A Nd promoted-Rh catalysts supported on polymer-derived carbon beads for vapor-phase methanol carbonylation was developed. Rh-Nd bimetallic catalysts obviously have higher activity than that of supported Rh catalyst...A Nd promoted-Rh catalysts supported on polymer-derived carbon beads for vapor-phase methanol carbonylation was developed. Rh-Nd bimetallic catalysts obviously have higher activity than that of supported Rh catalyst under similar reaction condition. The difference between the activity of above two catalyst systems is clearly caused by the intrinsic properties generated by the introduction of Nd.展开更多
Copolymer of 2-vinylpyridine and vinylacetate coordinated with dicarbonylrhodium used as a catalyst for carbonylation of methanol to acetic acid and anhydride has been studied. The structural characteristics of the co...Copolymer of 2-vinylpyridine and vinylacetate coordinated with dicarbonylrhodium used as a catalyst for carbonylation of methanol to acetic acid and anhydride has been studied. The structural characteristics of the copolymer ligand and complex, and the influences of the reaction conditions on the carbonylation catalyzed by this polymer complex have been investigated. In comparison with small molecule catalyst of Rh complex, the bidentate copolymer coordinated complex has better thermal stability. The reaction mechanism of the carbonylation reaction is also illustrated.展开更多
The kinetic study of carbonylation of methanol-acetic acid mixture to acetic acid and acetic anhydride over a cis-dicarbonylrhodium complex (MVM' Rh) coordinated with the ethylene diacrylate (M') crosslinked c...The kinetic study of carbonylation of methanol-acetic acid mixture to acetic acid and acetic anhydride over a cis-dicarbonylrhodium complex (MVM' Rh) coordinated with the ethylene diacrylate (M') crosslinked copolymer of methyl acrylate (M) and 2-vinylpyddine (V)shows that the rate of reaction is zero order with respect to both reactants methanol and carbon monoxide, but first order in the concentrations of promoter methyl iodide and rhodium in the complex. Polar solvents can accelerate the reaction. Activation parameters were calculated from the experimental results, being comparable to that of the homogeneous system. A mechanism similar to that of soluble rhodium catalyst was proposed.展开更多
A series of porous microspheres of linear and ethylene diacrylate (M') cross-linked copolymers of 2-vinylpyridine (V) and methyl acrylate (M) reacted with tetracarbonyldichlorodirhodium to form a series of cis-dic...A series of porous microspheres of linear and ethylene diacrylate (M') cross-linked copolymers of 2-vinylpyridine (V) and methyl acrylate (M) reacted with tetracarbonyldichlorodirhodium to form a series of cis-dicarbonylrhodium chelate complex (MVRh and MVM 'Rh). They are thermally stable yet very reactive in the carbonylation of methanol to acetic acid, and of methanol-acetic acid mixture to acetic acid and acetic anhydride with a selectivity of 100% under relatively mild and anhydrous conditions.展开更多
Heterogeneous halide-free carbonylation of methanol to acetates,including methyl acetate(MA)and acetic acid,using non-precious metal catalysts has been a topic of interest for decades.The key issue is that the water p...Heterogeneous halide-free carbonylation of methanol to acetates,including methyl acetate(MA)and acetic acid,using non-precious metal catalysts has been a topic of interest for decades.The key issue is that the water produced by methanol dehydration inhibits the formation of acetyl species and reduces the MA selectivity.Here,we report that CuCeO_(x)/H-mordenite(H-MOR)catalyst can nearly eliminate the inhibiting effect of water on carbonylation by a water-gas shift reaction(WGSR)on-site,and can thus achieve 96.5%methanol conversion with 87.4%MA selectivity for the halide-free carbonylation of methanol.The results of powder X-ray diffraction,transmission electron microscopy,and scanning electron microscopy show that the Cu and Ce species are highly dispersed on H-MOR even when the CuCeO_(x)contents are as high as 29 wt-%.Fourier transform infrared spectroscopy and CO chemisorption analysis reveal that a small portion of Cu species can migrate into the channel of H-MOR when CuCeO_(x)/H-MOR is calcined at 500℃and these Cu species are converted into Cu^(+) sites upon reduction.The Cu^(+) sites facilitate the WGSR and are also active sites for methanol carbonylation.The introduction of Ce benefits the inhibition of coke deposits and thus enhances the catalyst stability.展开更多
Methyl formate is one of the most important intermediates in C1 chemistry, which has been employed in a wide range of industrial applications. Current synthesis methods for methyl formate mainly include esterification...Methyl formate is one of the most important intermediates in C1 chemistry, which has been employed in a wide range of industrial applications. Current synthesis methods for methyl formate mainly include esterification of methanol and formic acid, liquid-phase methanol carbonylation, oxidative dehydrogenation of methanol, one-step syngas synthesis, and carbon dioxide hydrogenation and condensation with methanol, Liquid-phase methanol carbonylation is currently a main commercially viable process devel- oped by BASF Corp, for the industrial production of methyl formate. Recently, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences has developed a new synthesis method to con- vert coal to methyl formate (denoted as CTMF), Different from the liquid-phase methanol carbonylation using homogeneous catalysts, CTMF method features with vapor-phase methanol carbonylation using het- erogeneous nanocatalysts, which can effectively utilize the coal-based syngas and produce value-added fine chemicals (i.e., methyl formate). The newly developed method not only provides a new methyl for- mate synthesis technology but also contributes to the development of strategies for synthesizing valuable chemicals from coal. In this review, we firstly provide introduction on the development of existing methyl formate synthesis methods and then highlight the research progress of CTMF method. Finally, a perspec- tive on the future of CTMF is given,展开更多
文摘A Nd promoted-Rh catalysts supported on polymer-derived carbon beads for vapor-phase methanol carbonylation was developed. Rh-Nd bimetallic catalysts obviously have higher activity than that of supported Rh catalyst under similar reaction condition. The difference between the activity of above two catalyst systems is clearly caused by the intrinsic properties generated by the introduction of Nd.
