Co-oxidation of arsenic(Ⅲ) and iron(Ⅱ) ions by pressurized oxygen in acidic solutions

The co-oxidation of As(Ⅲ) and Fe(Ⅱ) in acidic solutions by pressured oxygen was studied under an oxygen pressure between 0.5 and2.0 MPa at a temperature of 150℃. It was confirmed that without Fe(Ⅱ) ions, As(Ⅲ) ions in the solutions are virtually non-oxidizable by pressured oxygen even at a temperature as high as 200℃ and an oxygen pressure up to 2.0 MPa. Fe(Ⅱ) ions in the solutions did have a catalysis effect on the oxidation of As(Ⅲ), possibly attributable to the production of such strong oxidants as hydroxyl free radicals(OH·) and Fe(IV) in the oxidation process of Fe(Ⅱ). The effects of such factors as the initial molar ratio of Fe(Ⅱ)/As(Ⅲ), initial pH value of the solution, oxygen pressure, and the addition of radical scavengers on the oxidation efficiencies of As(Ⅲ) and Fe(Ⅱ) were studied. It was found that the oxidation of As(Ⅲ) was limited in the co-oxidation process due to the accumulation of the As(Ⅲ) oxidation product, As(V), in the solutions.     

Oxidation Behavior of Micro-Crystalline Coatings of 310S Stainless Steel

Micro-crystalline coatings of 310S stainless steels were produced by unbalanced magnetron sputter deposition. Isothermal oxidation behavior of the coated and uncoated specimens has been studied using a thermogravimetric analysis (TGA) station. The oxidation time was 50h and the temperature was 1 000℃. The oxidation rates of the coated specimens was found to be much lower than the uncoated specimens after 50 h of oxidation. The oxidation kinetic curves of the coated specimens consisted of three stages: approximately parabolic at the first stage, speeding up at the second stage, and slow down at the third stage. The increase of the oxidation rate at the second stage nasattributed to the fast diffuison of Fe though the fine grained Cr₂O₃ layer formed on the micro-crystalline coatings.The top view and cross-section microstructures of the oxides formed on the coated and the uncoated specimens were studied with SEM and EDS. It was observed that the nucleation of oxide on the coated specimens was much enhanced at the initial oxidation stage. This was explained as the result of reduction in the critical free energy change and increase in the supply of chromium ions.     

低氧LiF–NdF3熔盐体系阳极过程的电化学行为研究

The oxidation of oxygen ions and the generation of an anode effect at a low oxygen content of 150 mg/kg were discussed in this paper. Cyclic voltammetry and square-wave voltammetry tests were conducted to explore the anodic processes of LiF–NdF₃ melt after a lengthy period of pre-electrolysis purification at 1000°C (during which the oxygen content reduced from 413 to 150 mg/kg). The oxidation process of oxygen ions was found to have two stages: oxidation product adsorption and CO/CO₂ gas evolution. The adsorption stage was controlled by diffusion, whereas the gas evolution was controlled by the electrochemical reaction. In comparison with oxygen content of 413 mg/kg, the decrease in the amplitude of the current at low oxygen content of 150 mg/kg was much gentler during the forward scanning process when the anode effect occurred. Fluorine-ion oxidation peaks that occurred at about 4.2 V vs. Li/Li+ could be clearly observed in the reverse scanning processes, in which fluorine ions were oxidized and perfluorocarbons were produced, which resulted in an anode effect.     

Consolidation mechanism of gold concentrates containing sulfur and carbon during oxygen-enriched air roasting

Consolidation in calcines is a common problem in the oxygen-enriched air roasting of refractory gold concentrates containing sulfur and carbon when the initial temperature is greater than 600℃. To determine the phases that caused consolidation, gold concentrates were roasted under different conditions and the calcines were mainly detected by X-ray diffraction (XRD). The possible underlying mechanism was then studied through comparisons of the XRD patterns of different calcines. The results indicated that the generation of calcium magnesium silicate, iron-doped calcium aluminosilicate, and calcium aluminate caused the consolidation. Furthermore, an enriched oxygen atmosphere accelerated the oxidation reaction and the emitted heat increased the local temperature in calcines. The local temperature was inferred to have increased to the generation temperature zone of the corresponding liquid phases. Oxidation of the pyrite and decomposition of the dolomite and muscovite mainly occurred at the initial stage of oxygen-enriched air roasting. Calcium was confirmed to be essential to the consolidation process.     

