Synthesis of diethyl carbonate from ethanol through different routes: A thermodynamic and comparative analysis

In this study, thermodynamic analysis of various possible synthesis routes of diethyl carbonates (DEC), a benign organic carbonate, was carried out and a comparative analysis was performed. Chemical equilibrium constants at standard conditions were calculated using Gibbs free energy of the system. The Benson group contribution method was used to estimate standard heat of formation and standard entropy change of some raw materials/components like dimethyl carbonate. Variation of heat capacity (C_p) with temperature was estimated for different components from the Rozicka‐Domalski model. Variation of chemical equilibrium constants with temperature and pressure was studied for various routes. Synthesis of DEC from ethylene carbonate (EC) was also found to be better considering equilibrium constants at room temperature. The CO₂ route was found to be the most unfavourable route for DEC synthesis due to stability of CO₂ molecules. Moreover, DEC synthesis through the urea route was found to be best at high temperatures since the equilibrium constants were found to increase exponentially. Experiments were conducted for DEC synthesis using the EC route at two temperatures. Activity coefficients were calculated using the UNIFAC model. Experimentally and theoretically determined chemical equilibrium constant values were found to be similar. PRO/II was also used to minimize Gibbs free energy of the system and estimate the equilibrium constants and the results were comparable with those obtained by the equilibrium constant method and the trend was found to be the same for both the methods.     

尿素直接醇解合成碳酸二甲酯研究进展

综述了尿素直接醇解合成碳酸二甲酯的热力学,反应工艺和相应催化剂的研究进展。反应工艺主要为间歇和连续工艺,间歇工艺操作简单、但受热力学影响,产品产率较低且后续产物分离困难;连续工艺可使产物及时移出,提高产率,且后续分离变得相对简单。对两种工艺所用催化剂进行了讨论。     

Effects of solvents and salts on the thermal stability of LiC6

Accelerating rate calorimetry (ARC) was used to study the thermal stability of Li_0.81C₆ in dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylene carbonate (EC), and an EC/DEC mixture as well as in LiPF₆- and LiBOB-based electrolytes. ARC results show that linear carbonates like DMC or DEC react strongly with Li_0.81C₆ and that robust passivating layers do not form. By contrast, the cyclic carbonate, EC, creates a robust passivating film that limits the rate of reaction between Li_0.81C₆ and EC as the temperature increases. X-ray diffraction shows that the addition of LiPF₆ to EC/DEC changes the surface film that forms on Li_0.81C₆ at elevated temperature to one dominated by LiF instead of lithium-alkyl carbonate or lithium carbonate. This increases the thermal stability of Li_0.81C₆ in LiPF₆ electrolyte compared to pure EC/DEC solvent. By an apparently similar mechanism, the addition of only 0.2 M LiBOB to EC/DEC greatly improves the thermal stability of Li_0.81C₆. ARC results for Li_0.81C₆ in pure and mixed salt LiPF₆ and LiBOB EC/DEC electrolytes of various molarities shed light on the reasons for the beneficial effect of the salts.     

Surface film formation on a graphite negative electrode in lithium-ion batteries: AFM study on the effects of co-solvents in ethylene carbonate-based solutions

In situ AFM observation of the basal plane of highly oriented pyrolytic graphite (HOPG) was performed before and after cyclic voltammetry in 1 mol dm⁻³ LiClO₄ dissolved in ethylene carbonate (EC), EC+diethyl carbonate (DEC), and EC+dimethyl carbonate (DMC) to clarify the effects of co-solvents in EC-based solutions on surface film formation on graphite negative electrodes in lithium-ion cells. In each solution, surface film formation involved the following two different processes: (i) intercalation of solvated lithium ions and their decomposition beneath the surface; and (ii) direct decomposition of solvent molecules on the basal plane to form a precipitate layer. The most remarkable difference among these solvent systems was that solvent co-intercalation took place more extensively in EC+DEC than in EC+DMC or EC. Raman analysis of ion-solvent interactions revealed that a lithium ion is solvated by three EC molecules and one DEC molecule in EC+DEC, whereas it is solvated exclusively by EC in EC+DMC and in EC, which suggested that the presence of linear alkyl carbonates in the solvation shell of lithium ion enhance the degree of solvent co-intercalation that occurs in the initial stage of the surface film formation.     

