Kinetics of nickel leaching from roasting-dissolving residue of spent catalyst with sulfuric acid

Sulfuric acid leaching process was applied to extract nickel from roasting-dissolving residue of a spent catalyst, the effect of different parameters on nickel extraction was investigated by leaching experiments, and the leaching kinetics of nickel was analyzed. The experimental results indicate that the effects of particle size and sulfuric acid concentration on the nickel extraction are remarkable; the effect of reaction temperature is mild; while the effect of stirring speed in the range of 400–1 200 r/min is negligible. Decreasing particle size or increasing sulfuric acid concentration and reaction temperature, the nickel extraction efficiency is improved. 93.5% of nickel in residue is extracted under suitable leaching conditions, including particle size (0.074–0.100) mm, sulfuric acid concentration 30% (mass fraction), temperature 80 °C, reaction time 180 min, mass ratio of liquid to solid 10 and stirring speed 800 r/min. The leaching kinetics analyses shows that the reaction rate of leaching process is controlled by diffusion through the product layer, and the calculated activation energy of 15.8 kJ/mol is characteristic for a diffusion controlled process. Foundation item: Project (50574101) supported by the National Natural Science Foundation of China; Project (2003UDBEA00C020) supported by the Collaborative Project of School and Province of Yunnan Province, China     

Beckmann Rearrangement of Erythromycin A 9（E）－Oxime

9-Deoxo-6-deoxy-6, 9-epoxy-9, 9α-didehydro-9α-aza-9α-homoerythromycin A ( 1 ), 9-deoxo-11-deoxy-9, 11-epoxy-9, 9α-didehydro-9α-aza-9α-homoerythromycin A (2) and 9α-aza-9α-homoerythromycin cyclic lac-tam (3) were synthesized by the Beckmann rearrangement of erythromycin A 9(E )-oxime (4). The structures of compounds (1), (2) and (3) have been identified by their spectral data. The reaction mechanism was also dis-cussed. The yield of the Beckmann rearrangement of compounds (4) was better than that reported in literatures.     

氨水改性催化环己酮肟Beckmann重排反应的研究

为研究氨水改性对具有MFI结构的Silicalite-1分子筛催化环己酮肟气相Beckmann重排反应性能的影响,选用两种水热合成工艺合成了单斜和正交两种晶系的Silicalite-1分子筛,并用氨水分别对其进行改性处理。通过XRD和IR表征考察了不同合成方法、不同的处理温度、时间等因素对催化剂晶体结构、表面硅羟基的影响。表征结果说明氨水处理时间和温度可能会改变分子筛的晶系、表面硅羟基的强度和种类。改性前后Silicalite-1催化Beckmann重排反应评价的结果说明重排反应的主活性中心是硅羟基窝,但活性中心和MFI结构的晶系没有关系。碱处理能够减弱副反应活性中心末端硅羟基,提高催化剂的稳定性和产物己内酰胺的选择性。     

Determination of the entropy change for electrode reaction and dilute enthalpy of some ions by thermo-eletrochemical technology

Based on thermo-electrochemical equation for an electrode reaction, the entropy change of it can be obtained by the thermo - electrochemical technology (TECT). The entropy changes of Fe (CN) ₆ ⁻³ /Fe (CN) ₆ ⁻⁴ , H⁺/H₂(P⁰), Cu⁺²/Cu and Zn⁺²/Zn electrode reaction systems and the dilute enthalpies of the H⁺, Cu²⁺ and Zn²⁺ ions under the ion concentrations studied have been determined by a specially designed thermo-electrochemical equipment. The enthalpy change and entropy change for the five systems at unlimitedly diluted concentrations agree well with the literature. Project supporterd by the National Natural Science Foundation of China Synopsis of the first author Fang Zheng, Ph. D. and professor, born in April 1944, majoring the metallurgical thermodynamics and thermoelectrochemistry, supervised and participated in three projects supported by the National Natural Science Fundation of China and some other projects. More than 70 academic papers have been published.     

New technique of comprehensive utilization of spent Al2O3 -based catalyst

A new technology was developed to recover multiple valuable elements from the spent Al2O3-based catalyst by X-ray phase analysis and exploratory experiments. The experimental results show that in the condition of roasting temperature of 750 ℃ and roasting time of 30 min, molar ratio of Na2O to Al2O3 of 1.2, the leaching rates of alumina, vanadium and molybdenum in the spent catalyst are 97.2%, 95.8% and 98.9%, respectively. Vanadium and molybdenum in sodium aluminate solution can be recovered by precipitators A and B, and the precipitation rates of vanadium and molybdenum are 94. 8% and 92. 6%. Al（OH）3 was prepared from sodium aluminate solution in the carbonation decomposition process, and the purity of Al2O3 is 99. 9% after calcination, the recovery of alumina reaches 90. 6% in the whole process; the Ni-Co concentrate was leached by sulfuric acid, a nickel recovery of 98. 2% and cobalt recovery over 98.5% can be obtained under the experimental condition of 30% H2SO4, 80 ℃, reaction time 4 h, mass ratio of liquid to solid 8, stirring rate 800 r/min.     

