Synthesis of dimethyl carbonate from methanol and CO<sub>2</sub> under low pressure

Liu, Kai; Liu, Chun

doi:10.1039/d1ra06676e

Cited by 10 publications

(4 citation statements)

References 44 publications

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“…DMC has garnered substantial interest as a versatile chemical intermediate and fuel additive with an environmentally benign profile. In fuel blends, DMC can function as an oxygenate to improve combustion efficiency, substituting for the toxic gasoline additive methyl tert-butyl ether (MTBE) [4]. Additionally, DMC readily biodegrades in the atmosphere without producing toxic or corrosive byproducts, overcoming critical concerns around traditional alkylating agents like dimethyl sulfate and phosgene used for chemical syntheses [5].…”

Section: Introductionmentioning

confidence: 99%

Enhancing DMC Production from CO2: Tuning Oxygen Vacancies and In Situ Water Removal

Wang,

Li,

et al. 2024

Energies

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The direct synthesis of dimethyl carbonate (DMC) from methanol and CO2 presents an attractive route to turn abundant CO2 into value-added chemicals. However, insufficient DMC yields arise due to the inert nature of CO2 and the limitations of reaction equilibrium. Oxygen vacancies are known to facilitate CO2 activation and improve catalytic performance. In this work, we have demonstrated that tuning oxygen vacancies in catalysts and implementing in situ water removal can enable highly efficient DMC production from CO2. CexZryO2 nanorods with abundant oxygen vacancies were synthesized via a hydrothermal method. In liquid-phase DMC synthesis, the Ce10Zr1O2 nanorods exhibited a 1.7- and 1.4-times higher DMC yield compared to CeO2 nanoparticles and undoped CeO2 nanorods, respectively. Zr doping yielded a CeZr solid solution with increased oxygen vacancies, promoting CO2 adsorption and activation. In addition, adding 2-cyanopyridine as an organic dehydrating agent achieved an outstanding 87% methanol conversion and >99% DMC selectivity by shifting the reaction equilibrium to the desired product. Moreover, mixing CeO2 nanoparticles with hydrophobic fumed SiO2 in gas-phase DMC synthesis led to a doubling of DMC yield. This significant increase was attributed to the faster diffusion of water molecules away from the catalyst surface, facilitated by the hydrophobic SiO2. This study illustrates an effective dual strategy of enhancing oxygen vacancies and implementing in situ water removal to boost DMC production from CO2. The strategy can also be applied to other reactions impacted by water accumulation.

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Section: Introductionmentioning

confidence: 99%

Enhancing DMC Production from CO2: Tuning Oxygen Vacancies and In Situ Water Removal

Wang,

Li,

et al. 2024

Energies

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“…Some research has been reported on application of CO 2 chemisorption such as the [BASE-H][ROC(O)O] formation for synthesis of useful organic compounds. − In previous studies for diethyl carbonate (DEC) synthesis, Wu et al. and Kim et al independently reported DRC synthesis in the presence of organic bases, but they do not address the formation of [BASE-H][ROC(O)O] and its impact on the reaction outcome, nor did they investigated DRC synthesis under low-pressure and low-concentration CO 2 . , By contrast, Liu et al and Nozaki et al accomplished DRC synthesis under low-pressure CO 2 via [BASE-H][ROC(O)O]; CH 2 Br 2 and alkyl triflates were used as halogenated alkylating agents. , Herein, we report a cooperative combination of DBU for the chemical capture of CO 2 , tetraalkyl orthosilicate (Si(OR) 4 , TROS) as the dehydrating agent, and CeO 2 as the catalyst for the synthesis of DRC using atmospheric pressure CO 2 (Scheme ). This system demonstrates environmentally friendly DRC synthesis using low-pressure and low-concentration CO 2 without utilizing halogenated alkylating agents, even under reaction conditions with no large excess of either CO 2 , alcohol, or a dehydrating agent.…”

Section: Introductionmentioning

confidence: 99%

“… 19 , 37 By contrast, Liu et al and Nozaki et al accomplished DRC synthesis under low-pressure CO 2 via [BASE-H][ROC(O)O]; CH 2 Br 2 and alkyl triflates were used as halogenated alkylating agents. 38 , 39 Herein, we report a cooperative combination of DBU for the chemical capture of CO 2 , tetraalkyl orthosilicate (Si(OR) 4 , TROS) as the dehydrating agent, and CeO 2 as the catalyst for the synthesis of DRC using atmospheric pressure CO 2 ( Scheme 2 ). This system demonstrates environmentally friendly DRC synthesis using low-pressure and low-concentration CO 2 without utilizing halogenated alkylating agents, even under reaction conditions with no large excess of either CO 2 , alcohol, or a dehydrating agent.…”

