Niobium-containing catalysts—the state of the art

This review article is devoted to the materials containing niobium, which have been discovered or developed in the past few years and exhibit the potential application in heterogeneous catalysis. Niobium oxides and mixed oxides as well as sulfides, nitrides (oxynitrides), carbides (oxycarbides), and phosphates are considered. Among the catalytic processes in which Nb-containing materials were tested, liquid and gas phase oxidation is described in details, and the role of niobium in the prevention of the catalyst from SO₂ poisoning is mentioned.     

Polystyrene‐supported polyoxyethylene bound potassium permanganate as a heterogeneous oxidizing agent

Oxidation behavior of a 2 mol % divinylbenzene (DVB)‐crosslinked polystyrene‐supported permanganate function was investigated toward low molecular weight primary and secondary alcohols and aldehydes. The permanganate function was attached to a polystyrene support through cyclic polyoxyethylene (POE) units immobilized on the support. Contrary to the oxidations catalyzed by low molecular weight permanganate reagents, the oxidation of primary alcohol terminated in the aldehyde stage. The secondary alcohols were converted to the respective ketone and aldehyde to acid. The effect of the variable parameters similar to solvent, temperature, and reagent to substrate ratio was followed. Nonpolar cyclohexane was found to be the best solvent for the present study. Also the reactivity increased with increasing temperature. The oxidizing reagent possesses a long shelf life and could be recycled several times without reduction of capacity and mechanical stability. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3708–3717, 2003     

磷酸酯类离子液体在燃油深度脱硫中的应用

研究了3种磷酸酯类离子液体,即1,3-二甲基咪唑磷酸二甲酯盐([MM im]DM P)、1-乙基-3-甲基咪唑磷酸二乙酯盐([EM im]DEP)和1-丁基-3-甲基咪唑磷酸二丁酯盐([BM im]DBP)的制备过程,考察了这3种磷酸酯类离子液体对模型油中3-甲基噻吩、苯并噻吩和二苯并噻吩的脱除效果及磷酸酯类离子液体的电化学再生方法。实验结果表明,这3种磷酸酯类离子液体的脱硫能力强弱顺序为:[EM im]DEP>[BM im]DBP[MM im]DM P;且对二苯并噻吩的脱除效果最好,对苯并噻吩的脱除效果次之,对3-甲基噻吩的脱除效果较差。以[EM im]DEP为萃取剂,油剂质量比为1∶1时,经5次萃取后,二苯并噻吩的脱除率可达到99.5%。利用电解法对[EM im]DEP进行了再生,在5~10V电压下电解10h,[EM im]DEP的脱硫率可以达到新鲜[EM im]DEP的90%以上。     

Recovery of gold cyanide using inherently conducting polymers

Removal of gold from basic solutions containing [Au(CN)₂]^? has been demonstrated using the inherently conducting polymer polypyrrole. Polymers containing sulfonated aromatic dopants have been found to display a significant ability to remove gold from such solutions. Experiments performed in solutions containing both gold and copper cyanide complexes indicate that the recovery process is not highly selective. However, the polypyrroles used display significantly faster rates of gold recovery than activated carbon. © 2003 Society of Chemical Industry     

基于MODBUS协议的激光雕刻切割系统HMI人机交互设备

近年来,国内激光雕刻切割控制器技术发展迅速,基于PC的传统控制器已相当成熟.为了显著提高工业生产效率,适应工业生产规模扩张的需要以及工业对系统稳定性要求的提高,目前国内几家专业运动控制器厂家已经实现了激光雕刻切割控制器的完全脱机运行.本文针对脱机控制器的需要设计一款人机交互设备,该设备采用AT89C55WD单片机为主控制器,采用标准的MODBUS协议实现HMI与脱机控制器的可靠通讯.     

Precision measurement of energy and position resolutions of the BTeV electromagnetic calorimeter prototype

The energy dependence of the energy and position resolutions of the electromagnetic calorimeter prototype made of lead tungstate crystals produced in Bogoroditsk (Russia) and Shanghai (China) is presented. These measurements were carried out at the Protvino accelerator using a 1–45 GeV electron beam. The crystals were coupled to photomultiplier tubes. The dependence of energy and position resolutions on different factors as well as the measured electromagnetic shower lateral profile are presented.     

