Synthesis Of Dimethyl Carbonate Research Articles

Platelet Ceria Catalysts from Solution Combustion and Effect of Iron Doping for Synthesis of Dimethyl Carbonate from CO2.

Solution combustion (SC) remains among the most promising synthetic strategies for the production of crystalline nanopowders from an aqueous medium, due to its easiness, time and cost-effectiveness, scalability and eco-friendliness. In this work, this method was selected to obtain anisometric ceria-based nanoparticles applied as catalysts for the direct synthesis of dimethyl carbonate. The catalytic performances were studied for the ceria and Fe-doped ceria from SC (CeO2-SC, Ce0.9Fe0.1O2-SC) in comparison with the ceria nanorods (CeO2-HT, Ce0.9Fe0.1O2-HT) obtained by hydrothermal (HT) method, one of the most studied systems in the literature. Indeed, the ceria nanoparticles obtained by SC were found to be highly crystalline, platelet-shaped, arranged in a mosaic-like assembly and with smaller crystallite size (≈6 nm vs. ≈17 nm) and higher surface area (80 m2 g-1 vs. 26 m2 g-1) for the undoped sample with respect to the Fe-doped counterpart. Although all samples exhibit an anisometric morphology that should favor the exposition of specific crystalline planes, HT-samples showed better performances due to higher oxygen vacancies concentration and lower amount of strong basic and acid sites.

Unveiling the Pivotal Role of Ce Coordination Structures and Their Surface Arrangements in Governing 2-Cyanopyridine Hydrolysis for Direct Dimethyl Carbonate Synthesis from CO2 and Methanol

Unveiling the Pivotal Role of Ce Coordination Structures and Their Surface Arrangements in Governing 2-Cyanopyridine Hydrolysis for Direct Dimethyl Carbonate Synthesis from CO₂ and Methanol

Mechanism study on the influence of surface properties on the synthesis of dimethyl carbonate from CO2 and methanol over ceria catalysts

The direct synthesis of dimethyl carbonate (DMC) from CO2 and methanol has attracted much attention as an environmentally benign and alternative route for conventional routes. Herein, a series of cerium oxide catalysts with various textural features and surface properties were prepared by the one-pot synthesis method for the direct DMC synthesis from CO2 and methanol, and the structure-performance relationship was investigated in detail. Characterization results revealed that both of surface acid-base properties and the oxygen vacancies contents decreased with the rising crystallinity at increasingly higher calcination temperature accompanied by an unexpectedly volcano-shaped trend of DMC yield observed on the catalysts. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) studies indicated that the adsorption rate of methanol is slower than that of CO2 and the methanol activation state largely influences the formation of key intermediate. Although the enhanced surface acidity-basicity and oxygen vacancies brought by low-temperature calcination could facilitate the activation of CO2, the presence of excess strongly basic sites on low-crystallinity sample was detrimental to DMC synthesis due to the preferred formation of unreactive mono/polydentate carbonates as well as the further impediment of methanol activation. Moreover, with the use of 2-cyanopyridine as a dehydration reagent, the DMC synthesis was found to be both influenced by the promotion from the rapid in situ removal of water and the inhibition from the competitive adsorption of hydration products on the same active sites.

Simulation and optimization of DMC synthesis process based on conventional and advanced exergy analyses

Dimethyl carbonate has received more and more attentions as an organic solvent in electrolytes. Aiming at the problem of high energy consumption in the process of dimethyl carbonate (DMC) production, the root of the problem was analyzed by using exergy analysis, which provides a theoretical basis for the construction of energy-saving process. Firstly, the overall process of DMC production was constructed, including propylene carbonate (PC) synthesis, DMC synthesis, azeotrope separation and propylene glycol (PG) purification processes. Secondly, the conventional and advanced exergy analyses of the four proposed processes were carried out. The distributions of exergy and exergy destruction were obtained through conventional exergy analysis. The exergy destructions were further divided through advanced exergy analysis, and the avoidable parts were focused on. Based on the above analyses, the corresponding heat integration processes were proposed. Finally, the conventional processes and the heat integration processes were evaluated with the performance indicators of the exergy destruction, total annual cost (TAC), total energy consumption (TEC) and CO2 emissions.

