Reductive leaching of manganese from low-grade pyrolusite ore in sulfuric acid using pyrolysis-pretreated sawdust as a reductant

Manganese (Mn) leaching and recovery from low-grade pyrolusite ore were studied using sulfuric acid (H₂SO₄) as a leachant and pyrolysis-pretreated sawdust as a reductant. The effects of the dosage of pyrolysis-pretreated sawdust to pyrolusite ore, the concentration of sulfuric acid, the liquid/solid ratio, the leaching temperature, and the leaching time on manganese and iron leaching efficiencies were investigated. Analysis of manganese and iron leaching efficiencies revealed that a high manganese leaching efficiency was achieved with low iron extraction. The optimal leaching efficiency was determined to be 20wt% pyrolysis-pretreated sawdust and 3.0 mol/L H₂SO₄ using a liquid/ solid ratio of 6.0 mL/g for 90 min at 90℃. Other low-grade pyrolusite ores were tested, and the results showed that they responded well with manganese leaching efficiencies greater than 98%.     

硫酸中香蕉皮还原低品位锰矿的浸出行为及动力学模型

Manganese was leached from a low-grade manganese ore (LGMO) using banana peel as the reductant in a dilute sulfuric acid medium. The effects of banana peel amount, H₂SO₄ concentration, reaction temperature, and time on Mn leaching from the complex LGMO were studied. A leaching efficiency of ~98% was achieved at a leaching time of 2 h, banana peel amount of 4 g, leaching temperature of 120°C, manganese ore amount of 5 g, and sulfuric acid concentration of 15vol%. The phase, microstructural, and chemical analyses of LGMO samples before and after the leaching process confirmed the successful leaching of manganese. Furthermore, the leaching process followed the shrinking core model and the leaching rate was controlled by a surface chemical reaction (1 ? (1 ? x)1/3 = kt) mechanism with an apparent activation energy of 40.19 kJ·mol?1.     

Reductive leaching of low-grade manganese ore with pre-processed cornstalk

Cornstalk is usually directly used as a reductant in reductive leaching manganese. However, low utilization of cornstalk makes low manganese dissolution ratio. In the research, pretreatment for cornstalk was proposed to improve manganese dissolution ratio. Cornstalk was preprocessed by a heated sulfuric acid solution (1.2 M of sulfuric acid concentration) for 10 min at 80°C. Thereafter, both the pretreated solu-tion and the residue were used as a reductant for manganese leaching. This method not only exhibited superior activity for hydrolyzing corn-stalk but also enhanced manganese dissolution. These effects were attributed to an increase in the amount of reductive sugars resulting from lignin hydrolysis. Through acid pretreatment for cornstalk, the manganese dissolution ratio was improved from 50.14%to 83.46%. The pre-sent work demonstrates for the first time the effective acid pretreatment of cornstalk to provide a cost-effective reductant for manganese leaching.     

Sulfuric acid leaching kinetics of South African chromite

The sulfuric acid leaching kinetics of South African chromite was investigated. The negative influence of a solid product layer constituted of a silicon-rich phase and chromium-rich sulfate was eliminated by crushing the chromite and by selecting proper leaching conditions. The dimensionless change in specific surface area and the conversion rate of the chromite were observed to exhibit a proportional relationship. A modified shrinking particle model was developed to account for the change in reactive surface area, and the model was fitted to experimental data. The resulting model was observed to describe experimental findings very well. Kinetics analysis revealed that the leaching process is controlled by a chemical reaction under the employed experimental conditions and the activation energy of the reaction is 48 kJ·mol-1.     

硫铁矿和锰矿浓硫酸熟化法生产硫酸锰

论述用两矿浓硫酸熟化法生产硫酸锰的工艺过程及操作方法，该法具有工艺简单、锰收率高及节约原（燃）材料的特点，所采用的锰矿中锰含量为26%，锰浸出率达95%，回收率为90%，硫酸锰产品纯度为98.9%。     

钛白废盐制备MnCO3粉体的研究

以钛白废盐为原料,采用沉淀法制备了MnCO3粉体,研究了工艺条件对MnCO3产率和纯度的影响,对制备的样品进行了XRD、TEM和FT-IR表征.研究结果表明,随着NaHCO3加入量的增加,MnCO3产率逐渐升高;随着反应温度升高,MnCO3产率逐渐增大,而纯度略有所降低;随着反应时间延长,MnCO3产率升高,纯度基本保持不变.样品的表征结果表明所制备的粉体为MnCO3晶体,为具有较好的分散状态的无规则的纳米颗粒和直径约为10 nm的条形纳米棒.     

