Effect of cobalt (nickel) content on the catalytic performance of molybdenum carbides in dry-methane reforming

The dry-methane reforming (DMR) behavior of Co-Mo and Ni-Mo carbide catalysts has been studied in order to establish the effect of the cobalt or nickel content of molybdenum carbide DMR catalysts. The results indicate that incorporating cobalt into the Mo₂C structure at a Co/Mo ratio of 0.4, i.e. a Co_0.4Mo₁C_x catalyst, gives a DMR activity and stability that are markedly higher than those of Mo₂C catalysts. With respect to the Ni-Mo carbide catalysts, a Ni/Mo atom ratio of 0.2 (i.e. an Ni_0.2Mo₁C_x catalyst), gives the maximum synergistic interaction between Ni and Mo. However, higher molar ratios decrease the promoting effect and facilitate the phase separation of the promoter. These results are proved by X-ray diffraction, X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy and N₂-adsorption studies, and are also reflected in the poor catalytic stability of both the Co-Mo and the Ni-Mo carbide catalysts.     

高碳镍钼矿碱性还原熔炼-水浸分离与提取镍钼

在理论分析的基础上,以贵州遵义镍钼矿为原料,提出了镍钼矿碱性还原熔炼?水浸提钼的清洁冶金新工艺,考察了Na2CO3用量、温度、还原剂用量、反应时间对镍还原率及钼浸出率的影响,在最优条件下进行了扩大实验. 结果表明,在碱性介质及强还原气氛下,镍钼矿中的镍被还原成高品位镍铁合金,钼转化为可溶性的钼酸盐;最佳工艺条件为Na2CO3用量为理论量的2倍、熔炼温度1000℃、还原剂添加量为镍钼矿的5wt%、反应时间1.5 h. 最佳条件下扩大实验金属镍回收率为94.92%,金属钼挥发率为9.36%,浸出率为99.94%,固硫率接近100%,得到了高品位镍铁合金和含钼浸出液,镍钼有效分离.     

钛合金表面止焊剂脉冲式激光清洗工艺

采用脉冲式激光清洗钛合金表面的止焊剂。先通过调节功率和频率得到合适的单脉冲能量为2.0～5.0 mJ。再对比了不同单脉冲能量和光斑搭接率组合下的清洗效果,得到较优的激光清洗参数为:光斑搭接率0%～40%,功率120～200 W,频率40～50 kHz。经过较佳工艺激光清洗并酸洗后,钛合金表面品质、力学性能、显微组织及氢、氧含量均符合要求。     

Surface modification of poly(tetrafluoroethylene) with pulsed hydrogen plasma

Surface modification of polymers by pulsed plasma has been investigated to minimize degradation reactions occurring at the same time as the surface modification reactions. The hydrogen radical, ion, and electron concentrations in the hydrogen plasma were simulated as a function of the elapsed time after turning off the discharge. The contact angle measurement showed that hydrogen plasma treatment, regardless of pulsed or continuous plasma, led to degradation reactions as well as defluorination and oxidation on PTFE surfaces. The degradation reactions of PTFE chains initiated by the pulsed hydrogen plasma were not as vigorous as those by the continuous hydrogen plasma. A combination of the on‐time/off‐time of 30/270μs in the pulsed hydrogen plasma was efficacious in modifying PTFE surfaces. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 340–348, 2002     

Poly(dimethylaminoethylmethacryloylpropanesulfonate)‐suitable polymer additive for pulsed electrodeposition of nanocrystalline nickel

Nano‐nickel (n‐Ni) is deposited by a pulsed electrodeposition (PED) in the presence of nonionogenic (poly(ethylene glycol), poly(N‐vinylpyrrolidone), starch), anionogenic (gum arabic, sodium alginate), cationic (quaternized guar gum), and polyampholytic (polyzwitterionic) poly(dimethylaminoethylmethacryloylpropanesulfonate) (PDMAEMPS) polymers. It is established that, by PED (40 mA/cm², t_on = 1 ms, t_off = 50 ms, 323 K), the size of the nanocrystalline particles produced in the presence of PDMAEMPS is far less (by a factor of 6–10) than those obtained in the presence of other polymer additives. These comparative results emphasize a new possibility of controlling the nanograin size of the electrodeposited metals by PED. The dramatic difference in the size of the nickel particles and the unique ability of the polyzwitterionic (PZI) additives are connected by the specific for the polyzwitterionic macromolecular conformation response to the pulsatile electric potential. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 2967–2971, 2006     

