Synthesis and characterization of Ce–La oxides for the formation of dimethyl carbonate by transesterification of propylene carbonate

A series of cerium–lanthanum catalysts prepared using the co-precipitation method were investigated for transesterification of propylene carbonate (PC) with methanol to produce dimethyl carbonate (DMC). Synthesized catalysts were characterized by XRD, CO₂- and NH₃-TPD, N₂ adsorption/desorption and SEM–EDX techniques. Studies were carried out to study the effect of reaction conditions such as methanol/PC molar ratio (4–12), catalyst dose (2–10 wt.% of PC), reaction time (2–10 h) and temperature (140–180 °C) on the DMC yield. Highest PC conversion and DMC yield of 72% and 74%, respectively, were observed with catalysts having a 1:4 Ce/La molar ratio.     

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.     

Synthesis of Dimethyl Carbonate from Methyl Carbamate and Methanol Using a Fixed‐Bed Reactor

Several mixed oxide catalysts were prepared by coprecipitation for dimethyl carbonate (DMC) synthesis from methyl carbamate and methanol. During the batch process, the DMC yield was below 35 %. In order to minimize the unfavorable thermodynamic equilibrium and side reactions for the DMC synthesis, a fixed‐bed reactor was designed. A maximum DMC yield of ～ 73 % could be realized over a ZnO‐Al₂O₃ catalyst. The effects of reaction conditions for this type of reactor were investigated in detail.     

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.     

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     

Studies of precipitated polymerization of acrylamide with quaternary ammonium cationic comonomer in potassium citrate solution

Copolymer particles consisting of acrylamide (AM) and cationic comonomer 2‐methyl acryloyloxyethyl trimethyl ammonium chloride (DMC) were prepared by precipitation polymerization in an solution of potassium citrate using ammonium persulfate ((NH₄)₂S₂O₈) and sodium sulfite (Na₂SO₃) as an initiator. The product poly(acrylamide‐2‐methyl acryloyloxyethyl trimethyl ammonium chloride) [Poly(DMC‐AM)] is a water‐soluble cationic polyelectrolyte. The solubility of DMC, AM and Poly(DMC‐AM) in potassium citrate solution were measured, combined with the theory of solubility parameter, and the experiment results indicate that the solubility of DMC and AM is much higher than that of Poly(DMC‐AM), and also the mechanism of copolymer precipitated in salt solution was discussed. The factors influencing the conversion of comonomers were examined, such as salt mass fraction, polymerization temperature, monomers mass fraction, initiator mass fraction, and so on. The results of experiments indicate that the best conditions are salt mass fraction = 57%, monomers mass fraction = 3%, m(DMC) : m(AM) = 3 : 1, initiator mass fraction = 0.08%, polymerization temperature = 50°C, reaction time = 2 h, and the conversion is 86.4%. And the qualitative analysis experimental method for copolymer by infrared absorption spectrum show that [Poly(DMC‐AM)] was successfully synthesized by precipitation polymerization. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Highly selective synthesis of dimethyl carbonate from urea and methanol catalyzed by ionic liquids

Direct synthesis of dimethyl carbonate from methanol and urea using ionic liquids, such as Et₃NHCl–FeCl₃, Et₃NHCl–ZnCl₂, Et₃NHCl–CuCl₂, Et₃NHCl–SnCl₂ and emimBr–ZnCl₂, as catalysts were investigated. Among the ionic liquids, Et₃NHCl–ZnCl₂ or emimBr–ZnCl₂ exhibited higher activity for the synthetic reaction and surprisingly high selectivity to DMC. The effects of the various reaction conditions, i.e. reaction temperature, molar ratio of methanol to urea, and amount and composition of catalysts, on the synthesis of DMC were discussed in a systematic way. The reaction mechanism and the reasons why raised activity and high selectivity of the catalyst are maintained were explored.     

