Investigation on leaching of malachite by citric acid

Leaching of an oxidized copper ore containing malachite, as a new approach, was investigated by an organic reagent, citric acid. Sulfuric acid is the most common reagent in the leaching of oxide copper ores, but it has several side effects such as severe adverse impact on the environment. In this investigation, the effects of particle size, acid concentration, leaching time, solid/liquid ratio, temperature, and stirring speed were optimized. According to the experimental results, malachite leaching by citric acid was technically feasible. Optimum leaching conditions were found as follows:the range of particle size, 105-150 μm; acid concentration, 0.2 M; leaching time, 30 min; solid/liquid ratio, 1:20 g/mL; temperature, 40℃; and stirring speed, 200 r/min. Under the optimum conditions, 91.61% of copper was extracted.     

红热钒渣吹氧氧化后碱浸提钒

红热钒渣吹氧氧化仅１０ｍｉｎ左右，经碱浸压煮提钒，钒浸出率可达９０％以上。吹氧过程中，增添ＣａＯ，控制合适ＭｇＯ与钒渣的重量比，减小供氧速率，可获得高的ＣＦｅ＾３＋／ＣＦｅ＾２＋。碱浸时，钒浸出率主要随ＣＦｅ＾３＋／ＣＦｅ＾２＋的增大而升高，保温时间、浸出温度、Ｎａ２ＣＯ３和ＮａＯＨ的加入比，渣水质量比对钒浸出率都有影响，碱浸压煮时充氧和水洗残渣也可以提高钒的总浸出率。     

硫氧混合铅锌矿中锌的氧化氨浸动力学

常压低温条件下在NH3-(NH4)2 SO4体系中使用过硫酸铵作为氧化剂对硫氧混合铅锌矿中的锌进行浸出实验,系统研究了搅拌速度、浸出剂浓度、氧化剂浓度与温度对于锌浸出率的影响.结果表明,在最优条件下锌的浸出率可达93.2%,且浸出过程中几乎没有其他离子进入溶液,实现了锌的选择性高效浸出,从而简化了后续的浸出液净化与材料制备过程.动力学研究表明,硫氧混合铅锌矿中锌的氧化氨浸过程遵循固体产物层扩散控制的未反应核收缩模型,浸出反应的表观活化能为17.89 kJ·mol-1.     

三氯化铁浸出硫化铅精矿炼铅新工艺

应用正交试验及对其结果的方差分析法，对三氯化铁浸出硫化铅精矿进行了研究，找出了影响浸出率的主要因素和浸出最佳工艺条件。同时，用浸出产物氯化铅进行了熔融盐电解冶炼金属铅的研究，试验证明浸出－熔融盐电解炼新工艺是可行的。     

含碳酸盐脉石氧化铜矿的酸浸动力学

针对碳酸盐脉石对氧化铜矿酸浸动力学的影响进行探讨,研究了温度、酸度、矿石粒径、液固质量比、振荡速度等因素对含碳酸盐脉石氧化铜矿浸出的影响.结果表明,高温、高酸度、高液固质量比、小粒径和高振荡速度利于矿石的浸出,但碳酸盐脉石使得酸耗增加.考虑浸出成本确定合理的浸出条件为温度303 K、酸度35 g·L-1、矿石粒径0.074~0.125 mm、液固质量比3﹕1以及振荡速度180 r·min-1,浸出180 min后铜浸出率达53.6%.对浸出前后矿石表面形貌进行分析.结果显示碳酸盐脉石与酸反应后在矿石表面形成CaSO4·2H2 O沉淀,覆盖在颗粒表面,限制了矿石颗粒孔裂隙的发育.基于收缩未反应核模型对浸出动力学进行分析,发现碳酸盐脉石反应生成的沉淀阻碍了浸出反应,固体产物层扩散为浸出反应的控制步骤,反应的表观活化能为8.65 kJ·mol-1.     

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.     

