Process mineralogy approach to optimize curing-leaching in vanadium-bearing stone coal processing plants

The purpose of this study is to apply process mineralogy as a practical tool to further understand and analyze the reasons for low leaching rates in the curing-leaching process of vanadium-bearing stone coal and to find a solution or improvement to optimize the leaching index. Using vanadium-bearing stone coal with the V₂O₅ mass fraction of 0.88% as the research object, the effects of particle size, mineral composition, and sulfuric acid curing on the feed, intermediate, an...     

Dissolution kinetics of malachite in ammonia/ammonium sulphate solution

The dissolution kinetics of malachite was investigated in ammonia/ammonium sulphate solution. The effects of ammonia and ammonium sulphate concentration, pH, leaching time, reaction temperature, and particle size were determined. The results show that the optimum leaching conditions for malachite ore with a copper extraction more than 96.8% are ammonia/ammonium concentration 3.0 mol/L NH₄OH + 1.5 mol/L (NH₄)₂SO₄, liquid-to-solid ratio 25:1 mL/g, leaching time 120 min, stirring speed 500 r/min, reaction temperature 25 °C and particle size finer than 0.045 mm. The dissolution process of malachite with an activation energy of 26.75 kJ/mol is controlled by the interface transfer and diffusion across the product layer. A semi-empirical rate equation is obtained to describe the leaching process and the reaction orders with respect to concentration of ammonia and ammonium sulphate are 2.983 0 and 0.941 1, respectively.     

Atom transfer radical polymerization of methyl methacrylate in [Hmim][HCOO]/THF mixtures

The atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) employing ethyl 2-bromoisobutyrate (EBiB)/CuBr as the initiating system was analyzed at 30, 40, 50 and 60 ℃ in N-methylimidazolium formate ([Hmim][HCOO])/THF mixtures. The polymerization was performed in a well-controlled manner as evidenced by kinetic study and the chain extension result. The apparent activation energy and the enthalpy of equilibrium for the preequilibrium were also investigated. Results show that Ea(app)=47.86 kJ/mol, △H0eq=25.67 kJ/mol.     

可逆反应辅助煤基乙二醇分离精制-缩醛交换反应动力学

目前煤制乙二醇生产工艺中依然存在分离精制技术难题,即副产物1,2-丁二醇与乙二醇存在共沸现象,且相对挥发度极低,常规精馏分离方法能耗高、收率低、产品质量差。针对此难题,课题组前期提出一种利用可逆反应来强化分离精制的新方法,但该方法中缩醛反应步骤存在缩醛交换过程,对该工艺的设计计算造成较大影响。作者主要针对缩醛反应步骤中的1,2-丁二醇与2-乙基-1,3-二氧戊环的缩醛交换反应动力学进行探究,通过催化剂粒径、研究转速、催化剂用量、反应温度、反应物进料摩尔比例等因素对反应过程的影响,得到了正逆反应的活化能分别为70.48 kJ/mol和80.14 kJ/mol,正逆反应的指前因子分别为3.79×10¹⁰ L/（mol·min·g）和1.95×10¹² L/（mol·min·g）,采用二级拟均相模型可以很好的对实验数据进行拟合。研究结果还表明该反应为可逆放热反应,反应热为-7.83 kJ/mol。通过该反应动力学的研究发现,合理控制反应条件可以有效提高1,2-丁二醇转化率,降低乙二醇转化率,从而实现分离,为该过程的模拟设计提供了可靠的基础数据,有助于工业化推广应用。     

Adsorption of Pb^2＋ on macroporous weak acid adsorbent resin from aqueous solutions： Batch and column studies

The adsorption properties of a novel macroporous weak acid resin (D152) for Pb²⁺ were investigated with chemical methods. The optimal adsorption condition of D152 resin for Pb²⁺ is at pH 6.00 in HAc-NaAc medium. The statically saturated adsorption capacity is 527 mg/g at 298 K. Pb²⁺ adsorbed on D152 resin can be eluted with 0.05 mol/L HCl quantitatively. The adsorption rate constants determined under various temperatures are k _{288 K}=2.22×10⁻⁵ s^t-1, k _{298 K}=2.51×10⁻⁵ s⁻¹, and k _{308 K}= 2.95×10⁻⁵ s⁻¹, respectively. The apparent activation energy, E _a is 10.5 kJ/mol, and the adsorption parameters of thermodynamics are ΔH ^Θ=13.3 kJ/mol, ΔS ^Θ=119 J/(mol·K), and ΔG ^Θ 298 K =−22.2 kJ/mol, respectively. The adsorption behavior of D152 resin for Pb²⁺ follows Langmuir model. Foundation item: Project(2008F70059) supported by the Scientific and Technological Research Planning of Zhejiang Province, China     