Lanthanum dopant induced transition from the ferroelectric to the relaxor state in 0.7PFW-0.3PT ceramics

In this paper, Pb_1-xLa_x(Fe_2/3W_1/3)_0.7Ti_0.3O₃ ceramics are synthesized by the conventional reaction method and the dielectric properties are investigated with the empirical law and ordering models. The lattice structure changes from tetragonal to pseudocubic after doping with lanthanum and the pyrochlore phase is induced as the amount of lanthanum dopants exceeds 5%. The effects of lanthanum dopants on the resistivity, the diffused phase transition, the space charge polarization and the dielectric loss are investigated. According to the ordering models, the long range order (LRO) ferroelectric is changed to the short range order (SRO) relaxor with the use of lanthanum dopants. It is suggested that growth of the 1:1 ordered domain is impeded by increasing the amounts of lanthanum dopants since the excess positive charge of the 1:1 ordered domain Pb_1-xLa_x(Fe_1/2W_1/2)O₃ is enhanced. Furthermore, the p-type carriers are neutralized by the electron compensation which is induced by the fewer lanthanum dopants.     

Copolymerization of epoxides and carbon dioxide by using double metal cyanide complex (DMC) with high crystallinity

Zn₃ [Co(CN)₆]₂ based double metal cyanide complex(Co-Zn DMC) is synthesized and characterized by element analysis, FT-IR, TG-FTIR, XRD and TEM. The composition of Co-Zn DMC summarized by elemental analysis has been confirmed by TG-FTIR. The catalyst has high crystallinity according to strong crystalline peaks shown in XRD and diffraction spot observed by TEM. Copolymerization of epoxides and carbon dioxide are successfully catalyzed by Co-Zn DMC. The efficiency of catalysts is as high as 7488 g polymer/g catalyst for CO₂/propylene oxide (PO), 1100 g polymer/g catalyst for CO₂/ethylene oxide (EO), which are higher than that reported ever before. The effects of various reaction conditions such as amount of the catalyst, reaction time and temperature on the copolymerization are investigated. The results show that insertion of CO₂ into chains is significantly affected by the catalyst quantity and ambient temperature. The weight percentage of byproduct cyclic carbonate can be easily controlled to be less than 5% while the molar fraction of CO₂ in backbone (f_co2) is more than 30%.     

Effect of lanthanum content on the conduction behaviors and relaxation processes of lead lanthanum zirconate titanate antiferroelectric ceramics

(Pb_1-xLa_x) (Zr_0.92Ti_0.08)_1-x/4O₃ (PLZT x/92/8, x = 3, 5 and 7 at%) ceramics with compositions near the antiferroelectric (AFE)-ferroelectric (FE) phase boundary were fabricated by a solid-state reaction method. The effect of lanthanum content on the conduction behaviors and relaxation processes has been investigated. It was verified that the main phase with orthorhombic structure was formed in all compositions. The increase of lanthanum substitution resulted in an enhancement of diffuse phase transition. Impedance analysis suggested that the ac conductivity decreased with increasing lanthanum content. Moreover, thermally stimulated depolarization current study was utilized to establish the correlation between defect structures and relaxation processes. It showed three peaks with distinct characteristics, which originated from dipole orientation, oxygen vacancy migration and phase transition respectively. The oxygen vacancy-related defects induced by lanthanum doping were mainly responsible for the variation of conduction behaviors and relaxation processes.     

Facile preparation and characterization of lanthanum oxide powders by the calcination of lanthanum carbonate hydrate in microwave field

Micron-sized lanthanum oxide powders are prepared by the calcination of lanthanum carbonate hydrate in microwave field. The decomposition process of lanthanum carbonate hydrate was analyzed by TG-DSC and indicates the reaction undergoes three stages, resulting in the generation of lanthanum oxide at 770 °C. For microwave assisted calcination, XRD patterns demonstrate that hexagonal La₂O₃ structure is initially formed after calcination at 650 °C for 2 h, and FT-IR analyses confirm the decomposition of precursor is complete after calcination at 750 °C for 2 h. SEM investigations reveal that 800 °C is the optimal calcination temperature to generate La₂O₃ powders with uniform morphologies. In comparison, conventionally calcination experiments are carried out in electrical furnace. Both XRD and FT-IR analyses are in consistence with TG-DSC, which indicate the temperature required for fully decomposition of lanthanum carbonate hydrate by conventional heating is higher than that of microwave heating. SEM images present irregular morphologies and wide particle size distribution of conventionally prepared samples. All the techniques are utilized to prove the feasibility of decomposing La₂(CO₃)₃ to generate La₂O₃ in microwave field and highlight the advantages of microwave heating.     

