In situ formation of multiple catalysts for enhancing the hydrogen storage of MgH_(2) by adding porous Ni_(3)ZnC_(0.7)/Ni loaded carbon nanotubes microspheres

MgH_(2) is considered one of the most promising hydrogen storage materials because of its safety,high efficiency,high hydrogen storage quantity and low cost characteristics.But some shortcomings are still existed:high operating temperature and poor hydrogen absorption dynamics,which limit its application.Porous Ni_(3)ZnC_(0.7)/Ni loaded carbon nanotubes microspheres(NZC/Ni@CNT)is prepared by facile filtration and calcination method.Then the different amount of NZC/Ni@CNT(2.5,5.0 and 7.5 wt%)is added to the MgH_(2) by ball milling.Among the three samples with different amount of NZC/Ni@CNT(2.5,5.0 and 7.5 wt%),the MgH_(2)-5 wt%NZC/Ni@CNT composite exhibits the best hydrogen storage performances.After testing,the MgH_(2)-5 wt%NZC/Ni@CNT begins to release hydrogen at around 110℃ and hydrogen absorption capacity reaches 2.34 wt%H_(2) at 80℃ within 60 min.Moreover,the composite can release about 5.36 wt%H_(2) at 300℃.In addition,hydrogen absorption and desorption activation energies of the MgH_(2)-5 wt%NZC/Ni@CNT composite are reduced to 37.28 and 84.22 KJ/mol H_(2),respectively.The in situ generated Mg_(2)NiH_(4)/Mg_(2)Ni can serve as a"hydrogen pump"that plays the main role in providing more activation sites and hydrogen diffusion channels which promotes H_(2) dissociation during hydrogen absorption process.In addition,the evenly dispersed Zn and MgZn2 in Mg and MgH_(2) could provide sites for Mg/MgH_(2) nucleation and hydrogen diffusion channel.This attempt clearly proved that the bimetallic carbide Ni_(3)ZnC_(0.7) is a effective additive for the hydrogen storage performances modification of MgH_(2),and the facile synthesis of the Ni_(3)ZnC_(0.7)/Ni@CNT can provide directions of better designing high performance carbide catalysts for improving MgH_(2).

Some insight on the structure/activity relationship of metal nanoparticles in Cu/SiO2 catalysts

The activity of two Cu/SiO2 catalysts prepared by the chemisorption hydrolysis technique has been tested in the hydrogenation reaction of 3-methyl-cyclohexanone. Both catalysts were found to be very active at 60 ℃ and 1 atm of H2. Characterization of the materials by FT-IR of adsorbed CO and TEM put in light the presence of well formed Cu cristallites. By assuming a cuboctahedral model we could show that the hydrogenation activity is linked to high coordination sites on the metal particle. A comparison is also reported with a sample prepared by ammonia evaporation that was found to be inactive in the hydrogenation reaction under the same experimental conditions.

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.

PHOTODEGRADATION OF p-NITROCHLORBENZENE(p-NCB)USING NANOMETER-SIZED ZnO PARTICLES PREPARED BY REACTIVE EVAPORATION METHOD

Photocatalytic degradations of p-nitrochlorbenzene (p-NCB) with distilled water wereinvestigated with ZnO crystals (catalyst) of 70nm in diameter under UV irradiation.The suitable experimental conditions are determined as: ZnO 0.25g, pH 7, p-NCBconcentration 30mg/L. These variables in terms of the degradation rate have beendiscussed, which was defined as the rate of the initial degradation to the final degrada-tion of p-NCB. When all of the experimental degradation rate values are plotted as afunction of irradiation time, all of the points appeared on a single line for wide range ofp-NCB degradations. On the basis of these results, it has been concluded that at lowerZnO catalyst amount, much of the light is transmitted through the slurry in the con-tainer beaker, while at higher catalyst amount, all the incident photons are observedby the slurry. Degradation rates of p-NCB were found to decrease with increasingsolution pH. It has been concluded that the maximum degradation rate values of p-NCB under principally the same experimental conditions mentioned above are 97.4%,98.8% and 95.5% at 100min respectively. The results suggest that the photocatalyticdegradation is initiated by an oxidation of the p-NCB through ZnO surface-adsorbedhydroxyl radicals. Absorption spectra are recorded using spectrophotometer before andafter UV-irradiation in the wavelength range 200-400nm at room temperature. Itis found that the variation of irradiation time over the range 20-100min resulted inchange in the form of the spectrum linear absorption and a higher maximum valuewill be obtained at longer irradiation time.