响应面法优化葡萄糖还原浸出半氧化锰矿的研究

采用响应面法优化葡萄糖还原浸出半氧化锰矿的工艺,以锰浸出率为响应值,对硫酸用量/矿量、葡萄糖用量/矿量、氟化铵用量/矿量和浸取时间四因素进行建模。结果表明,这些因素与锰浸出率的关系符合二次模型,各个因素对锰浸出率影响均极其显著,各个因素的二次方以及硫酸用量/矿量与葡萄糖用量/矿量的交互作用对锰浸出率影响较显著。最优工艺条件为：硫酸用量/矿量0.880 g/g、葡萄糖用量/矿量0.059 g/g、氟化铵用量/矿量0.04 g/g、浸取时间6 h。在此条件下,锰浸出率为93.09%,与模型预测值93.18%无显著差异,而相同条件下未加氟化铵的锰浸出率为82.37%。     

Optimization of reaction conditions for the electroleaching of manganese from low-grade pyrolusite

In the present study, a response surface methodology was used to optimize the electroleaching of Mn from low-grade pyrolusite. Ferrous sulfate heptahydrate was used in this reaction as a reducing agent in sulfuric acid solutions. The effect of six process variables, including the mass ratio of ferrous sulfate heptahydrate to pyrolusite, mass ratio of sulfuric acid to pyrolusite, liquid-to-solid ratio, current density, leaching temperature, and leaching time, as well as their binary interactions, were modeled. The results revealed that the order of these factors with respect to their effects on the leaching efficiency were mass ratio of ferrous sulfate heptahydrate to pyrolusite > leaching time > mass ratio of sulfuric acid to pyrolusite > liquid-to-solid ratio > leaching temperature > current density. The optimum conditions were as follows: 1.10:1 mass ratio of ferrous sulfate heptahydrate to pyrolusite, 0.9:1 mass ratio of sulfuric acid to pyrolusite, liquid-to-solid ratio of 0.7:1, current density of 947 A/m2, leaching time of 180 min, and leaching temperature of 73℃. Under these conditions, the predicted leaching efficiency for Mn was 94.1%; the obtained experimental result was 95.7%, which confirmed the validity of the model.     

含铜难处理金矿选择性浸出试验研究

针对某含铜难处理金矿进行了碘化法和石硫合剂(lime sulfur synthetic solution,LSSS)法的选择性浸金的研究。结果表明,在碘单质质量浓度为8g/L,浸出时间为2h的条件下,碘化法浸出金的浸出率为88.1%,而且铜的浸出率不足1%。在石硫合剂质量分数为25%,浸出时间为6h的条件下,LSSS法浸出金的浸出率仅为73.5%。对比碘化浸出和石硫合剂浸出效果可知,碘化法对该含铜难处理金矿不仅浸出速度快、浸出率高而且铜几乎不被浸出,具有很强的选择性浸金作用。     

Recovery of valuable metals from waste diamond cutters through ammonia-ammonium sulfate leaching

Copper and zinc were recovered from waste diamond cutters through leaching with an ammonia-ammonium sulfate system and air as an oxidant. The effects of experimental parameters on the leaching process were investigated, and the potential-pH (E-pH) diagrams of Cu-NH₃-SO₄2--H₂O and Zn-NH₃-SO₄2--H₂O at 25℃ were drawn. Results showed that the optimal parameters for the leaching reaction are as follows:reaction temperature, 45℃; leaching duration, 3 h; liquid-to-solid ratio, 50:1 (mL/g); stirring speed, 200 r/min; ammonia concentration, 4.0 mol/L; ammonium sulfate concentration, 1.0 mol/L; and air flow rate, 0.2 L/min. The results of the kinetics study indicated that the leaching is controlled by the surface chemical reaction at temperatures below 35℃, and the leaching is controlled by diffusion through the product layer at temperatures above 35℃.     

用草酸在硫酸溶液中从中性浸出渣中还原浸出铟

The present study evaluates the reductive leaching of indium from indium-bearing zinc ferrite using oxalic acid as a reducer in sulfuric acid solution. The effect of main factors affecting the process rate, including the oxalic-acid-to-sulfuric-acid ratio, stirring rate, grain size, temperature, and the initial concentration of synergic acid, was precisely evaluated. The results confirmed the acceptable efficiency of dissolving indium in the presence of oxalic acid. The shrinking-core model with a chemical-reaction-controlled step can correctly describe the kinetics of indium dissolution. On the basis of an apparent activation energy of 44.55 kJ/mol and a reaction order with respect to the acid concentration of 1.14, the presence of oxalic acid was found to reduce the sensitivity to temperature changes and to increase the effect of changes in acid concentration. Finally, the equation of the kinetic model based on the factors under study is presented.     

Hydrometallurgical leaching and kinetic modeling of low-grade manganese ore with banana peel in sulfuric acid

Manganese was leached from a low-grade manganese ore(LGMO) using banana peel as the reductant in a dilute sulfuric acid medium. The effects of banana peel amount, H_2SO_4 concentration, reaction temperature, and time on Mn leaching from the complex LGMO were studied. A leaching efficiency of ～98% was achieved at a leaching time of 2 h, banana peel amount of 4 g, leaching temperature of 120°C,manganese ore amount of 5 g, and sulfuric acid concentration of 15 vol%. The phase, microstructural, and chemical analyses of LGMO samples before and after the leaching process confirmed the successful leaching of manganese. Furthermore, the leaching process followed the shrinking core model and the leaching rate was controlled by a surface chemical reaction(1-(1-x)~(1/3)=kt) mechanism with an apparent activation energy of 40.19 k J·mol~(-1).     

