Effect of lanthanum addition on the thiophene hydrodesulfurization activity over Al-MCM-41 supported molybdenum catalysts

A series of Al-MCM-41 modified with 1–7% lanthanum were used as supports to prepare the Mo/La–Al-MCM-41 catalysts containing 10 wt.% molybdenum. The supports and catalysts were characterized with XRD, BET, XPS, TPD, TEM and SEM, and their catalytic activities were tested for thiophene hydrodesulfurization. The La addition did not cause any significant collapse of the structure and morphology of Al-MCM-41 samples, and increased the acidity of Al-MCM-41 samples. The Mo/La–Al-MCM-41 catalysts showed higher thiophene HDS activity than non-modified catalysts. The La-modified catalysts showed an enhanced butene selectivity but a decreased tetrahydrothiophene selectivity, indicating that the La–Al-MCM-41 supports contained a larger amount of acid sites.     

Characteristics of Al-MCM-41 supported Pt catalysts: effect of Al distribution in Al-MCM-41 on its catalytic activity in naphthalene hydrogenation

Naphthalene hydrogenation was carried out in a high-pressure batch reactor over platinum catalysts supported on Al-MCM-41 where aluminum was incorporated through two different methods: a direct sol–gel method (Pre) and post-synthetic grafting method (Post). The catalytic reaction was also performed in the presence of dibenzothiophene to investigate the sulfur tolerance. The hydrogenation activity, selectivity and the sulfur tolerance strongly depended on the acidic nature of Al-MCM-41 support. It was suggested that the acid sites of Al-MCM-41-Post be more accessible than those of Al-MCM-Pre due to different aluminum distribution within the pore wall. The naphthalene and tetralin conversion increased with the acid amount of the supports in Pt/Al-MCM-41 catalysts. The acid sites in bifunctional catalysts seemed to contribute to alternative pathway by the spillover hydrogen in the acid–metal interfacial region for naphthalene hydrogenation, since the metal dispersions were kept constant for Pt/Al-MCM-41 catalysts. The trans-decalin selectivity generally increased with temperature or acid amount. The acid sites seemed to enhance the sulfur tolerance of supported platinum catalysts due to the electron-deficient state of metal.     

Ni2P/Al-MCM-41催化剂的制备及其加氢脱硫性能

以硅酸钠为硅源、硫酸铝为铝源、十六烷基三甲基溴化铵（CTAB）作模板剂,采用共沸蒸馏与超声波分散技术相结合的方法制备了介孔分子筛Al-MCM-41。以Al-MCM-41为载体、硝酸镍和磷酸氢二氨为原料,采用超声波振荡、程序升温还原法制备了Ni₂P/Al-MCM-41催化剂,并对Al-MCM-41和Ni₂P/Al-MCM-41进行了傅里叶变换红外光谱、比表面积测定、X射线衍射、扫描电镜表征。考察了Ni₂P/Al-MCM-41催化剂对噻吩加氢脱硫的催化性能。结果表明：采用超声波制得的Al-MCM-41其比表面积、孔容和孔径明显高于常规搅拌制得的Al-MCM-41,共沸蒸馏制得的Al-MCM-41其比表面积、孔容和孔径高于未共沸蒸馏的Al-MCM-41;在反应时间为5 h、548 K、3.5 MPa条件下,Ni₂P/Al-MCM-41催化剂对噻吩加氢脱硫的转化率接近100%。     

Room temperature efficacious synthesis of diphenylmethane over Fe/Al-MCM-41 catalysts

Fe/Al-MCM-41 (Si/Al = 25, 50, 75 and 100) were synthesized. Their catalytic activity was evaluated towards benzylation of benzene with benzyl chloride in liquid phase. The catalytic activity of Fe/Al-MCM-41(25) was higher than the other catalysts. Diphenylmethane(DPM) was obtained as the major product with 100% selectivity and with 100% conversion of benzyl chloride under optimum condition. The effect of temperature and the feed ratio, on the activity of Fe/Al-MCM-41(25) and selectivity towards DPM was studied and a possible reaction mechanism was proposed.     