二氧化碳合成碳酸二甲酯的研究进展

由CO₂合成碳酸二甲酯（DMC）是一条对化学工业和环境保护都具有吸引力的工业路线。综述了以CO₂为原料的两种合成方法（直接法和间接法）的最新研究。着重论述直接法合成中的催化剂以及反应条件对DMC收率的影响。CO₂直接合成DMC有望成为一条重要的工业路线。     

我国碳酸二甲酯生产现状及发展建议

通过对不同碳酸二甲酯生产方法的比较,并针对我国目前碳酸二甲酯的发展现状,提出了采用尿素两步醇解法生产工艺。建议将尿素、碳酸丙烯酯和碳酸二甲酯3套生产装置联用,有助于国内碳酸二甲酯生产企业走出亏损的困境。     

Sustainable Dimethyl Carbonate Production from Ethylene Oxide and Methanol

A large-scale dimethyl carbonate (DMC) production process from ethylene oxide (EO), CO₂, and methanol was simulated and optimized. Unlike most industrial processes of DMC production, the direct conversion of EO and CO₂ to ethylene carbonate (EC) and EC transesterification to DMC were performed in a single reactor. The reaction volume and the reactor operating pressure were selected as decision variables and evaluated. The key performance parameters, e.g., conversion per pass and CO₂ intensity, were compared with conventional commercialized routes or novel promising processes in the literature.     

Methodologies for chemical utilization of CO2 to valuable compounds through molecular activation by efficient catalysts

The reactions of CO₂ with oxirane to produce cyclic carbonate, and with aziridine to afford oxazolidine have been of interest as a useful method for its fixation by a chemical process. Highly efficient processes employing recyclable CO₂-phlilic homogeneous catalyst were devised for environmentally benign synthesis of cyclic carbonates and oxazolidinones under supercritical CO₂ without any organic solvent. These processes represent pathways for greener chemical fixations of CO₂ to afford industrial useful materials such as organic carbonates and oxazolidinones with great potential applications.     

A study of electrochemical kinetics of lithium ion in organic electrolytes

Limiting current densities equivalent to the transport-controlling step of lithium ions in organic electrolytes were measured by using a rotating disk electrode (RDE). The diffusion coefficients of lithium ion in the electrolyte of PC/LiClO₄, EC : DEC/LiPF₆ and EC : DMC/LiPF₆ were determined by the limiting current density data according to the Levich equation. The diffusion coefficients increased in the order of PC/LiClO₄<EC : DEC/LiPF₆<EC : DMC/ LiPF₆ with respect to molar concentration of lithium salt. The maximum value of diffusivity was 1.39x10-5cm²/s for 1M LiPF₆ in EC : DMC=1 : 1. Exchange current densities and transfer coefficients of each electrolyte were determined according to the Butler-Volmer equation.     

氧化锌催化尿素醇解制备碳酸二甲酯的研究

研究了在600 ℃焙烧氧化锌、醋酸锌和沉淀法制得碳酸锌而得到的氧化锌催化剂对尿素醇解制备碳酸二甲酯的催化作用。实验表明，通过引入少量的甲醇钠，使中间产物氨基甲酸甲酯的产率有明显提高。由此证明尿素醇解是分两步进行。探讨了在甲醇钠作用下氧化锌催化尿素醇解的影响因素。     

碳酸二甲酯和乙醇酯交换合成碳酸二乙酯工艺研究

碳酸二乙酯分子结构中含有活性基团乙氧基和羰基,化学性质活泼,是一种重要的有机合成中间体、溶剂和性能优良的燃料添加剂,在化工领域具有很高的应用价值。以碳酸二甲酯和乙醇为原料,甲醇钠为催化剂,通过酯交换反应合成碳酸二乙酯。气相色谱分析表明,在酯与醇物质的量比1∶20、催化剂用量为碳酸二甲酯质量的1.0%、反应温度78 ℃和反应时间1 h条件下,碳酸二甲酯转化率达99%,碳酸二乙酯和碳酸甲乙酯选择性分别为86%和14%。     