Effect of Particle Shape on Catalyst Deactivation during 2-Butene and Isobutane Alkylation of Liquid Phase in Fixed-Bed Reactor Using Particle-Resolved CFD Simulation

How catalyst shape affects its deactivation is a crucial issue for quickly decaying catalysts such as zeolite in 2-butene and isobutane alkylation.In this work,steady simulations are used to determine the temperature and species distribution in fixed beds filled with particles of four shapes.Subsequently,unsteady simulations are used to study the deactivation behavior of the catalysts based on the steady simulation results.We describe the deactivation rate and type of catalyst deactivation by defining a local internal diffusivity,which is affected by catalytic activity.The results reveal that the internal diffusion distance of the catalyst determines the deactivation rate,whereas the local internal diffusivity determines its deactivation type.

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 nano-particle size on product distribution and kinetic parameters of Fe/Cu/La catalyst in Fischer-Tropsch synthesis

Effects of nano-particle size on hydrocarbon production rates and distributions for precipitated Fe/Cu/La catalysts in Fischer-Tropsch synthesis were investigated.Nano-structured iron catalyst was prepared by micro-emulsion method.The concept of two superimposed AndersonSchulz-Flory （ASF） distributions has been applied for the representation of the effects of reaction conditions and nano-particles size on kinetics parameters and product distributions.These results reveal that by reducing the particle size of catalyst,the break in ASF distributions was decreased.Also useful different kinetics equations for synthesis of C3 to C9 and C10 to C22 were determined by using α1 and α2 chain growth probabilities.

A MSSBAUER SPECTROSCOPIC STUDY ON THE STRUCTURE OF Fe-M ULTRAFINE PARTICLE CATALYSTS (M=Mn, Zn, Mg)

The structure of Fe-M ultrafine particle catalysts was investigated by in situ Mossbauer spectroscopy. Emphasis has particularly been put on the effect of the second metal component. It was found that the incorporation of second metal component hinders the reduction and carburization of iron- containing phase in the presence of H2 and CO, and the degree of hindrance is in the order of Mg】Mn】Zn due to the interaction between iron and the second metal component. Consequently, the formation of light olefinic products is in the order of Fe- Mg】 Fe- Mn】 Fe- Zn catalysts consistent with the F-T synthesis performance.

Gold/Mg-Al mixed oxides catalysts for oxidative esterification of methacrolein:Effects of support size and composition on gold loading

Gold catalysts supported on Mg-Al mixed oxides for oxidative esterification of methacrolein are prepared by impregnation.Effects of the support particle size,concentration of HAuCl4 solution and Mg/Al ratio on gold loading and catalytic properties are investigated.The catalysts are characterized by CO_(2)-TPD,EDS,XPS,STEM and XRD techniques.Catalysts with smaller support particle size show more uniform gold distribution and higher gold dispersion,resulting in a higher catalytic performance,and the uniformity of gold and the activity of the catalysts with larger support particle size can be improved by decreasing the concentration of HAuCl4 solution.The Mg/Al molar ratio has significant effect on the uniformity of gold and the activity of the catalyst,and the optimum Mg/Al molar ratio is 0.1–0.2.This study underlines the importance of engineering support particle size,concentration of HAuCl4 solution and density of adsorption sites for efficient gold loading on support by impregnation.

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%.

Effect of CeO_(2)on Activity of Catalysts CuO/ZnO/Al_(2)O_(3)/CeO_(2)for Synthesis of Methanol

The size of the nanoparticles and the number of oxygen vacancies have a significant effect on the catalytic activity of copper-based catalysts used for the synthesis of methanol from syngas.In this study,the authors prepared a series of catalysts CuO/ZnO/Al_(2)O_(3)/CeO_(2)(CZAC)with CuO particles of different sizes and varying number of oxygen vacancies on the surface by changing the added volume of CeO2 by using the co-precipitation method.The properties of the catalysts were characterized and their activity was evaluated by using high-pressure fixed-bed reaction equipment.The results showed that the addition of CeO_(2)to CuO/ZnO/Al_(2)O_(3)not only influenced the size of the CuO particles and metal-metal interactions,but also had an effect on the concentrations of oxygen vacancies and strongly basic sites.The presence of CuO particles of small sizes and a large numbers of oxygen vacancies on the surface of the catalyst were beneficial to its activity for the synthesis of methanol.The catalyst CZAC,when modified by 5%of CeO_(2),recorded CuO particles of the smallest size(8.9 nm),strong intermetallic interactions,and the highest concentrations of oxygen vacancies and strongly basic sites.It also exhibited the highest catalytic activity,with a space-time yield of methanol of 0.315 g/(h·g)that was higher than that of the enterprise RK-5 catalyst[0.215 g/(h·g)].