Mechanism of crud formation in copper solvent extraction

The authors investigated the mechanism of crud formation in copper solvent extraction. It is indicated that pH value of solution and the phase ratio (O/A) are the main factors affecting crud formation in solvent extraction. The amount of crud extraction increases with aqueous pH value increase, and reduces with the increase of the phase ratio. Fe3 , Mg2 , fine air bubble and suspended particulates in leaching solution contribute to crud formation. One case is that a series of reactions of hydrolization and polymerization occurs for Fe3 , while pH＞2.5, polyhydric complex or Fe-SO4 complex are formed. Then the complex-ions of FeOH2 , Fe2(OH)4 2 cause poly-reaction, which is likely to lead emulsion. The study on Zeta potential indicates the repulsion between electriferous droplets in solvent extraction prevents phase coalescence, which is one of the major reasons for emulsion.     

Preparation of AgSnO2 composite powders by hydrothermal process

Silver-tin oxide powders were synthesized by the hydrothermal method with Ag（NH3）2^＋ solution and Na2SnO3 solution as raw materials and Na2SO3 as reductant. The precipitation conditions of Na2SnO3 solution and the reduction conditions of Ag（NH3）2^＋ were also investigated. The powders prepared were characterized by differential thermal analysis （DTA）, X-ray diffraction analysis （XRD）, scanning electron microscope （SEM） and energy spectrum analysis, The results show that pH value of the solution is a key parameter in the formation of Sn（OH）4 precipitate and the reduction reaction of Ag（NH3）2^＋ can release H^＋ ions, which results in synchronous precipitation of Sn（OH）6^2- as Sn（OH）4. The reduction of Ag（NH3）2^＋ and precipitation of Na2SnO3 occur simultaneously and the coprecipitation of silver and tin oxide is reached by the hydrothermal method. The silver-tin oxide composite powders have mainly flake shape of about 0.3 μm in thickness and there exists homogeneous distribution of tin oxide and silver in the powder synthesized.     

Synthesis and Characterization of a New Triple-layered Perovskite KSr2Nb3O10 and Its Protonated Compounds

New layered perovskites, KSr₂Nb₃O₁₀ and two new protonated niobates HSr₂Nb₃O₁₀·1.2H₂O and HSr₂Nb₃O₁₀, were synthesized by solid state reaction and ion-exchange reaction. These new compounds were characterized by EPMA, AAS, XRD, IR, DTA and so on. The structure may be described as treble perovskite sheets [Sr₂Nb₃O₁₀]⁻ interleaved with K⁺, H₃O⁺ or H⁺. These new compounds are new members of the Dion-Jacobsonseries with n=3 for the general formula M[A_n−1Nb_nO_3n+1], and their indexed X-ray powder diffraction data were first reported in the paper. FANG Liang: Born in 1970 Funded by Natural Science Foundation of China (No. 50002007), Major Program of Chinese Education Ministry and Open Foundation of State Key Lab. of Advanced Tech. for Materials Synthesis and Processing.     

The dynamics of acid treatment in the preparation of porous glass

1　IntroductionPorousglasswithahighsilicacontentisoneofnewfunctionalmaterials ,andithasaprosperousprospectinapplications .Inrecentyears ,porousglasswaspaidatten tionbyinternationalmaterialspecialistsandscholars[1 4] .However,thephase separationglasseswerefragileandbreakableduringtheacidtreatment,limitingtheapplica tionsofporousglass .Herein ,inthispapertheeffectsoftreatmenttime ,temperatureandacidconcentrationinthepreparationofporousglasswithhighsilicawereemphas izedonandthedynamicsandmechanis…     

The Mechanism of Sol-Gel Synthesis of Normal Spinel LiMn2O4 with Chelation of Citric Acid

The sol-gel process of citric acid chelating with metal cations for the synthesis of normol spinel LiMn2O4 and the reaction mechanion mechavism were investigated by means of XRD,TG-DTA,and SEM ,the results show that at the beginning lithium citrate and chelate compound of citic acid with manganese ions formed ,and then with heating the esterification and condensation reacions occured between them and glyol ,The products obtained are polymers in which metal cations are distibuted homogeneously on atomic scale that ensur hight reacivity to cations of Li^ and Mn^2 ,Firing the gel grepared by this process ,the lattice diffusions of solid reactant ions caused by non-homogeneity of reactants are elinimated and avoided .At 400℃ phase-pure LiMn2O4 with nanometer scale crystallization having precise stoichiometry and perfect crystallization can be obtained ,The model of chelate coordinated of double -molecule between citric acid and Mn^2 in the gel network is proosed ,It is important for explaining the dispersion state of Mn^2 and the formaiton process of gel by this model.     

