Kinetic process of oxidative leaching of chalcopyrite under low oxygen pressure and low temperature

Kinetic process of oxidative leaching of chalcopyrite in chloride acid hydroxide medium under oxygen pressure and low temperature was investigated. The effect on leaching rate of chalcopyrite caused by these factors such as ore granularity, vitriol concentration, sodium chloride concentration, oxygen pressure and temperature was discussed. The results show that the leaching rate of chalcopyrite increases with decreasing the ore granularity. At the early stage of oxidative reaction, the copper leaching rate increases with increasing the oxygen pressure and dosage of vitriol concentration, while oxygen pressure affects leaching less at the later stage. At low temperature, the earlier oxidative leaching process of chalcopyrite is controlled by chemical reactions while the later one by diffusion. The chalcopyrite oxidative leaching rate has close relation with ion concentration in the leaching solution. The higher ion concentration is propitious for chalcopyrite leaching.     

Kinetics of oxidative leaching of ocean polymetallic nodules in molten potassium hydroxide medium

The kinetics of oxidative leaching of ocean polymetallic nodules in molten potassium hydroxide medium was investigated in terms of the gas-flow rate, stirring rate, reaction time, reaction temperature and partial pressure of oxygen on the ratio of manganese conversion in ocean polymetallic nodules. The category of the rate controlling step was determined. The process of the liquid-phase oxidation reaction can be described by surface chemical reaction-controlled non-reaction shrinking core model(SCM), the apparent activation energy was achieved and the rate equation was put forward. From the equation, it can be concluded that the reaction rate mainly depends on the reaction temperature and the partial pressure of oxygen.     

THERMODYNAMIC STUDY OF CHROMITE CAUSTICFUSION PROCESS

1. General introductionChromate production from cblomite is an important basic industry in the field of chemical engineering and metallurgy. The conventional chromate production process consists ofthree procedures: roaSting of chromite with oxygen at high temperature (1150C) -- waterleaching -- multistage evaporation crystallization[ll. It works at a quite low utilization efficiency of resource and energy. A large amount of chromium-containing residue, chromitedusts and waste gases are discha…     

Dissolution kinetics of molybdite in KOH media at different temperatures

The dissolution kinetics of synthetic molybdite (MoO₃) in a potassium hydroxide (KOH) medium was studied by varying the system temperature, KOH concentration, and particle size. Additionally, the effects of the stirring rate and different reagents such as barium hydroxide (Ba(OH)₂), calcium hydroxide (Ca(OH)₂), and sodium hydroxide (NaOH) were also evaluated. The experiments were performed in a reactor with controlled temperature and agitation. The results indicated that the dissolution reaction mechanism of molybdite generates potassium molybdate (K₂MoO₄) without intermediate compounds. Temperature (6–80 °C), KOH concentration (0.0005–0.025 mol/L), and particle size (5–40 μm) positively affected the dissolution of molybdite. The maximum Mo recovery was 67.5% in 0.25 h for 80 °C and 0.01 mol/L KOH. At the lowest temperature (6 °C), which is near the freezing point of water (0 °C), a substantial amount of Mo was recovered (17.8% in 45 min). The kinetics equation describing the molybdite dissolution in a KOH environment indicated that diffusion occurs through the porous layer. The activation energy was calculated to be 47.81 kJ/mol. A reaction order of 1.0 with respect to KOH concentration was obtained and was found to be inversely proportional to the squared particle size. The kinetics equation was obtained. The dissolution of molybdite resulting from the oxidation of a molybdenite concentrate (MoS₂) led to a low molybdenum recovery, which was primarily caused by the consumption of KOH by impurities such as CaCO₃ and Cr(MO₄)₃.     

含钒钛转炉渣氧压酸浸过程V-Ti-H2O系的电位-pH图

为了分析含钒钛转炉渣氧压酸浸过程的热力学特点,根据高温水溶液中计算标准摩尔吉布斯自由能和活度系数的经验公式,通过计算得到了氧分压0.5MPa、对应离子的质量浓度0.1mol/kg、温度60～200℃条件下V-Ti-H2O系的电位-pH图。在pH〈2的酸性条件下,可溶性V3＋,VO2＋,VO2＋的稳定区几乎全部包含在TiO2的稳定区范围内,随着温度由60℃升高到200℃,钒、钛稳定共存区对应的氧化还原电位逐渐增大,pH逐渐降低。钒、钛稳定区的共存特点从热力学角度为转炉渣采用氧压酸浸工艺通过一步酸浸将钒浸出的同时使钛富集在渣中提供了理论依据。含钒钛转炉渣的氧压酸浸实验结果表明,在浸出温度140℃、氧分压0.5MPa、粒度0.055～0.075mm、液固比15：1、浸出时间120min、搅拌速度500r/min、初酸浓度200g/L的条件下,钒的浸出率为96.87%,钛的浸出率为8.76%。钒与钛通过氧压酸浸工艺能够得到有效分离,实验结果与热力学计算结果一致。     

