Praseodymium-containing catalysts for oxidative dehydrogenation of organic compounds

A method is developed for incorporating praseodymium into magnesium–aluminum hydrotalcites, which are precursors for oxide catalysts for oxidative dehydrogenation (ODH) of alkanes. Oxide catalyst samples that contain praseodymium and various combinations of magnesium, aluminum, chromium, vanadium, molybdenum, and niobium are prepared. The catalytic properties of the prepared catalysts in ethane, propane, and butane ODH reactions are studied. Into some of our studied multicomponent catalysts, the incorporation of praseodymium enhances the reaction selectivity and increases yields of desired products.     

Chromium,vanadium, molybdenum,tungsten, magnesium,and aluminum hydrotalcite hydroxo salts and oxide catalysts on their base

A method is developed for the synthesis of chromium-containing catalysts for the oxidative dehydrogenation (ODH) of alkanes, comprising the precipitation, from nitrate solutions, of mixtures of isomorphic hydrotalcite-type magnesium aluminum and magnesium chromium hydroxocarbonates and the incorporation of oxovanadate, oxomolybdate, and oxotungstate ions by means of anion exchange and subsequent heat treatment. A series of oxide catalyst samples with progressively more complex compositions were prepared: Mg-Al, V-Mg-Al, V-Mo-Mg-Al, Cr-V-Mg-Al, Cr-V-Mo-Mg-Al, and Cr-V-Mo-W-Mg-Al. The catalytic properties of these complex oxides in the ODH of ethane and propane are improved with progressively complex compositions. Chromium-containing catalysts have higher selectivities and provide higher conversions compared to state-of-the-art iron- and nickel-containing oxides.     

Europium oxide containing catalysts for oxidative dehydrogenation of alkanes

A method is developed to incorporate europium into Mg–Al hydrotalcites, which are precursors for oxide catalysts of oxidative dehydrogenation (ODH) of alkanes; samples of oxide catalysts are prepared, where europium oxide and gallium, magnesium, aluminum, chromium, vanadium, molybdenum, and niobium oxides are contained in various combinations. The catalytic properties of these catalysts in the reactions of ethane, propane, and butane ODH are studied. The incorporation of europium into some of our studied multicomponent catalysts enhances the reaction selectivity and increases yields of desired products.     

Ytterbium-Containing Magnesium–Aluminum Hydroxo Salts with a Hydrotalcite-Type Structure

A method is developed for inserting ytterbium into Mg–Al hydroxo salts that have a hydrotalcitetype layered structure, as well as for the chemical analyses of complex hydroxo salts containing ytterbium in various combinations with magnesium, aluminum, chromium, vanadium, molybdenum, and niobium. The formation conditions of these hydroxo salts have been studied by potentiometric titration, their samples have been prepared, and X-ray diffraction patterns recorded. The prepared hydroxo salt samples have been tested as precursors for oxide catalysts of oxidative dehydrogenation (ODH) of alkanes.     

镁铝复合氧化物载体的制备与性质研究

以硝酸镁和硝酸铝为原料,用氨水溶液作为pH调节剂,采用共沉淀法制备了镁铝复合氧化物载体,研究了制备过程中镁铝比、pH调节剂种类、水解过程pH值的大小、反应温度、焙烧温度及回流晶化温度对复合氧化物载体理化性质的影响。并以RFCC汽油加氢脱硫为探针反应,考察了以镁铝复合氧化物为载体的催化剂选择性加氢脱硫性能。实验结果表明,在镁铝分子比为10、反应温度为80℃、pH值为9.5条件下制备的镁铝复合氧化物载体具有适宜的比表面积和均匀的孔分布,且晶型较完整,结晶度高。以该复合氧化物为载体制备的催化剂具有良好的RFCC汽油选择性加氢脱硫反应性能。     

Oxidative dehydrogenation of n-octane over a vanadium–magnesium oxide catalyst: Influence of the gas hourly space velocity