Extraction of molybdenum(VI) from sulfate solutions by LIX 622

The application of LIX 622 (oxime derivative) as an extraction reagent of molybdenum (VI) from sulfate media was studied. The extraction system was studied as a function of contact time, temperature, aqueous pH, diluent of the organic phase and metal and extractant concentrations. The extraction is exothermic and it is dependent on the organic diluent, aqueous pH and reagent concentration. The data have been analysed numerically to determine the stoichiometry of extracted species and their equilibrium constants. It was found that molybdenum was extracted into the organic phase by a complex mechanism which involves the formation of three species (MoO₂L₂, MoO₄H₃HL⁺HSO₄⁻ and MoO₄H₂HL, where L represents the extractant). Molybdenum stripping by acidic and ammonium hydroxide solutions was also studied. © 2000 Society of Chemical Industry     

电解制备焦磷酸锰（Ⅲ）盐工艺条件及动力学研究

首次采取二极室在焦磷酸介质中电解制备可溶性三价锰盐。分别研究了电流密度、焦磷酸浓度、电解温度等因素对电极反应制备可溶性三价锰盐浓度和电流效率的影响。通过单因素条件实验进行了工艺参数的优化,对工艺的影响因素进行了具体的解释分析,并对焦磷酸介质下锰（Ⅲ）/锰（Ⅱ）在石墨电极上的动力学参数进行了计算。最佳工艺条件:电解时间为5 h左右,电流密度为10.87 mA/cm²,电解温度为0 ℃,电解液为0.3 mol/L磷酸二氢锰+3 mol/L焦磷酸。在最佳工艺条件下电解制备可溶性三价锰的浓度最高,而且电流效率也较高。通过电化学测试的参数进行动力学计算,锰（Ⅲ）/锰（Ⅱ）在0.3 mol/L磷酸二氢锰+3 mol/L焦磷酸电解液中为准可逆过程,过程的条件电极电位为1.315 V vs.NHE,二价锰离子在这个体系中的扩散系数为8.347×10^-6 cm²/s。     

‘One-pot’ synthesis of two molybdenum/tungsten (VI)–copper(I) mixed metal clusters under catalysis of 1,10-phenathroline

Under the catalysis of 1,10-phenathroline (phen), (NH₄)₂ M'S₄ (M’ = Mo,W) reacts with CuSCN and dppm in mixed solvent MeCN/DMF (1:1) to yield two saddle-shaped clusters [WS₄Cu₄(SCN)₂ (dppm)₃]·3DMF·2CH₃CN (1) and [MoS₄Cu₄(SCN)₂ (dppm)₃]·4DMF (2) (dppm = bis (diphenylphosphino) methane). Compounds 1–2 were characterized by elemental analysis, IR, UV–Vis, ¹H NMR, ³¹P NMR, and single-crystal X-ray diffraction. Each [M'S₄]²⁻ (M’ = Mo, W) anion coordinates to four Cu atoms through four bridging S atoms, and all S atoms are coordinated with two Cu atoms. In each cluster the four Cu atoms are almost in one plane, and the M’ atom is above the plane. Cluster 1 was characterized by luminescent with the λ_em = 545 nm. The possible catalysis mechanism of phenathroline is discussed.     