A Kinetic Study of the Leaching of Molybdenite

A study of the rate of dissolution of molybdenite (MoS₂) in alkaline solution was carried out under carefully controlled conditions. Effects of temperature, oxygen over-pressure, and KOH concentration were evaluated. Studies were made in the temperature range 100°C to 175°C and in the pressure range 0 to 700 psia of oxygen. Under these conditions molybdenite was found to leach according to a linear mechanism. Both oxygen over-pressure and KOH concentration were found to control the rate of leaching. The mechanism has been explained in terms of adsorption of oxygen at the molybdenite surface followed by configurational rearrangement of the adsorbed molecules. The hydroxyl ion dependency is believed to be diffusion-controlled. Laboratory batch studies have shown that molybdenite can be readily dissolved in alkaline solutions under moderate conditions of temperature and pressure. Commercial application of this process to the production of ferro-molybdenum and molybdenum chemicals is promising in view of the ease of dissolution of molybdenite and the relatively noncorrosive conditions involved in the process.     

Leaching of chromite ore in concentrated KOH by catalytic oxidation using CuO as catalyst

CuO was used as a catalyst in the concentrated KOH solution to enhance the leaching of chromium from the chromite ore. The impacts of temperature, KOH-to-chromite ore mass ratio, CuO-to-chromite ore mass ratio, and gas flow rate on the chromium leaching rate were investigated. The results indicated that CuO played an important role in improving the chromium leaching rate. The leaching rate reached 98% after leaching for 6 h when CuO was applied, whereas it was only 60.8% without CuO under the same reaction conditions: temperature 230 °C, KOH-to-ore mass ratio 6:1, stirring speed 700 r/min, gas flow rate 1 L/min. According to the kinetics study, the catalytic oxidation was controlled by surface chemical reaction and the activation energy was calculated to be 15.79 kJ/mol when the temperature was above 230 °C. In contrast, without CuO, the rate-determining step was external diffusion and the apparent activation energy was 38.01 kJ/mol.     

Ag/CuO复合材料反应合成热力学分析

通过对Ag/CuO复合材料在反应合成制备中各元素、亚金属氧化物与1 mol氧气反应生成金属氧化物的标准自由焓的热力学计算,绘制了标准自由焓与温度关系图;考虑到氧压力对反应进行有重要影响,在标准自由焓与温度关系图中绘制了氧压力随温度变化的直线.结果表明:Ag与O_2,Cu_2O与O_2的反应是一种可逆反应,其发生可逆转变的温度分别为586.818,667.663 K;氧的压力对金属氧化物的分解有重要影响:压力越低,金属氧化物越易分解;并通过热力学分析结果,最终确定了Ag/CuO复合材料反应合成烧结工艺.     

铅阳极泥脱砷预处理研究

采用氢氧化钠溶液循环浸出法对铅阳极泥进行预脱砷,考察了液固比、氢氧化钠浓度、浸出温度和浸出时间对脱砷效果的影响;在液固比10∶1、氢氧化钠浓度2.5 mol/L、浸出温度80℃、浸出时间8 h的条件下,砷的浸出率可达94%以上;含砷浸出液经硫化钠沉砷后可返回浸出工序循环使用,硫化钠与砷质量比为3∶1时,沉砷率可达88%以上,同时回用浸出工序后,砷浸出率达94%以上,浸出液循环使用对脱砷没有影响。     

Effect of temperature,oxygen partial pressure and calcium lignosulphonate on chalcopyrite dissolution in sulfuric acid solution

The pressure leaching mechanism of chalcopyrite was studied by both leaching tests and in-situ electrochemical measurements. The effects of leaching temperature, oxygen partial pressure, and calcium lignosulphonate, on copper extraction and iron extraction of chalcopyrite pressure leaching were investigated. The leaching rate is accelerated by increasing the leaching temperature from 120 to 150 °C and increasing oxygen partial pressure to 0.7 MPa. The release of iron is faster than that of copper due to the formation of iron-depleted sulfides. Under the optimal leaching conditions without calcium lignosulphonate, the copper and iron extraction rates are 79% and 81%, respectively. The leaching process is mixedly controlled by surface reaction and product layer diffusion with an activation energy of 36.61 kJ/mol. Calcium lignosulphonate can effectively remove the sulfur passive layer, and the activation energy is 45.59 kJ/mol, suggesting that the leaching process with calcium lignosulphonate is controlled by surface chemical reactions. Elemental sulfur is the main leaching product, which is mixed with iron-depleted sulfides and leads to the passivation of chalcopyrite. Electrochemical studies suggest that increasing the oxygen partial pressure leads to increasing the cathodic reaction rate and weakening the passivation of chalcopyrite.     