The Role of K2CO3 in the Synthesis of Dimethyl Carbonate from CO2 and Methanol

The synthesis of dimethyl carbonate (DMC) from methanol and CO2 has also received widespread attention, and K2CO3 is usually used as a catalyst in the synthesis of DMC. In this work, the role of K2CO3 in synthesizing dimethyl carbonate (DMC) from methanol and CO2 was revisited. Interestingly, NMR results indicated that K2CO3 can react with methanol to form carbonate CH3OCOO−, an essential intermediate in the synthesis of DMC, which can be transformed into DMC in the presence of CH3I. In other words, K2CO3 can act as not only a catalyst but also a reactant to synthesize DMC from methanol and CO2.

Direct Synthesis of Dimethyl Carbonate from Methanol and CO2 over ZrO2 Catalysts Combined with a Dehydrating Agent and a Cocatalyst

Zirconia nanocrystals as catalysts for the direct synthesis of dimethyl carbonate (DMC) from methanol and carbon dioxide have received significant interest recently. In this paper, three zirconia-based catalysts presenting different monoclinic and tetragonal phase contents are prepared and characterized by X-ray diffraction (XRD), N2 adsorption–desorption, transmission electron microscopy (TEM), and temperature-programmed desorption of NH3 and CO2 (NH3-TPD and CO2-TPD). The catalytic performances of these solids are evaluated in terms of DMC production. This production is low when using the bare zirconias, but it is significantly increased in the presence of 1,1,1-trimethoxymethane (TMM) playing the role of a dehydrating agent, which shifts the thermodynamic equilibrium. Moreover, the production of DMC is further improved by adding a second solid catalyst (cocatalyst), the molecular sieve 13X, to accelerate the hydration of TMM. Hence, the molecular sieve 13X plays a dual role by trapping water molecules formed by the reaction of DMC synthesis and providing strong acidic sites catalyzing TMM hydrolysis. To the best of our knowledge, the combination of two solid catalysts in the reaction medium to accelerate the water elimination to obtain higher DMC production from CO2 and methanol has never been reported.

Ordered versus Non-Ordered Mesoporous CeO2-Based Systems for the Direct Synthesis of Dimethyl Carbonate from CO2.

In this work, non-ordered and ordered CeO2-based catalysts are proposed for CO2 conversion to dimethyl carbonate (DMC). Particularly, non-ordered mesoporous CeO2, consisting of small nanoparticles of about 8 nm, is compared with two highly porous (635-722 m2/g) ordered CeO2@SBA-15 nanocomposites obtained by two different impregnation strategies (a two-solvent impregnation method (TS) and a self-combustion (SC) method), with a final CeO2 loading of 10 wt%. Rietveld analyses on XRD data combined with TEM imaging evidence the influence of the impregnation strategy on the dispersion of the active phase as follows: nanoparticles of 8 nm for the TS composite vs. 3 nm for the SC composite. The catalytic results show comparable activities for the mesoporous ceria and the CeO2@SBA-15_SC nanocomposite, while a lower DMC yield is found for the CeO2@SBA-15_TS nanocomposite. This finding can presumably be ascribed to a partial obstruction of the pores by the CeO2 nanoparticles in the case of the TS composite, leading to a reduced accessibility of the active phase. On the other hand, in the case of the SC composite, where the CeO2 particle size is much lower than the pore size, there is an improved accessibility of the active phase to the molecules of the reactants.

Experimental Verification of Low-Pressure Kinetics Model for Direct Synthesis of Dimethyl Carbonate Over CeO2 Catalyst

AbstractDimethyl carbonate (DMC) has emerged as a promising candidate for sustainable chemical processes due to its remarkable versatility and low toxicity. From a green chemistry perspective, the direct synthesis of DMC has been considered the most promising route, as water is the only byproduct generated in the reaction between CO2 and methanol. However, this synthetic route has faced significant thermodynamic limitations, even at elevated pressure conditions. Therefore, a two-part study explored low-pressure synthesis of DMC via the direct route, and a low-pressure kinetic model for the CeO2 catalyst was developed based on the results. Proposed Langmuir–Hinshelwood mechanisms were verified using experimental data generated in our labs. The investigation suggests that DMC formation in the direct synthetic route is a surface reaction of CO2 and methanol on the catalyst. The kinetic model predictions closely aligned with experimental data, demonstrating a 17% mean absolute percentage error and indicating a high level of predictability. Additionally, a rigorous assessment was conducted on CO2 fixations in DMC synthesis, quantifying CO2 capture and its conversion into stable or high-value products, formally designated as CO2 Fixation (CO2Fix). The CO2Fix analysis revealed that, at a conversion rate of 27%, the process can achieve a "net zero" state when operated at an approximate pressure of 30 bar, thereby supporting the viability of low-pressure synthesis. Increasing the conversion rate to levels exceeding 95% significantly enhances the CO2Fix metric, potentially surpassing 3.5 or higher.

