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.     

In Situ Preparation of Functional Heterogeneous Organotin Catalyst Tethered on SBA-15

A stable heterogeneous organotin catalyst has been prepared by in situ tethering organotin compounds on SBA-15. This was verified by XRD, TEM, N₂ adsorption/desorption at −196 °C, FTIR and diffuse reflectance UV–vis spectral techniques. This material was much more active than the sample prepared by the grafting method for the direct synthesis of dimethyl carbonate (DMC) from methanol and CO₂ despite that its catalytic activity was dependent on the organotin amount. This could be attributed to the formation of organotin clusters with different structures and the larger surface area. After immobilization on the SBA-15 mesoporous material, the six-coordinated organotin clusters showed higher activity, compared to the tetrahedral Sn species. With increasing reaction temperature and CO₂ pressure, the catalytic activity considerably increased.     

Selective copolymerization of carbon dioxide with propylene oxide catalyzed by a nanolamellar double metal cyanide complex catalyst at low polymerization temperatures

Traditional cobalt-zinc double metal cyanide complex [Zn-Co(III)DMCC] catalysts could catalyze the copolymerization of carbon dioxide (CO₂) with propylene oxide (PO) to afford poly (propylene carbonate) (PPC) with high productivity. But the molecular weight (MW) of PPC and the polycarbonate selectivity were not satisfied. In this work, by using a nanolamellar Zn-Co(III) DMCC catalyst, the CO₂-PO copolymerization was successfully performed to yield PPC with high molecular weight (M_n: 36.5 kg/mol) and high molar fraction of CO₂ in the copolymer (FCO₂: 74.2%) at low polymerization temperatures (40∼80 °C). Improved selectivity (FCO₂: 72.6%) and productivity of the catalyst (6050 g polymer/g Zn) could be achieved at 60 °C within 10 h. The influences of water content on CO₂-PO copolymerization were quantitatively investigated for the first time. It was proposed that trace water in the reaction system not only acted as an efficient chain transfer agent, which decreased MW of the resultant copolymer, but also strongly interacted with zinc site of the catalyst, which led to low productivity of PPC and more amounts of cyclic propylene carbonate (cPC). These conclusions were also supported by the apparent kinetics of CO₂-PO copolymerization. ESI-MS results showed that all polymers have two end alkylhydroxyl groups. It was thus proposed that the alkylhydroxyl groups came from the initiation reaction of Zn-OH in the catalyst and the chain transfer reaction by H₂O. The proposed mechanism of chain initiation, propagation and chain transfer reaction were proved by the experimental results.     

Copolymerization of CO2 and cyclohexene oxide using a novel polymeric diimide catalyst

A catalyst for the copolymerization of CO₂ and cyclohexene oxide was prepared by using acetylacetone and 4,4′‐methylenedianiline. The catalyst was characterized as composed of a novel structure of the polymeric diimide Zn complex. The catalyst tended to produce an alternative copolymer with efficiency as high as 128 g polymer/g of catalyst. The obtained copolymers were characterized by IR and NMR. Effects of reaction conditions such as reaction time and temperature, CO₂ pressure, and catalyst concentration on copolymerization were investigated. Best results were obtained from the reaction at 90°C for 24 h, with catalyst concentration of 0.13 g/mL, and CO₂ pressure of 2–3 MPa. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1123–1128, 2003     

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.     

Hydrogen production by sorption-enhanced steam methane reforming process using CaO-Zr/Ni bifunctional sorbent–catalyst

A bifunctional CaO-Zr/Ni (13, 18, and 20.5 wt% NiO) sorbent–catalyst was developed using the wet-mixing/sonication technique and applied for hydrogen production by sorption-enhanced steam methane reforming (SESMR), an intensified process that integrates hydrogen production with CO₂ capture. The material was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and N₂ physisorption (BET). CO₂ sorption efficiency of the developed materials was evaluated during 25 CO₂ sorption/regeneration cycles. The prepared sorbent–catalysts were then applied in the SESMR during 10 reaction cycles. The results showed that the bifunctional sorbent–catalyst with 20.5 wt% NiO loading presented the most suitable activity. The H₂ yield of ∼91% at the end of the 10th SESMR cycle is considerably higher than equilibrium H₂ yield that could be obtained by traditional steam methane reforming.     