Recycling of Ammonia Wastewater During Vanadium Extraction from Shale

In the vanadium metallurgical industry, massive amounts of ammonia hydroxide or ammonia salt are added during the precipitation process to obtain V₂O₅; therefore, wastewater containing a high level of NH₄⁺ is generated, which poses a serious threat to environmental and hydrologic safety. In this article, a novel process was developed to recycle ammonia wastewater based on a combination of ammonia wastewater leaching and crystallization during vanadium extraction from shale. The effects of the NH₄⁺ concentration, temperature, time and liquid-to-solid ratio on the leaching efficiencies of vanadium, aluminum and potassium were investigated, and the results showed that 93.2% of vanadium, 86.3% of aluminum and 96.8% of potassium can be leached from sulfation-roasted shale. Subsequently, 80.6% of NH₄⁺ was separated from the leaching solution via cooling crystallization. Vanadium was recovered via a combined method of solvent extraction, precipitation and calcination. Therefore, ammonia wastewater was successfully recycled during vanadium extraction from shale.     

Zinc removal from hyperaccumulator Sedum alfredii Hance biomass

Leaching of heavy metals from Sedum alfredii Hance biomass was studied with ammonia-ammonium chloride solution as leaching agent. The research was carried out in two phases: 1) a leaching study to determine the zinc extraction efficiency of this leaching agent, and 2) a thermodynamic analysis to identify the likely reactions and stable Zn(II) species formed in the leaching systems. Taguchi orthogonal experiment, with four variable parameters, leaching temperature, molar ratio of NH₄Cl to NH_3, leaching time and solid-to-liquid(L/S) ratio, and each at three levels, was used to optimize the experiment parameters by the analysis of variances. The results indicate that leaching temperature has the most dominant effect on metal extraction performance, followed by molar ratio of NH₄Cl to NH₃, solid-to-liquid ratio and leaching time. The optimum condition was obtained as follows: temperature of 60°C, molecular ratio of NH₄Cl to NH₃ of 0.6, leaching time of 2 h and solid-to-liquid ratio of 5:1. The total zinc leaching efficiency under optimum conditions reaches 97.95%. The thermodynamic study indicates that the dominant species produced by the leaching process should be the soluble Zn(NH₃)₄₂⁺.     

KOH处理对ZnO纳米棒阵列结构及光电性能的影响(英文)

采用简单的化学沉积结合KOH碱刻蚀的方法,在导电玻璃(FTO)上生长ZnO纳米棒阵列(ZnONRs)。用X射线衍射(XRD)、扫描电子显微镜(SEM)、电流—电压(I—V)曲线对所得样品的晶型、形貌及光电性能进行测试,结果表明:ZnONRs呈纤铅矿型;ZnONRs的形貌及光电性能与KOH的浓度及刻蚀时间密切相关,经0.1mol/LKOH刻蚀1h后可得到排列高度有序且分布均匀的ZnONRs;KOH刻蚀后的ZnONRs与未刻蚀前高密度的ZnONRs相比,其光学性能得到提高。0.1mol/LKOH刻蚀1h的ZnONRs作为太阳能电池的光阳极,其光电转换效率、短路电流、开路电压较未刻蚀的ZnONRs分别提高了0.71%、2.79mA和0.03V。     

Ti_2Ni HYDRIDE COMPOSITE AS HYDROGEN CATHODE FOR ALKALINE WATER ELECTROLYSIS

1.IntroductionHydrogenasanenergyst0ragemediumhasattractedw0rldwideinterest,asitisacleanandfullyrecycleablesubstancewithapracticallyunlimitedsupplyThehydr0genenergy8ystemc0nsistsmainlyofthreepr0cesses:theproduction,transp0rt0rstorage,andutilizati0n0fhydr0gen.Large-scale,cheappr0duction0fhydr0genis0neofthekeylinksinthec0urseofdevel0pingthenovelhydr0genenergysystem.Waterelectrolysisisconsid-eredanimp0rtantmethodforlarge-scalepr0ducti0nofhydr0gent0day-However,loweringtheelectrolyticenergyconsumpt…     

Kinetics on leaching of potassium from phosphorus–potassium associated ore in HCl–H3PO4 media

In order to relieve the equipment corrosion, reduce chlorine and increase phosphorus contents in leaching solution, the leaching behavior of potassium from phosphorus–potassium associated ore in the mixed acids of hydrochloric acid and phosphoric acid was investigated. The effects of various factors, such as mass fraction of hydrochloric acid, solid-to-liquid ratio, material ratio (CaF₂ dosage (g)/mass of ore (g)) and leaching temperature were comprehensively studied. It was found that the dissolution fraction of potassium can reach more than 86% under the optimum conditions of leaching temperature 95 °C, HCl concentration 10%, leaching time 6 h, solid/liquid ratio 1:5, and material ratio 0.1. In addition, the leaching kinetics of potassium was successfully modeled by a semi-empirical kinetic model based on the classic shrinking core model. The data showed that the leaching process of potassium was controlled by the product layer diffusion and the apparent activation energy for the process was found to be 54.67 kJ/mol over the temperature range from 65 to 95 °C.     