Leaching kinetics of low grade zinc oxide ore in NH3-NH4Cl-H2O system

The leaching kinetics of low grade zinc oxide ore in NH3-NH4Cl-H2O system was studied. The effects of ore particle size, reaction temperature and the sum concentration of ammonium ion and ammonia on the leaching efficiency of zinc were examined. The leaching kinetics of low-grade zinc oxide ore in NH3-NH4Cl-H2O system follows the kinetic law of shrinking-core model. The results show that diffusion through the inert particle pores is the leaching kinetics rate controlling step. The calculated apparent activation energy of the process is about 7.057 kJ/mol. The leaching efficiency of zinc is 92.1% under the conditions of ore particle size of 69μm, holding at 80℃ for 60 min, sum ammonia concentration of 7.5 mol/L, the molar ratio of ammonium to ammonia being 2：1, and the ratio （g/mL） of solid to liquid being 1：10.     

Devitrification behaviour of rapidly solidified Al87Ni7Cu3Nd3 amorphous alloy prepared by melt spinning method

Rapidly solidified Al87Ni7Cu3Nd3 amorphous alloy was prepared by using melt spinning. Its calorimetric behavior was characterized by using differential scanning calorimeter in a continuous or isothermal heating mode. phase transformation was investigated, with a special interest in primary crystallization, by using an in-situ examination of X-ray diffractometry （XRD） and high resolution transmission electron microscopy （HRTEM）. The results show that, the whole devitrification of rapidly solidified Al87NiyCu3Nd3 amorphous alloy involves two main processes of primary crystallization and secondary crystallization that consist mainly of two reactions. For primary crystallization, the apparent activation energies, EIso and EKis and growth activation energies Eg are about 153, 166 and 288 kJ/mol, respectively. The interdiffusion of Al atoms is a rate-controlled step of formation of the a（Al） particles, but slow diffusion of Ni and Nd atoms plays a significant role in retarding growth of the α （Al） particles. For secondary crystallization, EIso, EKis and Eg of the first reaction are about 291,208 and 290 kJ/mol, and those of the second reaction are about 367, 269 and 372 kJ/mol. The two reactions of secondary crystallization are controlled mainly in an interface-controlled three-dimensional mode, depending mainly on slow diffusion of Ni and Nd atoms.     

Kinetics of leaching refractory gold ores by ultrasonic-assisted electro-chlorination

The resources of refractory gold ores are abundant, and their effective treatment can bring good economic benefits. This paper in-vestigated the kinetics of leaching gold from refractory gold ores by ultrasonic-assisted electro-chlorination. The effects of ultrasound time ratio, initial hydrochloric acid concentration and leaching temperature on the kinetic parameters were discussed. It is found that the leaching ratio goes up with all the factors increasing. The reaction kinetics is controlled by diffusion. When ultrasound improves the diffusion by re-ducing the diffusion resistance, the activation energy increases to 37.1 kJ/mol.     

Technological conditions and kinetics of leaching copper from complex copper oxide ore

The kinetic behavior of leaching copper from low grade copper oxide ore was investigated. The effects of leaching temperature, H₂SO₄ concentration, particle size of crude ore and agitation rate on the leaching efficiency of copper were also evaluated. And the kinetic equations of the leaching process were obtained. The results show that the leaching process can be described with a reaction model of shrinking core. The reaction can be divided into three stages. The first stage is the dissolution of free copper oxide and copper oxide wrapped by hematite-limonite ore. At this stage, the leaching efficiency is very fast (leaching efficiency is larger than 60%). The second stage is the leaching of diffluent copper oxides, whose apparent activation energy is 43.26 kJ/mol. During this process, the chemical reaction is the control step, and the reaction order of H₂SO₄ is 0.433 84. The third stage is the leaching of copper oxide wrapped by hematite-limonite and silicate ore with apparent activation energy of 16.08 kJ/mol, which belongs to the mixed control.     

Alteration of diaspore by thermal treatment

Diaspore (α-AlOOH) was heated at various temperatures from 300 to 1000 ℃ for 2 h. The alteration of diaspore by thermal treatment was investigated by differential thermal analysis, thermogravimetric analysis and X-ray diffraction. The mechanism of thermal decomposition of diaspore was discussed according to the Coats-Redfern equation. It is found that after thermal treatment at 500 ℃, diaspore is transformed entirely to corundum (α-Al2O3). Combined with the mass loss ratio obtained from the thermogravimetric analysis data, the activation energies for the thermal treatment of diaspore are calculated as Ea=10.4 kJ/mol below 400 ℃ and Eb=47.5 kJ/mol above 400 ℃, respectively, which is directly related to the structural alteration of diaspore during the thermal treatment. The results indicate that the thermal decomposition of diaspore is conducted primarily by means of an interfacial reaction.     