含钼铜精矿氧化焙烧-浸出分离钼研究

四川攀西地区的含钼铜精矿中,由于钼、铜矿物组成复杂,共生关系紧密,提出了氧化焙烧-浸出工艺进一步分离钼。将试样置入焙烧炉中进行氧化焙烧,使硫化物转化为CuO、MoO3、Fe2O3等氧化物后;添加NaOH、H2O与MoO3反应生成可溶性Na2MoO4,浸出渣作为铜精矿产品。研究结果表明:铜、钼等以氧化物形式赋存于焙烧矿中,氧化焙烧矿中的硫含量较低为0.53%,硫以SO2气相形式挥发;在焙烧温度650℃、焙烧时间120 min、氢氧化钠用量为30%、浸出温度60℃、浸出时间120min、浸出液固比2∶1的综合条件下,钼的浸出率为94.24%,铜精矿(浸出渣)中铜的质量分数为24.27%,钼分离效果明显。     

NaOH-Ca(OH)2分解独居石精矿的研究

为降低独居石分解工艺的加碱量,并提高独居石分解率,本研究在NaOH-Ca(OH)₂体系中对独居石精矿进行焙烧分解,采用XRD对焙烧产物进行物相分析,并结合焙烧矿中稀土元素在盐酸中的浸出率判断独居石分解效果.实验分别研究了NaOH添加量、Ca(OH)₂添加量、焙烧温度以及焙烧时间对独居石精矿分解的影响.结果表明,在NaOH-Ca(OH)₂体系中,独居石精矿分解的最佳工艺条件:NaOH添加量为25%,Ca(OH)₂添加量为20%,焙烧温度为800℃,焙烧时间为1.5h.该焙烧条件下独居石全部分解为稀土氧化物,浓盐酸对稀土浸出率可达到98%左右.与现有工业生产工艺相比,本研究工艺中碱添加量降低55%左右,独居石分解率提高2%左右.     

Mechanochemical leaching of chalcopyrite concentrate by sulfuric acid

This study aimed to introduce a new cost-effective methodology for increasing the leaching efficiency of chalcopyrite concentrates at ambient temperature and pressure. Mechanical activation was employed during the leaching (mechanochemical leaching) of chalcopyrite concentrates in a sulfuric acid medium at room temperature and atmospheric pressure. High energy ball milling process was used during the leaching to provide the mechanochemical leaching condition, and atomic absorption spectroscopy and cyclic voltammetry were used to determine the leaching behavior of chalcopyrite. Moreover, X-ray diffraction and scanning electron microscopy were used to characterize the chalcopyrite powder before and after leaching. The results demonstrated that mechanochemical leaching was effective; the extraction of copper increased significantly and continuously. Although the leaching efficiency of chalcopyrite was very low at ambient temperature, the percentages of copper dissolved in the presence of hydrogen peroxide (H₂O₂) and ferric sulfate (Fe₂(SO₄)₃) after 20 h of mechanochemical leaching reached 28% and 33%, respectively. Given the efficiency of the developed method and the facts that it does not require the use of an autoclave and can be conducted at room temperature and atmospheric pressure, it represents an economical and easy-to-use method for the leaching industry.     

Extracting copper from copper oxide ore by a zwitterionic reagent and dissolution kinetics

Sulfamic acid (SA), which possesses a zwitterionic structure, was applied as a leaching reagent for the first time for extracting copper from copper oxide ore. The effects of reaction time, temperature, particle size, reagent concentration, and stirring speed on this leaching were studied. The dissolution kinetics of malachite was illustrated with a three-dimensional diffusion model. A novel leaching effect of SA on malachite was eventually demonstrated. The leaching rate increased with decreasing particle size and increasing concentration, reaction temperature and stirring speed. The activation energy for SA leaching malachite was 33.23 kJ/mol. Furthermore, the effectiveness of SA as a new reagent for extracting copper from copper oxide ore was confirmed by experiment. This approach may provide a solution suitable for subsequent electrowinning. In addition, results reported herein may provide basic data that enable the leaching of other carbonate minerals of copper, zinc, cobalt and so on in an SA system.     