Chemical interactions between 3 mol% yttria-zirconia and Sr-doped lanthanum manganite

The chemical interactions between porous (La_0.8Sr_0.2)MnO₃ (LSM) film and 3 mol% yttria tetragonal zirconia (TZ3Y) substrate have been investigated over the temperature range of 1300–1500 °C in air. Two distinct reaction layers of fluorite-type cubic zirconia solid solution c-(Zr,Mn,La,Y)O₂ and lanthanum zirconate pyrochlore (La,Sr)₂(Zr,Y)₂O₇ were observed at the interface of LSM/TZ3Y. It has been found that the diffusion/dissolution of Mn ions in TZ3Y leads to the formation of the fluorite-type cubic zirconia solid solution, while the interaction of lanthanum with TZ3Y results in the formation of the lanthanum zirconate pyrochlore phase. Phase studies in the (ZrY)O₂–La₂O₃–Mn₃O₄ system show that the fluorite-type cubic zirconia solid solution phase c-(Zr,Mn,La,Y)O₂, rather than the tetragonal 3 mol% Y₂O₃–ZrO₂ phase, is in equilibrium with LSM perovskite at high temperatures. A ternary phase diagram of the system at the (ZrY)O₂-rich end at 1400 °C in air was proposed based on the experimental results. It is suggested that the fundamental reason for the beneficial effect of A-site non-stoichiometry or Mn excess of LSM in the inhibiting of the lanthanum zirconate formation is due to the fact that Mn₃O₄ does not equilibrate with lanthanum zirconate at high temperatures.     

Precipitation polymerization of acrylamide with quaternary ammonium cationic monomer in potassium carbonate solution initiated by plasma

Precipitation polymerization of 2‐(methacryloyloxyethyl) trimethyl ammonium chloride (DMC)‐co‐acrylamide (AM) [poly(AM‐DMC)] has been successfully performed in potassium carbonate (K₂CO₃)‐water media by plasma initiation. K₂CO₃ solution was selected because not only the higher solubility of AM and DMC comparing with that of poly(AM‐DMC), but the higher intrinsic viscosity of poly(AM‐DMC) could be obtained. A set of experiments was performed using different K₂CO₃ concentration (from 50 down to 10% (w/w)), thus the precipitation architecture was not obtained below 20% (w/w). And particles size, particles size distribution (7–120 μm), and intrinsic viscosity of poly(AM‐DMC) (ranging up to 455 cm³/g) were also summarized in this article. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 4060–4067, 2007     

Promotion of organotin modified SBA-15 in the selective carboxylation of BPA with DMC

Two-methylcarbonate-ended-BPA (DmC(1)) was selectively synthesized from dimethyl carbonate (DMC) and bisphenol A (BPA) over organotin modified SBA-15. Organotin modified samples were characterized by XRD, FT-IR, BET and TG, and the relations between catalytic performance and catalyst properties were discussed. When heterogeneous SBA-15(CH₂)₃SnOC₄H₉ was used as catalyst, DmC(1) achieved better yield and higher selectivity than that obtained over homogeneous (C₄H₉)₂SnO. The confined region effect of SBA-15(CH₂)₃SnOC₄H₉ was the main reason to promote the reaction between one-methylcarbonate-ended-BPA (MmC(1)) and DMC.     

A new process for the synthesis of diphenyl carbonate from dimethyl carbonate and phenol over heterogeneous catalysts

The two-step synthesis of diphenyl carbonate (DPC) from dimethyl carbonate (DMC) and phenol has been compared in liquid phase and gas phase, both over heterogeneous catalysts. In the first step, equilibrium yields of methyl phenyl carbonate (MPC) in the transesterification of DMC and phenol were very low at low temperatures in the liquid phase although reaction rates were fast. This endothermic reaction was more favorable at high temperatures in the gas-phase reaction. Titanium oxide catalysts supported on SiO₂ or activated carbon were found to be effective in a continuous gas flow reactor. In case of the second step, the disproportionation of MPC, selective formation of DPC was not feasible in the gas-phase reaction due to extensive side reactions. However, there was no by-product in the liquid-phase reaction over the TiO₂/SiO₂ catalyst. Therefore, our proposed two-step synthesis process consists of the gas-phase transesterification of DMC and phenol followed by the liquid-phase disproportionation of MPC to DPC, both over the TiO₂/SiO₂ catalyst. This revised version was published online in July 2006 with corrections to the Cover Date.     

