Direct Synthesis of Dimethyl Carbonate by Carboxylation of Methanol on Ceria‐Based Mixed Oxides

Hofmann, Helmut; Brandner, Armin; Claus, Peter

doi:10.1002/ceat.201200475

Cited by 30 publications

(19 citation statements)

References 52 publications

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“…Between 1,200 and 1,700 cm −1 , four bands (1,290, 1,346, 1,461, and 1,575 cm −1 ) associated with intermediate product, monodentate methyl carbonate (MMC), grew together, which meant some chemisorption methoxy groups reacted with CO 2 to produce MMC. At the same time, in the ν (CO) region, bands associated with on top methoxy group decreased, same as general opinions, 12 on top methoxy possessed the activity to react with adsorbed CO 2 to form MMC. However, the positions of other three kinds of methanol adsorption bands (1,000–1,060 cm −1 ) were too close, and it was difficult to estimate the change of every band.…”

Section: Resultssupporting

confidence: 72%

“…Among these methods, the direct synthesis of DMC from methanol and CO 2 appears as a promising pathway because of CO 2 chemical fixation and sustainable development. Different catalysts have been applied in this reaction to increase the CO 2 activation and improve the yield of DMC, such as organometallic compounds, 7 ZrO 2, 8,9 CeO 2, 10–12 MOF, 13 and Cu‐based 14,15 catalysts. CeO 2 exhibited excellent catalytic performance in DMC production among these catalysts 10 …”

Section: Introductionmentioning

confidence: 99%

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Influence of valence state of cerium ion on dimethyl carbonate synthesis from methanol and carbon dioxide over CeO₂

Zhang

Zhao

et al. 2020

Asia-Pacific J Chem Eng

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The relationship between valence state of cerium ion and the catalytic activity for dimethyl carbonate (DMC) synthesis directly from carbon dioxide and methanol was investigated by using four CeO2 catalysts calcined at the different temperatures, which showed different concentrations of Ce4+ analyzed by XPS. In situ Fourier transform infrared spectroscopy (FTIR) was used to probe CO2 and methanol adsorption species on ceria surface. With the calcination temperature increasing from 323 to 973 K, the concentration of Ce4+ increased, leading to larger proportion of active methanol adsorptions (Types I and II methoxy) and CO2 adsorptions (bidentate carbonate). Meanwhile, high‐calcination temperature also led to small surface area and more –OH group dehydration, which resulted in the less formation of active Types I and II methoxy and bidentate carbonate. As a result, the ceria calcined at 773 K showed the highest activity and the one calcined at 973 K performed the lowest.

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Section: Resultssupporting

confidence: 72%

Section: Introductionmentioning

confidence: 99%

Influence of valence state of cerium ion on dimethyl carbonate synthesis from methanol and carbon dioxide over CeO₂

Zhang

Zhao

et al. 2020

Asia-Pacific J Chem Eng

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“…According to previous studies, ZrO2 and ceria (CeO2) are the unique materials effectively catalyzing the DMC formation. [9][10][14][15][16][17][18][19][20][21] However, the major challenge is associated with the thermodynamics of Reaction 1, which is generally unfavorable due to equilibrium limitation. Even under thermodynamically favorable high-pressure conditions (ca.…”

Section: Introductionmentioning

confidence: 99%

Improving the Stability of CeO₂ Catalyst by Rare Earth Metal Promotion and Molecular Insights in the Dimethyl Carbonate Synthesis from CO₂ and Methanol with 2-Cyanopyridine

