Dimethyl carbonate synthesis from carbon dioxide and methanol over Ni-CufMoSiO(VSiO) catalysts

Shunhe, Zhong; Wang, J.W.; Xiao, Xinfeng; Li, H.S.

doi:10.1016/s0167-2991(00)80423-1

Cited by 9 publications

(4 citation statements)

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“…Few catalytic studies have been reported in batch operation at low pressure (0.12−0.5 MPa), where catalysts such as Cu 1.5 PMo 12 O 40 , 55 CeO 2 with acetonitrile as dehydrate 56 and heteropolyoxometalates 57,58 significantly increase of DMC yield compared with gas-phase reaction in continuous reaction system. Heterogeneous catalysts reported for gas-phase synthesis, Ni−Cu/MoSiO(VSiO), 59 Cu−KF/MgSiO, 60 H 3 PO 4 −V 2 O 5 , 61 Cu−Ni/VSO, 62 Cu−(Ni,V,O)/SiO 2 with photoassistance, 63 Cu−Ni/C 64 (C = graphite, 65 MWCNTs, 66 AC, 67 TEG, 68 graphite oxide, 69 GNS 70 ), Rh/ZSM-5, 71 CuCl 2 /AC, 72 Co 1.5 PW 12 O 40 73 and Cu−Ni/diatomite 74 in which the reaction was carried out at low pressure (0.1−1.2 MPa), moderate temperatures (353−500 K) and continuous flow, seem less productive compared to the homogeneous reaction. These studies have remarked that DMC obtained from reaction I is drastically limited by the chemical equilibrium leading to very low DMC yields partly due to the low methanol conversion at equilibrium, 18,35,75 but no deep studies about the limit of MeOH conversion had been done.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Heterogeneous catalysts reported for gas-phase synthesis, Ni–Cu/MoSiO(VSiO), Cu–KF/MgSiO, H 3 PO 4 –V 2 O 5 , Cu–Ni/VSO, Cu–(Ni,V,O)/SiO 2 with photoassistance, Cu–Ni/C (C = graphite, MWCNTs, AC, TEG, graphite oxide, GNS), Rh/ZSM-5, CuCl 2 /AC, Co 1.5 PW 12 O 40 and Cu–Ni/diatomite in which the reaction was carried out at low pressure (0.1–1.2 MPa), moderate temperatures (353–500 K) and continuous flow, seem less productive compared to the homogeneous reaction. These studies have remarked that DMC obtained from reaction is drastically limited by the chemical equilibrium leading to very low DMC yields partly due to the low methanol conversion at equilibrium, ,, but no deep studies about the limit of MeOH conversion had been done.…”

Section: Introductionmentioning

confidence: 99%

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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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Section: ■ Introductionmentioning

confidence: 99%

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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“…As the products (dimethyl carbonate and water) desorb from the active sites, these become available for the next catalytic cycle. A hexagonal structure surface model composed of alternate sites with M=O and Mn + vertices was previously postulated [42]. That structure does not match the number of adjacent active sites necessary for the individual reaction steps on the bimetallic Cu-Ni/AC catalyst reported here.…”

Section: Ftir Experimentsmentioning

confidence: 69%

Gas phase synthesis of dimethyl carbonate from CO2 and CH3OH over Cu-Ni/AC. A kinetic study

Arbeláez-Pérez

Domínguez-Cardozo

Orrego-Romero

et al. 2019

redin

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The catalytic activity for dimethyl carbonate formation from carbon dioxide and methanol over mono and bimetallic Cu:Ni supported on activated carbon is presented. Bimetallic catalysts exhibit higher catalytic activity than the monometallic samples, being Cu:Ni-2:1 (molar ratio) the best catalyst; X-Ray diffraction, transmission electron microscopy, and metal dispersion analysis provided insight into the improved activity. In situ FT-IR experiments were conducted to investigate the mechanism of formation of dimethyl carbonate from methanol and carbon dioxide over Cu-Ni:2-1. The kinetics of the direct synthesis of dimethyl carbonate in gas phase over Cu:Ni-2:1 supported on activated carbon catalyst was experimentally investigated at 12 bar and temperatures between 90 oC and 130 oC, varying the partial pressures of CO2 and methanol. Experimental kinetic data were consistent with a Langmuir–Hinshelwood model that included carbon dioxide and methanol adsorption on catalyst actives sites (Cu, Ni and Cu-Ni), and the reaction of adsorbed CO2 with methoxi species as the rate determining step. The estimated apparent activation energy was 94.2 kJ mol-1.

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“…Copper and nickel are active components of the catalysts. The presence of "VO n " species in catalyst may provide additional sites for reactant activation [34,43]. In the present study, a novel sulfuration method was employed to synthesize Cu-Ni@VSiO catalyst.…”

Section: Introductionmentioning

confidence: 99%

Continuous Dimethyl Carbonate Synthesis from CO2 and Methanol Using Cu-Ni@VSiO as Catalyst Synthesized by a Novel Sulfuration Method

et al. 2018

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Conversion of carbon dioxide into useful chemicals is a valuable task. One way to perform it is to transform CO 2 into dimethyl carbonate (DMC) by a reaction with methanol. Catalyst exerts significant impact on this process. During this work, Cu-Ni@VSiO bimetallic catalysts were successfully synthesized by traditional solution and novel sulfuration methods. The catalytic materials were characterized by several analytical techniques and were tested in a continuous fixed-bed reactor under different reaction conditions to promote DMC synthesis from CO 2 and methanol in the absence of dehydrating agents. The effects of reaction temperature, pressure, space velocity, metal loading, and bulk density on the catalytic performance were investigated in detail. It was found that the activity of Cu-Ni@VSiO catalyst with the support obtained by the novel sulfuration method is about three times higher when compared to that of the catalyst with the support that is synthesized by the traditional solution method. This result may stem from the difference in microstructure of the studied catalytic materials.

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Dimethyl carbonate synthesis from carbon dioxide and methanol over Ni-CufMoSiO(VSiO) catalysts

Cited by 9 publications

References 5 publications

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

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

Gas phase synthesis of dimethyl carbonate from CO2 and CH3OH over Cu-Ni/AC. A kinetic study

Continuous Dimethyl Carbonate Synthesis from CO2 and Methanol Using Cu-Ni@VSiO as Catalyst Synthesized by a Novel Sulfuration Method

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Dimethyl carbonate synthesis from carbon dioxide and methanol over Ni-CufMoSiO(VSiO) catalysts

Cited by 9 publications

References 5 publications

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

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

Gas phase synthesis of dimethyl carbonate from CO2 and CH3OH over Cu-Ni/AC. A kinetic study

Continuous Dimethyl Carbonate Synthesis from CO2 and Methanol Using Cu-Ni@VSiO as Catalyst Synthesized by a Novel Sulfuration Method

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

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