泡沫铝两步法制备工艺用新型发泡剂的热分解行为

研究一种适于两步法制备泡沫铝工艺用新型发泡剂的热分解行为,分析其分解过程中的动力学与热力学特征,以及发泡气体与熔体之间可能存在的反应。研究表明:该新型发泡剂具有分解温度范围宽、分解过程缓慢的特点;其在熔体中的发泡过程主要受化学反应控制;新型发泡剂所释放的氧化性气体与熔体发生反应,在气泡表面所形成的连续氧化膜,对稳定气泡形貌、减缓气泡的合并和长大有重要作用;该新型发泡剂在两步发泡法制备泡沫铝过程中表现出前期损耗率低、后期发泡效率高的优异性能。     

氯盐浸出硫化银之研究

用电位—log[Cl~-]图分析高铁氯盐体系浸出硫化银的热力学可能性。用试剂硫化银进行的动力学实验考察了粒度、浸出剂初始pH值、氯离子浓度、高铁离子浓度和温度等对银浸出率的影响。结果表明,浸出过程很好地符合“未反应芯”动力学模型,求得的表观活化能为56.24千焦/摩尔,得到动力学方程式为:1-2/3R-(1-R)2/3=1.02×10_(-4)r_0~(-2)[H~+]~(0.36)[Cl~-]~3[Fe(Ⅲ)]exp(-56240/RT)t,过程受固膜扩散控制。     

Kinetics of indium dissolution from marmatite with high indium content in pressure acid leaching

The kinetics of oxygen pressure acid leaching marmatite with high indium content was studied. The effects of particle size, agitation rate, temperature, H_2SO_4 concentration, and oxygen partial pressure on leaching rate of indium were investigated. The results show that when the agitation rate is above 600 r-min~(-1), its influence on indium leaching rate is insignificant. It is determined that the leaching rates increase with the increase in sulfuric acid concentration, temperature, partial oxygen pressure, and the decrease in particle size. Moreover, the results demonstrate that the process of indium leaching is controlled by interface chemical reaction, with apparent activation energy of 65.7 k J-mol~(-1). The apparent reaction orders of sulfuric acid and oxygen partial pressure are determined to be 0.749 and 1.260, respectively. The leaching reaction process follows shrinking unreacted core model. And finally, the kinetics model equation is established for indium.     

Developments in the carbonate processing of uranium ores

A new process for extracting uranium from ores with carbonate solutions is described. Leaching is carried out under oxygen pressure to ensure that all the uranium is converted to the soluble hexavalent state. By this method, alkaline leaching can be used successfully to treat a greater variety of ores, including pitchblende ores, than has been possible in the past. The advantages of carbonate leaching over conventional acid leaching processes are enhanced further by a new method which has been developed for recovering uranium from basic leach solutions. This is achieved by reducing the uranium to the tetravalent state with hydrogen in the presence of a suitable catalyst. A high grade uranium oxide product is precipitated directly from the leach solutions. Vanadium oxide also can be precipitated by this method. The chemistry of the leaching and precipitation reactions are discussed, and laboratory results are presented which illustrate the applicability of the process and describe the variables affecting leaching and precipitation rates, recoveries, and reagent consumption.     

Thermal decomposition kinetics of basic carbonate cobalt nanosheets obtained from spent Li-ion batteries: Deconvolution of overlapping complex reactions

A new non-isothermal method of kinetic analysis was employed to investigate the thermal decomposition kinetic modeling of the basic carbonate cobalt nanosheets (n-BCoC) synthesized from spent lithium-ion batteries (LIBs). Fraser–Suzuki function was applied to deconvoluting overlapping complex processes from the overall differential thermal curves obtained under the linear heating rate conditions, followed by the kinetic analysis of the discrete processes using a new kinetic analysis method. Results showed that the decomposition of n-BCoC in air occurred through two consecutive reactions in the 136–270 °C temperature intervals. Decomposition started by hydroxide component (Co(OH)₂) decomposition until to 65% and simultaneously carbonate phase decarbonation began. The process was continued by CO₂ evolution and finally carbonate cobalt nanosheets have been produced. The reaction mechanism of the whole process can be kinetically characterized by two successive reactions: a phase boundary contracting reaction followed by an Avrami–Erofeev equation. Mechanistic information obtained by the kinetic study was in good agreement with FT-IR (Fourier transform infrared spectroscopy) and SEM (scanning electron microscopy) results.