Chemical equilibrium controlled synthesis of polyoxymethylene dimethyl ethers over sulfated titania

The chemical equilibrium and reaction kinetic behavior in the synthesis of polyoxymethylene dimethyl ethers （DMMn） were investigated over sulfated titania in order to reveal the decisive factor controlling the reaction. The results showed that the molar ratio of adjacent DMMn products in equilibrium solution had the same value, which depended absolutely on the reaction temperature. Meanwhile, the reactions had the same DMMn products distributions under varied reaction conditions. The equilibrium constants of the related step-wise reactions for DMMn formation were equal, which were calculated based on the bulk compositions of the reaction solution. And thus, the selectivity to DMMn was mainly controlled by the chemical equilibrium, i.e., thermodynamic control. In brief, the present results provide some guidance for future synthesis of DMMn.

Characterization and performance of Cu/ZnO/Al_2O_3 catalysts prepared via decomposition of M(Cu,Zn)-ammonia complexes under sub-atmospheric pressure for methanol synthesis from H_2 and CO_2

Methanol synthesis from hydrogenation of CO2 is investigated over Cu/ZnO/Al2O3 catalysts prepared by decomposition of M（Cu,Zn）-ammonia complexes （DMAC） at various temperatures.The catalysts were characterized in detail,including X-ray diffraction,N2 adsorption-desorption,N2O chemisorption,temperature-programmed reduction and evolved gas analyses.The influences of DMAC temperature,reaction temperature and specific Cu surface area on catalytic performance are investigated.It is considered that the aurichalcite phase in the precursor plays a key role in improving the physiochemical properties and activities of the final catalysts.The catalyst from rich-aurichalcite precursor exhibits large specific Cu surface area and high space time yield of methanol （212 g/（Lcat·h）;T=513 K,p=3MPa,SV=12000 h-1）.

Isobutane dehydrogenation over chromia alumina catalysts prepared from MIL-101: Insight into chromium species on activity and selectivity

Various mesoporous chromia alumina catalysts were prepared by five different methods based on a metal-organic framework MIL-101 and their catalytic performances over isobutane dehydrogenation were investigated. The highly dispersed chromium species were produced on catalyst KCrAI-I1 with largest specific surface area of 198 m2-g-1 prepared with aluminium isopropoxide （Al（i-OC3HT）3） by ultrasonic im- pregnation method. However, the catalyst KCrAI-I2 synthesized by stirring impregnation possessed crystalline a-Cr203 phase, which was poorly dispersed. Two types of Cr-rich and Al-rich CrzA12_zO3 solid solutions, designated as CrAI-I and CrAI-II phase, were formed over the catalysts KCrAI-I3 （prepared by Al（i-OC3HT）3 with nitric acid regulation）, KCrA1-C4 （prepared by aluminium chloride hexahydrate） and KCrA1-N5 （prepared by aluminium nitrate nonahydrate）. Catalytic evaluation results revealed that KCrAI-I1 exhibited the high isobutane con- version due to its highly dispersed chromium species. However, KCrAI-I3, KCrA1-C4 and KCrA1-N5 showed the higher isobutene selectivity （95.2%-96.4%） on account of the formation of chromia alumina solid solutions in the catalysts. Moreover, the solid solution over the chromia alumina catalysts could greatly suppress the coke formation.

Catalytic behavior of Mo-Bi-Fe-Co-K-M-O(M=Ce,Gd,CeGd)catalysts for selective oxidation of isobutene