Oxidative dehydrogenation (ODH) of n-octane was carried out over a vanadium–magnesium oxide catalyst in a continuous flow fixed bed reactor. The catalyst was characterized by ICP–OES, powder XRD and SEM. The catalytic tests were carried out at different gas hourly space velocities (GHSVs), viz. 4000, 6000, 8000, and 10,000 h^?1. The best selectivity for octenes was obtained at the GHSV of 8000 h^?1, while that for C8 aromatics was attained at the GHSV of 6000 h^?1 at high temperatures (500 and 550 °C). The catalytic testing at the GHSV of 10,000 h^?1 showed the lowest activity, while that at the GHSV of 4000 h^?1 consistently showed the lowest ODH selectivity. Generally, the best ODH performance was obtained by the catalytic testing at the GHSVs of 6000 and 8000 h^?1. No phasic changes were observed after the catalytic testing.     

Fluorimetric determination of magnesium and aluminum via complexation with oxine in high-performance liquid chromatography

Aluminum and magnesium were determined by fluorimetric detection via pre-column and/or in-column derivatization with 8-hydroxyquinoline (oxine) in high-performance liquid chromatography. The oxine complex of aluminum was selectively detected when the eluent contained no oxine, whereas the aluminum and magnesium complexes could be simultaneously detected when the eluent contained oxine. The sensitivity was improved by using eluents containing oxine by a factor of 7.1 for aluminum, and the detection limits at S/N=3 were 18 and 16 ng/ml for magnesium and aluminum, respectively. The present system was applied to the determination of magnesium and aluminum in various water samples.     

Carbon-Doped BN Nanosheets for the Oxidative Dehydrogenation of Ethylbenzene

Carbon-based catalysts have demonstrated great potential for the aerobic oxidative dehydrogenation reaction (ODH). However, its widespread application is retarded by the unavoidable deactivation owing to the appearance of coking or combustion under ODH conditions. The synthesis and characterization of porous structure of BCN nanosheets as well as their application as a novel catalyst for ODH is reported. Such BCN nanosheets consist of hybridized, randomly distributed domains of h-BN and C phases, where C, B, and N were confirmed to covalent bond in the graphene-like layers. Our studies reveal that BCN exhibits both high activity and selectivity in oxidative dehydrogenation of ethylbenzene to styrene, as well as excellent oxidation resistance. The discovery of such a simple chemical process to synthesize highly active BCN allows the possibility of carbocatalysis to be explored.     

SBA-15 负载 β-Mg2V2O7 催化剂的制备及其催化丙烷选择氧化脱氢的性能

 以 MgO 修饰的 SBA-15 为载体, 采用浸渍法制备了负载 β-Mg2V2O7 催化剂, 并运用 X 射线衍射、拉曼光谱、紫外-可见漫反射光谱和 H2 程序升温还原等技术对催化剂 V 中心的结构和还原性能进行了表征. 结果表明, β-Mg2V2O7 具有与 α-Mg2V2O7 相同的结构单元, 但其催化丙烷氧化脱氢 (ODH) 反应的初始活性和初始选择性均低于后者. 与体相 β-Mg2V2O7 相比, 负载的 β-Mg2V2O7 上 V 中心分散度以及丙烷 ODH 反应活性和选择性更高, 520 oC 时丙烷 ODH 反应的初始活性提高了约 20 倍, 丙烯初始选择性也从体相的 88.3% 提高到 94.1%, 接近于 α-Mg2V2O7 (94.6%), 并且在 20% 的丙烷转化率时也表现出相似的规律. 这与表征催化剂选择性的两个本征动力学参数 k1/k2 (丙烷初级 ODH 和燃烧反应速率常数之比) 和 k3/k1 (次级丙烯燃烧和初级丙烷 ODH 反应速率常数之比) 反映出的规律一致. 这些对体相和负载的 Mg2V2O7 催化剂催化丙烷 ODH 反应本征特性的认识将有助于设计合成更高效的 Mg-V-O 催化剂, 如基于 α-Mg2V2O7 结构的高分散催化剂, 以获得更高的丙烷 ODH 反应活性和选择性.     