Catalytic Decomposition of Nitric Oxide by LaCoO3 Nano-particles Prepared by Rotary CVD

Catalytic direct decomposition of NO by perovskite-type catalysts has attracted much attention for the various possible components and the unique structure. LaCoO_3 nanoparticles were precipitated on a-Al_2O_3 micro powders by rotary chemical vapor deposition（rotary CVD） and its catalytic performance for the decomposition of NO was investigated. LaCoO_3 nano-particles with 100 nm in average diameter and 1.5% in mass were uniformly dispersed on a-Al_2O_3 powder. The conversion of NO increased with increasing temperature from 400 to 950 ℃, and reached 28.7% at 950 ℃. The gas velocity of transformed NO on LaCoO_3 nano-particles catalyst per mass unit was 7.7 mL/（g min）, showing a good catalytic activity over the calculated results of pure catalysts. After five times of aging performance experiments, the NO conversion kept the same value, showing a good aging performance and thermal stability.

CeMO_(δ)/3DOM ZrTiO_(4)(M=Mn,Fe,Co)催化剂的制备及其对炭烟颗粒的催化消除性能

消除柴油机尾气中的炭烟颗粒对人体健康和社会发展都具有重要的现实意义。采用胶体晶体模板法和等体积浸渍法制备了CeMO_(δ)/3DOM ZrTiO_(4)(M=Mn,Fe,Co)系列复合金属氧化物催化剂,利用X射线衍射仪、全自动比表面和孔隙分析仪、扫描电镜等表征了催化剂的物化性能,并测试了Ce M O_(δ)/3DOM ZrTiO_(4)(M=Mn,Fe,Co)系列催化剂对炭烟颗粒的催化消除性能。研究结果表明,所制备的催化剂均具有独特的三维有序大孔结构,其中CeMnO_(δ)/3DOM ZrTiO_(4)催化剂对炭烟的催化活性最高,是一种具有应用前景的复合金属氧化物催化剂。

填料性质对催化裂化油浆静电分离效率影响冷模试验研究

为分析静电分离法脱除催化裂化油浆中固含量影响因素,采用自制静电分离器试验装置,研究填料直径和材质对催化油浆中催化剂固体颗粒脱除效率影响规律。结合数值模拟,分析填料直径和材质对其接触点处电场强度变化的影响。结果表明,油浆中固体颗粒分离效率随填料直径增大而降低,氧化锆填料的分离效率最高,玻璃填料的分离效果最差。随填料直径和填料相对介电常数增大,填料接触点处的电场强度增大。在不同材质填料物化参数中,填料相对介电常数对油浆中固体颗粒静电分离影响过程起主要作用。

直接甲醇燃料电池阳极催化剂的失活机制及应对策略

甲醇氧化电催化剂是决定直接甲醇燃料电池(direct methanol fuel cells,DMFC)性能与成本的关键。目前,铂基催化剂是最有前途的高效甲醇氧化电催化剂,但在反应过程中存在活性位的迁移、团聚与浸出、中毒以及载体的腐蚀与坍塌等原因引起的失活问题,阻碍了其进一步商业化发展。如何提高直接甲醇燃料电池阳极催化剂的稳定性是一个亟待解决的难题。本文首先总结了甲醇的电氧化原理和催化反应机理,详细综述了阳极催化剂的失活机制以及抑制改善其失活方面所取得的研究进展。最后对该领域未来的发展方向进行了展望,并指出利用限域作用限制活性金属的迁移和聚集,构建多元合金,设计增强复合型载体,将理论研究和原位表征技术相结合,是今后开发更高效、稳定阳极催化剂的重点研究方向。

MnO_(δ)催化剂的制备及对柴油机尾气炭烟颗粒燃烧的催化性能

基于氧化锰(MnOx)催化剂优异的氧化还原性能,采用水热法制备了一系列具有层状结构的MnO_(δ)催化剂,并对其物化性能进行了表征.研究了水热反应温度、煅烧温度以及原料组成对催化剂晶体结构、形貌和氧化还原性能的影响,并将MnO_(δ)催化剂应用于柴油机尾气炭烟颗粒的催化燃烧.结果表明,当水热反应时间为12 h,煅烧温度为550℃,反应原料中KOH和K_(2)CO_(3)同时存在时,所制备的MnO_(δ)-t_(12)催化剂具有最佳的催化燃烧炭烟颗粒的活性,T_(10),T_(50)和T_(90)值分别为274,321和354℃.

