Particle/metal-based monolithic catalysts dual-bed reactor with beds-interspace supplementary oxygen:Construction and performance for oxidative coupling of methane

A novel particle/metal-based monolithic catalysts dual-bed reactor with beds-interspace supplementary oxygen is constructed comprising of the upper-layer 5 wt%Na2WO4-2 wt%Mn/SiO2 particle catalyst and the under-layer 3 wt%Ce-5 wt%Na2WO4-2 wt%Mn/SBA-15/Al2O3/FeCrA1 metal-based monolithic catalyst as well as a side tube in the interspaces of two layers for supplementing 02. The reaction performance of oxidative coupling of methane （OCM） in the dual-bed reactor system is evaluated. The effects of the reaction parameters such as feed CH4/O2 ratio, reaction temperature and side tube feed 02 flowrate on the catalytic performance are investigated. The results indicate that the suggested mode of dual-bed reactor exhibits an excellent performance for OCM. CH4 conversion of 33.2%, C2H4 selectivity of 46.5% and C2 yield of 22.5% could be obtained, which have been increased by 6.4%, 4.1% and 5.5%, respectively, as compared with 5 wt%Na2WO4-2 wt%Mn/SiO2 particle catalyst in a single-bed reactor and increased by 10.7%, 31.9% and 17.7%, respectively, as compared with 3 wt%Ce-5 wt%Na2WO4-2 wt%Mn/SBA-15/Al2O3/FeCrA1 metal-based monolithic catalyst in a single-bed reactor. The effective promotion of OCM performance in the reactor would supply a valuable reference for the industrialization of OCM process.

Effect of initial nickel particle size on stability of nickel catalysts for aqueous phase reforming

The deactivation behavior by crystallite growth of nickel nanoparticles on various supports（carbon nanofibers, zirconia, Si C, α-Al2O3 and γ-Al2O3） was investigated in the aqueous phase reforming of ethylene glycol. Supported Ni catalysts of ~10 wt% were prepared by impregnation of carbon nanofibers（CNF）,Zr O2, SiC, γ-Al2O3 and α-Al2O3. The extent of the Ni nanoparticle growth on various support materials follows the order CNF ~ ZrO2〉 SiC 〉 γ-Al2O3〉〉 α-Al2O3 which sequence, however, was determined by the initial Ni particle size. Based on the observed nickel leaching and the specific growth characteristics; the particle size distribution and the effect of loading on the growth rate, Ostwald ripening is suggested to be the main mechanism contributing to nickel particle growth. Remarkably, initially smaller Ni particles（~12 nm） supported on α-Al2O3 were found to outgrow Ni particles with initially larger size（~20 nm）. It is put forward that the higher susceptibility with respect to oxidation of the smaller Ni nanoparticles and differences in initial particle size distribution are responsible for this behavior.

Studies on the Preparation and Catalyticproperties of Fe-C-Mn Ultrafine particle Catalyst in F-T synthesis

Based on the Fe/C ultrafine particle obtained by means of laser pyrolysis method, a series of Fe-C-Mn ultrafine particle catalysts for F-T synthesis were prepared by adding certain amounts of Mn organic compounds to the Fe/C UFP. XRD and TEM tests for the obtained catalysts showed that the active phases, α-Fe, Fe3Cand (Fe,Mn)O. were directly obtained. and that the particle size was in the range of 2-4 nm. The catalysts so obtained have stable structure, long life, high activity and selectivity for light olefins, especially for propylene. Testing of the crystal structure in the process of the reaction demonstrated the carbonide mechanism of FT synthesis and the presence of α-Fe, FexCy and (Fe, Mn)O, thus supporting the belief that these are the active phases.

Effect of the Ni size on CH4/CO2 reforming over Ni/MgO catalyst：A DFT study

Carbon deposition is sensitive to the metal particle sizes of supported Ni catalysts in CH_4/CO_2 reforming.To explore the reason of this phenomenon,Ni4,Ni8,and Ni12 which re flect the different cluster thicknesses supported on the MgO(100) slabs,have been employed to simulate Ni/MgO catalysts,and the reaction pathways of CH_4/CO_2 reforming on Nix/MgO(100) models are investigated by density functional theory.The reforming mechanisms of CH_4/CO_2 on different Nix/MgO(100) indicate the energy barriers of CH_4 dissociated adsorption,CH dissociation,and C oxidation three factors are all declining with the decrease of the Ni cluster sizes.The Hirshfeld charges analyses of three steps as described above show only Ni atoms in bottom two layers can obtain electrons from the MgO supporters,and the main electron transfer occurs between adsorbed species and their directly contacted Ni atoms.Due to more electron-rich Ni atoms in contact with the MgO supporters,the Ni/MgO catalysts with small Ni particles have a strong metal particle size effect and lead to its better catalytic activity.

PREPARATION OF ULTRAFINE PARTICLE IRON-CARBONIDE CATALYST AND CHARACTERIZATION OF ITS CATALYTICAL BEHAVIOR

Studies on ultrafine particle catalyst have attracted many researchers' attention by its large surface area,higher activity and selectivity.Based on the mechanism of α-Fe and Fe_xC_y as the catalytical active species this paper reports for the first time the preparation method of Fe_3C ultrafine parti- cle catalyst,from highly dispersed amorphous Fe powder and free carbon.The Fe powder and free car- bon,prepared by laser pyrolysis technique,was then treated by washing and heating at high tempera- ture protected with N_2.The catalyst prepared under different experimental conditions was characterazed by means of XRD,electronic diffraction and TEM.It shows that the crystlline grain size is in a range of 1-4nm and composed of Fe_3C and α-Fe.It has been found that the ultrafine particle iron-carbonide catalyst exhibited much higher activity and selectivity to light olefins.At the standard atmosphere and 380℃ reaction temperature,the conversion of CO reached a maximum of 80%.

The Approximate Analytical Solution of Non-Linear Equation for Simultaneous Internal Mass and Heat Diffusion Effects

For the first time a mathematical modelling of porous catalyst particles subject to both internal mass concentration gradients as well as temperature gradients, in endothermic or exothermic reactions has been reported. This model contains a non-linear mass balance equation which is related to rate expression. This paper presents an approximate analytical method (Modified Adomian decomposition method) to solve the non-linear differential equations for chemical kinetics with diffusion effects. A simple and closed form of expressions pertaining to substrate concentration and utilization factor is presented for all value of diffusion parameters. These analytical results are compared with numerical results and found to be in good agreement.

Impacts of continuously regenerating trap and particle oxidation catalyst on the NO_2 and particulate matter emissions emitted from diesel engine

Two continuously regenerating diesel particulate filter （CRDPF） with different configurations and one particles oxidation catalyst （POC） were employed to perform experiments in a controlled laboratory setting to evaluate their effects on NO2, smoke and particle number emissions. The results showed that the application of the after-treatments increased the emission ratios of NO2/NOx significantly. The results of smoke emissions and particle number （PN） emissions indicated that both CRDPFs had sufficient capacity to remove more than 90% of total particulate matter （PM） and more than 97% of solid particles. However, the POC was able to remove the organic components of total PM, and only partially to remove the carbonaceous particles with size less than 30 nm. The negligible effects of POC on larger particles were observed due to its honeycomb structure leads to an inadequate residence time to oxidize the solid particles or trap them. The particles removal efficiencies of CRDPFs had high degree of correlations with the emission ratio of NO2/NOx. The PN emission results from two CRDPFs indicated that more NO2 generating in diesel oxidation catalyst section could obtain the higher removal efficiency of solid particles. However this also increased the risk of NO2 exposure in atmosphere.