Thermal Stability of Sol-Gel Hydrotalcites

Sol-Gel Hydrotalcites were synthesized using magnesium ethoxide and variable aluminum sources: aluminum acetilacetonate, aluminum chloride, aluminum nitrate and aluminum sulfate; in all cases, the gelation was done at pH 10. X-ray diffraction studies show that the crystallinity depends on the aluminum precursor used. The crystallinity was found in the order aluminum acetylcetonate>aluminum chloride>aluminum nitrate>aluminum sulfate. The precursor determines the sintering behavior as well.     

Carbon‐Doped BN Nanosheets for the Oxidative Dehydrogenation of Ethylbenzene

Carbon‐based catalysts have demonstrated great potential for the aerobic oxidative dehydrogenation reaction (ODH). However, its widespread application is retarded by the unavoidable deactivation owing to the appearance of coking or combustion under ODH conditions. The synthesis and characterization of porous structure of BCN nanosheets as well as their application as a novel catalyst for ODH is reported. Such BCN nanosheets consist of hybridized, randomly distributed domains of h‐BN and C phases, where C, B, and N were confirmed to covalent bond in the graphene‐like layers. Our studies reveal that BCN exhibits both high activity and selectivity in oxidative dehydrogenation of ethylbenzene to styrene, as well as excellent oxidation resistance. The discovery of such a simple chemical process to synthesize highly active BCN allows the possibility of carbocatalysis to be explored.     

静电纺丝法制备硼掺杂氧化硅纳米纤维用于低碳烷烃氧化脱氢制烯烃

乙烯和丙烯等低碳烯烃是重要的基础有机化工产品,广泛应用于化工生产的各个领域.相比于其他工艺,低碳烷烃氧化脱氢制烯烃工艺具有不受热力学平衡限制、无积炭等特点而被广泛研究.近年发现六方氮化硼(h-BN)、硼化硅(SiB6)和磷酸硼(BPO4)等非金属硼基催化剂能够高效催化烷烃氧化脱氢反应,并抑制产物烯烃的过度氧化,表现出高的催化活性和烯烃选择性.大量的研究表明,硼基催化剂活性起源于催化剂表面的"BO"物种(如B-O和B-OH等基团).氧化硼(B2O3)作为一种氧化气氛中化学性质稳定的含硼化合物,兼具丰富的"BO"位点,在反应条件下可形成多种结构以适用不同的化学环境,为制备高效的烷烃氧化脱氢催化剂提供了可能.在之前的研究中,多将B2O3浸渍在常规的TiO2,SiO2,A12O3等三维多孔载体上用于氧化脱氢反应.考虑到B2O3结构的灵活性和易于成键特性,需开发更为有效的合成策略,以提升B2O3催化剂在氧化脱氢反应中的活性和稳定性.本文采用静电纺丝技术合成了直径为100～150 nm的多孔掺硼二氧化硅纳米纤维(PBSN)用于低碳烷烃氧化脱氢反应.静电纺丝法合成的催化剂中硼物种在开放的氧化硅纤维骨架上均匀分散且稳定固载.一维纳米纤维结构不仅有利于扩散,且赋予催化剂在高重时空速(WHSV)条件下优异的烷烃氧化脱氢反应活性.在乙烷氧化脱氢反应中,当乙烷的转化率达到44.3％时,乙烯的选择性和产率分别为84％和44.2 μmol gcat-1 s-1.而在丙烷脱氢反应中,当丙烷转化率为19.2％时,总烯烃选择性及丙烯产率分别为90％和76.6 μmol gcat-1 s-1.在温度为545 ℃,丙烷WHSV高达84.6 h-1的条件下,催化剂保持长时间稳定.与其他负载型氧化硼催化剂相比,PBSN催化剂具有更高的烯烃选择性和稳定性.研究表明,在氧化硅负载B2O3催化剂催化丙烷氧化脱氢反应中,载体中Si-OH基团的存在可能会降低丙烯的选择性.瞬态分析和动力学实验表明,硼基催化剂催化烷烃氧化脱氢反应过程中O2的活化受到烷烃的影响.本文不仅为高效硼基催化剂的合成提供了新思路,也为深入理解该类催化剂上烷烃氧化脱氢反应过程提供了实验支撑.     

