Preparation of manganese sulfate from low-grade manganese carbonate ores by sulfuric acid leaching

In this study, a method for preparing pure manganese sulfate from low-grade ores with a granule mean size of 0.47 mm by direct acid leaching was developed. The effects of the types of leaching agents, sulfuric acid concentration, reaction temperature, and agitation rate on the leaching efficiency of manganese were investigated. We observed that sulfuric acid used as a leaching agent provides a similar leaching efficiency of manganese and superior selectivity against calcium compared to hydrochloric acid. The optimal leaching conditions in sulfuric acid media were determined; under the optimal conditions, the leaching efficiencies of Mn and Ca were 92.42% and 9.61%, respectively. Moreover, the kinetics of manganese leaching indicated that the leaching follows the diffusion-controlled model with an apparent activation energy of 12.28 kJ·mol-1. The purification conditions of the leaching solution were also discussed. The results show that manganese dioxide is a suitable oxidant of ferrous ions and sodium dimethyldithiocarbamate is an effective precipitant of heavy metals. Finally, through chemical analysis and X-ray diffraction analysis, the obtained product was determined to contain 98% of MnSO₄·H₂O.     

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%.     

微生物燃料电池用于低品位锰矿浸提的研究

为提高低品位锰矿的利用,实现有机废水对锰矿物粉的浸提,通过改造微生物燃料电池(MFC),在阴极反应池中增加电解室及矿物质室,构建用于锰矿湿法浸提的MFC反应器,实现有机废水与锰矿物粉的还原氧化反应的分离。结果显示,以乙酸钠为碳源,以低品位锰矿粉为阴极的MFC输出电压最高可达0.81 V,是以K₃[Fe(CN)₆]为阴极液(0.631 V)的1.23倍。在相同条件下,矿物浸提MFC对COD的去除率可达90.9%,高于对照组(87.5%),而降解时间为3 d,显著少于对照组(5.2 d)。在降解COD能力的提升上,可实现对低品位锰矿粉中MnO₂的还原,其锰含量由原矿粉的23%降至0.98%,浸提率可达95.7%。进一步通过高通量测序对阳极端菌群结构进行分析发现,其主要菌群为地杆菌属(Geobacter),相对于对照组的85%,矿物浸提MFC中该属比例占总菌群的95%。结果表明,矿物浸提MFC可有效地将有机降解与矿物浸提耦合,避免两者直接混合反应带来的二次废水污染及浸提产物硫酸锰的净化问题,在提高MFC产电效率、处理废水的同时,实现对低品位锰矿的浸提。     

Alkaline pretreatment for chlorine removal from high-chlorine rhodochrosite

Chloride in manganese ore adversely affects mineral extraction. The mechanisms and the factors that influence an alkali pretreatment to removal chlorine from manganese ore were explored to eliminate hazards posed by chlorine during the electrolysis of manganese. The results showed that sodium carbonate, when used as an alkaline additive, promoted the dissolution of insoluble chloride, enhanced the migration of chloride ions, and effectively stabilized Mn2+. The optimal conditions were a sodium carbonate concentration of 0.45 mol·L-1, a liquid-solid ratio of 5:1 mL·g-1, a reaction time of 1 h, and a temperature of 25°C. The chlorine removal efficiency was greater than 95%, and the ore grade (Mn) was increased by 2.7%.     

Structure and effect of diamagnetism on manganese lithium phosphate glass to cathode materials application

1-x(Li₂O–2P₂O₅)-xMnO₂ glasses where x ?= ?0.2, 0.3 and 0.4 ?mol%, respectively, were synthesized by melted-quenching method. The Mn and P oxidation states and local structures around Mn and P-ions including Mn–O and P–O bonding distances and coordination numbers have been studied via X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), respectively. XANES results exhibit a coexistence of oxidation state of Mn²⁺ and Mn³⁺ with a mean value of 2.82. Moreover, Mn and P K-edge EXAFS show the Mn–O and P–O bonding distances of approximately 2.083–2.094 ?Å and 1.766–1.774 ?Å, respectively. A paramagnetism was found for all Mn–P glasses. Additionally, the coercive field (H_c) and remnant magnetization (M_r) increased with increasing Mn contents. However, the low specific capacitances are seriously obtained (<40 ?F ?g^?1) suggesting the effect of natural diamagnetism of lithium phosphate based-glass unlike the borate based-glasses which originally exhibit paramagnetism.     

