A highly efficient La-modified ZnAl-LDO catalyst and its performance in the synthesis of dimethyl carbonate from methyl carbamate and methanol

In this paper,the highly efficient ZnAlLa layered double oxide(ZnAlLa-LDO)catalyst was evaluated and used in methyl carbamate(MC)alcoholysis synthesis of dimethyl carbonate.Under optimal conditions,the MC conversion was 33.5% and the dimethyl carbonate(DMC)selectivity was up to 92,4% at 443 K and in 9 h.The prepared catalysts were well characterized to investigate the effect on the catalytic performance and reaction catalysis mechanism.The experimental results show that the addition of La adjusted the structure and chemical properties of ZnAl composite oxide and that the synergistic effect among Zn,Al and La play a key role in adjusting the acid-base properties and stability of the catalyst,which definitely improved the DMC selectivity and catalytic stability.Based on the proposed reaction mechanism,two kinetic models of the catalytic reaction were established and modified:LangmuirHinshelwood and power-rate law kinetic model.The good agreement between kinetic models and experimental data showed that the power-rate law kinetic model based on the elementary reactions is a suitable model for providing a theoretical basis.The pre-exponential factor and activation energy of the main reaction are 5.77×10^(7)and 77.60 kJ·mol^(-1),respectively.

Efficient separation of phenols from coal tar with aqueous solution of amines by liquid-liquid extraction

In this paper,a method of extracting phenols from coal tar by amines aqueous solution was proposed.The effects of various amines on the extraction properties of phenols in coal tar were researched from the views of molecular structure.The parameters such as molar ratio,concentration,extraction time and temperature for the extraction of coal tar by the monoethanolamine and ethylenediamine aqueous solution were examined.The results show that the organic amine with more amino groups,hydroxyl structure and strong electronegativity exhibited better extraction performance.Under the optimal conditions,the extraction yields of phenols in coal tar by the monoethanolamine or ethylenediamine aqueous solution are above 80%,and the recovery yields of amines reach 99%.Furthermore,the probable geometries of complexes formed by the combination of phenols and organic amines were calculated by density function theory.In addition,several thermodynamic models were evaluated through comparing the relative deviation of simulation results by ASPEN PLUS to the experimental ones,which provide feasibility thermodynamic models for the simulation of extraction process.The present work affords a mild,efficient and green approach for the extraction of phenols from coal tar by an aqueous solution of amines in industry application.

Solvent-free partial oxidation of cyclohexane to KA oil over hydrotalcitederived Cu-MgAlO mixed metal oxides

A highly efficient and stable hydrotalcite-derived Cu-MgAlO catalyst was developed for the partial oxidation of cyclohexane with molecular oxygen.The physical–chemical properties of Cu-MgAlO catalysts were studied,and the results indicated that the copper component had been successfully introduced into the hydrotalcite unit layer structure.The catalytic reaction results showed that copper as the active species could activate CAH bond and effectively promote the decomposition of cyclohexyl hydroperoxide(CHHP)to the mixture of cyclohexanol and cyclohexanone(KA oil).8.3%of cyclohexane conversion and 82.9%of selectivity for KA oil were obtained over 9%Cu-MgAlO catalyst at 150℃with 0.6 MPa of oxygen pressure for 2 h.Especially,its catalytic performance was still stable after five runs.

Ultrasound-assisted co-precipitation synthesis of mesoporous Co_(3)O_(4)–CeO_(2)composite oxides for highly selective catalytic oxidation of cyclohexane

The one-step highly selective oxidation of cyclohexane into cyclohexanone and cyclohexanol as the essential intermediates of nylon-6 and nylon-66 is considerably challenging.Therefore,an efficient and low-cost catalyst must be urgently developed to improve the efficiency of this process.In this study,a Co_(3)O_(4)–CeO2 composite oxide catalyst was successfully prepared through ultrasound-assisted co-precipitation.This catalyst exhibited a higher selectivity to KA-oil,which was benefited from the synergistic effects between Co^(3+))/Co^(2+))and Ce^(4+)/Ce^(3+)redox pairs,than bulk CeO2 and/or Co_(3)O_(4).Under the optimum reaction conditions,89.6%selectivity to KA-oil with a cyclohexane conversion of 5.8%was achieved over Co_(3)O_(4)–CeO2.Its catalytic performance remained unchanged after five runs.Using the synergistic effects between the redox pairs of different transition metals,this study provides a feasible strategy to design high-performance catalysts for the selective oxidation of alkanes.

Metal salts with highly electronegative cations as efficient catalysts for the liquid-phase nitration of benzene by NO2 to nitrobenzene

Metal salts with highly electronegative cations have been used to effectively catalyze the liquid-phase nitration of benzene by NO2 to nitrobenzene under solventfree conditions. Several salts including FeCl3, ZrCl4, AlCl3, CuCl2, NiCl2, ZnCl2, MnCl2, Fe（NO3）3-9H2O, Bi （NO3）3·5H2O, Zr（NO3）4-SH2O, Cu（NO3）2.6H2O, Ni （NO3）2·6H2O, Zn（NO3）2·6H2O, Fe2（SO4）3, and CuSO4 were examined and anhydrous FeCl3 exhibited the best catalytic performance under the optimal reaction conditions. The benzene conversion and selectivity to nitrobenzene were both over 99%. In addition, it was determined that the metal counterion and the presence of water hydrates in the salt affects the catalytic activity. This method is simple and efficient and may have potential industrial application prospects.

Mesoporous silicon sulfonic acid as a highly efficient and stable catalyst for the selective hydroamination of cyclohexene with cyclohexylamine to dicyclohexylamine in the vapor phase

In this work,a new mesoporous silicon sulfonic acid catalyst derived from silicic acid has been successfully prepared by the chemical bonding method.The physicochemical properties of mesoporous silicon sulfonic acid catalysts have been systematically characterized using various techniques.The results demonstrate that sulfonic acid groups have been grafted on silicic acid by forming a new chemical bond(Si-O-S).The mesoporous silicon sulfonic acid exhibits excellent catalytic performance and stability in the vapor phase hydroamination reaction of cyclohexene with cyclohexylamine.Cyclohexene conversion of 61% and 97% selectivity to dicyclohexylamine was maintained after running the reaction for over 350 h at 280℃.The developed mesoporous silicon sulfonic acid catalyst shows advantages of low cost,superior acid site accessibility,and long term reactivity stability.Moreover,a possible catalytic hydroamination reaction mechanism over silicon sulfonic acid was suggested.It has been demonstrated that the sulfonic acid groups of the catalyst play an important role in the hydroamination.The present work provides a simple,efficient,and environmentally friendly method for the hydroamination of cyclohexene to valuable dicyclohexylamine,which also shows important industrial application prospects.

One-step synthesis of c-caprolactam via the liquid phase catalytic nitrosation of cyclohexane in the presence of concentrated sulfuric acid

A simple and efficient approach for the synthesis of e-caprolactam via the liquid phase nitrosation of cyclohexane and nitrosyl sulfuric acid in the presence of concentrated sulfuric acid has been developed. A series of novel A1VPO composites were prepared by an impregnation method and the composites were then employed to catalyze the nitrosation reaction of cyclohexane and nitrosyl sulfuric acid. Compared to the reaction using fuming sulfuric acid, the selectivity for the desired product was significantly improved using this one-step catalytic process. This method affords a shortcut to prepare ecaprolactam and its analogs from cyclohexane.