In the present work, the effect of oxides on the alkylation of benzene with 1-dodecene was comprehensively investigated over MCM-49 n-heptanol, n-heptaldehyde and n-heptanoic acid were selected as the model oxides her...In the present work, the effect of oxides on the alkylation of benzene with 1-dodecene was comprehensively investigated over MCM-49 n-heptanol, n-heptaldehyde and n-heptanoic acid were selected as the model oxides herein, and obvious decrease of lifetime could be caused by only trace amount of oxides added in the feedstocks. However, the deactivated catalysts were difficult to be regenerated by extraction with hot benzene. Additionally, coke-burning was also proved to be incapable to regenerate the deactivated catalysts mainly for the dealumination during calcination. Further characterizations complementary with DFT calculations were conducted to demonstrate that the deactivation was mainly due to the firm adsorption of oxides on the acid sites.展开更多
The catalytic performances of four HRh(CO)(PPh3)3-diphosphine (BISBI,BDPX, BDNA and BINAP) systems in 1-dodecene hydroformylation were investigated and compared with HRh(CO)(PPh3)3-PPh3 system. The catalyst system HR...The catalytic performances of four HRh(CO)(PPh3)3-diphosphine (BISBI,BDPX, BDNA and BINAP) systems in 1-dodecene hydroformylation were investigated and compared with HRh(CO)(PPh3)3-PPh3 system. The catalyst system HRh(CO)(PPh3)3-BISBI exhibited very high regioselectivity for the formation of linear aldehyde.展开更多
The hydroaminomethylation of 1-dodecene catalyzed by water soluble rhodium complex RhCl(CO)(TPPTS)2 in the presence of surfactant CTAB was investigated. High reactivity and selectivity for tertiary amine were achieved...The hydroaminomethylation of 1-dodecene catalyzed by water soluble rhodium complex RhCl(CO)(TPPTS)2 in the presence of surfactant CTAB was investigated. High reactivity and selectivity for tertiary amine were achieved under relatively mild conditions.展开更多
The promotion effect of cationic gemini surfactants for the hydroformylation of 1-dodecene in the organic/aqueous biphasic catalytic system is reported. The hydroformylation reaction in the presence of gemini surfacta...The promotion effect of cationic gemini surfactants for the hydroformylation of 1-dodecene in the organic/aqueous biphasic catalytic system is reported. The hydroformylation reaction in the presence of gemini surfactant occurred with higher turnover frequency and higher selectivity for linear aldehyde than using conventional monomeric surfactant CTAB.展开更多
Hydroformylation of 1-dodecene was studied in a biphasic system using water-soluble rhodium complex [RhCl(CO)(TPPTS)2] as catalyst in the presence of cetyl trimethyl ammonium bromide as surfactant to enhance the react...Hydroformylation of 1-dodecene was studied in a biphasic system using water-soluble rhodium complex [RhCl(CO)(TPPTS)2] as catalyst in the presence of cetyl trimethyl ammonium bromide as surfactant to enhance the reaction rate. Efforts were devoted to improve the performance of hydroformylation by exploring reactor the reaction configuration which enhanced the mixing, dispersion and interphase mass transfer. Experiments were carried out in a 0.5L autoclave at the total pressure of 1.1MPa and temperature from 363K to 373K. Several surface aeration configurations were tested, and higher hydroformylation rate with higher normal/branched aldehyde ratio produced were achieved. The experience suggest that improved reactor configuration by taking reaction engineering, measures is beneficial to better process economy in alkene hydroformylation.展开更多
Performances of 1-butyl-3-methylimidazolium aluminium chloride (BMIMClAlCl3) ionic liquid as catalyst for the alkylation of benzene with long chain olefins were investigated in a continuous operation mode. A small pil...Performances of 1-butyl-3-methylimidazolium aluminium chloride (BMIMClAlCl3) ionic liquid as catalyst for the alkylation of benzene with long chain olefins were investigated in a continuous operation mode. A small pilot plant with continuous mixingreactingseparatingrecycling functions, equipped with a static mixer reactor, a tube packed with metal Al thread and a combined liquidliquid settling phase separator, was introduced as an alternative. The results showed that the continuous fast mixing and separation of ionic liquid catalyst from reactant mixture could be synchronously accomplished within a wider flow rate ratio range of the recycling reaction mixture to the ionic liquid catalyst. The recycling of chloroaluminate ionic liquid was realized. ICPAES detection results of Al content in the reactants proves that in-situ Al compensation to the reaction system may be an important choice to prolong the stable running time of moisture-sensitive ionic liquid BMIMClAlCl3 when feedstock inevitably contains trace water. It suggests that the activity of chloroaluminate ionic liquid is recovered under the in-situ Al compensation operation.展开更多
文摘In the present work, the effect of oxides on the alkylation of benzene with 1-dodecene was comprehensively investigated over MCM-49 n-heptanol, n-heptaldehyde and n-heptanoic acid were selected as the model oxides herein, and obvious decrease of lifetime could be caused by only trace amount of oxides added in the feedstocks. However, the deactivated catalysts were difficult to be regenerated by extraction with hot benzene. Additionally, coke-burning was also proved to be incapable to regenerate the deactivated catalysts mainly for the dealumination during calcination. Further characterizations complementary with DFT calculations were conducted to demonstrate that the deactivation was mainly due to the firm adsorption of oxides on the acid sites.
