Synthesis of dimethyl carbonate in supercritical carbon dioxide

Ballivet‐Tkatchenko, Danielle; Ligabue, Rosane Angélica; Plasseraud, Laurent

doi:10.1590/s0104-66322006000100012

Cited by 14 publications

(5 citation statements)

References 14 publications

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“…Compounds derived from 1 after treatment with methanol under reflux contain bridging alkoxides, which are also inert toward CO 2 . This is in contrary to the case of many 1,3-diethoxydistannoxanes, which contain terminal alkoxy groups and react with CO 2 (28).…”

Section: Resultsmentioning

confidence: 71%

Tuning catalyst solubility in CO₂by changing molar volume

Munshi

Ghosh

Beckman

et al. 2010

Green Chemistry Letters and Reviews

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Poor-solvating property of supercritical carbon dioxide (scCO 2 ) has been a great challenge, which limits the use of CO 2 as a common ''green'' solvent. The present report describes that by increasing molar volume (v) and lowering the melting temperature, which lowers cohesive energy density or solubility parameter (d), it is possible to increase the solubility of metal-based catalysts in scCO 2 without using costly fluorinated or tailormade CO 2 -philic modifications. We have studied various chlorodistannoxanes (1) and CuÁb-diketonates (2) to support our views. The study of bio-diesel production and transesterification of hindered esters using 1 in scCO 2 shows a 2Á8-folds rate enhancement coupled with an easier catalyst and product separation than that in organic solvents. The methodology, which works at least within the range of Van der Waals sphere of interactions, can be useful to solubilizing the molecules in scCO 2 and carries great opportunity in catalysis as well as in separation science.

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Section: Resultsmentioning

confidence: 71%

Tuning catalyst solubility in CO₂by changing molar volume

Munshi

Ghosh

Beckman

et al. 2010

Green Chemistry Letters and Reviews

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“…Several catalysts have been reported for the one-step synthesis of DMC: − organometallic compounds based on Sn(IV) such as n -R 2 Sn(OMe) 2 (R = Me, Bu), series of n -butyl(alkoxy) stannanes, − decakis(diorganotin(IV)) oxoclusters and immobilized − were applied successfully where DMC yield reported was between 30 and 88% in these systems. The high performance had been partly attributed to the fact that reaction becomes thermodynamically favorable as the system pressure increases, such as described by Cai et al and Leino et al in theoretical studies of the dependence of Δ G rxn with pressure.…”

Section: Introductionmentioning

confidence: 99%

Modeling of Chemical Equilibrium and Gas Phase Behavior for the Direct Synthesis of Dimethyl Carbonate from CO₂ and Methanol

Bustamante

Orrego

Villegas

et al. 2012

Ind. Eng. Chem. Res.

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The chemical and gas phase equilibrium of the direct synthesis of dimethyl carbonate (DMC) from methanol (MeOH) and CO2 was modeled under mild conditions of temperature and pressure. Deviations from ideality for the quaternary mixture (CO2 + MeOH + DMC + H2O) were estimated using the γ – ϕ thermodynamic approach. Binary interaction parameters (k ij ) and UNIQUAC parameters (A ij ) were extracted from VLE data reported in the literature. The results show that MeOH conversion is enhanced by increasing the pressure and reducing the temperature; however, pressure and temperature are bounded by the dew point. Data of P, T, and vapor compositions obtained from modeling chemical equilibrium were used to predict dew points of the reacting mixture and to establish the region of T and P where the gas-phase reaction could be carried out. To avoid condensation, an increase in pressure must be accompanied by a temperature increase. Moreover, the larger the methanol concentration in the feed mixture is, the higher is the required temperature.

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“…The final dimer C is not the active catalyst, but it can be recycled into A , restarting the catalytic cycle. These interconversions during the reaction make the reaction kinetically unfavorable due to cleavage and formation of energetic bonds. ,− …”

Section: Resultsmentioning

confidence: 99%

Formation of Dimethyl Carbonate from CO₂ and Methanol Catalyzed by Me₂SnO: A Density Functional Theory Approach

2021

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The conversion of CO2 into dimethyl carbonate (DMC) is an environmental and industrial appealing topic because it contributes to reduce the emissions of CO2 and to increase its use as raw material. In the present study we employed the CAM-B3LYP/def2-SVP DFT approach to evaluate the thermodynamic and kinetic parameters for the catalytic conversion of CO2 and methanol into DMC. Starting with the activation of four methanol molecules by the [Me2SnO]2 dimer, we computed all the stationary points along the pathway to convert CO2 and methanol into the DMC. The capture of two CO2 molecules is promoted by an alkoxitin intermediate, in an exothermic process, with low activation energy. Formation of a first DMC occurs after an intramolecular rerrangement involving a tetrahedral intermediate. The formation of a second DMC may occur either in a process similar to the first one or by dimerization of the hemicarbonate formed after releasing the first DMC. In this pathway, the [Me2(OH)SnO(OMe)SnMe2]2 complex is formed. This complex is less reactive than [Me2Sn(OMe)2]2 but still conserves the catalytic activity. Identification of this mechanism suggests that the catalytic action of Me2SnO can be improved by modulating the formation of the final [Me2(OH)SnO(OMe)SnMe2]2 complex.

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Synthesis of dimethyl carbonate in supercritical carbon dioxide

Cited by 14 publications

References 14 publications

Tuning catalyst solubility in CO₂by changing molar volume

Tuning catalyst solubility in CO₂by changing molar volume

Modeling of Chemical Equilibrium and Gas Phase Behavior for the Direct Synthesis of Dimethyl Carbonate from CO₂ and Methanol

Formation of Dimethyl Carbonate from CO₂ and Methanol Catalyzed by Me₂SnO: A Density Functional Theory Approach

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Synthesis of dimethyl carbonate in supercritical carbon dioxide

Cited by 14 publications

References 14 publications

Tuning catalyst solubility in CO2by changing molar volume

Tuning catalyst solubility in CO2by changing molar volume

Modeling of Chemical Equilibrium and Gas Phase Behavior for the Direct Synthesis of Dimethyl Carbonate from CO2 and Methanol

Formation of Dimethyl Carbonate from CO2 and Methanol Catalyzed by Me2SnO: A Density Functional Theory Approach

Contact Info

Product

Resources

About

Tuning catalyst solubility in CO₂by changing molar volume

Tuning catalyst solubility in CO₂by changing molar volume

Modeling of Chemical Equilibrium and Gas Phase Behavior for the Direct Synthesis of Dimethyl Carbonate from CO₂ and Methanol

Formation of Dimethyl Carbonate from CO₂ and Methanol Catalyzed by Me₂SnO: A Density Functional Theory Approach