Coordination Structure of Aluminum in Magnesium Aluminum Hydroxide Studied by ^27Al NMR

The coordination structure of aluminum in magnesium aluminum hydroxide was studied by ^27Al NMR.The result showed that tetrahedral aluminum (Al^IV) existed in magnesium aluminum hydroxide,and the contents of Al^TV increased with the increase of the ratio of Al/Mg and with the peptizing temperature.Al^IV originated from the so-called Al13 polymer with the structure of one Al tetrahedron surrounded by twelve Al octahedrons.     

Effect of gallium, aluminium, and chromium on silica supported V-Mg-O catalysts during oxidative dehydrogenation of propane: Kinetic study

The oxidative dehydrogenation （ODH） of propane was conducted on gallium, aluminum, and chromium doped Si30VMgO catalysts. On doping, the concentrations of the phases responsible for the activity and selectivity increased in their concentrations. The reaction studies were conducted in a tubular steel reactor at temperatures of 753, 783, 813, and 843 K and atmospheric pressure. The total flow rates of the feed were chosen as 30, 40, 50, and 60 ml/min. The propane to oxygen ratios were chosen at 1 ： 1, 2 ： 1, and 3 ： 1, respectively. The effect of various dopants on the activity and selectivity of the catalysts was studied. Deactivation studies were conducted over all the catalysts. The kinetic data were analyzed in terms of power law models and Langmuir-Hinshelwood （LH） models. The kinetic data results were analyzed by comparing the effect of dopants. Statistical model discrimination was done for the proposed models. AIC and BIC criteria were used for discrimination of the models.     

镁铁和镁铁铝催化剂氢还原过程的研究

以水滑石为前体 ,制备了镁铁和镁铁铝复合氧化物催化剂 ,运用原位穆斯堡尔谱研究了催化剂在H2 气氛中的还原行为。结果表明 :由于Mg、Al的加入和固溶体的形成 ,相对地稳定了FeO物相 ,阻碍了H2 对铁离子的还原 ,使得Fe2 进一步还原为金属Fe0 的能力减弱 ;在还原过程中催化剂首先生成含Fe2 的固溶体FeO MgO或FeO MgO Al2O3,然后再完全还原成金属Fe0。     

In situ UV-visible spectroscopic measurements of kinetic parameters and active sites for catalytic oxidation of alkanes on vanadium oxides

In situ diffuse reflectance UV-visible spectroscopy was used to measure the dynamics of catalyst reduction and oxidation during propane oxidative dehydrogenation (ODH) on VOx/gamma-Al2O3. Transients in UV-visible intensity in the near-edge region were analyzed using a mechanistic model of ODH reactions. Rate constants per site for the kinetically relevant reduction step (C-H bond activation) measured using this analysis are slightly larger than those obtained from steady-state ODH rates normalized by surface V. The ratio of these values provides a measure of the fraction of the V surface sites that are active for ODH (0.6-0.7, for V surface densities of 2.3-34 V nm(-2)). This suggests that some of the V atoms are either inaccessible or inactive. Reoxidation rate constants, which cannot be obtained from steady-state analysis, are 10(3)-10(5) times larger than those for the C-H bond activation reduction step.     

Study on electric property at interface of positive sol of magnesium aluminum hydroxide

The isoelectric point (IEP) and zero point of charge (ZPC) of magnesium aluminumhydroxide were studied by electrophoresis method,potentiometric titration method,and elemental analysis.Results showed that the charge of magnesium aluminum hydroxide was composed of variable charge and permanent positive charge.Because of the permanent positive charge,the IEP and ZPC obtained were higher than calculated.The IEP decreased and ZPC increased as X increased.     