Effects of the structure of CeCu catalysts on the catalytic combustion of toluene in air

CeCu composite oxide catalysts were prepared by a hard-template method (CeCu-HT) and a complex method (CeCu-CA). The prepared CeCu composite oxide catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and Brunauer–Emmett–Teller (BET) analyses. The catalytic properties of the prepared CeCu composite oxide catalysts were also investigated by the catalytic combustion of toluene in air. XRD results showed that the synthesized CeCu composite oxide catalysts had different phase components and crystallinities but similar CeO₂CuO solid solution phases. Low-angle XRD, TEM, and BET results indicated that the prepared CeCu-HT catalyst had a developed ordered mesoporous structure and a large specific surface area of 206.1 m² g^?1. Toluene catalytic combustion results indicated that the CeCu-HT catalyst had higher toluene catalytic combustion activity in air than the CeCu-CA catalyst. The minimum reaction temperature at which toluene conversion exceeded 90% for toluene catalytic combustion on the CeCu-HT catalyst was 225 °C. The toluene catalytic combustion conversion on the CeCu-HT catalyst at 240 °C exceeded 99.3% with decreased toluene concentration in air to below 70 ppm. On the other hand, the toluene catalytic combustion conversion on the CeCu-CA catalyst was only 92% even when the reaction temperature reached 280 °C. The differences between the toluene catalytic combustion performances of the CeCu composite oxide catalysts prepared by different methods can be attributed to their discrepant compositions and structures.     

Ce cooperated layered double oxide with enhanced base sites activity for the synthesis of polycarbonate diols

The development of highly efficient alkaline catalysts with abundant base sites is of paramount importance for the synthesis of polycarbonate diols (PCDLs). And the application of heterogeneous catalysts is an effective strategy to address the effect of residual catalysts on the quality of PCDLs. Here, Ce cooperated layered double oxide (LDO-Ce) was used as a catalyst for the preparation of PCDLs via transesterification between dimethyl carbonate (DMC) and 1,4-butanediol (BDO). CO₂ temperature-programmed desorption (CO₂-TPD) profiles demonstrated that the introduction of Ce led to an increase in strong base sites of LDO-Ce, thus endowing LDO-Ce with excellent catalytic performance. Besides, LDO-Ce possessed satisfactory specific surface area and pore size. A possible catalytic mechanism was proposed to illustrate the transesterification process. The effects of the reaction conditions on the hydroxyl value, yield, and BDO conversion were further investigated in detail. The yield of PCDLs with a hydroxyl value of 112.2 mg KOH/g (corresponding to a number average molecular weight [M_n] of 1000 g/mol) was 92.44% under its optimum reaction conditions (w (catalyst) = 0.5%, n(DMC)/n(BDO) = 1.25, T-_{transesterification} = 130°C, t-_{transesterification} = 5 h, T-_{polycondensation} = 170°C, t-_{polycondensation} = 4 h, P-_{polycondensation} = 10 kPa). Moreover, LDO-Ce was easily removed after the transesterification process (Step 1), ensuring the quality of PCDLs, and it was recycled three times without significant loss of catalytic activity.     

A novel supported salenCrIIICl catalyst for alternating copolymerization of cyclohexene oxide with carbon dioxide

A novel heterogeneous catalyst was prepared by immobilizing salenCr^IIICl on a modified poly (aniline-co-o-aminophenol) (MPOAP). The FT-IR, TEM, XRD, XPS and ICP results indicated that salenCr^IIICl was successfully supported on MPOAP. The resulted catalyst (MPOAP-salenCr^IIICl) exhibited excellent catalytic performance for alternating copolymerization of cyclohexene oxide (CHO) with carbon dioxide (CO₂). Moreover, the supported catalyst had an obvious effect on the microstructures of the copolymerization and the obtained polymer was found to be a linear alternating copolymer with narrower molecular weight distribution. The TG and DTG results indicated that the product prepared by the supported catalyst possessed higher decomposition temperature.     