文摘Copolymer of 2-vinylpyridine and vinylacetate coordinated with dicarbonylrhodium used as a catalyst for carbonylation of methanol to acetic acid and anhydride has been studied. The structural characteristics of the copolymer ligand and complex, and the influences of the reaction conditions on the carbonylation catalyzed by this polymer complex have been investigated. In comparison with small molecule catalyst of Rh complex, the bidentate copolymer coordinated complex has better thermal stability. The reaction mechanism of the carbonylation reaction is also illustrated.
基金This work was supported by a Grant from the National Natural Science Foundation of China
文摘The kinetic study of carbonylation of methanol-acetic acid mixture to acetic acid and acetic anhydride over a cis-dicarbonylrhodium complex (MVM' Rh) coordinated with the ethylene diacrylate (M') crosslinked copolymer of methyl acrylate (M) and 2-vinylpyddine (V)shows that the rate of reaction is zero order with respect to both reactants methanol and carbon monoxide, but first order in the concentrations of promoter methyl iodide and rhodium in the complex. Polar solvents can accelerate the reaction. Activation parameters were calculated from the experimental results, being comparable to that of the homogeneous system. A mechanism similar to that of soluble rhodium catalyst was proposed.
基金This work was supported by a Grant from the National Natural Science Foundation of China
文摘A series of porous microspheres of linear and ethylene diacrylate (M') cross-linked copolymers of 2-vinylpyridine (V) and methyl acrylate (M) reacted with tetracarbonyldichlorodirhodium to form a series of cis-dicarbonylrhodium chelate complex (MVRh and MVM 'Rh). They are thermally stable yet very reactive in the carbonylation of methanol to acetic acid, and of methanol-acetic acid mixture to acetic acid and acetic anhydride with a selectivity of 100% under relatively mild and anhydrous conditions.
基金the National Key Research and Development Program of China(Grant Nos.2018YFB0604703,2017YFA0206801,and 2018YFB0604701)the National Natural Science Foundation of China(Grant Nos.21972113 and 91545115)+1 种基金the Program for Innovative Research Team in Chinese Universities(Grant No.IRT_14R31)the Fundamental Research Funds for the Central Universities(Grant No.20720190039).
文摘Heterogeneous halide-free carbonylation of methanol to acetates,including methyl acetate(MA)and acetic acid,using non-precious metal catalysts has been a topic of interest for decades.The key issue is that the water produced by methanol dehydration inhibits the formation of acetyl species and reduces the MA selectivity.Here,we report that CuCeO_(x)/H-mordenite(H-MOR)catalyst can nearly eliminate the inhibiting effect of water on carbonylation by a water-gas shift reaction(WGSR)on-site,and can thus achieve 96.5%methanol conversion with 87.4%MA selectivity for the halide-free carbonylation of methanol.The results of powder X-ray diffraction,transmission electron microscopy,and scanning electron microscopy show that the Cu and Ce species are highly dispersed on H-MOR even when the CuCeO_(x)contents are as high as 29 wt-%.Fourier transform infrared spectroscopy and CO chemisorption analysis reveal that a small portion of Cu species can migrate into the channel of H-MOR when CuCeO_(x)/H-MOR is calcined at 500℃and these Cu species are converted into Cu^(+) sites upon reduction.The Cu^(+) sites facilitate the WGSR and are also active sites for methanol carbonylation.The introduction of Ce benefits the inhibition of coke deposits and thus enhances the catalyst stability.
基金supported by the National Key R&D Program of China(2017YFA0206802)the National Natural Science Foundation of China(91545201,91645116,21403237)the Chinese Academy of Sciences(XDB20010100,ZDRW-CN-2016-1,QYZDJSSW-SLH028)
文摘Methyl formate is one of the most important intermediates in C1 chemistry, which has been employed in a wide range of industrial applications. Current synthesis methods for methyl formate mainly include esterification of methanol and formic acid, liquid-phase methanol carbonylation, oxidative dehydrogenation of methanol, one-step syngas synthesis, and carbon dioxide hydrogenation and condensation with methanol, Liquid-phase methanol carbonylation is currently a main commercially viable process devel- oped by BASF Corp, for the industrial production of methyl formate. Recently, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences has developed a new synthesis method to con- vert coal to methyl formate (denoted as CTMF), Different from the liquid-phase methanol carbonylation using homogeneous catalysts, CTMF method features with vapor-phase methanol carbonylation using het- erogeneous nanocatalysts, which can effectively utilize the coal-based syngas and produce value-added fine chemicals (i.e., methyl formate). The newly developed method not only provides a new methyl for- mate synthesis technology but also contributes to the development of strategies for synthesizing valuable chemicals from coal. In this review, we firstly provide introduction on the development of existing methyl formate synthesis methods and then highlight the research progress of CTMF method. Finally, a perspec- tive on the future of CTMF is given,