Hydroxyl-functionalization promoted activity and recovery of ionic liquids in direct dimethyl carbonate synthesis from CO2

Direct synthesis of dimethyl carbonate (DMC) from CO2 is promising for CO2 utilization, however its efficiency remains far from industrial-scale implementation for lack of customized catalysts. Herein, a hydroxyl-functionalized ionic liquid (HFIL) was developed to enhance catalytic activity, and importantly, to facilitate IL recovery through spontaneous phase separation. A high DMC yield (6.5 gDMC·kgcat−1·h−1) over HFIL was achieved under mild conditions compared to non- hydroxyl IL. Self-diffusion coefficients characterization revealed intensified diffusion of CH3OH and HFIL, alongside reduced blockage of active sites after hydroxyl functionalization. Density functional theory calculations elucidated that cation polarization induced by hydroxyl group facilitated the synergistic activation of both substrates and monomethyl carbonate intermediate. The reaction mechanism was further verified through diffuse reflectance infrared Fourier transform spectroscopy and theoretical calculations. The self-separation behavior was demonstrated by molecular dynamics simulations. The deep insights into hydroxyl effects towards direct DMC synthesis provide a pioneering perspective for CO2 capture and utilization using functionalized ILs.

Progress on the Catalysts for the Gas-Phase Carbonylation Synthesis of Dimethyl Carbonate from Methyl Nitrite and CO

Progress on the Catalysts for the Gas-Phase Carbonylation Synthesis of Dimethyl Carbonate from Methyl Nitrite and CO

Mn-doped CeO2 derived from Ce-MOF porous nanoribbons as highly active catalysts for the synthesis of dimethyl carbonate from CO2 and methanol.

It is desirable but challenging to develop highly-efficient catalysts for the direct synthesis of dimethyl carbonate (DMC) from methanol and CO2. The vacancy-mediated incorporation of heteroatom into surface reconstruction is an efficient method of defect engineering for enhancing the catalytic properties. In this work, manganese-doped cerium oxide porous nanoribbons (Mn/CeO2-BTC) were prepared derived from a Ce-BTC by a sacrificial template approach. It is found that the catalytic activity of Mn/CeO2-BTC catalysts can be readily controlled by varying the amount of Mn dopants and the as-synthesized 0.1-Mn/CeO2-BTC exhibited an outstanding activity for the synthesis of DMC from CO2 and methanol, which reached a high DMC yield (6.53 mmolDMC/gcat.) without any dehydrating agents. Based on characterization results, the enhanced performance may be attributed to the defective structures caused by Mn doping and the porous nanoribbons of the CeO2 crystals, which provide more surface oxygen vacancies and acidic-basic sites, favoring adsorption and activation of CO2 and methanol.

Evaluation of dimethyl carbonate production process from CO2 by rigorous simulation and detailed optimization

AbstractThe CO2‐derived dimethyl carbonate (DMC) synthesis process becomes greatly attentive but suffers high energy consumption in DMC distillation process. In this work, the DMC‐MeOH azeotropes separation process by pressure swing distillation and extractive distillation was compared, and key operating parameters, including the total number of trays and the feeding position of the mixture liquid, were optimized with the minimum total annual cost (TAC) as the objective function. On the basis of this optimization, economic evaluation of different distillation processes was conducted, and it was found that extractive distillation was more economical than pressure swing distillation. The application of the dividing‐wall distillation process upgraded by extractive distillation can significantly reduce the minimum annual total cost by 37.4% and 10.7% compared to the original pressure swing distillation and extractive distillation process, respectively. The optimization of relevant heat exchange network based on pinch technology resulted in energy consumption reduction by 27.2% and 25.9% for its hot and cold utilities, respectively. Carbon life cycle assessment (LCA) on the DMC distillation process revealed over 50% of energy as well as carbon emissions from steam consumption, whose reduction can significantly minimize CO2 emissions, energy consumption, and ultimate cost. © 2024 Society of Chemical Industry and John Wiley & Sons, Ltd.

