Recent advances in liquid-phase organic reactions using heteropolyacid and clay

ecent advances in liquid-phase organic reactions over solid acids are described based on the catalyses of acidic clays and silica-included heteropoly compounds. Zinc ion-exchanged smectite clays, particularly nontronite clays, were effectively applied as insoluble, readily recoverable solid acid catalysts to liquid-phase Friedel-Crafts reactions. Montmorillonite K10 catalyzes the synthesis of alkylporphyrin derivatives from aliphatic aldehydes and pyrroles more efficiently than the conventional homogeneous acids such as BF3 etherate. 12-Tungstophosphoric acid and its acidic Cs salt could be included in a silica matrix by means of sol-gel technique involving hydrolysis of ethyl orthosilicate forming insoluble and easily separable solid acid catalysts. These silica-included heteropoly compounds were thermally more stable than an ion-exchange resin catalyst such as Amberlyst-15, and catalyzed the hydrolysis of ethyl acetate in the liquid phase more efficiently than the resin, H-ZSM-5 and even than aqueous heteropolyacid.     

含氧催化剂的17O固体核磁共振谱学研究

含氧催化剂在工业催化等多个领域有重要应用.氧离子半径很大,而且往往出现在材料的关键位点,所以一般认为氧与吸附和催化过程密切相关.17O是氧的唯一有核磁共振响应的稳定同位素,其化学范围极宽(>1000 ppm),能灵敏反映结构信息;由于是四极核(I>1/2),其四极耦合作用也能用于结构研究.因此,17O固体核磁共振谱学应是一种能提供丰富催化剂结构信息的理想表征手段.然而,目前17O固体核磁共振研究催化剂并非常规手段,这主要是因为17O的天然丰度很低,同位素标记较为昂贵和困难,其较低的旋磁比和较大的四极耦合作用导致谱线加宽,难以获得高质量的谱图并加以解析.随着高磁场和高速魔角旋转等技术的发展,17O固体核磁共振谱学可以用于一系列简单氧化物和沸石等催化剂的结构研究.近年来,随着双旋转(DOR)、动态角旋转(DAS)、多量子魔角旋转(MQMAS)以及卫星跃迁魔角旋转(STMAS)等新技术的发展,能够消除二阶四极耦合作用带来的谱线展宽,显著提升谱图分辨率.而诸如交叉极化(CP)和旋转回波双共振(REDOR)技术,已经能用于探索氧与其它原子核空间相关方面的信息,成为研究催化剂相关作用的基础.本文综述了氧化物及相关催化剂17O固体核磁共振谱学研究的新进展.17O核磁共振谱学用于简单氧化物催化剂的结构研究,已经能够区分催化剂结构中不同晶相以及不同结晶学位点的氧物种,而1H→17O双共振实验也能用于选择表面羟基物种.对纳米氧化物结构的近期研究表明,17O核磁共振能将纳米氧化铈材料表面第1、2、3层、表面羟基、与氧空位靠近的氧物种与“体相”氧物种区分开来;此外借助17O-水和纳米氧化物作用,实现表面选择标记,为进一步探索催化剂结构和催化机理提供了新的可能.对于复合氧化物和负载催化剂,17O核磁共振谱学能够有效研究与催化性能最为相关的界面结构.在重要的氧化物催化材料沸石的研究中,17O核磁共振也发挥了巨大作用.借助高分辨率17O核磁共振方法,能够区分沸石中Si-O-Si和Si-O-Al物种,在一部分沸石中还能将不同结晶学位置的T-O-T’物种区分开来,并观测到天然沸石中违反Lowenstein规则,出现Al-O-Al物种的情况.借助双共振实验能够对与催化活性最为相关的B酸位Si-O(H)-Al结构和酸性进行研究,这一方法与探针分子相结合,已经能够对沸石和小分子的相互作用进行研究,提供吸附过程的重要信息.包括杂多酸和层状双氢氧化物在内的重要含氧催化材料也能够借助17O固体核磁共振进行局域结构和相互作用的研究.随着表面选择标记和动态核极化等选择表面研究的17O核磁共振技术的发展,我们能实现更为高效的表面结构的17O核磁共振观测,这一谱学方法将提供更多有关含氧催化剂和外来物种相互作用的信息,为研究氧化物催化剂及其催化应用提供新的策略.     

