On the Catalytic Activity of Cobalt Oxide for the Steam Reforming of Ethanol

The paper presents an investigation on the catalytic activity for the ethanol steam reforming of Co₃O₄ oxidized, reduced and supported on MgO, and of CoO in MgO solid solution. Only samples containing metallic cobalt are found to be active for reforming reaction. H₂-TPR characterization of aged samples shows that reaction mixture oxidizes a small fraction of metallic cobalt to Co⁺². A distinct role of Co⁺² and Co⁰ in the reaction is enlightened.     

EXAFS Study on Structural Change of Charcoal-supported Ruthenium Catalysts during Lignin Gasification in Supercritical Water

Lignin gasification in supercritical water over charcoal supported ruthenium trivalent salts was studied using a batch reactor at 673 K. Ruthenium (III) nitrosyl nitrate on charcoal (Ru(NO)(NO₃)₃/C) was more active than ruthenium (III) chloride on charcoal (RuCl₃/C) for the gasification reaction. EXAFS analysis revealed that ruthenium metal particles were formed in both RuCl₃/C and Ru(NO)(NO₃)₃/C catalysts during the lignin gasification and that the size of ruthenium metal in Ru(NO)(NO₃)₃/C was smaller than that in RuCl₃/C. It was concluded that well-dispersed ruthenium metal particles were active for the lignin gasification in supercritical water.     

Co-production of hydrogen and multi-wall carbon nanotubes from ethanol decomposition over Fe/Al2O3 catalysts

The co-production of hydrogen and carbon nanotubes (CNTs) from the decomposition of ethanol over Fe/Al₂O₃ at different temperatures and feeding rates of ethanol was investigated systematically. The results indicated that Fe/Al₂O₃ was a quite active catalyst for the co-production of hydrogen and CNTs and that its activity and stability depended strongly on the Fe loading. Among all catalysts tested, 10 mol% Fe/Al₂O₃ was the most effective catalyst based on the ratio of hydrogen production, the total H₂ yield, and the quality of the CNTs formed. The efficiency of hydrogen production from ethanol decomposition over 10 mol% Fe/Al₂O₃ reached a maximum of 80% at 800 °C and the yield of CNTs with well-oriented growth and uniform diameter was 141%. In addition, the reaction of hydrogen and CNTs co-produced from ethanol decomposition was proposed.     

Co-Phen-HAA/MMT催化分子氧氧化苯乙烯及其动力学研究

采用离子交换和配位合成方法,通过配位链将配体引入金属蒙脱土层间,制备了Co-Phen-HAA/MMT负载型催化材料,采用IR,XRD、SEM的现代分析测试技术,分析了催化材料的结构,XRD显示蒙脱土层间距增大0.577nm,表明配体进入金属蒙脱土的片层间;在分子氧的氧化作用下,考察了反应温度、时间、溶剂等因素对苯乙烯环氧化反应的影响.实验结果表明,最佳反应温度82℃,反应时间8 h,苯乙烯的转化率为93.9%,反应活化能41.35 kJ/mol.     

支撑液膜法脱除氨氮的动力学

研究了以聚丙烯为支撑膜、以D2EHPA为载体脱除废水中的氨氮的支撑液膜体系。通过实验确定了料液pH值、载体浓度等与铵离子渗透系数之间的关系;建立了动力学方程。     

Regenerable Sorbents for High-Temperature Desulfurization of Syngas from Biomass Gasification

Single-metal high-temperature solid sorbents for syngas cleaning using Mn, Ca, Fe, Cu, or Mo supported on γ-Al₂O₃ were synthesized, characterized, and tested in a fixed-bed reactor. H₂S and SO₂ concentrations in the gas after treatment at T = 400 to 700 °C were compared with thermodynamic calculations. The Mn-based sorbent showed the best ability to achieve a low sulfur residual in the gas, especially at temperatures above 600 °C. Sorbents with Fe, Cu, and Mo gave SO₂ formation in the initial phase, but this could be avoided by a pre-reduction treatment of the sorbent material.     

