应初期以丙烯和丁烯作为主要产物.两种醇类转化均以低碳烯烃作为主要产物,且存留物种和^(13)C CP MAS NMR分析均观察到芳烃物种,说明H-SAPO-34催化甲醇和丁醇转化存留在催化剂上的有机物种相近.虽然起始于不同的醇类反应,但H-SAPO-34上限域空间的酸催化环境都能引导甲醇和丁醇制取低碳烯烃的反应过程.
文摘A convenient and effective procedure was developed for the conversion of alcohol to olefin by tosylation and subsequent β-elimination promoted by silica gel in this study. Treatment of the alcohols with p-toluenesulfonyl chloride in pyridine at 0℃ af- fords tosylates which undergo β-elimination with silica gel in dichloromethane or chloroform at room temperature, yielding olefins with high productivity.
基金Supported by National Natural Science Foundation of China for Young Researchers ( No. 29606008) andTianjin Natural Science Foundation ( No. 993607111).
文摘Enhancing the dispersion and dissolution of substrate particles in substrate water suspension is a feasible way to improve steroid bioconversion. The aim of the present study is to investigate the effects of applying surfactant to microbial conversion system on the dispersion, solubilization and in turn bioconversion of steroid substrate. The model system is hydroxylation of substrate 19α- 17α-epoxy- 4-pregnene- 3.2It-dine by microbial enzymes from Rhizopus nigricanl. The results show that the presence of substrate leads to an increase in critical micelle concentration （ CMC） of surfactant PSE compared with the normal CMC of PSE in aqueous solution. The grinding time during substrate suspension preparation affects the substrate aqueous solubility differently with the varied surfactant concentrations while barely making any difference in substrate solubility in the absence of surfactant. The properly prolonged grinding time can make up for the loss in substrate solubility arising from the reduction in surfactant concentration. The surfactant complexes composed of surfactants PSE and MGE at appropriate ratios are screened out with orthodoxy experiment method. the interaction between PSE and MGE exerts the most prominent effects on substrate bioconversion, and the surfactant complexes show more beneficial effects on steroid bioconversion than the surfactant PSE used alone.