SO42-/TiO2-ZrO2复合氧化物固体酸催化剂的长叶烯芳构化催化性能

本工作用溶胶-凝胶法制备不同组成的SO42-/TiO2-ZrO2复合氧化物固体酸催化剂,用微型催化反应评价结合X-射线粉末衍射(XRD)、孔结构/BET表面积测试和NH3-程序升温脱附(NH3-TPD)等表征了SO42-/TiO2-ZrO2复合氧化物固体酸催化剂结构、表面酸性和长叶烯芳构化催化性能。复合氧化物固体酸SO42-/TiO2-ZrO2催化剂具有优良的长叶烯芳构化催化性能,并且其芳构化催化性能与催化剂组成和表面酸性密切相关。随催化剂中nZr/(nZr+nTi)增加,催化剂表面中等强度的酸中心量增加,芳构化产物选择性和收率明显增加,在nZr/(nZr+nTi)=0.5时达极大值。随nZr/(nZr+nTi)进一步增加,不仅催化剂表面酸中心量减少、原料转化率明显下降,而且催化剂酸强度增强,导致芳构化产物选择性和收率下降。催化长叶烯芳构化的二元复合氧化物固体酸SO42-/TiO2-ZrO2催化剂适宜的组成为nZr/(nZr+nTi)=0.5。     

Uniform Heterogeneous Catalysts: The Role of Solid-State Chemistry in their Development and Design

Heterogeneous catalysts are generally assumed to be multiphasic and multicomponent; many of them are, and this is one of the resons why disentangling the factors that govern their mode of action is so difficult. But there is a large class of heterogeneous catalysts where the solid is monophasic and where the activity may be envisaged as being dispersed in a spatially uniform fashion throughout its bulk. This is true both of zeolites and many other microporous catalysts on the one hand, and of certain mixed metal oxides, where the non-stoiohiometry is inextricably mingled with the catalysis, on the other. By recognizing this broad classification numerous operational advantages follow: the performance of existing catalysts and the design of those yet to be prepared can be placed on a rational footing; moreover, the myriad techniques of solid-state chemistry and physics, often regarded as inapplicable to the subtle and special problems of surface chemistry, are seen to be of direct relevance as probes for the structure and properties of proven uniform heterogeneous catalysts as well as for the synthesis and development of new ones. This review, which draws analogies with and lessons from the chemistry of enzyme catalysts, focuses largely on the catalytic conversions of hydrocarbons over zeolites, clays, microporous AlPO₄ and a wide range of metal oxides.     

Isomerization of n-hexane over silica-supported heteropoly acids promoted by the reduced Ce-Ni oxides

The structure and catalytic properties of silica-supported heteropoly acids promoted by the reduced Ce-Ni oxides are first studied by using chemical analysis XRD, FT-Raman, XPS, EPR, TG, surface area measurements, and microreactor test. It is found that silica-supported heteropoly acids have isomerization activity, but are very easy to deactivate by coke deposition. With the promotion of the reduced Ce-Ni oxides, however, the better activity and the higher selectivity to isomers could be obtained, suggesting that the reduced Ce-Ni oxides really have hydrogenating/dehydrogenating functions. Moreover, it is found that the presence of the reduced Ce-Ni oxides is not only beneficial for eliminating the coke deposition, but also effective for maintaining the structure of silica-supported heteropoly acids during reaction. The effect of the composition of the mechanical mixtures of silica-supported heteropoly acids and the Ce-Ni oxides on the catalytic properties has been explored.     

