Solid base catalysts derived from Ca-M-Al(M = Mg, La, Ce, Y) layered double hydroxides for dimethyl carbonate synthesis by transesterification of methanol with propylene carbonate

Composite solid base catalysts derived from Ca‐M‐Al(M=Mg,La,Ce,Y)layered double hydroxides(LDH)were synthesized,characterized and applied to the transesterification of methanol with propylene carbonate.X‐ray diffraction analyses of the catalysts show that all of the catalysts were in the form of composite oxides.Compared with the Ca‐Al LDH catalyst,the specific surface areas and pore volumes of the catalysts were increased with the introduction of Mg,La or Ce.The catalytic performance of these catalysts increases in the order of Ca‐Y‐Al<Ca‐Al<Ca‐Ce‐Al<Ca‐La‐Al<Ca‐Mg‐Al,which is consistent with the total surface basic amounts of these materials and the formation of especially strong basic sites following modification with Mg and La.The Ca‐Mg‐Al catalyst shows the highest(Ca+Mg):Al atomic ratio,indicating that it likely contains more unsaturated O2?ions,providing it with the highest concentration of very strong basic sites.The recyclability of these catalysts is improved following the addition of Mg,La,Ce or Y,with the Ca‐Mg‐Al maintaining a high level of activity after ten recycling trials.X‐ray diffraction analyses of fresh and used Ca‐Mg‐Al demonstrate that this catalyst is exceptionally stable,which could be of value in practical applications related to heterogeneous catalysis.

Dimethyl carbonate synthesis via transesterification catalyzed by quaternary ammonium salt functionalized chitosan

A quaternary ammonium salt covalently linked to chitosan was first used as a catalyst for dimethyl carbonate （DMC） synthesis by the transesterification of propylene carbonate （PC） with methanol. The effects of various reaction variables like reaction time, temperature and pressure on the catalytic performance were also investigated. 54% DMC yield and 71% PC conversion were obtained under the optimal reaction conditions. Notably, the catalyst was able to be reused with retention of high catalytic activity and selectivity. Consequently, the process presented here has great potential for industrial application due to its advantages such as stability, easy preparation from renewable biopolymer, and simple separation from products.

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,lithiumion 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,the 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],and[TBVPIL][PHO],with different crosslinking 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.

Deactivation mechanism of CaO in a flow type dimethyl carbonate synthesis process

It is well known that calcium oxide (CaO) has better catalytic efficiency than most heterogeneous catalysts in many transesterification reactions. However, the gradual deactivation problem prevents its large-scale application in industry. In this paper, the deactivation mechanism of CaO in a fixed-bed reactor is investigated based on the transesterification reaction of propylene carbonate and methanol. The leaching amount of CaO during the reaction was estimated by the concentration of Ca in the products. The pretreated and recovered catalysts were characterized by FT-IR, XRD, TG-MS and SEM-EDS. It is evident from experiments and characterization that the deactivation process of CaO is accompanied by the leaching of calcium species and the generation of CaCO3, which are also verified by DFT calculations. At high temperature and high weight hourly space velocity, the deactivation was attributed to the formation of dense CaCO3 shell, which prevents the contact between the feedstock and the active species inside.

A New Process for Synthesis of Dimethyl Carbonate from Ethylene Carbonate and Methanol without any Catalyst under Supercritical Conditions

Dimethyl carbonate was synthesized by transesterification reaction between ethylene carbonate and methanol under supercritical conditions without any catalyst. Experimental results showed that the residence time and the molar ratio of methanol to ethylene carbonate all can affect the conversion of ethylene carbonate. When the molar ratio of methanol to ethylene carbonate was 8:1, 81.2 % conversion can be achieved at 9.0 MPa and 250?C after 8 h.