黏结剂对甲醇制烯烃中单颗粒催化剂内部反应过程的影响

【目的】以甲醇制烯烃(methanol to olefins, MTO)为代表的非均相催化反应在现代化学工业中占据着重要的地位,研究MTO过程中单颗粒催化剂的反应、传质与传热过程,有助于系统理解催化反应机理、优化催化剂设计,实现工艺升级。【方法】建立单颗粒催化剂颗粒模型、反应动力学模型以及传质与传热模型;采用COMSOL Multiphysics 6.0软件模拟MTO反应过程,分别由二氧化硅、氧化铝和高岭土作为黏结剂,建立3种SAPO-34分子筛催化剂颗粒模拟模型;分析3种催化剂颗粒内甲醇扩散和温度传导过程,分析黏结剂对酸性位点、多甲基苯和多甲基萘的浓度分布的影响,将催化剂颗粒内部的传热、传质过程与化学反应进行耦合。【结果】甲醇分子向催化剂颗粒内部的扩散过程中,在t=100 s时甲醇浓度分布基本稳定,从颗粒边缘处向中部、核心处甲醇浓度依次减小;以二氧化硅为黏结剂的颗粒在中心处、边缘处的热力学温度分别为656、 627 K,颗粒内部的甲醇扩散速度最快;在MTO反应过程中,3种颗粒内部的热力学温度均为由中心向边缘处递减;随着MTO反应时间的增加,3种催化剂颗粒的酸性位点浓度平均值逐渐减小,多甲基苯、多甲基萘的浓度平均值逐渐增大;以二氧化硅为黏结剂的颗粒边缘处的的酸性位点浓度降幅最大,然后依次是颗粒的中部和核心处,颗粒内多甲基萘的分布更均匀。【结论】以二氧化硅为黏结剂的催化剂颗粒内部温度最高、温升最快,有效促进了MTO反应的进行,有利于颗粒内分子筛的充分利用和多甲基苯和多甲基萘的均匀分布。

溶解析出体系催化剂性能的影响因素探究

以MgCl_(2)、正丁醇、异丙醇和TiCl_(4)为原料,钛酸四乙酯为给电子体,通过溶解析出的方式制备了一种聚乙烯催化剂,并将其用于乙烯聚合。利用SEM、粒径分布、熔体流动速率(MFR)测试等方法研究了影响溶解析出体系催化剂性能的因素。实验结果表明,调节溶解析出体系中的镁钛摩尔比、含镁溶液含量和给电子体用量可有效调控催化剂颗粒中的结块、细粉含量、催化活性、氢调敏感性和聚合物的堆密度(BD)及颗粒形态。综合各影响因素开发的一种溶解析出体系高性能聚乙烯催化剂的聚合活性为32.23 kg/g,所得聚合物的BD为0.304 g/cm^(3),MFR(10 min)为0.49 g,综合性能优于参比工业催化剂。

Ni/Al_(2)O_(3)催化十二氢-N-乙基咔唑分解的粒径效应及动力学分析

采用浸渍法制备了不同粒径的Ni/Al_(2)O_(3)催化剂,利用XRD、H2化学吸附、N2吸附-脱附等方法对催化剂进行了表征,考察了Ni粒径和反应条件对十二氢-N-乙基咔唑(12H-NEC)脱烷基及脱氢反应性能的影响。实验结果表明,随Ni负载量的增加,Ni平均粒径逐渐增大,Ni/Al_(2)O_(3)催化剂对12H-NEC的脱氢及脱烷基活性均呈先增大后下降趋势。Ni/Al_(2)O_(3)催化剂的Ni粒径在10~70 nm范围内,Ni粒径越小越有利于12H-NEC稳定性,适宜的脱氢温度为220℃。在10Ni/Al_(2)O_(3)催化剂作用下,12H-NEC脱烷基反应为一级动力学控制,指数前因子和表观活化能分别为1.27×10^(6) h^(-1)和79.30 kJ/mol。