Efficient homogeneous catalysis of heteropoly acid and its characterization through etherifications of alcohol

A Keggin-type heteropoly acid revealed high catalytic activity for the etherification such as diethylene glycol with ethanol and cyclization of diethylene glycol in the homogeneous liquid. The catalytic activities of the heteropoly acid were much higher than those of conventional acid catalysts such as sulfuric acid, p-toluene sulfonic acid and phosphorous acid at the same catalyst concentrations or the same proton concentrations. On the basis of comparative measurement of electrical conductivity, acidity, and softness of anion for the solutions of acid catalysts, the efficient acid catalysis by heteropoly acid was suggested to due to be the specific properties of the heteropoly anion, which can be characterized by very weak basicity and great softness, together with the large size of the polyhedral structure.     

超临界流体状态下的异构烷烃与烯烃烷基化反应

成功地应用固体酸催化剂在超临界反应条件下进行了异构烷烃与丁烯的烷基化反应。在超临界反应条件下,固体酸催化剂在１４００ｈ的反应以后,仍保持１００％的烯烃转化率。探索出一个解决固体酸催化剂在烷基化反应中极易失活的有效方法。探讨了超临界流体抑制固体酸催化剂结炭失活的机制和烷基化反应中选择超临界反应条件的规律。     

Highly Efficient Esterification of an Equimolar Amount of Carboxylic Acids and Alcohols Catalyzed by ZrOCl_2·8H_2O

Esterification of carboxylic acids with alcohols is one of the most fundamental and useful transformations in organic synthesis. The most common catalysts are H2SO4 and TsOH. However, H2SO4 or TsOH-catalyzed esterification procedure has some problems such as corrosion, side reactions, difficulty in separation. Hence, recently, various solid acid catalysts such as ion-exchanged resins, molecular sieve, and heteropoly acids etc. have been employed for esterification reaction. However, the s…     

负载型杂多酸催化下N2O5对氯苯的选择性硝化研究

使用负载型杂多酸为催化剂,N2O5为硝化剂的新型硝化体系,对氯苯的硝化反应进行研究。文章分别考察了杂多酸类型、载体种类、杂多酸负载量及催化剂循环使用次数等因素对硝化反应的影响。结果证明,N2O5硝化反应属于酸催化反应,负载型杂多酸能显著提高N2O5的硝化能力;催化剂回收后可直接重复使用,催化活性没有明显的降低。在优化条件下,氯苯硝化反应得率为26%,对位选择性达到68.8%,表明N2O5是一种具有应用前景的硝化试剂,可取代传统的硝硫混酸硝化法,减少废酸处理,符合绿色环保要求。     

Heteropoly acids-catalyzed organic reactions in water: doubly green reactions

The organic reactions in water, as the most significant green solvent, have attracted much attention due to their unique properties over conventional organic ones. In the catalytic area, heteropoly acids (HPAs) are also promising green solid acids to replace environmentally harmful liquid acid catalysts. Herein, we wish to report the organic reactions catalyzed by HPAs, their salt, and polyoxometalates (POMs) in aqueous systems.     

Aluminium ions at polyelectrolyte interfaces. I. Mechanism of polyacrylic acid/aluminium oxide and humic acid/kaolinite complex formation

Understanding adsorption phenomena involving humic acids and clays is a difficult challenge owing to their complex nature. Thus, to progress in the study of such systems, attempts were made to replace natural systems by polyacids and oxides of simpler chemical and morphological structure. Since the present investigation was dedicated to determine some characteristics of acidic soils which contain traces of aluminium ions, these ions were added to the adsorbent/polyacid systems as trace constituents. Phenomena related to the interactions of humic or polyacrylic acid with aluminium oxide and kaolinite clay have been investigated and the well-differentiated interfacial behaviour of the oxide and kaolinite was determined and discussed. The results of electrophoretic mobility measurements demonstrated the huge time-dependent effect of polymeric layers adsorbed on oxides and modified clays. Received: 24 July 2000 Accepted: 20 December 2000     

气相硝化制备硝基苯的研究

研究了各种负载型杂多酸及其盐类对苯气相硝化的催化活性 ;探讨了载体、杂多酸类型、杂多酸负载量、反应温度、苯 /硝酸的摩尔比对硝化率的影响 .并用 ESR技术对催化剂进行了表征 .结果表明 ,二氧化硅负载杂多酸 (HPA)对苯气相硝化具有很好的催化活性 .对于 2 0 % H3PW1 2 O40 /Si O2 催化剂 ,苯 /硝酸的摩尔比为 2 ,反应温度为 15 5～ 16 0℃ ,空速 (SV)为 6 82 m L/(g cat.· h) ,硝基苯产率可达 90 .6 % ,硝基苯的时空收率 (STY)为0 .70 kg/(kg cat.· h) .     