Process design and economic optimization for the indirect synthesis of dimethyl carbonate from urea and methanol

Much attention has been paid for the synthesis of dimethyl carbonate(DMC) by urea indirect alcoholysis method, which had not been actually industrialized by now. The rigorous full process model was then necessary to optimize the process with heat integration. In this paper, a full process was designed and optimized for the DMC synthesis by urea indirect alcoholysis method based on Aspen Plus software.The technological analysis was developed to find how the process was influenced by the three main recycled materials of methanol, 1,2-propylene glycol(PG) and mixture of DMC–methanol. Simultaneously,the thermal optimization was taken into account for energy saving and the optimized process was proposed with heat integration. Moreover, the economic evaluation was implemented for the optimized process with total annualized cost(TAC) and cost of product(COP) according to the plant investment and operations. It was found that the 11.6% decrease in TAC was obtained for the optimized process compared to the original designed process. The COP analysis showed that the process was economically efficient for the production of DMC from urea and methanol.

Optimization and control of a reactive distillation process for the synthesis of dimethyl carbonate

Dimethyl carbonate is an environmentally benign and biodegradable chemical.Based on integration of reactive distillation and pressure-swing distillation technologies,a novel process for synthesis of dimethyl carbonate through transesterification with propylene carbonate and methanol has been developed by Huang et al.In this work,the optimization of this process was performed by minimizing the total TAC.The results show that the optimal design flowsheet can save energy consumption by 18.6% with the propylene carbonate conversion of 99.9%.Then,an effective plant-wide control structure for the process was developed.Dynamic simulation results demonstrate that the temperature/flow rate cascade control plus with simple temperature control can keep not only product purity but also the conversion of the reactant at their desired values in the face of the disturbance in reactant feed flow rate and feed composition.

Excess Molar Volumes and Viscosities of Binary Mixture of Diethyl Carbonate+Ethanol at Different Temperatures

The purpose of this work was to report excess molar volumes and dynamic viscosities of the binary mixture of diethyl carbonate （DEC）+ethanol. Densities and viscosities of the binary mixture of DEC+ethanol at temperatures 293.15 K—343.15 K and atmospheric pressure were determined over the entire composition range. Densities of the binary mixture of DEC+ethanol were measured by using a vibrating U-shaped sample tube densimeter. Viscosities were determined by using Ubbelohde suspended-level viscometer. Densities are accurate to 1.0×10-5 g·cm-3, and viscosities are reproducible within ±0.003 mPa·s. From these data, excess molar volumes and deviations in viscosity were calculated. Positive excess molar volumes and negative deviations in viscosity for DEC+ethanol system are due to the strong specific interactions.All excess molar vo-（lumes） and deviations in viscosity fit to the Redlich-Kister polynomial equation.The fitting parameters were presented,and the average deviations and standard deviations were also calculated.The errors of correlation are very small.It proves that it is valuable for estimating densities and viscosities of the binary mixture by the correlated equation.

A review on transesterification of propylene carbonate and methanol for dimethyl carbonate synthesis

Dimethyl carbonate(DMC)is widely applied in various fields according to its outstanding physico-chemical properties,especially as a solvent in electrolyte of lithium-ion batteries.More than 90%DMC in China is industrially produced from the propylene carbonate(PC)and methanol(MeOH)route because it is an environmentally friendly and highly efficient process.This review summarizes different DMC production technologies,homogeneous and heterogeneous catalysts,catalytic mechanisms,reaction kinetics and engineering,with particular focus on the relationship between catalyst preparation and catalytic performances.The advantages and disadvantages of various catalysts are categorically compared.Homogeneous catalysts are highly efficient but prone to deactivate and are difficult to separate.Heterogeneous catalysts are easy to separate and have the promising future in industrial application,but their low catalytic efficiency is still the critical bottleneck.From process aspect,the catalytic distillation technology would be promising to overcome the efficiency problem of solid catalysts.

Investigation on the deactivation cause of lead-zinc double oxide for the synthesis of diphenyl carbonate by transesterification

The deactivation cause of lead-zinc double oxide for synthesis of diphenyl carbonate （DPC） by transesterification of dimethyl carbonate （DMC） with phenol has been investigated. X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS）, infrared spectroscopy （IR）, thermogravimetry analysis （TG）, atomic absorption spectroscopy and elementary analysis are employed for the catalyst characterization. The results show that, the formation of Pb4O（OC6H5）6 through the reaction of phenol and lead species in the catalyst leads to the crystal phase change of active component and serious leaching of lead, which is the cause of the catalyst deactivation. In addition, the composition of the leached lead is ascertained to be a mixture of Pb4O（OC6H5）6 and PbO with the weight percentage of 62.7% and 37.3%, respectively.