硅锌矿在(NH4)2SO4-NH3-H2O体系中高液固比下的浸出动力学

通过实验研究硅锌矿在(NH4)2SO4-NH3-H2O体系中高液固比下的浸出动力学.采用粒径为96～109 μm的纯硅锌矿样品,在液固质量比为200时,考察搅拌速度、反应温度及总氨浓度对锌浸出率的影响.研究结果表明:提高温度和总氨浓度能显著提高浸出速率,而当搅拌速度大于250 r/min时,其对浸出速率的影响较小;浸出过程遵循孔隙扩散控制粒子模型,扩散与化学反应并非仅发生于颗粒外表面,而是发生在整个外表面及孔隙内部,浸出速度受孔隙扩散控制;浸出过程的表观活化能与反应级数分别为71.35 kJ/mol和4.27.     

Leaching kinetics of celestite in nitric acid solutions

In this study, strontium nitrate extraction from celestite in nitric acid solutions was investigated using the leaching method. The influences of acid concentration, solid-to-liquid ratio, stirring speed, and reaction temperature on the leaching of strontium from celestite concentrate were studied. The results showed that the leaching rate increased with increasing acid concentration, stirring speed, and temperature and decreased with increasing solid-to-liquid ratio. The particle size was fixed in all of the dissolution experiments. The results showed that the stirring speed and the temperature were the most influential parameters with respect to the leaching process. The kinetic model best fit control by diffusion through the product layer. The activation energy of the dissolution celestite in nitric acid solutions was calculated to be 42.22 kJ/mol.     

废催化剂焙烧水浸渣中硫酸浸取钴的动力学研究

以废催化剂处理过程中得到的镍钴渣为研究对象,采用硫酸浸出镍钴渣,使钴和镍得到有效回收,并对硫酸浸出钴的动力学进行探讨。研究结果表明:搅拌速度为400～1200r/min时对钴浸出率的影响非常小,物料粒度、硫酸浓度和反应温度等因素对钴浸出率则有较大影响;当反应温度为80℃,反应时间为180min,原料粒度为(0.074～0.100)mm,H2SO4浓度为6mol/L,搅拌速度为800r/min,固液比为1:10时,钴的浸出率为94.2%,镍的浸出率则为93.5%;硫酸浸出镍钴渣的反应受产物层内扩散控制,表观活化能为16.34kJ/mol。     

Deep cleaning of a metallurgical zinc leaching residue and recovery of valuable metals

Huge quantities of zinc leaching residues (ZLRs) generated from zinc production are dumped continuously around the world and pose a potential environmental threat because of their considerable amounts of entrained heavy metals (mainly lead). Most ZLRs have not been properly treated and the valuable metals in them have not yet been effectively recovered. Herein, the deep cleaning of a ZLR and recovery of valuable metals via a hydrometallurgical route were investigated. The cleaning process consists of two essential stages:acid leaching followed by calcium chloride leaching. The optimum conditions for extracting zinc, copper, and indium by acid leaching were a sulfuric acid concentration of 200 g·L-1, a liquid/solid ratio of 4:1 (mL/g), a leaching time of 2 h, and a temperature of 90℃. For lead and silver extractions, the optimum conditions were a calcium chloride concentration of 400 g·L-1, a pH value of 1.0, a leaching time of 1 h, and a temperature of 30℃. After calcium chloride leaching, silver and lead were extracted out and the lead was finally recovered as electrolytic lead by electrowinning. The anglesite phase, which poses the greatest potential environmental hazard, was removed from the ZLR after deep cleaning, thus reducing the cost of environmental management of ZLRs. The treatment of chlorine and spent electrolyte generated in the process was discussed.     

废弃电路板铜锡多金属粉隔膜电积回收锡实验研究

采用基于隔膜电积湿法冶金新工艺从废弃电路板铜锡多金属粉中高效提取金属锡,研究并优化了铜锡多金属粉浸出及隔膜电积提锡工艺.浸出实验结果表明,在温度为40℃,初始Sn~(4+)质量浓度50 g/L,HCl浓度4 mol/L,液固比为5∶1,循环浸出三次的条件下,锡浸出率约为96%,最终浸出液中Sn~(2+)质量浓度68.58 g/L.锡隔膜电积实验表明,在Sn~(2+)质量浓度40~100 g/L,HCl浓度3 mol/L,温度35℃,电流密度200 A/m2的条件下,阴极电流效率97.51%,能耗低于1 200 k Wh/t.在此优化条件下进行隔膜电积8 h,得到平整、致密且纯度99.9%的阴极锡板.     