固体酸催化剂结构与催化反应机理的核磁共振研究

Solid acid catalysts have been widely used in advanced petrochemical processes because of their environmental friendliness, high product selectivity, and easy product separation. Solid-state nuclear magnetic resonance (NMR) spectroscopy is a well-established tool for structure determination and dynamic study of various functional materials. In this review, we focus mainly on our research using solid-state NMR to characterize the acid properties and elucidate the catalytic reaction mechanism of solid acid catalysts. The acid strength of solid acids can be quantitatively measured from the chemical shifts of adsorbed probe molecules such as pyridine, acetone, trialkylphosphine oxides, and trimethylphosphine. The spatial proximity and synergetic effect of various acid sites on solid acid catalysts can be ascertained by two-dimensional (2D) double-quantum magic angle spinning (DQ MAS) NMR spectroscopy. Additionally, in situ solid-state NMR spectroscopy can be used to explore heterogeneous catalytic reaction mechanisms by monitoring the evolution of the reactants, intermediates, and products.     

Optimization of acidic treatment of bentonitic clays from the national layers

Investigations in the field of the development of inexpensive catalysts for the production of environmentally safe fuels, based on synthesis-gas from biomass, have been performed. The influence of acidic (sulphuric and phosphorous acids) treatment on the specific surface of Russian (Voronezh and Krasnodar) origins of bentonitic clays was investigated. For the determination of the optimal conditions of acidic treatment, the method of extremal experiment planning has been applied. The full factor experiment was chosen as the plan; in such an experiment, all factor combinations are implemented on all levels used for investigations. The variable parameters were as follows: the acid concentration, and the temperature and time of the acid treatment. The average pore diameter and the specific surface of clays were chosen as the response functions. The response surface appearance is very complex.     

固体酸催化合成柠檬酸三丁酯的研究进展

柠檬酸三丁酯是一种新型绿色无毒环保型增塑剂，被认为是传统非环保、有毒增塑剂——邻苯二甲酸酯的替代品，已经被广泛应用在高分子材料和石油化工等行业。本文综述了近年来固体酸催化合成柠檬酸三丁酯的研究进展，涉及到的催化剂包括固体超强酸、分子筛、杂多酸、负载型固体酸、离子液体，对它们的催化性能和催化机理进行了概述。固体酸克服了传统液体酸腐蚀性强、分离困难、后处理复杂等缺陷。并对固体酸催化剂的发展方向及前景进行了展望。     

Sulfide catalysts for hydropurification of oil fractions

Analysis of the literature on catalysis by transition metal sulfides is carried out. Problems which now can be considered solved, and unsolved problems are marked. Catalysts such as Co(Ni)Mo(W) on thermostable oxides are considered. Arguments in support of the hypothesis about formation in the oxide precursors of all this type catalysts of heteropoly compounds (HPC) of Mo(W) are considered. The formation of HPC occurs at the hydrothermal stage of the synthesis of the catalysts under contact of Mo(W) atoms and complexing agents in an acid medium. The role of the complexing agent can be played by atoms of the support (Si, Al, Ti, etc.) or atoms of the modifying additive.     

