Selective Conversion of Carbon Dioxide to Dimethyl Carbonate by Molecular Catalysis

Sakakura, Toshiyasu; Saito, Yuko; Okano, Makoto; Choi, Jun‐Chul; Sako, Takeshi

doi:10.1021/jo980460z

Cited by 174 publications

(89 citation statements)

References 18 publications

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“…Fig. 2 , a drastic decrease in the product yield with increasing CO In other reactions in scCO 2 2 pressure was sometimes observed [19][20][21][22][23][24][25]. This has been ascribed to dilution effect of scCO 2 .…”

Section: Methodsmentioning

confidence: 95%

Hydroformylation of 1-hexene using polymer-supported rhodium catalysts in supercritical carbon dioxide

Fujita

Akihara

Fujisawa

et al. 2007

Journal of Molecular Catalysis A: Chemical

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Hydroformylation of 1-hexene was carried out in supercritical CO 2 (scCO 2 ) and in organic solvents (toluene and ethyl acetate) using polymer-supported rhodium catalysts, which were prepared from polystyrene bound triphenylphosphine (TPP) and dicarbonylacetylecetonato rhodium. Preparation variables such as TPP/Rh ratio, time of rhodium precursor fixation on the support and time of syngas pretreatment do not indicate significant effects on the reaction. The product distribution slightly changes with CO 2 pressure. It increases appreciably as H pressure is raised in scCO but CO retards the reaction. The influence of H 2 2 2 pressure in scCO 2 is slightly different from that in toluene. Changes of the structure of rhodium complexes on the polymer during the catalyst preparation and the reaction were investigated by diffuse reflectance FT-IR. It should be noted that the catalyst is recyclable for the reaction in scCO 2 and the reaction rate and selectivity of the hydroformylation are much higher than those in the organic solvents.

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Section: Methodsmentioning

confidence: 95%

Hydroformylation of 1-hexene using polymer-supported rhodium catalysts in supercritical carbon dioxide

Fujita

Akihara

Fujisawa

et al. 2007

Journal of Molecular Catalysis A: Chemical

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“…O principal desafio das pesquisas de conversão é vencer a estabilidade termodinâmica desse gás, o que tem sido conseguido através do emprego de pressão e temperatura. Geralmente, as reações de conversão conduzem à formação de metanol, 4,[6][7][8][9] formaldeído, CO e metano , 3 tendo sido verificada a falta de eficiência e seletividade das reações. Outro inconveniente deste processo é a sua difícil implementação industrial.…”

Section: Introductionunclassified

Dimethylcarbonate: A Route for the Conversion of CO₂

Ferreira¹,

Vale²,

Andrade³

et al. 2013

Revista Virtual De Química

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This work describes the evaluation of the use of tin alkoxides as potential catalysts for an alternative route of CO 2 conversion into dimethylcarbonate. The study is in agreement with the pursuit of cleaner synthesis for dimethylcarbonate to replace phosgene, which is an extremely toxic reagent. Besides being a cleaner route, the proposed synthesis uses CO 2 as a reagent, which is regarded as the main greenhouse gas. There are several studies reporting proposed catalytic reactions for CO 2 conversion to economical valuable products. There are however technical challenges regarding conversion selectivity and stability of the catalyst. In the present work, some of the used catalysts seemed to be promising to diminish these reported difficulties.Keywords: CO 2 conversion; dimethylcarbonate; tin alkoxides. ResumoO presente trabalho descreve a avaliação da utilização de alcóxidos de estanho como possíveis catalisadores para uma rota alternativa de conversão de CO 2 a dimetilcarbonato. A proposta de rotas alternativas está concordante com a busca de uma síntese mais limpa para a produção de dimetilcarbonato que possa substituir a utilizada atualmente em escala industrial, que utiliza fosgênio como reagente. Além de ser uma rota mais limpa, a síntese proposta utiliza como reagente o dióxido de carbono, considerado principal gás do efeito estufa. Já existem muitos estudos relatando propostas de reações catalíticas para conversão de CO 2 em produtos com valor agregado. Porém, ainda há desafios nesta área que incluem desde a percentual de conversão desejado até a estabilidade e seletividade dos catalisadores. Neste trabalho, os catalisadores usados se mostraram promissores quanto à diminuição destas dificuldades relatadas.Palavras-chave: Conversão de CO 2 ; dimetilcarbonato; alcóxidos de estanho.

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“…To address this issue, chemical dehydration reagent was usually involved to shift the reaction forward to the carbonate side. In the similar reaction of the synthesis dimethyl carbonate (DMC), acetals [15] and orthoesters [16] were used as the organic dehydrants, respectively, and both the DMC yields could be effectively improved above 20-fold. However, the high cost of acetals and orthoesters makes them difficult for industrial production.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Diethyl Carbonate from Carbon Dioxide, Propylene Oxide and Ethanol over KNO3-CeO2 and KBr-KNO3-CeO2 Catalysts

et al. 2016

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Abstract:One-pot syntheses of diethyl carbonate (DEC) from CO 2 , propylene oxide and ethanol were carried out using different solid catalysts. The supercritical CO 2 extraction method was used to separate the liquid products and reactants from the catalysts after reaction. The KNO 3 -CeO 2 and KBr-KNO 3 -CeO 2 were found to be active for the reaction after calcinations. The catalyst was also reusable. The thermodynamic properties of the reaction were also evaluated. The effects of various conditions, such as reaction time, amount of catalysts, molar ratio of the reactants, the composition and calcination temperature of the catalysts on the conversion and yields, were investigated, and the yield of DEC was about 13.0% with a selectivity of 38.5% over KBr-KNO 3 -CeO 2 . The yield of DEC was improved about 10-fold by using KBr-KNO 3 -CeO 2 catalyst compared to CeO 2 .

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Selective Conversion of Carbon Dioxide to Dimethyl Carbonate by Molecular Catalysis

Cited by 174 publications

References 18 publications

Hydroformylation of 1-hexene using polymer-supported rhodium catalysts in supercritical carbon dioxide

Hydroformylation of 1-hexene using polymer-supported rhodium catalysts in supercritical carbon dioxide

Dimethylcarbonate: A Route for the Conversion of CO₂

Synthesis of Diethyl Carbonate from Carbon Dioxide, Propylene Oxide and Ethanol over KNO3-CeO2 and KBr-KNO3-CeO2 Catalysts

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Selective Conversion of Carbon Dioxide to Dimethyl Carbonate by Molecular Catalysis

Cited by 174 publications

References 18 publications

Hydroformylation of 1-hexene using polymer-supported rhodium catalysts in supercritical carbon dioxide

Hydroformylation of 1-hexene using polymer-supported rhodium catalysts in supercritical carbon dioxide

Dimethylcarbonate: A Route for the Conversion of CO2

Synthesis of Diethyl Carbonate from Carbon Dioxide, Propylene Oxide and Ethanol over KNO3-CeO2 and KBr-KNO3-CeO2 Catalysts

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Dimethylcarbonate: A Route for the Conversion of CO₂