Section: Introductionmentioning

confidence: 99%

Dialkyl Carbonate Synthesis Using Atmospheric Pressure of CO₂

Koizumi,

Nagae,

Takeuchi

et al. 2024

ACS Omega

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Dialkyl carbonates (DRCs) are valuable compounds widely used in the industry. The synthesis of DRC from CO 2 has attracted interest as an alternative to the current method, which uses phosgene. However, the reported approaches for DRC synthesis from CO 2 requires high-pressure and high-concentration CO 2 , resulting in elevated costs associated with CO 2 purification and manufacturing facilities. In this report, we present an environmentally friendly method for producing DRC from lowconcentration and low-pressure CO 2 via a dehydration condensation approach without the use of halogenated alkylating agents. This method involves the formation of monoalkyl carbonate [BASE-H][ROC(O)O] using a strong organic base and alcohols, tetraalkyl orthosilicates as dehydrating agents, and CeO 2 as the catalyst. Using the method, 39 and 30% of diethyl carbonate yields were accomplished with only 100 and 15 vol % CO 2 (CO 2 /N 2 = 15:85) gas bubbling at atmospheric pressure, even under reaction conditions with no large excess of either CO 2 , alcohol, or dehydration agent.

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“…Among them, CO 2 capture and fixation is an effective solution to environmental problems. The conversion of CO 2 to valuable organic compounds has received extensive attention in recent years, including benzimidazole, 3 dimethyl carbonate, 4 oxazolidinone, 5 methanol, 6 urea, 7 formic acid, 8 etc. Whereas CO 2 is thermodynamically stable and kinetically inert as a linearly symmetric molecule, making it difficult to convert into valuable chemicals 9 .…”

Section: Introductionmentioning

confidence: 99%

The efficient CO₂ fixation catalyzed by K‐doped g‐C₃N₄ catalyst for synthesizing benzimidazoles at atmospheric pressure

Zhang

Chen

et al. 2023

Greenhouse Gases

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The conversion of CO2 into valuable chemicals to reduce greenhouse gas emissions has received extensive attention. Converting CO2 into pharmaceutical intermediates via graphitic carbon nitride (CN) at atmospheric pressure is a challenge. In this work, a series of novel graphitic carbon nitrides (K‐CN) catalysts with different doping ratios of K were synthesized by post‐treatment of CN with KOH as a dopant under magnetic stirring. Herein, substrates of o‐phenylenediamine with different electron‐donating/withdrawing groups were employed to convert CO2 into high‐value heterocyclic benzimidazoles. The optimal reaction conditions were determined by a single factor optimization approach. A series of benzimidazole derivatives were synthesized with a yield of up to 96% under atmospheric pressure, indicating that the catalyst can efficiently fix CO2. This work not only designs a simple and low‐cost K‐CN catalyst but also provides a new pathway for converting CO2 into valuable benzimidazole derivatives at atmospheric pressure. © 2023 Society of Chemical Industry and John Wiley & Sons, Ltd.

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Synthesis of dimethyl carbonate from methanol and CO₂ under low pressure

Abstract: A mild and efficient approach for the synthesis of dimethyl carbonate from methanol and CO2 under low initial pressure was developed.

Cited by 10 publications

References 44 publications

Enhancing DMC Production from CO2: Tuning Oxygen Vacancies and In Situ Water Removal

Enhancing DMC Production from CO2: Tuning Oxygen Vacancies and In Situ Water Removal

Dialkyl Carbonate Synthesis Using Atmospheric Pressure of CO₂

The efficient CO₂ fixation catalyzed by K‐doped g‐C₃N₄ catalyst for synthesizing benzimidazoles at atmospheric pressure

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Synthesis of dimethyl carbonate from methanol and CO2 under low pressure

Abstract: A mild and efficient approach for the synthesis of dimethyl carbonate from methanol and CO2 under low initial pressure was developed.

Cited by 10 publications

References 44 publications

Enhancing DMC Production from CO2: Tuning Oxygen Vacancies and In Situ Water Removal

Enhancing DMC Production from CO2: Tuning Oxygen Vacancies and In Situ Water Removal

Dialkyl Carbonate Synthesis Using Atmospheric Pressure of CO2

The efficient CO2 fixation catalyzed by K‐doped g‐C3N4 catalyst for synthesizing benzimidazoles at atmospheric pressure

Contact Info

Product

Resources

About

Synthesis of dimethyl carbonate from methanol and CO₂ under low pressure

Dialkyl Carbonate Synthesis Using Atmospheric Pressure of CO₂

The efficient CO₂ fixation catalyzed by K‐doped g‐C₃N₄ catalyst for synthesizing benzimidazoles at atmospheric pressure