Simultaneous Synthesis of Dimethyl Carbonate and Poly（ethylene terephthalate） Using Alkali Metals as Catalysts

Dimethyl carbonate （DMC） and poly（ethylene terephthalate） was simultaneously synthesized by the transesterification of ethylene carbonate （EC） with dimethyl terephthalate （DMT） in this paper. This reaction is an excellent green chemical process without poisonous substance. Various alkali metals were used as the catalysts. The results showed alkali metals had catalytic activity in a certain extent. The effect of reaction condition was also studied. When the reaction was carded out under the following conditions： the reaction temperature 250℃, molar ratio of EC to DMT 3 ： 1, reaction time 3h, and catalyst amount 0.004 （molar ratio to DMT）, the yield of DMC was 68.9%.

Synthesis of Didodecyl Carbonate via Transesterification Catalyzed by KF/MgO

The catalytic properties of KF/MgO for the synthesis of didodecyl carbonate (DDC) by transesterification from dimethyl carbonate (DMC) and dodecanol were studied.The effects of loading amount of KF and calcining temperature were systemically investigated.The phase structure was characterized by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR).Interaction between KF and the carrier MgO occurred in the process of calcination,and a new phase K2MgF4 formed when calcining temperature was 673 K or above.FTIR results showed that K2CO3 was observed when catalysts calcined in air.When calcining temperature was 873 K and the loading mass amount of KF was 30%,the KF/MgO catalyst exhibited the optimal catalytic properties and the yield of DDC was maximized to 80%.The excellent catalytic properties of KF/MgO was ascribed to the formation of K2MgF4+K2CO3 during the calcination in air.

A catalyst-free novel synthesis of diethyl carbonate from ethyl carbamate in supercritical ethanol

Diethyl carbonate has been synthesized via the alcoholysis of ethyl carbamate in supercritical ethanol under catalyst-free conditions.The influences of various parameters such as reaction temperature,reaction time,reaction pressure,ethanol/ethyl molar ratios and reaction loading volume on the yield of DEC were studied systematically.The experimental results indicated that the alcoholysis of ethyl carbamate was greatly improved in supercritical ethanol.The optimal reaction conditions were as follows：a reaction temperature of 573 K,a reaction time of 30 min,a reaction pressure of 13.2 MPa,an ethanol/ethyl carbamate molar ratio of 10 and a reactor loading volume of 285 μL respectively.The optimal yield of DEC was 22.9%.

Efficient synthesis of dimethyl carbonate via transesterification of ethylene carbonate catalyzed by swelling poly(ionic liquid)s

The synthesis of dimethyl carbonate(DMC)via transesterification of ethylene carbonate(EC)and methanol(MeOH)was an environmental and practical strategy.Herein,poly(ionic liquid)s(PILs)with swelling abilities were synthesized by free radical copolymerization of N-vinylimidazolium ionic liquids,sodium 4-vinylbenzoate and cross-linker(1,8-triethylene glycoldiyl-3,3'-divinylimidazolium bromide([(EG)_(3)-DVIm]Br_(2)).The swelling abilities of PILs in various solvents were measured,and PILs could swell in methanol(MeOH).The swelling ability of PILs in MeOH could be modulated by changing the cross-linker content and chain length of 3-alkyl-substituents on imidazolium.The swollen state of PILs in MeOH presented a porous cross-linked network structure observed by the cryo-scanning electron microscope(cryo-SEM).The swelling PILs were used to catalyze the transesterification of ethylene carbonate(EC)and MeOH to prepare the DMC,and the catalytic activities was correlated with the swelling abilities of PILs.The PIL with 3-butyl-substituent and 2.5 mol%cross-linker(poly[VBIm-VBA-DVIm]-2.5%)had the highest swelling ratio(Q=12.4(g/g))in MeOH and EC mixed solvents and exhibited excellent catalytic activities,which was similar to corresponding homogeneous ionic liquid.Furthermore,the catalyst could be reused up to seven runs without any considerable loss of its initial activity.