Al-MCM-41 catalyzed decomposition of polypropylene and hybrid genetic algorithm for kinetics analysis

Mesoporous catalysts (Al-MCM-41) are synthesized by sol–gel and hydrothermal methods to study their effects on the catalytic decomposition of polypropylene (PP) sample. The catalysts are characterized by X-ray diffraction (XRD) analysis and nitrogen adsorption study. Since sol–gel Al-MCM-41 catalyst shows better catalytic activity, further experimental studies were conducted to find its reusability and its activity at five different heating rates. The constant pattern behaviour of the TG curves for different catalyst percentages possibly suggests existence of similar reaction mechanism where large polymer fragments are cracked on the external surface of the catalyst and then enters into the mesopores for further cracking. Thus, presence of catalyst surfaces not only converts the polymer into comparatively smaller fractions, but also makes the decomposition of PP energy effective. Kinetics parameters are estimated based on 15 different decomposition models and the multi-heating rate experimental data both for catalytic and noncatalytic decomposition of PP using hybrid genetic algorithm (HGA). Suitability of the model is tested using corrected Akaike's Information Criteria (AIC_c). Results show that Nucleation and Growth model better predicted the experimental TGA data. However, nth order model also shows good AIC_c score and well predicted the experimental TGA data. Thus, though apparently it seems that Nucleation and Growth model controls the decomposition of PP sample, further investigation in detail including infrared or mass spectroscopy, morphology study using SEM or TEM during such decomposition is very much essential to conclude upon the actual reaction mechanism that controls decomposition of PP sample.     

不同硅铝比Al-MCM-41介孔分子筛的表征及催化合成氯乙酸正辛酯

以十六烷基三甲基溴化铵( CTAB)为模板剂,正硅酸乙酯(TEOS)为硅源,乙二胺为碱性介质,当n(TEOS)∶n( NaAl02)∶n(CTAB)∶n(H2NCH2CH2NH2)∶n(H2O)=1∶x∶0.12∶ 3.5∶130,其中x=0.1,0.033,0.02,0.01,0.006 7时,水热法合成了Al - MCM - 41介孔分子筛.通过XRD,N2吸附-脱附,NH3 - TPD和TEM等手段对不同硅铝比(n(Si)/n(Al))的Al - MCM -41介孔分子筛进行了表征.结果表明,当n(Si)/n( Al)由150减小至30时,Al - MCM -41介孔分子筛仍具有典型的六方介孔结构特征,但当n( Si)/n(Al)=10时,样品结构有序性下降.Al - MCM - 41介孔分子筛酸量随着n( Si)/n( Al)减小而增大.将Al - MCM - 41介孔分子筛用于催化合成氯乙酸正辛酯,相同反应条件下,n( Si) /n( Al) =30的Al - MCM - 41介孔分子筛为催化剂时酯化率最高,由此表明,Al - MCM - 41介孔分子筛作为催化剂,反应酯化率不仅取决于样品酸量,也与其晶体结构相关.当Al - MCM - 41介孔分子筛用量为氯乙酸质量的3％,反应温度为120～140℃,n(氯乙酸)∶n(正辛醇)=1∶1.2时,酯化率可达94.34％.     

苯加氢催化剂Pd/MCM—41催化性能的研究

对负载型催化剂Pd/MCM—41进行了透射电镜及N2吸附表征。结果表明,金属Pd主要以纳米粒子的形式负载在分子筛表面,MCM—41的基本结构未被破坏。将Pd/MCM—41用于苯加氢反应,研究了反应温度和反应压力对催化活性的影响。结果表明,随着反应温度、反应压力的增加,苯的转化率得到有效提高。     

Acidity and catalytic activity of mesoporous ZSM-5 in comparison with zeolite ZSM-5, Al-MCM-41 and silica–alumina

Acidity of mesoporous HZSM-5 prepared using amphiphilic organosilane template molecules was measured. Brønsted acid sites were observed in the prepared sample, and the number and the strength of Brønsted acid sites were determined quantitatively by a method of infrared-mass spectroscopy/temperature-programmed desorption (IRMS-TPD) of ammonia. ΔH for ammonia adsorption as an index of the strength was ca. 150 kJ mol⁻¹ that was almost the same as on usual HZSM-5, but the number was smaller than that of HZSM-5. From the measured acidity, it was concluded that the mesoporous materials contained a smaller concentration of Brønsted acid site notable on the structure of HZSM-5. Measurements of turnover frequency (TOF) in the catalytic cracking of octane supported the conclusion. Density functional calculations showed that the defect sites Al–OH and Si–OH attached to the Brønsted acid site changed the strength of the acid sites to show some possible structures of the weak and strong Brønsted acid sites included in the mesoporous HZSM-5. Acidities of Al-MCM-41 and silica–alumina were also measured, and the difference in the solid acidities of these materials was discussed.     