Structural changes in isothermal crystallization process of polyoxymethylene investigated by time-resolved FTIR, SAXS and WAXS measurements

Structural evolution in the isothermal crystallization process of polyoxymethylene from the molten state has been investigated by carrying out the time-resolved measurements of infrared spectra and synchrotron small angle X-ray scattering (SAXS) and wide angle X-ray scattering. In case of isothermal crystallization at 130 °C, for example, the infrared bands intrinsic of folded chain crystal (FCC) morphology appeared at first, and then the bands of extended chain crystal (ECC) morphology were detected with time delay of ca. 150 s. In the SAXS experiment at 130 °C, the lamellar stacking structure of the long period of ca. 15 nm was observed at first, which changed rapidly to ca. 12 nm in a short time. The SAXS peak with the long period of ca. 6 nm started to appear with a time delay of ca. 150 s after the initial lamellae appeared and coexisted with the initially-observed 12 nm peak. Judging from the timing to detect these characteristic infrared and SAXS signals, a good correspondence was found to exist between the stacked lamellar structure of 12 nm long period and FCC morphology and between the structure of 6 nm long period and ECC morphology. The quantitative analysis was made for the SAXS data on the basis of the lamellar insertion model combined with the paracrystalline theory of the second-kind of disorder. The following structural evolution was deduced from all these results. Immediately after the temperature jump from the melt to 130 °C, the stacked lamellar structure of FCC morphology was generated at first. New lamellae were formed from the amorphous region in between the originally-existing lamellae about 150 s later, where the random chain segments bridging the adjacent lamellae were extended to form the taut tie chains, giving infrared bands of ECC morphology. This inserted lamellar structure of 6 nm long period coexisted at a population of ca. 6% with the initially-formed lamellar stacking structure of 12 nm long period. When the experiment was made at 150 °C, only the formation of stacked lamellar structure of FCC morphology was observed and the insertion of new lamella did not occur.     

锂离子电池用聚合物电解质的最新进展II.含液聚合物电解质

由于干态聚合物电解质目前还不能满足聚合物锂离子电池的应用要求,人们致力于开发含液体增塑剂的聚合物电解质,包括凝胶型和微孔型两类体系。本文综述了含液聚合物电解质的最新进展,重点论述了各种新体系和新方法。     

Segmented polymer networks containing amino‐dendrimers

Polymer networks in which poly(propylene imine) dendrimers (Astramol?) are connected to each other by linear polytetrahydrofuran (polyTHF) segments, were prepared by two methods. The first method was a one‐step procedure in which bifunctionally living polyTHF, obtained by initiation of the THF polymerization with trifluoromethane sulfonic anhydride (triflic anhydride), was reacted with an amino‐dendrimer. This reaction was very fast but did not allow formation of the end products. The second method was a two‐step procedure. In a first step, living polyTHF, prepared with acryloyloxybutyl triflate as initiator, was grafted on an amino‐dendrimer, to form a star‐like, acrylate‐terminated polyTHF multi‐macromonomer with the dendrimer as core. In a second step, networks were obtained by Michael addition between the acrylate end‐groups and unreacted amino‐groups of the dendrimer. This cross‐linking reaction occurred spontaneously upon heating of the solution of the multi‐macromonomer with gelation times varying from a few minutes to a few hours, depending on the temperature and the composition of the prepolymers. With this method it was possible to prepare networks in the form of coatings or films. © 2003 Society of Chemical Industry     

Electro-organic synthesis without supporting electrolyte: Possibilities of solid polymer electrolyte technology

The application of ion exchange membranes as solid polymer electrolytes (SPE) in fuel cells is state-of-the-art. This technology needs no supporting electrolyte; consequently it can be applied for electro-organic syntheses in order to save process steps. In this case the process is not predetermined to a maximized energy efficiency so that the selection of the cell design, of the electrode materials and of the operating conditions can be focused on a high selectivity of the electrode reactions. The electro-osmotic stream, which is caused by the solvation shells of the ions during their migration through the membrane, and hence is a typical property of SPE technology, has a significant effect on the electrode reactions. It generates enhanced mass transfer at the electrodes, which is beneficial for reaction selectivity. It can be influenced by the choice of, and possibly by the preparation of, the membrane. An additional remarkable advantage of SPE technology is the exceptional long durability of oxide coated electrodes. By combination of several process engineering methods stable operation of SPE cells has been realized, even for examples of non-aqueous reaction systems. Experiments up to 6000 h duration and in cells of up to 250 cm² membrane area show the potential for industrial application.