Efficient Synthesis of Dimethyl Carbonate via Transesterification of Ethylene Carbonate Catalyzed by CN-SiAlO Composites

Efficient Synthesis of Dimethyl Carbonate via Transesterification of Ethylene Carbonate Catalyzed by CN-SiAlO Composites

Facile One-Pot Preparation of Organotin-Oxometalate Polymers for Efficient Synthesis of Dimethyl Carbonate from CO2

Facile One-Pot Preparation of Organotin-Oxometalate Polymers for Efficient Synthesis of Dimethyl Carbonate from CO₂

Tuning the cross-linked structure of basic poly(ionic liquid) to develop an efficient catalyst for the conversion of vinyl carbonate to dimethyl carbonate

Dimethyl carbonate (DMC) is a crucial chemical raw material widely used in organic synthesis, lithium-ion battery electrolytes, and various other fields. The current primary industrial process employs a conventional sodium methoxide basic catalyst to produce DMC through the transesterification reaction between vinyl carbonate and methanol. However, the utilization of this catalyst presents several challenges during the process, including equipment corrosion, generation of solid waste, susceptibility to deactivation, and complexities in separation and recovery. To address these limitations, a series of alkaline poly(ionic liquid)s, i.e., [DVBPIL][PHO], [DVCPIL][PHO], [TBVPIL][PHO], with different cross-linking degrees and structures were synthesized through the construction of cross-linked polymeric monomers and functionalization. These poly(ionic liquid)s exhibit cross-linked structures and controllable cationic and anionic characteristics. Research was conducted to investigate the effect of the cross-linking degree and structure on the catalytic performance of transesterification in synthesizing DMC. It was discovered that the appropriate cross-linking degree and structure of the [DVCPIL][PHO] catalyst resulted in a DMC yield of up to 80.6%. Furthermore, this catalyst material exhibited good stability, maintaining its catalytic activity after repeated use five times without significant changes. The results of this study demonstrate the potential for using alkaline poly(ionic liquid)s as a highly efficient and sustainable alternative to traditional catalysts for the transesterification synthesis of DMC.

A Review of Catalysts for Synthesis of Dimethyl Carbonate

Dimethyl carbonate (DMC) is widely used as an intermediate and solvent in the organic chemical industry. In recent years, compared with the traditional DMC production methods (phosgene method, transesterification method), methanol oxidation carbonylation method, gas-phase methyl nitrite method, and the direct synthesis of CO2 and methanol method have made much progress in the synthesis process and development of catalysts. The key to the industrial application of DMC synthesis technology is the design and development of high-performance catalysts. Therefore, this paper reviews the research status of the methanol oxidative carbonylation method, gas-phase methyl nitrite method, and direct synthesis method of CO2 and methanol in the aspects of new catalyst design, catalyst preparation, and catalytic mechanism, and puts forward the problems to be solved and the future development direction of DMC catalysts.

Dimethyl Carbonate Synthesis from CO2 over CeO2 with Electron-Enriched Lattice Oxygen Species.

Direct synthesis of dimethyl carbonate (DMC) from CO2 plays an important role in carbon neutrality, but its efficiency is still far from the practical application, due to the limited understanding of the reaction mechanism and rational design of efficient catalyst. Herein, abundant electron-enriched lattice oxygen species were introduced into CeO2 catalyst by constructing the point defects and crystal-terminated phases in the crystal reconstruction process. Benefitting from the acid-base properties modulated by the electron-enriched lattice oxygen, the optimized CeO2 catalyst exhibited a much higher DMC yield of 22.2 mmol g-1 than the reported metal-oxide-based catalysts at the similar conditions. Mechanistic investigations illustrated that the electron-enriched lattice oxygen can provide abundant sites for CO2 adsorption and activation, and was advantageous of the formation of the weakly adsorbed active methoxy species. These were facilitating to the coupling of methoxy and CO2 for the key *CH3OCOO intermediate formation. More importantly, the weakened adsorption of *CH3OCOO on the electron-enriched lattice oxygen can switch the rate-determining-step (RDS) of DMC synthesis from *CH3OCOO formation to *CH3OCOO dissociation, and lower the corresponding activation barriers, thus giving rise to a high performance. This work provides insights into the underlying reaction mechanism for DMC synthesis from CO2 and methanol and the design of highly efficient catalysts.