Electrochemical kinetics of gold dissolving in alkaline thiourea solution

1 INTRODUCTIONEssentially , determination of electrode reac-tion mechanism is just the determination of thecourse of electrode reaction and the rate-determi-ning step[1 5]. Based on the previous results[6 11],gold dissolution mechanism undergoes the follow-ing courses in alkaline thiourea solution: adsorp-tion of thiourea on active points of electrode sur-face and formation of Au[SC(NH2)2]ads; chargetransfer fromactive gold atomto thiourea moleculeand formation of Au[SC(NH2)2]a+ds; Au-…     

Electrochemical behavior of K3Fe（CN）6 in water-in-oil microemulsion

A water-in-oil (W/O) microemulsion composed of Triton X-100, n-hexanol, n-hexane and water solution with hydrochloric acid was prepared. K₃Fe(CN)₆ was added in as a water-soluble electroactive probe, and its electrochemical behavior was investigated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). It is found that the H⁺ concentration of the water phase has a great effect on the conductivity of the W/O microemulsion, and hence influences the electrochemical behavior of K₃Fe(CN)₆. When the pH value of water phase is about 7, the electrical conductivity of the W/O microemulsion is only 1.2×10⁻⁶ S/cm, and K₃Fe(CN)₆ almost cannot react at the glassy carbon electrode. But when the H⁺ concentration is more than 3 mol/L, the W/O microemulsion has a good electrical conductivity and K₃Fe(CN)₆ shows good electrochemical performance in it. The results of CV and EIS studies indicate that the electrochemical behavior of Fe(CN)₆ ³⁻/Fe(CN)₆ ⁴⁻ in the W/O microemulsion is different from that in the aqueous solution. This may be due to the unique liquid structure of the W/O microemulsion and the unique mass transfer in the W/O microemulsion. Foundation item: Projects(20673036, J0830415) supported by the National Natural Science Foundation of China; Projects(05JT1026, 2007JT2013) supported by the Science Technology Project of Hunan Province, China     

Synthesis and coloring properties of Cd（S1-xSex） pigments by precipitate-hydrothermal method

Cd（S1-xSex） pigments （red to yellow） were synthesized by precipitate-hydrothermal method. The structure, morphology and hue of the powder were characterized by X-ray diffractometry （XRD）, scanning electron microscopy （SEM）, energy dispersive X-ray spectroscopy （EDAX） and CIE chromaticity. The optimum synthesis conditions were obtained and reaction mechanism was further analyzed as well. The results show that molar ratio of S to Se, pH value and hydrothermal reaction conditions have great effects on the hues of the pigments. Pigments with vivid hues are obtained under the conditions that pH value is about 13.0, hydrothermal reaction condition is at 140 ℃ for 4 h or at 160 ℃ for 6 h. The reaction mechanism is that Se^2- of Cd（S1-xSex） substitutes S^2- of CdS and then forms a continuous solid solution.     

Aerobic oxidation behavior of α-ionone catalyzed by N-hydroxyphthalimide combined with acetylacetone cobalt(II)

A practical catalytic method to oxidize α-ionone with molecular oxygen using N-hydroxyphthalimide(NHPI) combined with acetylacetone cobatt(II) (Co(acac)₂) was developed, and the probable catalytic mechanism was proposed. The influences of the reaction conditions on conversion of α-ionone and the selectivity of the major product (5-keto-α-ionone) were investigated, and the technical parameters for 5-keto-α-ionone were optimized. The results show that the primary product is 5-keto-α-ionone, and by-products include epoxy-α-ionone, as well as rearrangement products 4-keto-β-ionone and epoxy-β-ionone, which are characterized by infrared spectra, proton nuclear magnetic resonance spectra, mass spectra and elemental analysis. The selectivity of 5-keto-α-ionone and the conversion of α-ionone are 55.0% and 97.0%, respectively, when 30%(molar fraction) NHPI, 1.0%(molar fraction) Co(acac)₂ and no solvent are employed under O₂ pressure of 1.0 MPa and the reaction temperature of 65 °C for 11 h. The procedure shows good reproducibility in the parallel experiments. Foundation item: Project(50573019) supported by the National Natural Science Foundation of China     

Infrared-to-green upconversion properties of Er^3＋/Yb^3＋ co-doped TeO2-TiO2-K2O glasses upon excitation with 976 nm lasers diode