Electrochemical investigation of the anode processes in LiF–NdF_3 melt with low oxygen content

The oxidation of oxygen ions and the generation of an anode effect at a low oxygen content of 150 mg/kg were discussed in this paper. Cyclic voltammetry and square-wave voltammetry tests were conducted to explore the anodic processes of LiF–NdF_3 melt after a lengthy period of pre-electrolysis purification at 1000°C(during which the oxygen content reduced from 413 to 150 mg/kg). The oxidation process of oxygen ions was found to have two stages: oxidation product adsorption and CO/CO_2 gas evolution. The adsorption stage was controlled by diffusion, whereas the gas evolution was controlled by the electrochemical reaction. In comparison with oxygen content of 413 mg/kg, the decrease in the amplitude of the current at low oxygen content of 150 mg/kg was much gentler during the forward scanning process when the anode effect occurred. Fluorine-ion oxidation peaks that occurred at about 4.2 V vs. Li/Li+ could be clearly observed in the reverse scanning processes, in which fluorine ions were oxidized and perfluorocarbons were produced, which resulted in an anode effect.     

Degradation of the antibiotic sulfamonomethoxine sodium in aqueous solution by photo-Fenton oxidation

In this study, photo-Fenton oxidation was applied to degradation of sulfamonomethoxine sodium (SMMS) in aqueous solution. The operation parameters of pH, temperature, and concentrations of H2O2, Fe2+ and SMMS were investigated. The optimum conditions for the photo-Fenton process were determined as follows: [SMMS]=4.53 mg/L, pH 4.0, [H2O2]=0.49 mmol/L, [Fe2+]= 19.51 μmol/L and T=25°C. Under these conditions 98.5% of the SMMS degraded. The kinetics were also studied, and degradation of SMMS by the photo-Fenton process could be described by first-order kinetics. The apparent activation energy was calculated as 23.95 kJ/mol. Mineralization of the process was investigated by measuring the chemical oxygen demand (COD), and the COD decreased by 99% after 120 min. This process could be used as a pretreatment method for wastewater containing sulfamonomethoxine sodium.     

Seepage effects of groundwater and its make-up water on triggering ground subsidence

The functioning mechanism of groundwater and its make-up water in the process of ground subsidence was studied from such three aspects as osmotic corrasion, osmotic pressure effect and concretion effect. As to osmotic corrasion, its forming conditions, mechanical mechanism and process were analyzed. As to osmotic pressure effect, it was mainly studied from hydrostatic pressurizing effect, sop softening effect and negative pressure sealing effect. Through concretion and saturation of soil, the factors of concretion settlement were analyzed. The results showed that both groundwater and its make-up water are important triggering factors to ground subsidence.     

Liquid-phase aerobic oxidation of benzyl alcohol catalyzed by mechanochemically synthesized manganese oxide

Benzyl alcohol oxidation by molecular oxygen using solid manganese oxide as a catalyst and n-heptane as the solvent was studied in the liquid phase. The catalyst was synthesized by a simple mechanochemical process at room temperature and was characterized by different physical methods. The catalyst was highly active and 100% selective for benzyl alcohol conversion to benzaldehyde. The solid catalyst can be recovered from the reaction mixture by simple filtration and can be re-used. We found n-heptane to be an excellent solvent for the oxidation reaction, and that the catalyst did not leach into solution.     

Photocatalytic Oxidation of NOx with Porous TiO2 Nanometer Thin Film

A new kind of porous nano-TiO2 composite films was prepared on the glass substrate with the water glass as hinders and the sodium fluorosilicate as solidifying reagent. The morphologies of the films were studied by scanning electron microscope(SEM). The UV-Vis spectrophotometer was also used to investigate the absorption of the films. The gasphase photocatalytic oxidation of nitrogen oxides on the composite film was carried out in TiO2 UV system, and some important factors affecting the photocatalytic oxidation were also studied such as the catalyst concentration, vapor pressure and the presence of oxygen. The results showed the conversion of NOx reached 97.5% after 2 h UV-irradiation. The final product of photo-oxidation was detected to be HNO3 hy FT-IR. The way of photocatalytic oxidation of NOx was possibly useful in the practical application.     