MoO_3/SO_4^(2-)-TiO_2 catalyst for transesterification of dimethyl cabonate with phenol

A new MoO3/SO4 2--TiO2 catalyst was prepared by a conventional impregnation of SO4 2-/TiO2 as carrier with an aqueous solution of ammonium molybdate and used for the synthesis of transesterification of dimethyl carbonate(DMC)with phenol.A series of MoO3/SO4 2--TiO2 catalysts with different MoO3 loadings were investigated and characterized using X-ray diffraction(XRD),Fourier transform infrared spectrometer(FTIR),NH3-temperature programmed desorption(NH3-TPD)and X-ray photoelectron spectroscopy(XPS).The results show that MoO3 loading is related to the activity of transesterification reaction.With the increase of MoO3 loading,the activity of transesterification reaction increases.The sulfur species in the catalyst have an influence on the molybdenum species,and lead to an increase in the electropositive of molybdenum,which promotes the catalytic activity of MoO3/SO4 2--TiO2.Among the series of catalysts prepared,MoO3/SO4 2--TiO2 with 10% MoO3 and 823 K calcinated is found to be the most active catalyst for transesterification reaction.Under the reaction conditions of 453 K and 12 h,the conversion of DMC is 30.5 %,and the yields of MPC and DPC reach 21.2 % and 8.7 %,respectively.

Protic ionic liquid-promoted synthesis of dimethyl carbonate from ethylene carbonate and methanol

In this work,the protic ionic liquid[DBUH][Im](1,8-diazabicyclo[5.4.0]-7-undeceniumimidazolide)was developed as an efficient catalyst for the transesterification of ethylene carbonate with methanol to produce dimethyl carbonate.At 70℃,up to 97%conversion of ethylene carbonate and 91%yield of dimethyl ca rbonate were obtained with 1 mol%[DBUH][Im](relative to ethylene carbonate)as catalyst in 2 h.Even at room temperature,the conversion of ethylene carbonate can reach 94%and the yield of dimethyl carbonate can approach 81%for 6 h.Catalytic mechanism investigation showed the high catalytic efficiency of this ionic liquid results from the synergistic activation effect,wherein the cation can activate ethylene carbonate and the anion can activate methanol through hydrogen bond formatio n.Although the reusability of the ionic liquid need to be further improved,high efficiency and comme rcial availability of[DBUH][Im]render it a promising catalyst for the preparation of dimethyl carbonate.

钙铈基催化剂上碳酸丙烯酯和甲醇制备碳酸二甲酯的研究

采用溶胶凝胶法制备了不同比例的钙铈基催化剂,并研究了其对于碳酸丙烯酯和甲醇制备碳酸二甲酯的酯交换反应性能。结果表明,Ca∶Ce=9的催化剂在反应时间2 h,温度40℃,甲醇与碳酸丙烯酯物质的量比为15∶1,催化剂用量为碳酸丙烯酯用量4%的条件下,碳酸丙烯酯转化率达到91.1%,碳酸二甲酯选择性达到91.7%。采用XRD、N2吸附-脱附、FT-IR、XPS和CO_(2)-TPD对催化剂进行了表征。结果表明,催化剂表面的氧空穴越多,中等碱性位数量越多,越有利于甲醇的活化,催化剂的活性越好。

微通道反应器中碳酸乙烯酯、甲醇及乙醇的反应规律研究

在使用微通道反应器的条件下,以甲醇钠作为催化剂,碳酸乙烯酯、甲醇及乙醇为原料进行酯交换反应,对生成的主产物碳酸二甲酯、碳酸二乙酯及碳酸甲乙酯的合成工艺进行研究。最终得出反应规律为:停留时间为2 min时,反应达到平衡状态;随着物料配比的升高,产物含量随之增加;随着催化剂含量升高,产物含量随之增加,但催化剂含量升高至一定值时,DMC含量减少,直至平衡;随着温度的升高,DMC含量随之增加,但温度的上升对DEC、EMC含量影响不大。