The energy transfer and upconversion of Er^3＋/Yb^3＋ co-doped TeO2-TiO2-K2O glasses upon excitation with 976 nm lasers diode were studied. The tellurite glasses were prepared by conventional melting methods. Their optical properties and sensitization upconversion spectra were performed. The dependence of green upconversion lu- minescence intensity on the mole ratio of Yb^3＋ to Er^3＋ and Er^3＋ concentration were discussed in detail. When the mole ratio of Yb^3＋ to Er^3＋ is 25/1 and Er^3＋ concentration is 0.1% （mole fraction）, or when the mole ratio of Yb^3＋ to Er^3＋ is 10/1 and Er^3＋ concentration is 0.15 %, the optimal upconversion luminescence intensity is obtained. The obtained glasses can be one of the potential candidates for lasers-diode pumping microchip solid-state lasers.     

Hexagonal hematite platelets synthesized from pyrite cinders by hydrothermal process

Well-crystallized hexagonal hematite (α-Fe2O3) platelets were synthesized by hydrothermal process,using a highly concentrated ferric hydroxide as precursor.The precursor was prepared by adding ammonia to the ferric sulfate solution which was obtained by leaching pyrite cinders with sulfuric acid.Structure and morphology of the synthesized products were investigated by X-ray diffraction,scanning electron microscope,transmission electron microscope and selected area electron diffraction.The results reveal tha...     

Synthesis of lanthanum tris (mono- i -octyl phthalate) and its thermal stability for polyvinyl chloride

A novel type of thermal stabilizer—lanthanum tris (mono-i-octyl phthalate) (LTMP) was synthesized by double-decomposition reaction of sodium mono-i-octyl phthalate with lanthanum chloride at 60 °C. Sodium mono-i-octyl phthalate was prepared by sodium hydrate and mono-i-octyl phthalate prepared by reaction of isooctyl alcohol and phthalic anhydride in the presence of sulfuric acid catalyst at 110 °C. The yield of lanthanum tris (mono-i-octyl phthalate) is about 84.5%. Its thermal stabilities were measured by heat-ageing oven test when incorporated into PVC. The experimental results show that the heat stability time is about 40min at 190 °C when adding 3phr (per hundred resin) to PVC. The thermal stability of this product is better than that of Ca-Zn complex and basic lead salt stabilizers, and equal to that of dibutyltin diaurate. Foundation item: The Key Program of 9^th Five-Year Plan of China(No. 96-119-04-03-05) Biography of the first author: LIU You-nian, associate professor, born in Oct. 1964, majoring in fine chemical engineering & separation processes.     

Synthesis and characterization of 2-cetyl-3-20 keto acid(N-ethyl perfluorinated octyl sulfonamide) N-ethyl ester

2-Cetyl-3-20 keto acid(N-ethyl perfluorinated octyl sulfonamide) N- ethyl ester was synthesized by the reaction of N-ethyl-N-hydroxyethyl perfluorinated octyl sulfonamide and alky ketene dimer. The experimental results show that the yield of products can be 89% when the molar ratio of perfluorinated octyl sulfonamide to ketene dimer is 1:1.1 and the reaction lasts about four hours at 80 °C. The structure of the product was characterized by FTIR and ¹HNMR. The product can dissolve in polar solvents such as NMP, DMAC, THF, DMSO, CHCl₃, and 10% weight-loss temperature measured by TGA is 202 °C. Funded by the National High-Tech Foundation(No. 2003 AA305920)     

Synthesis,characterization and catalytic application of H<Subscript>3</Subscript>PW<Subscript>12</Subscript>O<Subscript>40</Subscript>/MCM-48 in the esterification of methacrylic acid with n-butyl alcohol

A novel environmental friendly catalyst, H3PW12O40/MCM-48, was prepared by impregnation method. The catalysts were characterized by means of XRD and FT-IR. The synthesis of n-butyl methacrylate catalyzed by H3PW12O40/MCM-48 was studied with methacrylic acid and n-butyl alcohol as reactants. H3PW12O40/MCM-48 is an excellent catalyst for synthesizing n-butyl methacrylate and Keggin structure of H3PW12O40 kept unchanged after being impregnated on surface of the molecular sieve support. Effects of n（methacrylic acid）：n（n-butyl alcohol）, catalyst dosage, cyclohexane（water-stripped reagent） and reaction time on yields of the product were investigated. The optimum conditions have been found, that is, molar ratio of acid to alcohol is 1：1.6, mass ratio of catalyst used to the reactants is 0.5% and reaction time is 2.0 h. Under these conditions, the yield of n-butyl methacrylate can reach 93.7%.