New structure model of oxygen-evolving center and mechanism for oxygen evolution in photosynthesis

So far, many important questions and problems concerning the structure and mechanism of photosynthetic oxygen evolution are still unsolved. On the basis of recent achievements in this field, a new structure model is proposed whereby two H2O molecules bind asymmetrically to two manganese ions (Mn1Ⅱ and Mn4Ⅲ) at the open end of "C" shaped cluster and keep rather large distance. Two histidine residues coordinate to the other two manganese ions in higher oxidation state (Mn2Ⅳ and Mn3Ⅳ ) through their nitrogen atoms of the imidazole. Cl bound as terminal ligand to Mn4Ⅲl is connected to Ca, and the latter is needed to maintain the special configuration of two Mn2O2 units by bridged-oxo and bridged-carboxylate ligands. The whole structure of oxygen evolution center is asymmetry. A new mechanism for oxygen evolution invokes predictions of asymmetric oxidation of two H2O molecules, dynamic structural changes of oxygen e-volving center and indirect proton transport, etc. Only in S2 state, could Mn1Ⅳ = O. intermediate with high oxidation potential be formed. The S2→S3 process occurs with significant structural changes, as well as intramolecular and intermolecular hydrogen transfer. The S3 state corresponds to intermediate of Mn1Ⅳ-O… H… O-Mn4Ⅳ . During S3→ [S4] →S0, the O-O bond is formed only in S4 state. The change of nucleophilic interaction between Cl and manganese ions different oxidation states has consequence for the significant structural changes in H2O oxidation process.     

Effect of Process Factors on Microstructure of Semisolid Continuous Casting Billets

Semisolid continuous casting (SSCC) is a new technology to produce billets for semisolid metal forming (SSMF). The effect of process factors, such as pouring temperature, stirring rate, preheating temperature and thermal conductivity of stirring chamber, on the microstructure of SSCC billets was studied by means of the factorial experimental method. The results show that the microstructure of SSCC billets can be controlled by the above-mentioned four process factors. In order to obtain fine and rounded granular grains in an SSCC billet, the pouring temperature, preheating temperature and stirring rate should be kept in a moderate range, and the thermal conductivity of stirring chamber should be high. The regression equations with the process factors connecting the microstructure was also set up based on experimental data.     

Microstructure and oxidation resistance of SiC–MoSi2 multi-phase coating for SiC coated C/C composites

In order to improve the anti-oxidation of C/C composites, a SiC–MoSi2multi-phase coating for SiC coated carbon/carbon composites(C/C)was prepared by low pressure chemical vapor deposition(LPCVD) using methyltrichlorosilane(MTS) as precursor, combined with slurry painting from MoSi2 powder. The phase composition and morphology were analyzed by scanning electron microscope(SEM) and X-ray diffraction(XRD) methods, and the deposition mechanism was discussed. The isothermal oxidation and thermal shock resistance were investigated in a furnace containing air environment at 1500 1C. The results show that the as-prepared SiC–MoSi2coating consists of MoSi2 particles as a dispersing phase and CVD–SiC as a continuous phase. The weight loss of the coated samples is 1.51% after oxidation at 1500 1C for 90 h, and 4.79% after 30 thermal cycles between 1500 1C and room temperature. The penetrable cracks and cavities in the coating served as the diffusion channel of oxygen, resulted in the oxidation of C/C composites, and led to the weight loss in oxidation.     