基金We thank the National Basic Research Project of China(G2000048008)for the financial support.
文摘The catalytic performances of four HRh(CO)(PPh3)3-diphosphine (BISBI,BDPX, BDNA and BINAP) systems in 1-dodecene hydroformylation were investigated and compared with HRh(CO)(PPh3)3-PPh3 system. The catalyst system HRh(CO)(PPh3)3-BISBI exhibited very high regioselectivity for the formation of linear aldehyde.
文摘The hydroaminomethylation of 1-dodecene catalyzed by water soluble rhodium complex RhCl(CO)(TPPTS)2 in the presence of surfactant CTAB was investigated. High reactivity and selectivity for tertiary amine were achieved under relatively mild conditions.
文摘The promotion effect of cationic gemini surfactants for the hydroformylation of 1-dodecene in the organic/aqueous biphasic catalytic system is reported. The hydroformylation reaction in the presence of gemini surfactant occurred with higher turnover frequency and higher selectivity for linear aldehyde than using conventional monomeric surfactant CTAB.
基金the National Natural Science Foundation of China (No. 29792074) and SINOPEC.
文摘Hydroformylation of 1-dodecene was studied in a biphasic system using water-soluble rhodium complex [RhCl(CO)(TPPTS)2] as catalyst in the presence of cetyl trimethyl ammonium bromide as surfactant to enhance the reaction rate. Efforts were devoted to improve the performance of hydroformylation by exploring reactor the reaction configuration which enhanced the mixing, dispersion and interphase mass transfer. Experiments were carried out in a 0.5L autoclave at the total pressure of 1.1MPa and temperature from 363K to 373K. Several surface aeration configurations were tested, and higher hydroformylation rate with higher normal/branched aldehyde ratio produced were achieved. The experience suggest that improved reactor configuration by taking reaction engineering, measures is beneficial to better process economy in alkene hydroformylation.
基金State Key Fundamental Research Program (No.G2000048006)
文摘Performances of 1-butyl-3-methylimidazolium aluminium chloride (BMIMClAlCl3) ionic liquid as catalyst for the alkylation of benzene with long chain olefins were investigated in a continuous operation mode. A small pilot plant with continuous mixingreactingseparatingrecycling functions, equipped with a static mixer reactor, a tube packed with metal Al thread and a combined liquidliquid settling phase separator, was introduced as an alternative. The results showed that the continuous fast mixing and separation of ionic liquid catalyst from reactant mixture could be synchronously accomplished within a wider flow rate ratio range of the recycling reaction mixture to the ionic liquid catalyst. The recycling of chloroaluminate ionic liquid was realized. ICPAES detection results of Al content in the reactants proves that in-situ Al compensation to the reaction system may be an important choice to prolong the stable running time of moisture-sensitive ionic liquid BMIMClAlCl3 when feedstock inevitably contains trace water. It suggests that the activity of chloroaluminate ionic liquid is recovered under the in-situ Al compensation operation.