用于氢化的铜铬氧化物催化剂的研究

通过铜铬氧化物催化剂用于豆油的选择氢化,研究了制备方法及氢化条件对催化剂活性的影响.在所用的五种催化剂中,以Adkins法制备的催化剂活性最好,碳酸氢铵法次之.文中还对催化剂焙烧气氛、焙烧温度、焙烧时间、铜铬原子比对催化剂活性的影响以及氢化温度、催化剂用量、搅拌速度、氢流速等对反应的影响进行了较详细的讨论.     

Catalysts based in cerium oxide for wet oxidation of acrylic acid in the prevention of environmental risks

Acrylic acid is a refractory compound for the non-catalytic wet oxidation (WO) process and can seriously damage the environment when released in industrial effluents. Oxidation of acrylic acid by catalytic wet oxidation (CWO) was studied in slurry conditions in a high-pressure batch reactor at 200 °C and 15 bar of oxygen partial pressure. Several solid cerium-based catalysts prepared in our laboratory were used (Ag/Ce, Co/Ce, Mn/Ce, CeO, MnO) and evaluated in terms of activity, selectivity and stability. Mn/Ce shows the higher activity in 2 h with 97.7% reduction of total organic carbon (TOC) followed by: MnO(95.5%)>Ag/Ce(85.0%)>Co/Ce(65.1%)>CeO(61.2%). Attempts were also carried out to analyze the influence of different Mn/Ce molar ratios. High percentages of Mn lead to practically total organic carbon concentration (TOC) abatements while low ratios lead to the formation of non-oxidizable compounds. Acrylic acid was readily degraded by all the catalysts pointing out the high importance of using a catalytic process. pH was an indicator of the reaction pathway and acetic acid was found as the major reaction intermediate compound; however it is completely oxidized after 2 h with exception for Co/Ce, CeO and MnO. Carbon adsorption and leaching of metals were poorly found for Mn/Ce indicating high stability. The catalyst microstructure after the reaction was analyzed and formation of whiskers of β-MnO₂ (or less probably MnOOH) were observed at the catalyst surface. Therefore, Mn/Ce revealed to be a promising catalyst for the treatment of effluents containing acrylic acid; nevertheless, its commercialization depends on further research.     

Study of the Catalytic Ozonation of Humic Substances in Water and Their Ozonation Byproducts

It is shown that using transition metals, especially Mn(II) and Ag(I), during ozonation of humic substances in water allows important reductions in the content of organic matter. Characterization of the organic compounds resulting from ozonation was made by concentrating the sample through liquid-liquid extraction or derivation with PFBOA.HCl, along with the GC/MS and GC/ECD techniques. In total, 110 different organic compounds were identified using GC/MS; mainly carboxylic acids, aromatics, hydrocarbons, aldehydes, ketones, and furan-carboxylic acids. The percentages of elimination or formation levels reached during ozonation are discussed.     

Functionalization of carbon support and its influence on the electrocatalytic behaviour of Pt/C in H2 and CO electrooxidation

Chemical modification of Carbon Vulcan XC-72R for fuel cell applications has been undertaken. Treated carbons were used as carriers for the deposition of Pt nanoparticles and used as electrocatalysts. The influence of the carbon treatment, as well as that of the Pt nanoparticles generation and their deposition route has been studied. The behaviour of the electrocatalysts in the CO and hydrogen oxidation reaction (HOR) has been studied. It was observed that carbon pre-treatment lead to difference behaviour in the CO oxidation reaction compared with the performance over non treated supports. In this way, CO oxidation was controlled by the nature of the support rather than by the nature of the Pt particles alone.     

The efficiency of methanol conversion to CO2 on thin films of Pt and PtRu fuel cell catalysts

Yields were determined for the CO₂ produced upon the electrochemical oxidation of 1.0 M methanol in 0.1 M HClO₄ at the following four fuel cell catalyst systems: Pt black, Pt at 10 wt.% metal loading on Vulcan XC-72R carbon (C/Pt, 10%), PtRu black at 50 at.% Pt, 50 at.% Ru (PtRu (50:50) black), and PtRu at 30 wt.% Pt, 15 wt.% Ru loading on Vulcan XC-72R carbon (C/PtRu, 30 wt.% Pt, 15 wt.% Ru). Samples were electrolyzed in a small volume (50 μl) arrangement for a period of 180 s keeping the reactant depletion in the cell below 1%. The dissolved CO₂ produced was determined ex situ by infrared spectroscopy in a micro-volume transmission flow cell. For the PtRu materials, the efficiencies for CO₂ formation were near 100% at reaction potentials in the range between 0.4 V (versus the reversible hydrogen electrode (RHE), V_RHE ) and 0.9 V_RHE. At the Pt catalysts, the yields of CO₂ approached 80% between 0.8 and 1.1 V_RHE and declined rapidly below 0.8 V_RHE.     

纳米载体铜基催化剂对低碳醇合成的影响

本文用沉积-沉淀法制备了新型纳米载体低碳醇合成催化剂，并与共沉淀法所制备的催化剂进行了对比，结果表明，纳米载体催化剂活性高、耐热性能好、醇收率高纳米载体对纳米载体催化剂活性大小的影响顺序为：纳米Al2O3＞纳米ZnO-ZnAl2O4＞纳米MgAl2O4＞纳米MgO.工艺参数对反应性能的影响结果表明，反应温度低，甲醇选择性高；但温度太高（＞320℃）CO2。选择性升高，且整个反应为动力学控制；压力升高可提高活性和C1-C2OH选择性，但C4OH选择性下降；结合空速对产物分布的影响，反应可能按Smith和Anderson的缩聚机理进行．     

SO_4~(2-)/TiO_2-Hβ固体超强酸催化合成乙酸正丁酯

采用均匀沉淀法制备的SO24-/TiO2-Hβ复合型固体超强酸催化剂应用于乙酸正丁酯的合成中,得出最佳合成条件为反应时间4h,原料正丁醇与乙酸的摩尔配比1.3∶1,催化剂用量为乙酸用量的3%,乙酸正丁酯的收率95.6%。     

从废铑催化剂中提取铑粉

介绍了从大庆石化总厂丁辛醇生产装置排出的废铑催化剂回收Rh的工艺流程及其生产方法，包括焚烧、溶解、电解回收、酸洗、焙烧等工序，该回收工艺简单，成本低，Rh总回收率＞95％，所得Rh纯度＞99.5%。