Solvent extraction and recovery of Y(III) and Yb(III) from fluorspar mineral

Yttrium and ytterbium were extracted from sulfuric acid medium using triphenylarsine (TPAs) dissolved in kerosene. The influence of different factors, such as shaking time, extractants, metal ions, sulfate ion concentrations, as well as temperature, was studied in detail. From the slope analysis method and IR measurements, the structure of the extracted species was suggested as MSO₄(HSO₄)·TPAs, where M refers to Y(III) or Yb(III). The equilibrium constants (K_ex) and thermodynamic parameters, such as the change in enthalpy (ΔH), free energy (ΔG), and entropy (ΔS), were calculated. The method of extraction and stripping was applied to obtain the aforementioned metals from a sample of fluorspar mineral giving a recovery yield of 88.2% and 83.5% for yttrium and ytterbium, respectively.     

Applications of Transition Metals in Organic Synthesis and Polymerization

1 Results Classic oxidants require rigorous control of the experimental conditions added with the problem of lack of selectivity. Catalysis by transition metals with environmentally safe oxidants provides synthetic routes to minimize pollution by giving environmental benign by-products. Fe (Ⅵ) is a powerful and a selective oxidant with Fe(Ⅲ) as a by-product, while hydrogen peroxide is clean with water as the only by-product. Separation of sodium or potassium ferrates requires tedious processes. Association of a ferric salt with a clay support had been reported previously also[1-2],which prompted us to find out a way in which sodium ferrate could be used in solution itself. Presence of copper nano-particles adsorbed on solid support, accelerate the process. Present study[3] describes the oxidation of organic substrates with in-situ prepared Fe(Ⅵ)in combination of montmorillonite K10 and metallic copper nano-particles without following the tedious and lengthy process of separation of Fe(Ⅵ). Apart from it the catalytic activities of three transition metals palladium(Ⅱ), iridium(Ⅲ) and rhodium(Ⅲ) in solution phase and under solvent less conditions were studied in the oxidation of various organic compounds by hydrogen peroxide[4] and cerium(Ⅳ) sulphate. In the oxidation by hydrogen peroxide (with substrate: catalyst ratio 1∶62 500 to 1∶1 961) palladium(Ⅱ) was found to be the most efficient catalyst, while iridium(Ⅲ) (catalyst: substrate ratio 1∶57 to 151) was so much efficient with cerium(Ⅳ) that it oxidizes even cyclohexane and benzene giving rise to 44% and 51.8% yields of carbonyl compounds.     

Application of the gel casting process in iron powder metallurgy

The effects of various gel casting process parameters such as the dispersant and solid loading on the rheology of Fe slurries, molding, and sintering behaviors were studied. The relationship between solid loading and viscidity in the process of iron base powder metallurgy was researched to obtain better microstructure and properties. The results showed that the viscosity of Fe slurries is obviously reduced with the increase of the dispersant. The suitable parameters are as follows: the solid loading is 61% and sintering temperature is 1180℃. Iron parts with relatively high density and better properties were obtained by the gel casting process.     

Catalytic oxidation of phenol in wastewater-A new application of the amorphous Fe78Si9B13 alloy

The amorphous Fe78Si9B13 alloy was used as a heterogeneous Fenton catalyst in the process of phenol degradation.The influences of main operating parameters such as reaction temperature,catalyst amount,hydrogen peroxide dosage and initial pH of solution on phenol degradation rate were investigated.The maximum mineralization of phenol was achieved at 60°C,6 g/L Fe78Si9B13, 0.31 mol/L hydrogen peroxide,with an initial pH of 2.5.More than 99%of phenol was completely removed under the optimum conditions within 10 min for a solution containing 1000 mg/L of phenol.Batch experiments for solutions containing phenol con- centrations ranging from 50 to 2000 mg/L were investigated under the above conditions and the same excellent degradation rate was obtained.The Fe78Si9B13 showed better catalytic activity than iron powder and Fe 2+ .Addition of n-butannol(hydroxyl radical scavenger)decreased the degradation rate of phenol,which demonstrates that hydroxyl radicals were mainly responsible for the removal of phenol.We demonstrated that phenol may be degraded by hydroxyl radicals decomposed by hydrogen peroxide on the surface of Fe78Si9B13 and illustrated the reaction mechanism for this process.This amorphous alloy exhibited high stability in recycling experiments and showed excellent reuse performance even after continuous operations of 8 cycles.     