Comprehensive recovery of gold and base-metal sulfide minerals from a low-grade refractory ore

The comprehensive recovery of small amounts of valuable minerals such as gold and base-metal sulfide minerals from a low-grade refractory ore was investigated. The following treatment strategy was applied to a sample of this ore: gold flotation–gold concentrate leaching–lead and zinc flotation from the gold concentrate leaching residue. Closed-circuit trials of gold flotation yielded a gold concentrate that assayed at 40.23 g·t-1 Au with a recovery of 86.25%. The gold concentrate leaching rate was 98.76%. Two variants of lead-zinc flotation from the residue—preferential flotation of lead and zinc and bulk flotation of lead and zinc—were tested using the middling processing method. Foam from the reflotation was returned to the lead rougher flotation or lead–zinc bulk flotation, whereas middlings from reflotation were discarded. Sulfur concentrate was a byproduct. The combined strategy of flotation, leaching, and flotation is recommended for the treatment of this kind of ore.     

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.     

ZrO_2-supported α-MnO_2:Improving low-temperature activity and stability for catalytic oxidation of methane

The single phaseα-Mn O_2and in-situ supportedα-Mn O_2/Zr O_2with different ratios of Mn/Zr were synthesized by one-pot hydrothermal method.They showed superior activity for catalytic oxidation of methane and even better than that of 1%Pt/Al_2O_3.The T_(50)of Mn O_2/Zr O_2catalysts with different ratios of Mn/Zr were located in the range of 315–335°C at a WHSV of 90 L g~(-1)h~(-1),whereas that of Pt/Al_2O_3was 380°C.After sulfur ageing,the Mn O_2/Zr O_2catalysts with Mn/Zr ratio of 2:1(2Mn O_2/1Zr O_2)and 1:1(1Mn O_2/1Zr O_2)exhibited satisfying sulfur resistance in comparison to the pure Mn O_2.The 2Mn O_2/1Zr O_2catalyst also showed acceptable catalytic stability,and the addition of 10 vol%CO_2had no obvious negative effect on its stability,whereas the addition of2.6 vol%H_2O caused slight but reversible decreasing methane oxidative activity.     

芦丁还原浸出低品位软锰矿的研究

为了研究糖蜜酒精废液中有机物还原浸出软锰矿的机理,采用芦丁为还原剂,在酸性介质中直接浸出低品位软锰矿。通过正交实验和单因素实验,研究了芦丁浓度、硫酸浓度、反应温度、浸出时间等因素对锰浸出率的影响,并对反应过程机理进行了初步探讨。实验结果表明,影响锰浸出率的主要因素依次为反应温度、硫酸浓度、浸出时间和芦丁浓度;当硫酸初始浓度2.35 mol/L,芦丁初始浓度0.041 mol/L,反应温度90℃,浸出时间90 m in时,锰浸出率达94.9%。     

Effect of exogenous lanthanum on accumulation of cadmium and its chemical form in Tomatoes

In the condition that soil is polluted by Cd(20 mg·L-1),two varieties of tomato(Lycopersicon esculintum Mill.)(plant high Cd-enriched variety(Yufen109)and plant low Cd-enriched variety(4641))treated with LaCl3 of different concentration(0,10 and 20mg·L-1)were determined for their effect on plant dry weight,anti-oxidase activity(CAT,SOD and POD),tomato fruit Cd chemical form and Cd accumulation.The results show that 10 mg?L-1LaCl3 can increase dry weight of plant at various positions and can reduce the concentration of Cd of different forms.Spraying with LaCl3(10,20 mg·L-1)can reduce Cd concentration in leaves,stems,roots and fruits of tomato plants with lowering rates of 13.7%-31.9%,9.5%-30.6%,10.8%-44.5%and 19.4%-37.0%,respectively.Suitable amount of lanthanum(10 mg·L-1 LaCl3)can increase yield of tomatoes,reduce Cd accumulation in the fruit.In the two tomato varieties,Lanthanum and Cadmium react interactively,expressing to be coexisting of both synergism and antagonistic.     

具有降解对硝基酚功能的硝化菌

硝化细菌是城市污水处理厂水处理系统中的重要功能菌.该硝化菌能否抵御有毒污染物的冲击,是衡量污水处理系统能否稳定运行的指标之一.用对硝基酚(PNP)对普通的硝化菌进行驯化,得到一种具有降解PNP功能的硝化菌.结果表明:经过驯化后的硝化细菌同时具有降解硝基酚和硝化功能.在含有质量浓度为100 mg·L~(-1) PNP的溶液中,与普通硝化菌相比,经过驯化后的硝化菌对NH_4~+-N去除速率高出33%.此外,驯化后的硝化菌对PNP的去除速率是普通硝化菌的33倍.     