Simultaneous isomerization of n-heptane and saturation of benzene over Pt/Beta catalysts: The influence of zeolite crystal size on product selectivity and sulfur resistance

In this work we show that decreasing the zeolite crystal size has a clear benefit on product selectivity and sulfur resistance of Pt/Beta catalysts during the simultaneous hydroisomerization of n-heptane and hydrogenation of benzene. The higher isomerization selectivity of the catalyst prepared from a nanocrystalline Beta zeolite can be ascribed to a faster diffusion of the iso-C₇ products through the small crystallites preventing cracking reactions to occur, while the improved sulfur resistance can be related to a better dispersion of Pt owing to its higher surface area and mesoporosity.     

杂多化合物催化剂在异丁烷选择氧化中的研究进展

概述了几种生产甲基丙烯酸的工艺路线,介绍了杂多化合物催化剂催化异丁烷一步氧化制甲基丙烯酸的反应机理,综述了引入其他元素、助剂或载体及部分还原催化剂等杂多化合物催化剂的改性方面的研究进展,展望了未来杂多化合物催化剂的发展方向。     

负载杂多酸(盐)的表征及其在苹果酯合成反应中的催化性能

用浸渍法制备了一系列负载型磷钨酸及其铯盐催化剂,载体包括超稳Y沸石（USY）、脱铝超稳Y沸石（DUSY）、SiO₂和SBA-15,测定了催化剂的比表面积和酸强度,并在乙酰乙酸乙酯与乙二醇液相缩合制取苹果酯反应中考察了催化剂的性能.结果表明,这些负载型杂多化合物催化剂都表现出较高的催化活性.然而,催化剂在水中的溶脱性能实验表明,负载型磷钨酸催化剂存在严重的活性组分流失现象,不能重复使用,而DUSY负载的磷钨酸铯盐催化剂不仅表现出较高的催化活性,而且显示出较好的重复使用性能.在优化的反应条件下30% (质量分数) Cs_2.5H_0.5PW/DUSY催化剂上乙酰乙酸乙酯的转化率可达98.7%,苹果酯的选择性大于97%.     

负载型杂多酸催化甲苯异丙基化反应

以等体积浸渍法制备了负载型杂多酸PWH/SiO2催化剂,采用高压流动微反装置研究了其催化甲苯与异丙醇烷基化反应结果的规律,关联表征结果确定制备负载磷钨酸的适宜条件为：负载量40%,焙烧温度200℃。其催化甲苯与异丙醇烷基化反应适宜反应条件是：反应温度为200℃,甲苯与异丙醇的摩尔比为4∶1,体积空速为2h?1,在此条件下,异丙醇的转化率最高达到92.94%,烷基化反应选择性达83.89%。     

乙醛酸法合成香兰素缩合反应的催化研究

以愈创木酚和乙醛酸为原料，通过催化缩合反应合成香兰素的中间体3-甲氧基-4-羟基扁桃酸（MHMA）。研究了不同种类催化剂对愈创木酚-乙醛酸法合成香兰素的缩舍反应的影响。结果表明：1^#催化剂对愈创木酚和乙醛酸缩合反应的活性较高，乙醛酸的转化率可达95％以上，3-甲氧基-4-羟基扁桃酸的选择性达85％。     

Complex metal oxide catalysts for selective oxidation of propane and derivatives: II. The relationship among catalyst preparation, structure and catalytic properties