2018

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The unmatched efficiency of the direct dimethyl carbonate (DMC) synthesis from CO2 and methanol over CeO2 catalysts in the presence of an organic dehydrating agent (2cyanopyridine, 2-CP) was recently reported with high DMC yield (>90%) in both batch and continuous operations. However, the CeO2 catalyst gradually deactivates in the timescale of days due to suggested surface poisoning by 2-picolinamide (2-PA) produced by hydration of 2-CP. This work seeks for active and stable CeO2-based catalysts and aims to understand the material factors influencing the catalytic performance. Surface modification of CeO2 by the addition of rare earth metal (REM) was found effective to improve the catalyst stability. Surface basicity and reducibility of the Ce 4+ species play important roles in preventing catalyst deactivation by stabilizing the reactive methoxy species in comparison to the poisoning species (2-PA or species alike). This has been evidenced by in situ ATR-IR spectroscopy. CeO2 materials promoted with 1 wt% rare earth metals (La, Gd, and Pr) greatly enhanced the catalyst stability while retaining the high catalytic activity of CeO2. Among them, 1 wt% Pr promotion to CeO2 was the most effective, affording 35% higher DMC yield in comparison to bare CeO2 after 150 h time on stream under the optimized reaction condition of 30 bar and 120 °C.

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“…This behaviour is also seen in literature for the carbonation of methanol but with higher temperature, the yield may decrease. Indeed, the reaction is exothermic so this decrease can be due to the reaction thermodynamics [31,32]. Although temperature can improve conversion, the yield of DEC seems to have a limited value.…”

Section: Pervaporation Experimentsmentioning

confidence: 99%

Organic carbonates synthesis improved by pervaporation for CO2 utilisation

Décultot

Ledoux

Fournier-Salaün

et al. 2019

Green Processing and Synthesis

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This work is focused on the synthesis of organic carbonates from CO2 and ethanol. A parametric study of the synthesis of diethyl carbonate from ethanol is performed in a 100 mL batch reactor. The influence of pressure and temperature is studied and we prove that the presence of water strongly decreases the yield in diethyl carbonate as an equilibrium is quickly reached. One method to improve this yield is to remove water from the reaction mixture to shift the equilibrium toward the formation of carbonates. The chemical methods give good results but separation and regeneration associated steps are prohibitive. For these reasons, a physical technique like pervaporation is chosen to remove water. The study of a pervaporation cell with membrane PERVAP 4100 gives good results for the dehydration of ethanol alone even at low concentrations of water from 0.33 %wt to 0.15 %wt. Twelve experiments on the dehydration of a mixture of ethanol, diethyl carbonate and water are performed. The calculated separation factors show a very good selectivity for water. That means that even in the presence of diethyl carbonate, the membrane has still a selective water permeability.

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Direct Synthesis of Dimethyl Carbonate by Carboxylation of Methanol on Ceria‐Based Mixed Oxides

Cited by 30 publications

References 52 publications

Influence of valence state of cerium ion on dimethyl carbonate synthesis from methanol and carbon dioxide over CeO₂

Influence of valence state of cerium ion on dimethyl carbonate synthesis from methanol and carbon dioxide over CeO₂

Improving the Stability of CeO₂ Catalyst by Rare Earth Metal Promotion and Molecular Insights in the Dimethyl Carbonate Synthesis from CO₂ and Methanol with 2-Cyanopyridine

Organic carbonates synthesis improved by pervaporation for CO2 utilisation

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Direct Synthesis of Dimethyl Carbonate by Carboxylation of Methanol on Ceria‐Based Mixed Oxides

Cited by 30 publications

References 52 publications

Influence of valence state of cerium ion on dimethyl carbonate synthesis from methanol and carbon dioxide over CeO2

Influence of valence state of cerium ion on dimethyl carbonate synthesis from methanol and carbon dioxide over CeO2

Improving the Stability of CeO2 Catalyst by Rare Earth Metal Promotion and Molecular Insights in the Dimethyl Carbonate Synthesis from CO2 and Methanol with 2-Cyanopyridine

Organic carbonates synthesis improved by pervaporation for CO2 utilisation

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Influence of valence state of cerium ion on dimethyl carbonate synthesis from methanol and carbon dioxide over CeO₂

Influence of valence state of cerium ion on dimethyl carbonate synthesis from methanol and carbon dioxide over CeO₂

Improving the Stability of CeO₂ Catalyst by Rare Earth Metal Promotion and Molecular Insights in the Dimethyl Carbonate Synthesis from CO₂ and Methanol with 2-Cyanopyridine