Dawson结构钼钒磷杂多化合物催化乙苯选择氧化的活性研究

合成了系列Ｄａｗｓｏｎ结构钼钒杂多化合物，并将其用于 苯的过氧化氢选择氧化研究，实验发现，对于该类反应，其最佳的工艺条件为：乙苯２．５ｍｍｏｌ，催化剂０．０２ｍｍｏｌ，溶剂１０ｍＬ、３０％Ｈ２Ｏ２２．５ｍｍｏｌ，乙酸为该类最佳溶剂，而在与之性质相近的甲酸中则活性极低，即该反应过程与过氧酸的存在无关，讨论了反应过程中催化剂的状态及活性中间体，并运用ＵＶ－Ｖｉｓ、ＥＳＲ等手段进行了表征，实验结果有最佳     

Catalytic conversion of lignocellulosic biomass to fine chemicals and fuels

Lignocellulosic biomass is the most abundant and bio-renewable resource with great potential for sustainable production of chemicals and fuels. This critical review provides insights into the state-of the-art accomplishments in the chemocatalytic technologies to generate fuels and value-added chemicals from lignocellulosic biomass, with an emphasis on its major component, cellulose. Catalytic hydrolysis, solvolysis, liquefaction, pyrolysis, gasification, hydrogenolysis and hydrogenation are the major processes presently studied. Regarding catalytic hydrolysis, the acid catalysts cover inorganic or organic acids and various solid acids such as sulfonated carbon, zeolites, heteropolyacids and oxides. Liquefaction and fast pyrolysis of cellulose are primarily conducted over catalysts with proper acidity/basicity. Gasification is typically conducted over supported noble metal catalysts. Reaction conditions, solvents and catalysts are the prime factors that affect the yield and composition of the target products. Most of processes yield a complex mixture, leading to problematic upgrading and separation. An emerging technique is to integrate hydrolysis, liquefaction or pyrolysis with hydrogenation over multifunctional solid catalysts to convert lignocellulosic biomass to value-added fine chemicals and bio-hydrocarbon fuels. And the promising catalysts might be supported transition metal catalysts and zeolite-related materials. There still exist technological barriers that need to be overcome (229 references).     

微波水热改性制备S_2O_8~(2-)/Fe_2O_3-SiO_2固体酸及催化性能

对共沉淀法得到的Fe2O3-SiO2混合氧化物前驱物进行微波水热改性处理,经浸渍(NH4)2S2O8后再焙烧得S2O82-/Fe2O3-SiO2固体酸催化剂。用XRD、TEM、N2气吸附/脱附及化学分析方法对其进行了表征,用乙酸/丁醇酯化催化反应评估固体酸的催化性能,并与通常条件下制得的催化剂进行了比较。结果显示,引入SiO2会延迟Fe2O3晶体的形成与长大;对前驱物用250W的微波水热改性处理1.5h,制得的固体酸具有适中的比表面积、均匀的孔径分布,含硫量为6.02%,比表面积为37.1m2/g。该固体酸对乙酸丁醇酯化反应有很高的催化活性,催化酯化反应3h,乙酸的转化率高达97.7%。     

酸功能化-温控型三元杂多酸离子液体的合成、表征及其酯催化性能

采用酸化-乙醚萃取法制备了不同钒取代数目的 Keggin结构的磷钨钒杂多酸,并进一步通过离子交换法合成了磺酸功能化的杂多酸离子液体催化剂,采用核磁、元素分析、红外、紫外、X射线衍射、热重-差示扫描、电位滴定等分析手段对所得样品进行了表征,考察了所得样品对氯乙酸和正戊醇的酯化反应性能和重复使用性能。结果表明,所制备的杂多酸离子液体是一种具有温度响应特性的无定型结构化合物,仍保留Keggin结构和较高的酸强度,该催化剂在反应温度下与反应物形成一相,而反应结束温度降低后,催化剂和产物又形成两相,通过简单的倾倒法就可以快速分离催化剂和反应产物。与杂多酸以及未磺酸化的杂多酸离子液体相比,磺酸功能化的杂多酸离子液体具有更高的酯催化活性。在优化的反应条件下,[PyPS]4PW11VO40(PyPS为1-(3-磺酸基)丙基吡啶)对氯乙酸的转化率可达到97.6%,重复使用4次后转化率为91.9%,而催化剂的结构未有明显变化。