Recovery of valuable metals from a low-grade nickel ore using an ammonium sulfate roasting-leaching process

Metal leaching from a low-grade nickel ore was investigated using an ammonium sulfate roasting-water leaching process. The nickel ore was mixed with ammonium sulfate, followed by roasting and finally leaching with water. During the process the effects of the amount of ammonium sulfate, roasting temperature, and roasting time on the leaching recovery of metal elements were analyzed. The optimum technological parameters were determined as follows:ammonium sulfate/ore ratio, 0.8 g/g; roasting temperature, 400℃; and roasting time, 2 h. Under the optimum condition the leaching recoveries of Ni, Cu, Fe, and Mg were 83.48%, 76.24%, 56.43%, and 62.15%, respectively. Furthermore, the dissolution kinetics of Ni and Mg from the nickel ore was studied. The apparent activation energies for the leaching reaction of Ni and Mg were 18.782 and 10.038 kJ·mol-1, which were consistent with the values of diffusion control reactions. Therefore, the results demonstrated that the leaching recoveries of Ni and Mg were controlled by diffusion.     

Direct electrochemistry and electrocatalysis of horseradish peroxidase in MnO2 nanosheet film

A novel material MnO2 nanosheet has been used as the support matrix for the immobilization of horseradish peroxidase （HRP）. HRP entrapped in MnO2 nanosheet film exhibits facile direct electron transfer with the electron transfer rate constant of 6.86 s^-1. The HRP/MnO2 nanosheet film gives a reversible redox couple with the apparent formal peak potential （E^0＇） of -0.315 V （vs. Ag/AgCl） in pH 6.5 phosphate buffer solution （PBS）. The formal potential E^0＇ of HRP shifts linearly with pH with a slope of -53.75 mV.pH^-1, denoting that an electron transfer accompanies single-proton transportation. The immobilized HRP shows an electrocatslytic activity to the reduction of H2O2. The response time of the biosensor for H2O2 is less than 3 s, and the detection limit is 0.21 μmol · L^-1 based on signal/noise = 3.     

Sanitary Sewage Treatment with Jet Inner-loop Bioreactor

0　IntroductionThejetloopreactorhasthecharacteristicsofbothjetandloopflow .Ononehand ,theairsuckedinisdispersedintosmallgasbubblesbecauseoftheshearingforcecausedbythehighvelocityjet,producinganincreasedinterfacialcontactbe tweengasandliquid ,thusthemasstransferefficiencyisin creased .Ontheotherhand ,aregularloopflowisformedbecauseofmutualimpetusofbothjetandair lift,thusdramaticallyim provestheperformancesofmixture ,diffusion ,masstransferandheattransferofthematerial.Withoutmechanicdriving ,the…     

Bioleaching of zinc from gold ores using Acidithiobacillus ferrooxidans

The present work investigated microbial leaching of zinc from ore using Acidithiobacillus ferrooxidans (ATCC 14859). The ore samples, consisted of 13wt% zinc, were obtained from a gold mine in north-eastern Thailand. A shake flask study was performed on the ore samples using a rotary shaker under the following fixed conditions (250 r·min⁻¹, 30°C for 16 d). The influence of various conditions, namely medium type (with and without iron), particle ore size (<20, 20-40, 40-60, 60-100, and >100 mesh), ore density (20 kg·m⁻³, 50 kg·m⁻³, and 100 kg·m⁻³), and pH of the medium (2, 2.5, 2.8, and 3), were investigated. The microbial leaching was assessed by determining the concentration of zinc in the medium and compared with the initial sample concentration. The results show that Acidithiobacillus ferrooxidans can successfully leach zinc by as much as 6 times compared with the control experiment (without Acidithiobacillus ferrooxidans ferrooxidans). The maximum efficiency (92.3%) for microbial leaching is obtained in iron-containing medium, 20-40 mesh ore sizes, 20 kg·m⁻³ ore density at pH 2.8, and the zinc content is found in the medium at about 120 mg·L⁻¹.     

UV/visible spectroscopic analysis of CO<Superscript>3+</Superscript> and CO<Superscript>2+</Superscript> during the dissolution of cobalt from mixed Co-Cu oxidized ores

The leaching of cobalt from four-mixed Co-Cu oxidized ores containing cobalt at levels ranging from 0.5wt% to 34wt% was studied and the results has been reported. Conventional dissolution of these oxidized Co-Cu ores with diluted H₂SO₄ and SO₂ as a reducing agent resulted in a substantial improvement in the solution based recovery of cobalt. UV/visible spectroscopic analysis of the leached solutions indicated that the increased cobalt content in the solution was a result of flushing the acidified cobalt leaching solution with SO₂. Furthermore, UV/visible spectroscopy confirmed that as SO₂ was flushed into the acidified leaching solution, Co³⁺ bearing minerals were reduced to the readily soluble Co²⁺ bearing minerals, and this resulted in the increase of total cobalt in the collected solution. The mechanism of the reduction of Co³⁺ to Co²⁺ bearing minerals when SO₂ is flushed during the leaching of mixed Co-Cu oxidized ores, including the stability trends of Co³⁺, Co²⁺, and Cu²⁺ complexes, as shown by their UV/visible spectra, are also discussed.     