Selective separation of cobalt and nickel by supported liquid membranes

The selective separation of cobalt from acidic media, containing both equimolar and nonequimolar mixtures of cobalt and nickel, was examined by supported liquid membranes using Alamine 336 as mobile carrier dissolved in various diluents. The membrane support was microporous hydrophobic polypropylene Celgard 2500 (25 μm thick, 0.209 × 0.054 μm pore size and 55% porosity). Acetic acid-Na acetate buffer was used for the adjustment of the feed pH which was critical. Various parameters were experimentally studied and the optimum conditions were determined.     

Highly selective transport of transesterification reaction compounds through supported liquid membranes containing ionic liquids based on the tetrafluoroborate anion

We previously reported the selective simultaneous separation of the substrates and products of a transesterification reaction (vinyl butyrate, 1-butanol, butyl butyrate and butyric acid) through supported liquid membranes (SLMs) based on 1-n-alkyl-3-methylimidazolium cations combined with tetrafluoroborate, hexafluorophosphate and bis{(trifluoromethyl)sulfonyl}imide anions. The best results were obtained by the use of tetrafluoroborate based ionic liquids, which led us to further investigate the use of these new supported liquid membranes for the selective separation of different substrates and products of transesterification reactions. With this aim, the permeability of sixteen different organic compounds (vinyl esters, aliphatic esters, alcohols and carboxylic acids) through SLMs containing tetrafluoroborate based ionic liquids ([bmim⁺][BF₄⁻] and [omim⁺][BF₄⁻]) were evaluated. It was found that permeability increased as the alkyl chain length decreased for the same organic functional group. In addition, significant permeability differences were found between the different organic functional groups.As regards the operational stability of these SLMs, they were seen to be very stable when tested over eight continuous cycles of 48 h each.     

Nuclear Magnetic Resonance of Physisorbed 129Xe Used as a Probe to Investigate Porous Solids

Xenon is an inert gas with a large electronic environment that makes it sensitive to any interaction, even physical. In the case of ¹²⁹Xe isotope (spin 1/2), the resulting electronic perturbation is directly transmitted to the nucleus and, therefore, affects the nuclear magnetic resonance chemical shift. In this review, we report exhaustively up to 1996 the many applications of this technique in both fundamental and applied research in the fields of microporous and mesoporous solids.     

Organofunctionalized catalyst surfaces highly active and selective for carbon–carbon bond-forming reactions

This article illustrates two types of organofunctionalized heterogeneous catalysts for variety of organic carbon–carbon bond-forming reactions, summarizing our previous reports and also presenting new data. Organic amines with an alkoxysilane moiety were immobilized on inorganic silica-alumina surfaces (SA-NR₂) by simple silane-coupling reactions between the silica-alumina surface (SA) and the alkoxysilane. This SA-NR₂ acted as acid–base bifunctional heterogeneous catalysts for carbon–carbon bond-forming reactions, such as cyano-ethoxycarbonylation, Michael reaction of nitriles, and nitro-aldol reaction. These reactions did not occur with either SA or homogeneous amine compounds. In addition, the mixture of SA and homogeneous amine showed low catalytic activity due to undesirable acid–base neutralization reaction. Achiral organic silane-coupling reagents with a variety of functional groups were also immobilized on a SiO₂ surface that had been immobilized with chiral bis(oxazoline) (BOX), to which Cu ions were coordinated to make chiral Cu–BOX complexes on the SiO₂ surface. The SiO₂-supported Cu–BOX complex catalyst functionalized with achiral 3-methacryloxypropyltrimethoxysilane dramatically increased enantioselectivity in the asymmetric Diels–Alder reaction of cyclopentadiene and 3-acryloyl-2-oxazolidinone. The organofunctionalized catalysts showed much better performances for the C–C bond-forming reactions compared to the corresponding homogeneous systems. The heterogeneous catalysts thus obtained were characterized by solid-state ¹³C and ²⁹Si MAS NMR, FT-IR, UV/vis, XAFS, ESR, XRF, and elemental analysis.