The effects of the preparation methods on the structure and catalytic performance of the MVTeNb (M=Mo or W) complex metal oxides (CMO) in selective oxidation of propane to acrylic acid (AA) were investigated. Preparation methods can play as significant roles as the chemical composition in determining the structures and catalytic properties of a CMO catalyst. Undesirable preparation methods or conditions can lead to the formation of ineffective crystal phases in the resulting catalysts, leading to poor catalytic activity or selectivity. An effective MoVTeNb oxide catalyst for propane selective oxidation to acrylic acid could be obtained with a combination of a proper metal ratio and proper preparation procedures. Certain drying methods, such as freeze dry and heat evaporation, are undesirable because phase segregation tends to occur during such processes, which negatively affect the catalytic performance. The preferred drying method is the rotavap method, which favors the formation of an effective crystal phase and suppresses the formation of impurity phases. The preferred calcination atmosphere is an inert atmosphere while a calcination atmosphere containing oxygen leads to the formation of significant amounts of MO₃ in MVTeNb oxides (M=Mo or W), which is known to be inactive in propane oxidation. It is proposed that an effective MoVTeNb oxide catalyst for propane selective oxidation to acrylic acid should contain at least two major crystal Phases A and B. Based on studies of oxides of pure Phase A and those exclusively enriched with Phase B, X-ray diffraction (XRD) characteristics of the two major crystal phases (A and B) have been identified and their catalytic functions studied. It is proposed that Phase A is active in propane activation but relatively unselective for the acrylic acid formation, while Phase B is reasonably active for propane activation and fairly selective for acrylic acid formation. It has been shown that using MoVTeNb oxide catalyst with a proper ratio of Phases A and B and synergy between them, very high propane conversion (73%) and acrylic acid selectivity (58%) can be achieved at the same time.     

Isobutane/butene alkylation over supported heteropoly acid catalysts: I. Influence of the structure of silica

Catalysts consisting of heteropoly acids (HPAs) supported on different silica and mesoporous molecular sieves have been prepared by impregnation and the sol–gel method, respectively, and their catalytic behavior in fixed‐bed alkylation of isobutane with butene has been investigated. The activity, selectivity and stability of the supported‐HPA catalysts could be correlated with the surface acidity of the catalysts, the structure of supports as well as the time on stream (TOS). In the fixed‐bed reactor, the acidity of the heteropoly acid is favorable to the formation of dimerization products (C ₈ ⁼ ); especially, the pore size of supports was seen to have an important effect on activity and product distribution of the catalysts. Contrary to the traditional solid‐acid catalysts, the supported‐HPA catalysts own an excellent stability for alkylation, which makes it possible for these supported catalysts to replace the liquid‐acid catalysts used in industry. This revised version was published online in July 2006 with corrections to the Cover Date.     

Supported solid and heteropoly acid catalysts for production of biodiesel

Biodiesel has developed attraction of most researchers recently because of its renewable resources and environmental benefits. Transesterification process in the presence of catalysts is the most common way, which is used for biodiesel production. Heterogeneous acid catalysts are considered more reliable than any other catalysts to carry out most vital reactions related to green chemistry (biodiesel production), because the production of biodiesel from solid acid catalysts is considered economically favorable. Nowadays, biodiesel is preparing from low quality feedstock by using solid acids catalysts in many research laboratory throughout the world. This article discusses how much catalyst shapes affect the efficiency of catalyst during catalysis. Different types of supports (zinc oxide, alumina, zirconia, and silica) are used to increase the efficiency of catalysts. Supported Lewis acid, Brønsted acid, and heteropoly acid catalysts show good efficiency for the catalytic transesterification of oil with alcohol. Heteropoly acid catalysts are tremendous and environment friendly acid catalyst and have ability to tolerate contaminations of oil resources such as water contents and free fatty acids (FFAs) contents. Keggin-type heteropoly acids are easily available and having stable structure while Wells–Dawson-type heteropoly acids are included in super acid class, due to these reasons heteropoly acids are considered as best acidic catalysts for biodiesel production by catalytic transesterification process. Therefore, this review also focused on the deactivation, regeneration and advantages of supported solid acid catalysts used for the catalytic production of biodiesel through transesterification.     

