Fischer-Tropsch reaction over cobalt catalysts supported on zirconia-modified activated carbon

An attractive Fischer-Tropsch catalyst was prepared using an activated carbon as carrier to support cobalt based catalysts. Zr promoted Co/AC catalysts remarkably enhanced the activity and the selectivity toward diesel distillates and lower the methane selectivity. This modification may be attributed to specific behavior of activated carbon with high surface area and the weak interaction between metallic cobalt active sites and activated carbon. It was emphasized that the pore size of activated carbon played a very important role in restricting the growth of carbon chain to wax.

板栗壳对水中Cu~(2+)吸附性能的研究

【目的】研究食品加工剩余物板栗壳对水中Cu2+的吸附性能,为其用于含铜废水的处理提供理论依据。【方法】研究吸附质溶液pH、Cu2+质量浓度、吸附剂用量、粒径、吸附温度和时间对板栗壳吸附Cu2+效果的影响,探讨吸剂和吸附剂循环利用次数对解吸和再生的影响;并采用穿透曲线和洗脱曲线对动态吸附进行了分析。【结果】吸附质溶液pH值为6、Cu2+起始质量浓度为20 mg/L、吸附剂粒径为0.25 mm时的吸附效果较好,该吸附为放热过程,升高温度虽然可以加快吸附进程,但却降低了吸附量和去除率。Na+和Ca2+对Cu2+的解吸置换能力较弱,0.1mol/L HCl可使96.1%的Cu2+得以解吸回收。通过Thomas模型预测,在固定床柱吸附条件下饱和吸附量为10.94mg/g。【结论】板栗壳对水中Cu2+的吸附性能较好,因而具有很好的应用前景。

板栗壳吸附Cu~(2+)的平衡与动力学研究及工艺设计

研究了板栗壳吸附Cu2+的平衡、动力学和热力学特征并对吸附工艺进行设计.采用Langmuir和Freundlich等温线对静态吸附平衡数据进行了拟合,同时采用准一级动力学和准二级动力学模型对静态吸附动力学数据进行了拟合,并计算了吸附过程的热力学参数自由能变(ΔGo)、焓变(ΔHo)和熵变(ΔSo).结果表明,平衡实验数据符合Langmuir等温吸附模型,分离因子RL值在0～1之间,为有利吸附;动力学实验数据符合准二级动力学方程,平衡吸附量随Cu2+起始浓度增大而增大;ΔHo和ΔSo分别为12.206kJ·mol-1和21.534J·mol-·1K-1,ΔGo为负值,表明板栗壳吸附Cu2+为放热过程,可以自发进行,吸附过程增加了固液界面的混乱度.基于Langmuir等温吸附模型推导出的板栗壳用量计算公式可用于预测将一定体积一定起始浓度Cu2+溶液经过吸附降至所需浓度的板栗壳用量.

Chemisorption and reaction characteristics of methyl radicals on Cu(110)

Methyl radicals are generated by pyrolysis of azomethane, and the condition for achieving neat adsorption on Cu(110) is described for studying their chemisorption and reaction characteristics. The radical-surface system is examined by X-ray photoemission spectroscopy, ultraviolet photoemission spectroscopy, temperature-programmed desorption, low-energy electron diffraction (LEED), and high-resolution electron energy loss spectroscopy under ultrahigh vacuum conditions. It is observed that a small fraction of impinging CH3 radicals decompose into methylene possibly on surface defect sites. This type of CH2 radical has no apparent effect on CH3(ads) surface chemistry initiated by dehydrogenation to form active CH2(ads) followed by chain reactions to yield high-mass alkyl products. All thermal desorption products, such as H-2, CH4, C2H4, C2H6, and C3H6, are detected with a single desorption peak near 475 K. The product yields increase with surface coverage until saturation corresponding to 0.50 monolayer of CH3(ads). The mass distribution is, however, invariant with initial CH3(ads) coverage, and all desorbed species exhibit first-order reaction kinetics. LEED measurement reveals a c(2 x 2) adsorbate structure independent of the amount of gaseous exposure. This strongly suggests that the radicals aggregate into close-packed two-dimensional islands at any exposure. The islanding behavior can be correlated with the reaction kinetics and is deemed to be essential for the chain propagation reactions. Some relevant aspects of the CH3/Cu(111) system are also presented. The new results are compared with those of prior studies employing methyl halides as radical sources. Major differences are found in the product distribution and desorption kinetics, and these are attributed to the influence of surface halogen atoms present in those earlier investigations.