Supercritical carbon dioxide extraction of lithium-ion battery electrolytes

Two different separator materials (polyethylene fleece – Freudenberg 2190 and porous glass fiber – Whatman^® GF/D) and two different lithium-ion battery electrolytes have been investigated regarding their behavior in an autoclave extraction with supercritical helium head pressure carbon dioxide (sc HHPCO₂). Mixtures of dimethyl carbonate (DMC)/ethylene carbonate (EC) and ethylmethyl carbonate (EMC)/EC, each with 1 mol/L LiPF₆ were used.In addition to these proof of principle experiments, the developed extraction method was further applied to real battery samples. Commercial 18650 cells (after formation and aging) were opened and the jelly roll was extracted with sc HHPCO₂. Extracts were analyzed with gas and ion chromatography (GC, IC). Recovery rates and extract compositions strongly depend on the material of which the electrolyte is extracted. Further structure determination of electrolyte aging products was performed with different ionization modes in GC–mass spectrometry (GC–MS) experiments. Diethyl carbonate (DEC), dimethyl-2,5-dioxahexane dicarboxylate (DMDOHC), ethylmethyl-2,5-dioxahexane dicarboxylate (EMDOHC) and diethyl-2,5-dioxahexane dicarboxylate (DEDOHC) are aging products of electrolyte degradation which were successfully extracted and identified. Their concentrations correlate with solid electrolyte interphase (SEI) growth on the negative electrode which was investigated with scanning electron microscopy (SEM).     

氧化锌的制备及其对碳酸二甲酯合成的催化作用

通过焙烧醋酸锌法、微波活化ZnO法、溶胶-凝胶法和沉淀法制备得到四种ZnO催化剂，并对其进行尿素与甲醇反应制碳酸二甲酯(DMC)活性测定以及XRD和SEM表征。结果表明，溶胶-凝胶法制备得到的ZnO催化剂颗粒大小均匀，催化活性好，DMC收率为8.17％。还提出ZnO催化尿素与甲醇反应制DMC的反应机理。     

In situ FTIR study of the Cu electrode/ethylene carbonate + dimethyl carbonate solution interface

The interfacial phenomena between Cu electrode and solution of lithium perchlorate in ethylene carbonate (EC)-dimethyl carbonate (DMC) have been investigated using in situ reflection absorption Fourier transform infrared (FTIR) spectroscopy and single reflection ATR-FTIR spectroscopy. The ATR spectra confirmed the bands due to free EC and DMC and the molecules solvated to lithium ions in the solution. The bands due to the result of the interaction between ClO₄⁻ and DMC in the mixture solution also appeared in the ATR spectra. In the FTIR spectra, the potential dependence on the concentration of EC and DMC in the vicinity of the Cu electrode was observed. It was understood that the reversible changes in the concentration of free EC and DMC and solvated EC and DMC in the diffuse double layer take place with changing in potential. As the potential decreased, the free EC and DMC concentrations increased, while the concentration of the EC and DMC solvated to lithium ions decreased. Thus, it can be concluded that the equilibrium shifts from Li⁺(EC)₂(DMC)₂ to Li⁺(EC)₂(DMC) + DMC or Li⁺(EC)(DMC)₂ + EC as the potential decreases. The bands due to (CH₂OCO₂Li)₂ and CH₃OCO₂Li were observed for an irreversible reaction.     

Hydrogen bond activation strategy for cyclic carbonates synthesis from epoxides and CO2: current state-of-the art of catalyst development and reaction analysis

Chemical fixation of CO₂ into useful organic compounds has been attracting much attention from the viewpoint of CO₂ emission reduction and energy structure reformation. A useful and widely investigated chemical utilization of CO₂ is the cycloaddition of CO₂ to epoxides for the synthesis of cyclic carbonates. Efforts have been paid to the design and preparation of various catalyst systems that are active and selective to the production of the desired products under mild conditions and in green processes. This article is to review the current state of the catalyst development and the experimental and theoretical analysis of reaction mechanism for the cyclic carbonate synthesis from epoxides, one of currently important reactions involving CO₂ as a reactant with 100% atom economy. Particular attention is given to the catalysis of multifunctional catalyst systems such as metal- and hydrogen-bond donor (HBD)-based catalysts.     

An in situ Raman study of dimethyl carbonate synthesis from carbon dioxide and methanol over zirconia

In situ Raman spectroscopy has been used to investigate the mechanism of dimethyl carbonate (DMC) synthesis via the reaction of methanol with carbon dioxide over zirconia. Methanol adsorption leads to the appearance of adsorbed methoxide groups, whereas CO₂ adsorption leads to the formation of carbonate species. Monomethyl carbonate species, (CH₃O)COO(Zr)₂, are formed by the reaction of methoxide and monodentate carbonate species and DMC is formed via the further reaction of monomethyl carbonate species with methanol. This sequence is supported by evidence that DMC decomposition on zirconia proceeds via the reverse of the proposed mechanism.     