Selective synthesis of oligo(carbonate-ether) diols from copolymerization of CO<Subscript>2</Subscript> and propylene oxide under zinc-cobalt double metal cyanide complex

Colorless oligo(carbonate-ether) diols were selectively synthesized in high efficiency from copolymerization of CO₂ and propylene oxide (PO) using Zn₃[Co(CN)₆]₂-based double metal cyanide complex (DMC) as catalyst and different molecular weight polypropylene glycols (PPGs) as chain transfer agent. The catalytic activity was related to carbonate unit content and molecular weight of target oligo(carbonate-ether) diols, for oligo(carbonate-ether) diol with number average molecular weight of 6.4 kg/mol and carbonate unit content of 34.3 %, it reached 10.0 kg oligomer/g DMC catalyst during 10 h of copolymerization. Generally, the number average molecular weight of the oligo(carbonate-ether) diol was tunable between 1.8 kg/mol and 6.4 kg/mol, and the molecular weight distribution was controllable between 1.14 and 1.83. Moreover, the carbonate unit content in the oligo-diols can be adjusted between 15.3 % and 62.5 %, lower temperature and higher CO₂ pressure were favorable for higher carbonate content. Better selectivity of oligo(carbonate-ether)diol over propylene carbonate(PC) was realized, where the weight ratio of PC (W_PC) was controlled less than 8.0 wt%. We also found that the alkali metal ion residue may play an important role in PC formation, in some cases this effect may be more significant than backbiting process, removing the residual alkali metal ion should be meaningful in the future to further reduce the PC formation.     

Supported imidazole as heterogeneous catalyst for the synthesis of cyclic carbonates from epoxides and CO2

Imidazole anchored onto a silica matrix, by means of a propyl linkage, is found to be an effective heterogeneous catalyst for the synthesis of cyclic carbonates from epoxides and CO₂ in near quantitative yield. The versatility of this catalyst is demonstrated by using different substrates (epichlorohydrin, propylene oxide, butylene oxide and styrene oxide) for this cycloaddition reaction. These CO₂ insertion reactions were typically carried out in the temperature range of 343 to 403 K at 0.6 MPa CO₂ pressure under solvent-free conditions. Several spectroscopic methods were used to characterize the catalyst and study the integrity of the fresh and spent catalysts.     

Heterogeneous transesterification processes by using CaO supported on zinc oxide as basic catalysts

Zinc oxide, obtained by thermal decomposition of zinc oxalate, has been impregnated with different amounts of calcium oxide, and used as solid catalyst for transesterification processes. Catalysts have been characterized by chemical analysis, XRD, XPS, FT-IR, SEM, N₂ adsorption–desorption at 77 K and CO₂-TPD. The catalytic behaviour has been evaluated by choosing two transesterification processes: a simple model such as the reaction between ethyl butyrate and methanol and the production of biodiesel from sunflower oil and methanol. Calcium oxide is stabilized by filling the mesoporous network of ZnO, as reveal the corresponding pore size distributions, thus avoiding the lixiviation of the active phase in the reaction medium. These supported CaO catalysts, thermally activated at 1073 K, can give rise to FAME (fatty acid methyl esters) yield higher than 90%, after 2 h of reaction, when a methanol:oil molar ratio of 12 and 1.3 wt% of the catalyst with a 16 wt% CaO were employed.     