Flexible micro-supercapacitors fabricated from MnO2 nanosheet/graphene composites with black phosphorus additive

Supercapacitors are widely used for powering flexible/wearable electronics owing to their excellent charge storage capabilities. In this study, MnO₂ nanosheets were grown on the surface of graphene using a simple water bath method to prepare graphene/MnO₂ composites for fabricating supercapacitors. In addition, two-dimensional black phosphorus was introduced as an additive into the electronic ink based on the as-prepared graphene/MnO₂ composites. The characterization and electrochemical analyses results showed that adding black phosphorus considerably improved the capacitive performance of the material, yielding a high specific capacitance of 241.5 ?F ?g^-1 at 0.1 ?A ?g^-1 and an impressive rate capability improvement from 52.5% to 80.3%. Then the micro-supercapacitor having an area-specific capacitance of 20.15 ?mF ?cm^-2 at a scanning rate of 2 ?mV ?s^-1 was utilized to demonstrate the practical applicability of this material. To further evaluate the practical applicability of this micro-supercapacitor, the micro-supercapacitor was integrated with a flexible thin-film pressure sensor on paper and cloth through screen printing.     

微气泡臭氧氧化处理酸性大红3R废水的影响因素

为了研究微气泡臭氧氧化技术处理废水的影响因素,采用微气泡臭氧氧化技术处理酸性大红3R废水,考察臭氧投加量、酸性大红3R废水初始浓度和投加活性炭对微气泡臭氧氧化过程中脱色率、TOC去除率、pH值以及臭氧利用率的影响。结果表明,提高臭氧投加量或降低酸性大红3R废水的初始浓度,酸性大红3R废水的脱色速率和TOC去除速率均有所上升,但臭氧利用率下降。煤质活性炭对微气泡臭氧氧化具有较强的催化活性,能够显著提高酸性大红3R废水的脱色速率和TOC去除速率。臭氧投加量为48.3 mg/min、酸性大红3R废水的初始质量浓度为100mg/L时,处理效果较好。此条件下,处理30min时脱色率达到100%,处理120min时TOC去除率达到78.0%,TOC去除表观反应速率常数为0.015min~(-1),臭氧利用率始终高于99%。而投加5g/L煤质活性炭后,处理15 min后脱色率达到100%,处理120 min时TOC去除率可达到91.2%,TOC去除表观反应速率常数提高至0.037min~(-1)。处理过程中出现中间产物小分子有机酸的积累并继续氧化降解,使得废水的pH值呈现先下降后升高的趋势。可见,对微气泡臭氧氧化影响因素进行优化,可提高污染物去除速率及臭氧利用率,显著改善处理性能。     

锰氧化物改性分子筛的制备及其在含酚废水处理中的应用

根据催化氧化原理,利用4A分子筛为载体,次氯酸钠（NaClO）为氧化剂,通过硫酸锰（MnSO₄）在其表面的原位氧化来制备对环境无害的锰氧化物（MnO_x）改性的分子筛（MnO_x@MS）材料.通过场发射扫描电镜（FE-SEM）和X射线衍射（XRD）对材料进行了表征.XRD分析表明：Mn元素是以MnO_x形式存在,在pH为7.2时,反应得到的MnO_x中Mn离子的价态最高.测试表明：Mn离子的价态越高对含酚废水的处理效果就越好.采用在最优条件下得到的MnO_x@MS材料作为催化剂,对过氧化氢（H₂O₂）氧化降解含酚废水进行研究,考察了不同体系、温度、pH值和H₂O₂用量对苯酚降解的影响.结果表明：在优化的降解条件下,120 min内,未改性分子筛对苯酚的去除率仅为35%,而MnO_x@MS改性材料对苯酚的去除率达到82%,说明通过MnO_x改性后的分子筛,对苯酚的氧化降解能力大大提高.     

谷胱甘肽和二氧化锰的氧化还原反应在生物领域上的应用

谷胱甘肽(GSH)是一种普遍存在的生物硫醇,具有清除毒素、维持氧化还原稳态和调控基因的作用,GSH的异常水平可能是多种疾病的触发因素.过渡金属氧化物二氧化锰(MnO_2)具有很强的氧化能力,能被GSH还原为Mn~(2+),可用于磁共振成像(MRI)以及肿瘤治疗.GSH和MnO_2之间的氧化还原反应已成为科研工作者不断研究和探索的方向.综述了GSH和MnO_2的氧化还原反应的最新研究进展.