杂原子磷铝分子筛BSiAPO-5的合成结构及催化性能的研究

用水热合成法合成了一种硼-硅磷铝分子筛,通过化学分析、测定晶胞参数及用XRD,MAS—NMR方法进行表征,证实了硼、硅原子进入了分子筛骨架,并且具有和AIPO4-5相似的结构;用IR,NH3-TPD表征方法测出了它的酸性,测定结果表明,它具有L酸和B酸中心,以中等强度酸为主。在苯与烯烃烷基化反应中表现出良好的催化活性和长寿命,并且对2-LAB和3-LAB具有高选择性,有可能替代HF成为一种环境友好的新型催化剂。     

Hydrolytic decomposition of CF4 over alumina-based binary metal oxide catalysts: high catalytic activity of gallia-alumina catalyst

The hydrolytic decomposition of CF₄ has been conducted on gallia promoted alumina (Ga-Al oxide) catalysts at 803–903 K and 0.1 MPa. Steady state activity on 20% Ga-Al oxide was 15 times of that on Ce10%-AlPO₄ catalyst, on which the highest activity has been reported. The catalytic activity was further improved by incorporation of sulfate anion in Ga-Al oxide and by applying sol–gel method in preparation of the catalyst. XRD spectra of Ga-Al oxides showed a shift of diffraction peaks assigned to γ-alumina toward lower angles, indicating the formation of gallia-alumina solid solution. In situ FT-IR of pyridine adsorption spectra of Ga-Al oxides showed peaks solely attributable to Lewis acid (L-acid) sites at 1445–1455, ca. 1495, 1577, ca. 1594, and ca. 1622 cm⁻¹. The steady state catalytic activities increased with increasing peak areas at 1446 or 1622 cm⁻¹ of Ga-Al oxides with various Ga%, suggesting participation of Lewis acid sites into the reaction. It is demonstrate from surface area measurements of Ga-Al oxide catalyst before and after the reaction that not only higher catalytic activity but also higher catalyst stability were observed on Ga-Al oxide, Ga-Al oxide with sulfate, and Ga-Al oxide prepared by sol–gel method than on their parent oxides of alumina, Ga-Al oxide, and Ga-Al oxide prepared by incipient wetness method, respectively.     

Au/Fe3O4纳米复合材料的制备及其催化性能

通过将金纳米粒子铆接到Fe3O4载体表面,制得了Au/Fe3O4纳米复合粒子。首先以对苯二酚为还原剂还原HAuCl4制得球形金纳米粒子;然后采用溶剂热法制备Fe3O4磁性纳米颗粒,并用巯基丙酸(MPA)对其修饰;最后通过MPA与金纳米粒子之间的相互作用,将金纳米颗粒固定到Fe3O4表面。采用透射电子显微镜(TEM)、扫描电子显微镜(SEM)、X射线衍射仪(XRD)、傅里叶变换红外光谱仪(FTIR)和振动样品磁强计(VSM)和紫外-可见分光光度计(UV-vis)对所制备材料进行形貌、晶型、磁性和催化性能的表征。结果表明,金纳米颗粒成功包覆在Fe3O4表面,所得到的Au/Fe3O4复合纳米材料具有单分散性和超顺磁性,并且对NaBH4还原对硝基苯酚(4-NP)制备对氨基苯酚(4-AP)的反应显示出优良的催化性能。     

Efficient Activation of Coal Fly Ash for Silica and Alumina Leaches and the Dependence of Pb(II) Removal Capacity on the Crystallization Conditions of Al-MCM-41

In this study, four different coal fly ashes (CFAs) were used as raw materials of silica and alumina for the preparation of the alumina-containing Mobil Composition of Matter No. 41 (Al-MCM-41) and the exploration of an activation strategy that is efficient and universal for various CFAs. Alkaline hydrothermal and alkaline fusion activations proceeded at different temperatures to determine the best treatment parameters. We controlled the pore structure and surface hydroxyl density of the CFA-derived Al-MCM-41 by changing the crystallization temperature and aging time. The products were characterized by small-angle X-ray diffraction, nitrogen isotherms, Fourier-transform infrared spectroscopy, ²⁹Si silica magic-angle spinning nuclear magnetic resonance, and transmission electron microscopy, and they were then grafted with thiol groups to remove Pb(II) from aqueous solutions. This paper innovatively evaluates the CFA activation strategies using energy consumption analysis and determines the optimal activation methodology and parameters. This paper also unveils the effect of the crystallization condition of Al-MCM-41 on its subsequent Pb(II) removal capacity. The results show that the appropriate selection of crystallization parameters can considerably increase the removal capacity over Pb(II), providing a new path to tackle the ever-increasing concern of aquic heavy-metal pollution.