Formation of hydrotalcite in aqueous solutions and intercalation of ATP by anion exchange

The formation reaction and the intercalation of adenosine triphosphate (ATP) were studied for hydrotalcite (HT), a layered double hydroxide (LDH) of magnesium and aluminum. Hydrotalcite with nitrate ions in the interlayer (HT-NO(3)) was formed (A) by dropwise addition of a solution of magnesium and aluminum nitrates (pH ca. 3) to a sodium hydroxide solution (pH ca. 14) until the pH decreased from 14 to 10 and (B) by dropwise addition of the NaOH solution to the solution of magnesium and aluminum nitrates with pH increasing from 3 to 10. The precipitate obtained with method B was contaminated with aluminum hydroxide and the crystallinity of the product was low, possibly because aluminum hydroxide precipitates at pH 4 or 5 and remains even after HT-NO(3) forms at pH above 8. With method A, however, the precipitate was pure HT-NO(3) with increased crystallinity, since the solubility of aluminum hydroxide at pH above and around 10 is high as dissolved aluminate anions are stable in this high pH region, and there was no aluminum hydroxide contamination. The formed HT-NO(3) had a composition of [Mg(0.71)Al(0.29)(OH)(2)](NO(3))(0.29).0.58H(2)O. To intercalate ATP anions into the HT-NO(3), HT-NO(3) was dispersed in an ATP solution at pH 7. It was found that the interlayer nitrate ions were completely exchanged with ATP anions by ion exchange, and the interlayer distance expanded almost twice with a free space distance of 1.2 nm. The composition of HT-ATP was established as [Mg(0.68)Al(0.32)(OH)(2)](ATP)(0.080)0.88H(2)O. The increased distance could be explained with a calculated molecular configuration of the ATP as follows: An ATP molecule is bound to an interlayer surface with the triphosphate group, the adenosine group bends owing to its bond angles and projects into the interlayer to a height of 1 nm, and the adenosine groups aligned in the interlayer support the interlayer distance.     

Static SIMS studies of carboxylic acids on gold and aluminium–magnesium alloy surfaces

Static secondary ion mass spectrometry was used to study the surface reactions and lateral distributions of fatty carboxylic acid molecules on sputter‐deposited gold and aluminium surfaces, as well as commercial aluminium–magnesium alloy surfaces, cleaned using UV/ozone. Films were prepared by spin coating dilute solutions of stearic acid and lauric acid onto the above surfaces. These carboxylic acids were shown to react with the oxide formed on the aluminium and aluminum–magnesium alloy substrates to produce a deprotonated acid anion, stabilized by the formation of a magnesium soap on the aluminium–magnesium alloy surface. Secondary ion imaging of stearic acid films revealed the formation of C‐type crystals. Copyright © 2003 John Wiley & Sons, Ltd.     

Mechanical properties,thermal stability,sound absorption,and flame retardancy of rigid PU foam composites containing a fire‐retarding agent: Effect of magnesium hydroxide and aluminum hydroxide

Isocyanate, polyether polyol, a flame retardant (10 wt%), and aluminum hydroxide/magnesium hydroxide (0, 5, 10, 15, and 20 wt%) are used to form the rigid polyurethane (PU) foam, while nylon nonwoven fabrics and a polyester aluminum foil are combined to serve as the panel. The rigid PU foam and panel are combined to form the rigid foam composites. The cell structure, compressive stress, combustion resistance, thermal stability, sound absorption, and electromagnetic interference shielding effectiveness (EMI SE) of the rigid foam composites are evaluated, examining the effects of using aluminum hydroxide and magnesium hydroxide. Compared with magnesium hydroxide, aluminum hydroxide exhibits superior performance to the rigid foam composites. When aluminum hydroxide is 20 wt%, the rigid foam composite has an optimal density of 0.153 g/cm³, an average cell size of 0.2466 mm, a maximum compressive stress of 546.44 Kpa, an optimal limiting oxygen index (LOI) of 29.5%, an optimal EMI SE of 40 dB, and excellent thermal stability and sound absorption.