尿素直接醇解法合成碳酸二甲酯催化剂研究进展

综述了甲醇与尿素醇解法催化合成碳酸二甲酯所用催化剂的研究进展，尿素醇解法合成碳酸二甲酯具有原料价廉易得、工艺简单、操作条件温和、反应过程无水生成和反应产生的氨气可以回收利用等优点，具有工业化前景。     

Synthesis of Polycarbonate Precursors over Titanosilicate Molecular Sieves

A novel catalytic application of titanosilicate molecular sieves (TS-1 and TiMCM-41), in the synthesis of polycarbonate precursors like cyclic carbonates and dimethyl and diphenyl carbonates, avoiding toxic chemicals like phosgene or CO, is reported. Cyclic carbonates were prepared, over TS-1 and TiMCM-41, in high yields, by cycloaddition of CO₂ to epoxides, like epichlorohydrin, propylene oxide and styrene oxide, at low temperatures and pressures. Further, transesterification of the cyclic carbonates with methanol and phenol, over TiMCM-41, yielded other polycarbonate precursors like dimethyl carbonate (DMC) and diphenyl carbonate (DPC). The cyclic carbonates could also be synthesized from the olefins in the same reactor by reacting the olefins, in the presence of TiMCM-41, with a mixture of an epoxidizing agent (like H₂O₂ or tert-butyl hydroperoxide) and CO₂.     

Efficient synthesis of organic carbonates and poly(1,4‐butylene carbonate‐co‐terephthalate)s

Dimethyl carbonate (DMC) is an environmentally benign chemical currently produced using CO₂. Using the conventional Dean–Stark apparatus, a method was developed for the effective and selective removal of the methanol generated in the transesterification of DMC with alcohol. Using this device, various diols (HO‐A‐OH; A = (CH₂)₄, (CH₂)₂O(CH₂)₂, CH₂C₆H₁₀CH₂, and CH₂C₆H₄CH₂) were converted to mixtures of the corresponding MeOC(O)[O‐A‐OC(O)]OMe and MeOC(O)[O‐A‐OC(O)]₂OMe. Dialkyl carbonates such as dibutyl carbonate, dibenzyl carbonate, and diallyl carbonate were also efficiently prepared from the corresponding alcohols using this device. The compound prepared from 1,4‐butanediol, MeOC(O)[O(CH₂)₄OC(O)]_1.5OMe, was subjected to polycondensation with HO(CH₂)₄[O₂CC₆H₄CO₂(CH₂)₄]_1.5OH or HO(CH₂)₄[O₂CC₆H₄CO₂(CH₂)₄]_1.8OH, which directly was prepared from terephthalic acid and 1,4‐butanediol. The polycondensation afforded high‐molecular‐weight poly(1,4‐butylene carbonate‐co‐terephthalate)s (PBCTs) with M_w of 80–270 kDa and 0.40–0.46 terephthalate mole fractions. PBCTs are attractive materials with potential biodegradability and LDPE‐like thermal properties. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44951.     

Electrochemical synthesis of dimethyl carbonate from methanol,CO2 and propylene oxide in an ionic liquid

BACKGROUND: Dimethyl carbonate (DMC) can be used effectively as an environmentally benign substitute for highly toxic phosgene and dimethyl sulfate in carbonylation and methylation, as well as a promising octane booster owing to its high oxygen content. Two‐step transesterification from epoxide, methanol, and CO₂ is widely used in the bulk production of DMC. However, major disadvantages of this process are high energy consumption, and high investment and production costs. A one pot synthesis of DMC from carbon dioxide, methanol, and epoxide was, therefore, developed. But the yields of DMC are below 70% due to the thermodynamic limitation. RESULTS: Electrochemical synthesis of DMC was conducted with platinum electrodes from methanol, CO₂ and propylene oxide in an ionic liquid was conducted. The bmimBr (1‐butyl‐3‐methylimidazolium bromide)‐methanol‐propylene oxide system with CO₂ bubbling allows DMC to be effectively synthesized and a high yield (75.5%) was achieved. CONCLUSION: In this electrolysis, redox reactions of substrates, CO₂, methanol, and propylene oxide, on Pt electrodes were carried out, producing the activated particles, CH₃O^?, CH₃OH⁺, CO₂^? and PO^?, resulting in the effective synthesis of DMC with a 75.5% yield in an ionic liquid (bmimBr). Finally, a mechanism for this synthesis reaction was proposed, which is very different from those reported in the literature. Copyright © 2011 Society of Chemical Industry