Extraction and separation of molybdenum(VI) from acidic media by fatty hydrazides

BACKGROUND: The increasing demand for molybdenum has encouraged the development of low‐cost and environmentally friendly extractants to recycle and recover this metal. In the present study, solvent extraction of Mo(VI) from acidic media using a mixture of fatty hydrazides synthesised from palm olein as the extractant was carried out. The effects of various parameters such as acid, diluent, contact time, extractant concentration, metal ion concentration and stripping agent and the separation of Mo(VI) from other metal ions such as Co(II), Ni(II), Al(III) and Mn(II) were investigated. RESULTS: It was found that the extraction of Mo(VI) into the organic phase involved the formation of 1:3 complexes. Mo(VI) was successfully separated from commonly associated metal ions such as Ni(II), Co(II), Al(III) and Mn(II). Mo(VI) stripping from the loaded organic phase was studied using different acidic and alkaline solutions and was found to be optimal with ammonium hydroxide solution. CONCLUSION: These results are useful for the development of a method to recover Mo(VI) from acidic media utilising fatty hydrazides as the extractant. Copyright © 2008 Society of Chemical Industry     

Studies on the synthesis of sodium ates (NaH2PO4, Na2HPO4, Na3PO4) using membrane electrolysis

Comparative studies have been carried out on the electrosynthesis of sodium phosphates in the cathode compartment of an industrial membrane cell supplied with phosphoric acid of concentrations ranging from 1 to 2 mol dm^–3. The anode compartment of the cell was supplied with brine containing 25% NaCl. Du Pont Nafion^® membranes of types N-423, N-901 and N-961 were used. It was found that current efficiencies for the production of sodium phosphates exceeded 96%, this being higher than that for sodium hydroxide and, in spite of the different properties of the membranes, these efficiencies were similar. With N-423 membrane, the current efficiency was 2 3% lower than that for other membranes, but at the same time, the voltage of the cell was lower by 8 12%. Thus, N-423 membrane gives better performance during sodium phosphate synthesis as compared to membranes N-901 and N-961.     

Electrochemical production of ferrate(vi) using sinusoidal alternating current superimposed on direct current. Pure iron electrode

The current yield for the anodic oxidation of a pure iron (99.95%) electrode to ferrate(VI) ions in 14 M NaOH between 30 and 60 °C using a sinusoidal alternating current (a.c.) at amplitudes in the range 38–88 mA cm–2 and frequencies in the range 0.5 mHz to 5 kHz superimposed on direct current (d.c.) of 16 mAcm–2 was measured under conditions of bubble induced convection in a batch cell. The current yield for ferrate(VI) synthesis exhibited a complex dependence on temperature and a.c. frequency, but generally a maximum was observed in a frequency range 2–50Hz depending on the a.c. amplitude. A global maximum current yield after 180 min of electrolysis of 33% was reached at the following conditions: a.c. amplitude of 88 mA cm–2, a.c. frequency of 50 Hz and temperature of 40 °C. At the optimum conditions the highest d.c. electrolysis yield was 23%. Thus, operation with the a.c. component leads to an increase in the yield by 43% with respect to d.c. electrolysis alone.     

Direct extraction of Mo(VI) from sulfate solution by synergistic extractants in the rotation column

Direct extraction of molybdenum from sulfate solution with synergistic extractants (mixture of D₂EHPA and TBP) was studied in the rotation column. The influence of extractant concentration and initial pH of aqueous phase was studied in the bench scale experiments. The outcomes demonstrated that the synergistic solvent extraction enhances the constancy of the extracted complexes for transfer into the organic phase. In the continuous experiments, the effect of different operating parameters such as speed of agitation, inlet solvent flow rate and inlet aqueous flow rate on the holdup, mean drop size, drop size distribution, slip and characteristic velocities and extraction percentage were examined. Modified correlations were proposed for prediction of hydrodynamic parameters with consideration of reaction extraction condition in the rotation column. Furthermore, these correlations were compared with the experimental data. According to the results, the direct extraction of Mo (VI) from aqueous solution and sulfuric media with extraction efficiency of 90.4% was obtained at higher rotor speed (240 r·min^-1 rpm) in this column.     

Simple and efficient method for the oxidation of sulfides to sulfones using hydrogen peroxide and a Mo(VI) based catalyst

A simple and efficient method for the oxidation of sulfides to sulfones at room temperature using ammonium heptamolybdate and 30% H₂O₂ is developed. The reactions provide excellent yields within short time, also sensitive functional groups such as allyl, vinyl, propargyl, alcohol, ketone, ester, pyridine and nitrile are found to be tolerated.     