Recovery of molybdenum from residues by simultaneous ultrafine milling and alkali leaching

A new technology of treating molybdenum residues by simultaneous ultmfme milling and alkali leaching was put forward to recover molybdenum from metallurgical residues. The effects of residue size, milling time, solid content, n(Na2CO3)/n(Mo) and slurry pH value on molybdenum leaching rate were investigated. The results indicate that a simpler process, lower slurry temperature, 50% shorter treating time, 60% decrease of Na2CO3 content and 15% increase of molybdenum leaching rate can be obtained by the new technology compared with the traditional process. The leaching kinetic equation was determined, and calculation of active energy (E = 56.2 kJ/mol) shows that the leaching process of molybdenum residues by simultaneous ultmfine milling and alkali leaching is controlled by chemical reaction. Potential exists for the new process to form the basis for an economically viable, environmentally friendly process to recover valuable elements from residues.     

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     

二氧化硫液相浸取低品位软锰矿的动力学

研究了液相中二氧化硫对低品位软锰矿的浸出行为。考察了液相搅拌转速、温度、二氧化硫浓度及pH对锰浸出率的影响,研究了软锰矿粒径及表面元素相对含量随锰浸出率的变化,并对其浸出的动力学模型进行了分析。实验结果表明,搅拌转速为400r/min时可消除外扩散对锰浸出率的影响。锰浸出率随温度、二氧化硫浓度的升高而增大,随pH的增大而减小。当锰浸出率为80%时,软锰矿粒径减小约20%,表面锰含量减小73%,硅元素含量增大18%。动力学研究结果表明,软锰矿的浸出过程为扩散-化学反应混合控制过程,反应的活化能为36.85KJ/mol,二氧化硫浓度、氢离子反应级数分别为1.5595和0.5884。     

Grain growth kinetics of SnO<Subscript>2</Subscript> nanocrystals synthesized by precipitation method

Monodispersed spheroidal SnO₂ nanocrystals with the grain size of 8–30 nm were synthesized by the precipitation method using SnCl₄·5H₂O (stannic chloride hydrate) as raw materials. Differential scanning calorimetry/thermogravimetry (DSC/TG), X-ray diffraction (XRD) and transmission electron microscope (TEM) were used to characterize the structure of SnO₂ nanocrystals. The influences of the calcination temperature and time on the lattice constant, the lattice distortion and the grain size of SnO₂ nanocrystals were discussed based on the XRD results. The grain growth kinetics of SnO₂ nanocrystals during calcination process was simulated with a conventional grain growth model which only took into account of diffusion and with a new isothermal model proposed by our group, which took into account of both diffusion and surface reactions. Using conventional model, the grain growth rate constant of SnO₂ crystals is 1.55×10⁴ nm⁵/min with a pre-exponential factor of 5 and an activation energy of 108.62 kJ/mol. Compared with the convention model, the new isothermal model is more realistic in reflecting the grain growth behavior of SnO₂ nanocrystals during the calcination process. This indicates that the grain growth of SnO₂ nanocrystals is controlled by both diffusion and reaction factors, and the effect of surface reactivity on the grain growth of SnO₂ nanocrystals could not be ignored. A combined activation energy estimated with the new isothermal model is 53.46 kJ/mol.     

Adsorption and desorption properties of D318 resin for Cr（Ⅵ）

The adsorption capability of D318 resin for Cr(VI) was investigated by chemistry analysis. Experimental results show that D318 resin has the best adsorption ability for Cr(VI) at pH=3.16 in HAc-NaAc medium. The statically saturated adsorption capacity of the resin is 265.4 mg/g. The thermodynamic adsorption parameters, enthalpy change ΔH and free energy change ΔG ₂₉₈ of the adsorption reaction are 4.81 and −5.16 kJ/mol, respectively. The apparent activation energy E _a is 22.4 kJ/mol. The adsorption behavior obeys the Freundlich isotherm. The molar coordination ratio of the functional group of resin to Cr(VI) is 3:2. Cr(VI) adsorbed on D318 resin can be eluted by 5%NaOH-5%NaCl quantitatively. Foundation item: Project (Y304121) supported by the Natural Science Foundation of Zhejiang Province, China     

Near-infrared quantum cutting in Pr3+-Yb3+ Co-doped oxyfluoride glass ceramics containing CaF2 nanocrystals