Highly efficient synthesis of dimethyl carbonate from methanol and carbon dioxide using IL/DBU/SmOCl as a novel ternary catalytic system

Excellent yield of dimethyl carbonate (DMC) was obtained by direct physical or chemical adsorption of carbon dioxide on [EmimOH][NTf₂] ionic liquid (IL) in the presence of samarium oxychloride (SmOCl) and 1,8-diazabicyclo[2.2.2]undec-7-ene (DBU) as a super base. The novel ternary catalyst system consisting of [EmimOH][NTf₂], DBU, and SmOCl was found to appreciably convert methanol (13.01%) to DMC with excellent selectivity (99.13%). The adsorption of CO₂ on IL in the presence of DBU was analyzed by ¹³C experiment. Moreover, catalytic reactivity of SmOCl and OH-functional group was proved by a predictable mechanism. Various parameters such as reaction temperature, pressure, reaction time, and reusability of catalyst were investigated to maximize DMC yield.     

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.     

Kinetics studies of dimethyl carbonate synthesis from urea and methanol over ZnO catalyst

A kinetic experiment of dimethyl carbonate (DMC) synthesis by urea methanol over ZnO catalyst was carried out in an isothermal fixed-bed reactor. A kinetic model based on the mole fraction was proposed and the kinetic parameters were estimated from the experimental results. The model predictions were compared with the experimental data and fair agreements were found. The effects of the reaction temperature (443–473 K), space time (0–4.7 h mol⁻¹ kg _cat ) and urea mass percent (5–9%) in feed on DMC mole fraction were investigated. It was found that the reactions are mainly influenced by the reaction temperature and space time rather than urea mass percent in feed. The experimental and simulated results indicated that the reaction from MC to DMC was the rate-controlling step in the DMC synthesis process from urea and methanol. It is important to remove the DMC and byproduct ammonia to achieve a high selectivity of DMC. This implies that reactive distillation might be used in the DMC synthesis on an industrial scale to achieve a higher selectivity of DMC.     

氧化锌催化丁二酸二甲酯和碳酸乙烯酯的耦合反应

研究了ZnO催化碳酸乙烯酯和丁二酸二甲酯耦合反应合成聚丁二酸乙二醇酯预聚体和碳酸二甲酯的新工艺。考察了ZnO催化剂焙烧温度对耦合反应的催化活性,优化了反应条件。并对ZnO催化剂进行XRD、BET和NH₃-TPD表征。以FTIR和¹H NMR表征聚丁二酸乙二醇酯预聚体。结果表明,在225~235℃,EC/DMSu摩尔比为2,催化剂/(EC+DMSu)摩尔比为0.005,反应时间为3 h的反应条件下,碳酸二甲酯收率为59.7%,聚丁二酸乙二醇酯预聚物的特性黏度为0.3857 dl·g^-1。通过XRD和NH₃-TPD分析,推测ZnO表面的晶体缺陷和弱酸性是影响耦合反应催化活性的原因。     

Catalytic synthesis of 1,6‐dicarbamate hexane over MgO/ZrO2

MgO/ZrO₂ catalyst was prepared for the synthesis of 1,6‐dicarbamate hexane (HDC) using dimethyl carbonate (DMC) and 1,6‐diamine hexane (HDA) as raw materials. When the catalyst is calcined at 600 °C and MgO load is 6 wt%, the catalyst exhibits better activity. When the concentration of catalyst is 2 g (100 mL)^?1 DMC, n(HDA):n(DMC) = 1:10, reaction time is 6 h under reflux temperature, and the yield of 1,6‐dicarbamate hexane is 53.1%. HDC yield decreases from 53.1% to 35.3% after MgO/ZrO₂ being used for three times. The decrease in specific surface area may be attributed to deactivation of MgO/ZrO₂. Copyright © 2007 Society of Chemical Industry