改性磷矿渣稳定铅污染土的赋存形态及浸出特性试验研究

采用改性磷矿渣(MPS)对铅(Pb)污染土进行稳定化处理.基于浸出试验、形态提取试验和矿物分析试验,研究了改性磷矿渣(MPS)添加量对稳定土中Pb的浸出特性、赋存形态和矿物成分的影响规律,并与相同添加量的普通硅酸盐水泥(OPC)作对比.结果表明：MPS和OPC均可降低污染土中Pb的浸出特性,但MPS对Pb稳定效果明显优于OPC.与OPC稳定土相比,MPS稳定土具有更好的环境安全特性和较低的溶出风险.形态提取试验表明：OPC可促进Pb从弱酸提取态向可还原态转化,而MPS可促进Pb从弱酸提取态向可氧化态转化,污染土中Pb赋存形态的改变是MPS和OPC稳定土Pb变化的主要原因.矿物分析试验表明：OPC对Pb的稳定机制为包裹、吸附和沉淀作用,而MPS稳定对Pb的稳定机制为生成难溶的氟磷氯铅矿沉淀.铅污染土中矿物成分的变化是Pb赋存形态和浸出特性变化的根本原因.     

含铀硼精矿碳解过程中铀硼分离

含铀硼精矿在ＣＯ中还原焙烧得到熟矿粉，硼的活性为９０．８３％，用通ＣＯ２的碳酸钠水溶液碳解，Ｂ２Ｏ３溶出率在８６％以上，铀溶出率４．８８％，碳酸体系中加适量ＦｅＳ，铀溶出率降至０．６２％以下，较好地实现了铀硼分离。     

Dissolution characteristics of sericite in chalcopyrite bioleaching and its effect on copper extraction

The effects of sericite particle size, rotation speed, and leaching temperature on sericite dissolution and copper extraction in a chalcopyrite bioleaching system were examined. Finer particles, appropriate temperature and rotation speed for Acidithiobacillus ferrooxidans resulted in a higher Al3+ dissolution concentration. The Al3+ dissolution concentration reached its highest concentration of 38.66 mg/L after 48-d leaching when the sericite particle size, temperature, and rotation speed were -43 μm, 30℃, and 160 r/min, respectively. Meanwhile, the sericite particle size, rotation speed, and temperature can affect copper extraction. The copper extraction rate is higher when the sericite particle size is finer. An appropriately high temperature is favorable for copper leaching. The dissolution of sericite fitted the shrinking core model, 1-(2/3)α-(1-α)2/3=k₁t, which indicates that internal diffusion is the decision step controlling the overall reaction rate in the leaching process. Scanning electron microscopy analysis showed small precipitates covered on the surface of sericite after leaching, which increased the diffusion resistance of the leaching solution and dissolved ions.     

难处理金精矿的加压氧化一氯化浸出实验

采用加压氧化法对国内某难处理金精矿进行预处理,考察了反应温度、精矿粒度、氧分压、初酸浓度、反应时间对金精矿脱硫率和金浸出率的影响.利用XRD,XRF,SEM,EDX技术对金精矿原矿及浸出渣进行分析表征,实验结果表明,在反应温度180℃,精矿粒度-0.075～+0.061 mm,氧分压0.8 MPa,初酸质量浓度60 g...     

金属在福州地热水中的腐蚀热力学研究──(I)、铜—地热水系统

作者从热力学角度以电位－ｐＨ图探讨金属在福州地热水中的腐蚀趋势．本文报导铜－地热水系统，采用ＢＡＳＩＣ语言编制程序在ＡＰＰＬＥ－Ⅱ微机上计算高温热力学数据，并以ＤＸＹ－８００绘图仪绘制电位－ｐＨ图．同时，测定了铜在福州Ｇｗ２井地热水中的实际腐蚀电位．结果表明：在此地热水中，当温度低于３１８Ｋ，铜表面生成Ｃｕ２Ｏ膜，高于３１８Ｋ，生成ＣｕＯ膜，二者都位于钝化区．