Dimethyl Carbonate Synthesis from CO2 over CeO2 with Electron‐Enriched Lattice Oxygen Species

AbstractDirect synthesis of dimethyl carbonate (DMC) from CO2 plays an important role in carbon neutrality, but its efficiency is still far from the practical application, due to the limited understanding of the reaction mechanism and rational design of efficient catalyst. Herein, abundant electron‐enriched lattice oxygen species were introduced into CeO2 catalyst by constructing the point defects and crystal‐terminated phases in the crystal reconstruction process. Benefitting from the acid‐base properties modulated by the electron‐enriched lattice oxygen, the optimized CeO2 catalyst exhibited a much higher DMC yield of 22.2 mmol g‐1 than the reported metal‐oxide‐based catalysts at the similar conditions. Mechanistic investigations illustrated that the electron‐enriched lattice oxygen can provide abundant sites for CO2 adsorption and activation, and was advantageous of the formation of the weakly adsorbed active methoxy species. These were facilitating to the coupling of methoxy and CO2 for the key *CH3OCOO intermediate formation. More importantly, the weakened adsorption of *CH3OCOO on the electron‐enriched lattice oxygen can switch the rate‐determining‐step (RDS) of DMC synthesis from *CH3OCOO formation to *CH3OCOO dissociation, and lower the corresponding activation barriers, thus giving rise to a high performance. This work provides insights into the underlying reaction mechanism for DMC synthesis from CO2 and methanol and the design of highly efficient catalysts.

Facile one-pot synthesis of niobium-containing carbon nitride and the catalytic application for synthesis of dimethyl carbonate

Dimethyl carbonate (DMC) is a building block in wide chemical-related fields and the transesterification of ethylene carbonate (EC) and methanol/ethanol is a sustainable route for the synthesis of DMC. Herein, in order to explore efficient heterogeneous catalysts, niobium-containing carbon nitride materials were synthesized by a convenient one-pot calcination method. By reserving the main chemical functionalities of carbon nitride, the Nb-CN composites contained both acidic and basic properties, and Nb can be dispersed by carbon nitride. In the transesterification of EC with methanol, under the reaction temperature of 140 °C and reaction time of 4 h, the conversion of EC and the selectivity of DMC reached 53.8% and 100%, respectively, and the activity of the catalyst did not decrease significantly after several recycling runs. Furthermore, the Nb-CN could promote transesterification reactions of other cyclic carbonate and alcohols.

Boosting Dimethyl Carbonate Production from CO2 and Methanol using Ceria-Ionic Liquid Catalyst.

As a crucial strategy towards a sustainable chemical industry, the direct synthesis of dimethyl carbonate (DMC) from renewable carbon dioxide (CO2) and methanol (MeOH) is studied using CeO2 nanoparticles modified with 1-butyl-3-methylimidazolium hydrogen carbonate ([BMIm][HCO3]) devoid of stoichiometric dehydrating agents. The synthesized CeO2@[BMIm][HCO3] catalyst having high thermal stability harnesses the unique physicochemical properties of CeO2 and the ionic liquid to exhibit a DMC yield of 10.4 % and a methanol conversion of 16.1 % at optimal conditions (pressure of CO2=5 MPa; temperature=130 °C). The catalytic behavior of CeO2@[BMIm][HCO3] studied with a detailed XRD, XPS, CO2 and NH3-TPD, Raman spectroscopy, TGA, FTIR, SEM and TEM suggests that the synergy between the two catalytic components originating from an increased surface oxygen vacancies boosts the overall catalytic performance. After several recycling tests, the catalyst demonstrated no significant reduction in DMC yield and methanol conversion. This platform is an attractive approach to synthesize thermally stable nanoparticle@ionic liquid that retains and merges the physical attributes of both materials for producing useful bulk chemicals from readily available chemical resources.