Liquid-phase hydrodechlorination of chlorinated benzenes over active carbon supported nickel catalysts under mild conditions

Liquid phase hydrodechlorination of chlorinated benzenes was studied over Ni/active carbon (Ni/AC), Ni/gamma-Al2O3, Ni/SiO2 and Raney Ni. The complete dechlorination of chlorobenzene (ClBz) was realized at 333-343 K on Ni/AC under hydrogen atmosphere of 1.0 MPa in the presence of alkaline hydroxide. Dichloro- and trichlorobenzenes were also hydrodechlorinated with 50-95% yields of benzene under the similar conditions, as above. The reaction follows zero-order to ClBz concentration and 1.9 order to hydrogen pressure. The reaction does not proceed in the absence of alkaline hydroxide, suggesting the complete coverage of active nickel surface with produced chlorine and the removal of the chlorine ion with hydroxide ion as a rate-limiting step. The active catalysts were characterized by H-2 chemisorption and transmission electron microscopy techniques. The apparent activity strongly depends on the active area of nickel on catalyst surface. (C) 2004 Published by Elsevier B.V.

长期施肥对黑土中Cu、Cd含量及其剖面分布的影响

以经过8个不同施肥处理的黑土样品为材料,研究长期不同施肥处理下,黑土中Cu、Cd含量的差异。采用原子吸收分光光度法和Tessier-连续提取法,研究黑土中全Cu、全Cd和有效Cu、有效Cd的含量差异。结果表明,有机肥的长期施用,会使土壤中Cu、Cd与有机质发生络合并使Cu、Cd在土壤表层累积;秸秆和氮磷钾(S+NPK)化肥的长期配合施用,有利于作物对有效Cu和Cd的吸收,从而使Cu、Cd在土壤中没有明显积累;NP及NPK处理下,二铵、氯化钾肥对土壤中Cu、Cd积累的影响不明显。长期耕作不施肥(CK)处理时,因无外源Cu、Cd,以及作物对有效Cu、Cd的长期吸收,土壤中Cu、Cd含量低于不耕作不施肥(休闲)处理的。从垂直剖面上看,Cu、Cd主要积累在黑土表层,而表层以下不同施肥处理间Cu、Cd含量的差异和变幅不大。有机肥料能明显地向土壤中带入Cu、Cd,造成Cu、Cd在土壤表层的积累,并由于植物体的吸收对人体造成潜在危害,而其他化学肥料对土壤中Cu和Cd积累的影响不明显。本研究为人们的生产实践提供了施肥理论和依据,并且对土壤的污染防治也具有现实意义。

Multi-walled carbon nanotubes supported Pt-Fe cathodic catalyst for direct methanol fuel cell

Multi-walled carbon nanotubes supported Pt-Fe cathodic catalyst shows higher specific activity towards oxygen reduction reaction as compared to Pt/MWNTs when employed as cathodic catalyst in direct methanol fuel cell.

Electrocatalytic properties of Cu-Zr amorphous alloy towards the electrochemical hydrogenation of nitrobenzene

The Cu-Zr amorphous alloy was studied as an electrocatalyst towards the electrochemical hydrogenation of nitrobenzene. The electrocatalyst was activated by chemical etching in HF solution. Resulted changes in the morphology, chemical composition and crystalline structure of the electrocatalyst surface were characterised by scanning electron microscopy, X-ray diffraction and Auger electron spectroscopy. The electrocatalytic properties of the Cu-Zr amorphous alloy were assessed by voltammetric measurements. Due to the formation and aggregation of Zr residue modified Cu nanocrystals on the surface caused by the selective dissolution of Zr components in the chemical etching, the activated amorphous alloy is an effective electrocatalyst for the electrochemical reduction reaction of nitrobenzene with aniline as the main product. The positive shift of the peak potential and accompanying increase in the value of peak current in voltammograms with increasing Cu content and decreasing Zr content of the alloy surface in the chemical etching are indicative of improved electrocatalytic activity. (C) 2002 Elsevier Science B.V. All rights reserved.

Activated carbon supported bimetallic CoMo carbides synthesized by carbothermal hydrogen reduction

A carbothermal hydrogen reduction method was employed for the preparation of activated carbon supported bimetallic carbide. The resultant samples were characterized by BET surface area measurement, X-ray diffraction, and temperature-programmed reduction-mass spectroscopy. The results showed that nanostructured beta-Mo2C can be formed on the activated carbon by carbothermal hydrogen reduction above 700 degreesC. The particle sizes of beta-Mo2C increase with increasing reaction temperatures and Mo loading. The bimetallic CoMo carbide can be synthesized by the carbothermal hydrogen reduction even around 600 degreesC. The bimetallic CoMo carbide is from carbothermal hydrogen reduction of CoMoO4 precursor and is easily formed when the Co/Mo molar ratio is 1.0. Separation of the bimetallic CoMo carbide phase into Mo carbide and Co metal occurs when the temperature of the reduction is above 700 degreesC. The addition of a second metal such as Co and Ni, decreases the formation temperature of carbide because the second metal promotes formation of CHx species from reactive carbon atoms or groups on carbon material and hydrogen, which further carburizes oxide precursors. (C) 2003 Elsevier Science Ltd. All rights reserved.