Effect of Cr_2O_3 addition on the oxidation induration mechanism of Hongge vanadium titanomagnetite pellets

As part of a research project to develop a novel clean smelting process for the comprehensive utilization of Hongge vanadium titanomagnetite(HVTM), in this study, the effect of Cr2O3 addition on the oxidation induration mechanism of HVTM pellets(HVTMPs) was investigated in detail. The results showed that the compressive strength of the HVTMPs was greatly weakened by the Cr_2O_3 addition, mainly because of a substantial increase in the porosity of the HVTMPs. The Cr_2O_3 addition marginally affected the phase composition but greatly affected the microstructural changes of the HVTMPs. Increased amounts of Cr_2O_3 resulted in a decrease in the uniform distribution of the hematite grains and in an increase in the Fe–Cr solid solutions(Fe_(1.2)Cr_(0.8)O_3 and Fe_(0.7)Cr_(1.3)O_3) embedded in the hematite grains. Moreover, the compact hematite was destroyed by forming a dispersed structure and the hematite recrystallization was hindered during the oxidation induration, which adversely affected the compressive strength. On the basis of these results, a schematic was formulated to describe the oxidation induration mechanism with different amounts of added Cr_2O_3. This study provides theoretical and technical foundations for the effective production of HVTMPs and a reference for chromium-bearing minerals.     

Variation law of gas holdup in an autoclave during the pressure leaching process by using a mixed-flow agitator

The multiphase reaction process of pressure leaching is mainly carried out in the liquid phase. Therefore, gas holdup is essential for the gas-liquid-solid phase reaction and the extraction rate of valuable metals. In this paper, a transparent quartz autoclave, a six blades disc turbine-type agitator, and a high-speed camera were used to investigate the gas holdup of the pressure leaching process. Furthermore, experiments determining the effects of agitation rate, temperature, and oxygen partial pressure on gas holdup were carried out. The results showed that when the agitation rate increased from 350 to 600 r/min, the gas holdup increased from 0.10% to 0.64%. When the temperature increased from 363 to 423 K, the gas holdup increased from 0.14% to 0.20%. When the oxygen partial pressure increased from 0.1 to 0.8 MPa, the gas holdup increased from 0.13% to 0.19%. A similar criteria relationship was established by Homogeneous Principle and Buckingham's theorem. Comprehensively, empirical equation of gas holdup was deduced on the basis of experimental data and the similarity theory, where the criterion equation was determined as ε=4.54×10-11n3.65P_g0.18. It can be seen from the formula that agitation rate made the most important impact on gas holdup in the pressure leaching process using the mixed-flow agitator.     

Modeling and finite element analysis of rod and wire steel rolling process

Two thermomechanical coupled elastic-plastic finite element (FE) models were developed for predicting the 12-pass continuous rolling process of GCrl 5 rod and wire steel. The distances between stands in the proposed models were set according to the actual values, and the billets were shortened in the models to reduce the calculation time. To keep the continuity of simulation, a technique was developed to transfer temperature data between the meshes of different models in terms of nodal parameters by interpolation functions. The different process variables related to the rolling process, such as temperature, total equivalent plastic strain, equivalent plastic strain rate, and contact friction force, were analyzed. Also, the proposed models were applied to analyze the reason for the occurrence of an excessive spread in width. Meanwhile, it was also utilized to assess the influence of the roll diameter change on the simulated results such as temperature and rolling force. The simulated results of temperature are found to agree well with the measured results.     

Equilibrium between titanium ions and high-purity titanium electrorefining in a NaCl-KCl melt

TiCl_x (x = 2.17) was prepared by using titanium sponge to reduce the concentration of TiCl₄ in a NaCl-KCl melt under negative pressure. The as-prepared NaCl-KCl-TiCl_x melt was employed as the electrolyte, and two parallel crude titanium plates and one high-purity titanium plate were used as the anode and cathode, respectively. A series of electrochemical tests were performed to investigate the influence of electrolytic parameters on the current efficiency and quality of cathodic products. The results indicated that the quality of cathodic products was related to the current efficiency, which is significantly dependent on the current density and the initial concentration of titanium ions. The significance of this study is the attainment of high-purity titanium with a low oxygen content of 30×10-6.