The further improvement of methacrolein(MAL)selectivity from isobutene(IB)oxidation is crucial and challenging.In this study,based on the typical Mo-Bi-Fe-Co-K-O mixed metal oxide,the rare earth element Gd-doped,Ce-doped and CeGd co-doped catalysts were prepared by co-precipitation strategy to increase the selectivity of MAL from 47.9%to 49.8%,64.2% and 68.6%,respectively.In order to elucidate in-depth the promoting effect of Ce and/or Gd,various characterizations were utilized including X-ray diffraction patterns(XRD),Raman,X-ray fluorescence spectrometry(XRF),X-ray photoelectron spectroscopy(XPS),O_(2)-temperature programmed desorption(O_(2)-TPD),H2-temperature programmed reduction(H2-TPR),CO_(2)-temperature programmed desorption(CO_(2)-TPD),IB-temperature programmed desorption(i-C4-TPD)and in-situ IB-Fourier transform infrared spectroscopy(IB-FTIR).Both Ce and Gd finely regulate the bulk and surface structure of the catalyst,thus altering the redox ability,oxygen mobility and storage ability and basicity.Compared with Ce,Gd addition slightly regulates the variation of Co^(2+)/Co^(3+)redox couples,greatly enhances the interaction among the components on the catalyst,thus only increases the content of surface oxygen species and has little effect on their mobility.While Cecontaining catalyst performs stronger oxygen storage and migration ability,thus leading to the overproduction of surface Odefectspecies,which are proposed to be the active sites for the production of MAL and COx.The CeGd co-doped catalyst possesses the proper content of surface Odefectspecies,thus exhibits much higher MAL selectivity.Moreover,the promoting mechanism of Ce and/or Gd over IB oxidation is proposed.Therefore,this work is helpful for understanding the influence of rare earth elements on the structure of mixed metal oxides and the olefin selective oxidation reaction.

Effect of impregnation strategy on catalytic hydrogenation behavior of PtCo catalysts supported on La2O2CO3 nanorods

Small Pt and Pt-Co nanoparticles（NPs） stabilized on La2 O2 CO3 nanorods（LOC） were prepared by wet impregnation method,and probed in liquid-phase chemoselective hydrogenation of crotonaldehyde（CRAL） to crotyl alcohol（CROL）.It is found that incorporation of Co atoms into Pt catalyst significantly improves the hydrogenation activity and desired selectivity to CROL as it destroys the Pt-lanthanum interfaces and results into the formation of Pt-Co particles.In addition,a close examination of catalyst surface and reactive performance suggests that the impregnation sequence of Pt and Co exerts great influence on the physicochemical property and the catalytic hydrogenation behavior of PtCo/LOC catalysts.As a result of the interaction between Pt and Co species,high alloying degree of Pt-Co NPs is obtained in the co-impregnated catalyst（Pt-Co/LOC）,thus achieving the highest hydrogenation activity.The selective deposit of Co atoms onto the low-coordinated Pt sites leads to the smallest metal particle size and high dispersion of Pt-Co NPs over the Pt/Co/LOC,giving rise to the highest selectivity and yield to CROL.

Enhancement of La2O3 to Li-Mn/WO3/TiO2 for oxidative coupling of methane

A series of La2O3-promoted Li-Mn/WO3/TiO2 catalysts were prepared by varying the concentration of La2O3 promoter.The effect of La2O3 promoter on its properties and catalytic performance for OCM was characterized with XRD,FT-IR,O2-TPD,Raman,CO2-TPD,H2-TPR,XPS and CH4-TPSR,The results show that all the La2O3-promoted Li-Mn/WO3/TiO2 catalysts possess a larger amount of strong basic sites and more abundant chemisorbed oxygen species in comparison with Li-Mn/WO3/TiO2,which is beneficial to OCM reaction.Furthermore,La2O3 promoter can enhance the mobility of the oxygen species and the Mn species redox ability,which can also be favorable for the improvement of the catalytic performance for OCM,Due to the optimal synergistic interaction of these factors,5 wt%La2O3-Li-Mn/WO3/TiO2 exhibits the best performance among all the catalysts,on which the highest C2 yield of 19.2% is achieved at 750℃.

Role of cerium dopants in MoVNbo multi-metal oxide catalysts for selective oxidation of ethane

The effect of Ce on the structure of MoVNbCeO multi-metal oxide catalysts and the performance of ethane selective oxidation was investigated.These multi-metal oxide catalysts with superior oxidizability exhibit high catalytic activity,and vanadium acts as the active center for ethane oxidation reaction.The improved catalytic activity is related to the increased V^(5+) content on the catalyst surface,which results from the enhanced transformation of the electrons between V and Ce.Moreover,Ce effectively promotes oxygen adsorption,activation,and mobility.And the presence of Ce can also prevent MoO_(3) formation and stabilize the Mo_(5)O_(14)-like structure.In addition,the catalyst with a moderate amount of Ce exhibits outstanding catalytic performance.Especially,the MVN-Ce catalyst with a Ce/V ratio of 0.1 exhibits the best performance:the total selectivity of the catalyst toward C_(2)H_(4) and CH_(3) COOH is the highest(72%) at the ethane conversion of 31%.Therefore,MoVNbCeO multi-metal oxides are promising candidates for selective oxidation.