Nanosized silica‐supported metallocene/MAO catalyst for propylene polymerization

A nanosized silica particle was used as the support to prepare an Et[Ind]₂ZrCl₂/MAO catalyst for propylene polymerization of polypropylene. The catalyst and the polymer produced were characterized with nitrogen adsorption, ICP, DSC, SEM, TEM, XRD, solution viscometer, ¹³C NMR and optical microscopy. The effects of polymerization temperature and [Al]/[Zr] ratio on catalyst activity and polymer melting point were investigated. Under identical reaction conditions, nanosized catalyst exhibited better polymerization activity than the microsized catalyst (e.g., the former had 64% higher activity than the latter at the optimum polymerization temperature (50°C) and [Al]/[Zr] = 570). DSC results indicated that polymer melting point increased with the increase of [Al]/[Zr] ratio and with the decrease of polymerization temperature. XRD results showed that the percentage of γ crystals increased with decreasing [Al]/[Zr] ratio. Electron microscopic results showed that the polymer particle size increased with increasing polymerization temperature. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2573–2580, 2006     

Effects of morphology and composition on catalytic performance of double metal cyanide complex catalyst

Double metal cyanide (DMC) complexes based on Zn₃[Co(CN)₆]₂ were prepared using different zinc salts and complexing agents and They were characterized by elemental analysis, IR and XRD. The catalytic properties of DMC complexes were determined in polymerization of propylene oxide. Great differences in morphology of DMC complexes was were correlated with preparation route as well as with the kind of zinc salts employed. The catalytic activity was strongly dependent on the morphology of DMC complexes and composition of catalysts. The study revealed that the amorphous catalyst made from ZnCl₂ and t-BuOH had the highest activity (up to 26 kg polymer/g catalyst). The DMC catalyst was non-stoichiometric. Polymerization of propylene oxide (PO) catalyzed by DMC proceeded in a controlled manner. The molecular weight of each polymer was controlled by the monomer/initiator ratio, the values of molecular weight distribution (MWD) were in the range of 1.23–1.48. The polymer has an atactic structure and a head-to-tail regiosequance.     

Synthesis,Characterization and Application of Co–MgO Mixed Oxides in Oxidation of Carbon Monoxide

The present work deals with the synthesis of nanostructured Co–MgO mixed oxides with different weight ratios of cobalt by a facile co-precipitation method as a catalyst for low-temperature CO oxidation. The prepared samples were characterized by X-ray diffraction (XRD), N₂ adsorption/desorption (BET), Fourier transform infrared spectroscopy (FTIR), and transmission and scanning electron microscopies (TEM and SEM) techniques. The results revealed that inexpensive cobalt–magnesium mixed metal oxide nanoparticles have a high potential as catalyst in low-temperature CO oxidation. The Co–MgO mixed oxide with 30 wt.% cobalt had the highest activity. The results showed that the catalysts pretreated under O₂-containing atmosphere possessed higher activity compared to the catalyst pretreated under H₂ atmosphere. Co–MgO catalyst showed a good repeatability in reaction condition. The stability test exhibited that the Co–MgO mixed oxides were highly stable for CO oxidation over a 30 h time on stream in the feed gas containing a high amount of moisture and CO₂.     

Preparation and characterization of nanosized copper (II) oxide embedded in hyper-cross-linked polystyrene: Highly efficient catalyst for aqueous-phase oxidation of aldehydes to carboxylic acids

Preparation and catalytic properties of nanosized copper (II) oxide embedded in hypercrosslinked polystyrene (HPS) were investigated in this article. The CuO@HPS nanocomposite was characterized by inductively coupled plasma optical emission spectrometry (ICP-OES), Fourier transform infrared spectroscopy (FT-IR), N₂-sorption analysis, X-ray powder diffraction (XRD), energy dispersive X-ray spectroscopy analysis (EDS), and transmission electron microscopy (TEM). The TEM analysis showed that the mean diameter of the resulted particles is ~ 4 nm.The nanocomposite was found to be efficient and durable catalyst in the oxidation of aldehydes to the corresponding carboxylic acids in water. The catalyst can be recycled and reused in 4 reaction runs.     