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.     

Ultrasound effects on zinc recovery from EAF dust by sulfuric acid leaching

In this work, an ultrasound-assisted leaching process was studied for the recovery of zinc from electric arc furnace (EAF) dust, in which zinc was mainly present in the form of franklinite (60%). Hydrometallurgy is emerging as a preferred process for the recovery of a variety of metals, and the use of ultrasound could offer advantages over the conventional leaching process, especially for the dissolution of franklinite. Franklinite is a refractory phase that is difficult to leach and represents the main obstacle in conventional hydrometallurgy processing. Atmospheric leaching with different sulfuric acid concentrations (0.2-2.0 M) at two temperatures (323 and 353 K) was performed. The tests were conducted using both conventional and ultrasound-assisted leaching. After the leaching tests, the solid residues were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques, whereas the leach liquor was analyzed by inductively coupled plasma spectroscopy (ICP). The use of ultrasound facilitated the dissolution of franklinite at low acid concentrations and resulted in a greater zinc recovery under all of the investigated operating conditions.     

纤维硼镁矿的盐酸浸取动力学

以分段处理的方法,将纤维硼镁矿的盐酸浸取反应视作拟一级化学反应。把反应分成0—50%、50—70%及>70%三段,分别求得反应速率常数和表观活化能。当温度<80℃时,反应始终属化学反应控制;当温度>80℃时,反应前期系受液-固两相界面的传质速率控制,后期则仍属化学反应控制。这对确定生产操作条件具有重要的实践意义。     

Effect of desliming on the magnetic separation of low-grade ferruginous manganese ore

In the present investigation, magnetic separation studies using an induced roll magnetic separator were conducted to beneficiate low-grade ferruginous manganese ore. The feed ore was assayed to contain 22.4% Mn and 35.9% SiO₂, with a manganese-to-iron mass ratio (Mn:Fe ratio) of 1.6. This ore was characterized in detail using different techniques, including quantitative evaluation of minerals by scanning electron microscopy, which revealed that the ore is extremely siliceous in nature and that the associated gangue minerals are more or less evenly distributed in almost all of the size fractions in major proportion. Magnetic separation studies were conducted on both the as-received ore fines and the classified fines to enrich their manganese content and Mn:Fe ratio. The results indicated that the efficiency of separation for deslimed fines was better than that for the treated unclassified bulk sample. On the basis of these results, we proposed a process flow sheet for the beneficiation of low-grade manganese ore fines using a Floatex density separator as a pre-concentrator followed by two-stage magnetic separation. The overall recovery of manganese in the final product from the proposed flow sheet is 44.7% with an assay value of 45.8% and the Mn:Fe ratio of 3.1.     

低品位尾矿中锰资源的磁选回收利用

采用自主研发的高梯度水平励磁永磁磁辊对低品位碳酸锰尾矿进行湿式磁选试验,研究磨矿细度、磁场强度和矿浆浓度对湿式磁选效果的影响,从而获得富锰效果最佳的工艺参数.研究结果表明：与传统垂直励磁磁辊相比,水平励磁磁辊可显著提高锰品位与锰回收率,降低漏选率;在磨矿细度为80%,磁场强度为796.18 kA/m、矿浆浓度为20%的工艺参数下锰精矿品位可达到21%以上,锰回收率达到86%以上,在低品位尾矿有价金属资源回收利用方面工程的应用价值巨大.     

碱性氧化铜矿产氨菌浸出特性

为了研究碱性氧化铜矿产氨菌浸出特性,分析了产氨菌浸矿过程对矿石的作用.将云南某矿的碱性氧化铜矿置于含菌培养液、去菌培养液和氨水等5种浸矿溶液中,在同一条件下进行摇瓶浸矿实验,剖析溶液中各可能的浸矿因子.研究结果表明:产氨菌产氨能力较强,尿素培养液中氨质量浓度最大达8.93 g·L-1;产氨量与细菌含量呈正相关关系,细菌含量越高,产氨量越大;产氨菌主要通过产氨间接浸矿,此外产氨菌和其代谢产物都能直接作用于矿石,浸矿能力细菌产氨>细菌>细菌代谢产物,三者比值约为12:5:4.     

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.     

铁闪锌矿在硫酸浸出过程中的电化学行为

为研究铁闪锌矿氧化浸出机理,以人工合成铁闪锌矿的悬浮矿浆为研究对象,采用三电极体系对其在硫酸浸出过程中的电化学行为进行了研究.结果表明:在铁闪锌矿浸出过程中有H2S中间产物生成;通氧、元素硫分散剂以及氯离子引入浸出体系均能明显促进铁闪锌矿的电化学氧化;随硫酸浓度升高,铁闪锌矿的电化学氧化不断加强而闪锌矿的电化学氧化受抑.与闪锌矿相比,铁闪锌矿更易发生电化学氧化.在铁闪锌矿硫酸浸出过程中,其电化学氧化作用不容忽视.