The Pr³⁺-Yb³⁺ co-doped oxyfluoride glass-ceramics containing CaF₂ nanocrystals were obtained by thermal treatment on the as-made glasses. The structure of fluoride nanocrystals was investigated. The light-emitting mechanism of Pr³⁺-Yb³⁺ in the near infrared region was proposed and the fluorescence lifetime and quantum efficiency was calculated. The results indicate that the main phase in the oxyfluoride glassceramics is CaF₂ nanocrystal sized at 30 nm. Energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) have proved the incorporation of Pr³⁺ and Yb³⁺ into CaF₂ nanocrystal lattice. Near-infrared quantum cutting involving Yb³⁺ 980 nm and 1 015 nm (²F_5/2→² F _7/2) emission has been achieved upon the excitation of the ³ P ₀ energy level of Pr³⁺ at 482 nm. The fluorescence lifetime decreases sharply and quantum efficiency increases with increasing Yb³⁺ concentration, and the optimal quantum efficiency reaches 191%.     

冶炼废水处理污泥中金的浸出过程动力学

有色冶炼废水处理污泥中含有7.70 g/t的金和90.30 g/t的银,从污泥中提取金、银等有价金属,不仅可以减小污泥对环境的危害,还能较好地避免资源浪费.以硫氰酸铵为浸出剂对除砷后的二次污泥进行了浸金研究,并采用未反应核收缩模型对浸金过程的表观动力学进行了探讨,通过尝试法确定了浸出过程的控制步骤.结果表明,搅拌强度为250 r/min时,该浸出过程受固体产物层扩散控制,其动力学方程为1-2η/3-(1-η)2/3=kDt,反应扩散系数为D’=10.807 exp(-9 855/RT),cm5.359 4mol-1.119 8s-1,表观活化能为9.855kJ/mol.     

Extraction of vanadium from stone coal by modified salt-roasting process

In order to reduce the pollution of Cl₂ and HCl released during extracting vanadium from stone coal by sodium chloride roasting, a modified salt-roasting process was proposed by adding calcined lime in roasting process followed by H₂SO₄ leaching. The effects of parameters including roasting temperature, roasting time, addition mass ratio of NaCl, calcined lime upon leaching rate of vanadium and curing rate of chlorine were investigated, and the effects of leaching time and leaching temperature on leaching rate of vanadium were also studied. The results show that the vanadium leaching rate and the curing rate of chlorine are 67.3% and 51.5% (mass fraction), respectively, at roasting temperature of 750 °C, roasting time of 4 h, 15% sodium chloride and 8% (mass fraction) calcined lime, leaching temperature of room temperature, and leaching time of 4 h.     

Electrochemical behavior of CoCl2 in ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate

The electrochemical behavior of CoCl2 in 1-butyl-3-methylimidazolium hexafluorophosphate （[bmim]PF6） was investigated by cyclic voltammetry. The cyclic voltammograms were obtained from electrochemical measurement under different temperatures, and the reversible behavior for Co^2＋/Co^3＋ redox couple on glassy carbon electrode in [bmim]PF6 was confirmed by the characteristic of the peak currents. The diffusion coefficients （about 10^-11m^2/s） of Co^2＋ in [bmim]PF6 under different temperatures were evaluated from the dependence of the peak current density on the potential scan rates in cyclic voltammograms. It is found that the diffusion coefficient increases with increasing temperature. Diffusion activation energy of Co^2＋ in [bmim]PF6 is also calculated to be 23.4 kJ/mol according to the relationship between diffusion coefficient and temperature.     

Selective leaching of vanadium from V-Ti magnetite concentrates by pellet calcification roasting-H_2SO_4 leaching process

A novel method of pellet calcification roasting-H_2 SO_4 leaching was proposed to efficiently separate and extract vanadium(V) from vanadium-titanium(V-Ti) magnetite concentrates.The leaching rate of V is as high as 88.98%,while the leaching rate of impurity iron is only 1.79%.Moreover,the leached pellets can be used as raw materials for blast furnace ironmaking after secondary roasting.X-ray photoelectron spectroscopy(XPS) and scanning electron microscopy with energy dispersive X-ray spectrometry(SEMEDS) analyses showed that V~(3+) was oxidized to V~(5+) after roasting at 1200℃,and V~(5+) was then leached by H_2 SO_4.X-ray diffraction(XRD) analyses and single factor experiment revealed a minimal amount of dissolved Fe_2 O_3 during H_2 SO_4 leaching.Therefore,a high separation degree of V and iron(Fe) from V-Ti magnetite concentrate was achieved through H_2 SO_4 leaching.Compared with the traditional roastingleaching process,this process can achieve a high selectivity of V and Fe,and has excellent prospects for industrial production.