Modification of Si(100) surface by plasma-enhanced graft polymerization of allylpentafluorobenzene

Abstract - Hydrophobic fluoropolymer thin films were deposited on Si(100) substrates by plasma polymerization of allylpentafluorobenzene (APFB) under different glow discharge conditions, and in the presence and absence of Ar plasma pre-activation of the substrate surfaces. The FTIR and X-ray photoelectron spectroscopy (XPS) results suggested that the plasma polymerization proceeded mainly through the C=C bond of APFB, and the fluorinated aromatic structure in the deposited polymer films was preserved to different extents, depending on the radio-frequency (RF) power used for plasma polymerization. The use of a low RF power (~5 W) readily resulted in the deposition of thin films having nearly the same fluorinated aromatic structure as that of the APFB homopolymer. For the plasma-polymerized APFB (pp-APFB) films deposited on the Ar plasma-preactivated Si(100) surfaces, solvent extraction results suggested that the pp-APFB films became covalently tethered onto the silicon substrate surfaces. Thermogravimetric (TG) analysis results indicated that the thermal stability of the pp-APFB films had been enhanced substantially after annealing at 270°C in a vacuum oven.     

Controlled synthesis of Mg(OH)2 thin films by chemical solution deposition and their thermal transformation to MgO thin films

The chemical solution deposition of Mg(OH)₂ thin films on glass substrates and their transformation to MgO by annealing in air is presented. The chemical solution deposition consists of a chemical reaction employing an aqueous solution composed of magnesium sulfate, triethanolamine, ammonium hydroxide, and ammonium chloride. The as-deposited films were annealed at different temperatures ranging from 325 to 500?°C to identify the Mg(OH)₂-to-MgO transition temperature, which resulted to be around 375?°C. Annealing the as-deposited Mg(OH)₂ films at 500?°C results in homogeneous MgO thin films. The properties of the Mg(OH)₂ and MgO thin films were analyzed by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, UV–Vis spectroscopy, and by circular transmission line model. Results by X-ray diffraction show that the as-deposited thin films have a brucite structure (Mg(OH)₂), that transforms into the periclase phase (MgO) after annealing at 500?°C. For the as-deposited Mg(OH)₂ thin film, a nanowall surface morphology is found; this morphology is maintained after the annealing to obtain MgO, which occurred with the evident formation of pores on the nanowall surface. The assessed chemical composition from X-ray photoelectron spectroscopy yields Mg_0.36O_0.64 (O/Mg ratio of 1.8) for the as-deposited Mg(OH)₂ film, where the expected stoichiometric composition is Mg_0.33O_0.67 (O/Mg ratio of 2.0); the same assessment yields Mg_0.60O_0.40 (O/Mg ratio of 0.7) for the annealed thin film, which indicates the obtainment of a MgO material with oxygen vacancies, given the deviation from the stoichiometric composition of Mg_0.50O_0.50 (O/Mg ratio of 1.0). These results confirm the deposition of Mg(OH)₂ films and the obtainment of MgO after the heat-treatment. The energy band gap of the films is found to be 4.64 and 5.10?eV for the as-deposited and the film annealed at 500?°C, respectively. The resistivity of both Mg(OH)₂ and MgO thin films lies around 10⁸?Ω·cm.     

Surface modification of sintered magnesium oxide (MgO) with chromium oxide (Cr2O3) by pulsed laser irradiation in air and liquids