Tuning of activity, induction period and polymer properties of double metal cyanide catalyzed ring-opening polymerizations of propylene oxide by using quaternary ammonium salts

Polymerizations of propylene oxide (PO) have been carried out by using double metal cyanide (DMC) catalyst prepared by reacting ZnCl₂ and K₃[Co(CN)₆] in the presence of tert-butyl alcohol (^tBuOH) as a complexing agent. The catalytic activity and the induction period for PO polymerizations catalyzed by DMC are tunable by using various quaternary ammonium salts (QAS) as external additives. The DMC/QAS binary catalyst improves polymer properties as well such as molecular weight, molecular weight distribution, viscosity, and unsaturation level.     

Influence of CeO2 morphology on the catalytic oxidation of ethanol in air

Nano-CeO₂ catalysts of different shapes were synthesized at different hydrothermal crystallization temperatures from an alkaline aqueous solution. X-ray diffraction (XRD), transmission electron microscope (TEM), and H₂ temperature-programmed reduction (H₂-TPR) were used to study the synthesized nano-CeO₂ catalyst samples. The catalytic properties of the prepared nano-CeO₂ catalysts for the catalytic oxidation of ethanol in air were also investigated. TEM analysis showed that CeO₂ nanorod and nanocube catalysts have been synthesized at hydrothermal crystallization temperatures of 373 K and 453 K, respectively. XRD results showed that the synthesized nano-CeO₂ catalysts have similar cubic fluorite structures. H₂-TPR results indicated that CeO₂ nanorod and nanocube catalysts exhibit different reduction behaviors for H₂ and that the nanorod catalyst has better low-temperature reduction performance than the nanocube catalyst. Ethanol catalytic oxidation results indicated that oxidation and condensation products (including acetaldehyde, acetic acid, CO₂, and ethyl acetate) have been produced from the prepared catalysts. The ethyl acetate and acetic acid can be ignited by ethanol at low temperature on the CeO₂(R) catalyst to give low catalytic combustion temperature for ethyl acetate and acetic acid molecules. CeO₂ nanorods gave ethanol oxidation conversion rates above 99.2% at 443 K and CO₂ selectivity exceeding 99.6% at 483 K, while CeO₂ nanocubes gave ethanol oxidation conversion rates of about 95.1% until 508 K and CO₂ selectivity of only 93.86% at 543 K. CeO₂ nanorod is a potential low-cost and effective catalyst for removing trace amounts of ethanol to purify air.     

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     

Ring‐opening copolymerization of maleic anhydride with propylene oxide by double‐metal cyanide

Ring‐opening copolymerization of maleic anhydride (MA) with propylene oxide (PO) was successfully carried out by using double‐metal cyanide (DMC) based on Zn₃[Co(CN)₆]₂. The characteristics of the copolymerization are presented and discussed in this article. The structure of the copolymer was characterized with IR and ¹H‐NMR. Number‐average molecular weight (M_n) and molecular weight distribution (MWD) of the copolymer were measured by GPC. The results showed that DMC was a highly active catalyst for copolymerization of MA and PO, giving high yield at a low catalyst level of 80 mg/kg. The catalytic efficiency reached 10 kg polymer/g catalyst. Almost alternating copolymer was obtained when monomer charge molar ratio reached MA/PO ≥ 1. The copolymerization can be also carried out in many organic solvents; it was more favorable to be carried in polar solvents such as THF and acetone than in low‐polarity solvents such as diethyl ether and cyclohexane. The proper reaction temperature carried in the solvents was between 90 and 100 °C. The M_n was in the range of 2000–3000, and it was linear with the molar ratio of conversion monomer and DMC catalyst. The reactivity ratio of MA and PO in this reaction system was given by the extended Kelen–Tudos equation: η=[r₁+(r₂/α)]ξ?(r₂/α) at some high monomer conversion. The value of reactivity ratio r₁(MA) = 0 for MA cannot be polymerized itself by DMC catalyst, and r₂(PO) = 0.286. The kinetics of the copolymerization was studied. The results indicated that the copolymerization rate is first order with respect to monomer concentration. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1788–1792, 2004