Surface modification of ceramic materials by laser irradiation is widely used as a non-contact, fast and thermally activated process to generate micro and nanostructures. The effects of liquids while surface modification by laser irradiation of ceramic materials under liquid environment are least explored so far. This study reports the effects of pulsed laser irradiation in air and liquids on the microstructure and morphologies of ceramic materials. Chromium oxide (Cr₂O₃) was mixed in different concentrations (3, 5 and 7% in weight) into magnesium oxide (MgO) matrix and was sintered at 1650 °C. The structure and morphology of the sintered ceramic pellets were characterized using X-ray diffraction and scanning electron microscopy. Presence of the spinel magnesium chromium oxide (MgCr₂O₄) was identified in these samples. For surface modification of these samples, laser irradiation is carried out in air and liquids (methanol, isopropyl alcohol and acetone) using 2 ns pulsed lasers (532 nm) of different pulse repetition rates and energies. The microstructure and morphologies of the samples after irradiation was analyzed and their crystalline structure and composition were maintained after laser irradiation. It was observed that the surface morphologies of the ceramic pellets were modified by laser irradiation as a combined effect of the medium (air/liquids), energy fluence and the concentration of the Cr₂O₃ in MgO. Our results show that pulsed laser irradiation especially in liquids is an effective technique for modifying surface morphology of ceramic materials.     

Thermal imidization of poly(amic acid) on Si(100) surface modified by plasma polymerization of glycidyl methacrylate

The plasma polymerization of glycidyl methacrylate (GMA) on pristine and Ar plasma-pretreated Si(100) surfaces was carried out. The epoxide functional groups of the plasma-polymerized GMA (pp-GMA) could be preserved, to a large extent, through the control of the glow discharge parameters, such as the radio-frequency (RF) power, carrier gas flow rate, system pressure, and monomer temperature. The pp-GMA film was used as an adhesion promotion layer for the Si substrate. The polyimide (PI)/pp-GMA-Si laminates, formed by thermal imidization of the poly(amic acid) (PAA) precursor poly(pyromellitic dianhydride-co-4,4′-oxydianiline) (PMDA-ODA) on the pp-GMA-deposited Si surface (the pp-GMA-Si surface), exhibited a 180°-peel adhesion strength as high as 9.0 N/cm. This value was much higher than the negligible adhesion strength for the PI/Si laminates obtained from thermal imidization of the PAA precursor on both the pristine and the argon plasma-pretreated Si(100) surfaces. The high adhesion strength of the PI/pp-GMA-Si laminates was attributed to the synergistic effect of coupling the curing of epoxide functional groups in the pp-GMA layer with the imidization process of the PAA, and the fact that the plasma-deposited GMA chains were covalently tethered onto the Si(100) surface. The chemical composition and structure of the deposited films were characterized, respectively, by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy, while the surface morphology of the deposited films was characterized by atomic force microscopy (AFM).     

Optimization of process variables for a biosorption of nickel(II) using response surface method

The biosorption of nickel(II) was studied by using crab shell particles of diameter (d _p =0.012 mm) under different initial concentrations of nickel(II) in solution (0.01–5.0 g/l), temperature (20–40 °C), pH (2–6.5), and biosorbent dosages (0.5–10 g/l). The maximum removal of nickel(II) occurred at pH 6.5 and temperature 40 °C for a biosorbent dosage of 6 g/l. The results were modeled by response surface methodology (RSM), which determines the maximum biosorption of nickel(II) as a function of the above four independent variables, and the optimum values for the efficient biosorption of nickel(II) were obtained. The RSM studies were carried out using Box-Behnken design and the analysis of variance confirms the adequacy of the quadratic model with coefficient of correlation R² to be 0.9999. The quadratic model fitted the data well with Prob>F to be <0.0001, indicating the applicability of the present proposed model.     

脉冲电晕结合Ca(OH)2吸收法脱硫脱硝

Removal of SO2 and NOx by pulsed corona combined with in situ alkali absorption was experimentally investigated.In the reactor,a plate-wire-plate combination is devised for generating pulsed corona and then alkaline absorbent slurries were introduced into the reactor by a continuous band conveying system to capture the gaseous reaction products.It was found that both SO2 and NO could be removed by corona combined with in situ alkali absorption.The removal of SO2 increased to 75%with the corona discharge,compared with 60%removal only with Ca(OH)2 absorption.About 40%removal of NO was reached by pulsed corona combined with in situ Ca(OH)2 absorption.It was found that SO2 and NO in the gas stream are oxidized to SO3 and NO2 by pulsed corona respectively,and then absorbed by the alkali in the reactor.The removals of SO2 as well as NO were higher with Ca(OH)2 as the absorbent,compared with using CaCO3 or ZnO.