Leaching process and kinetics of manganese in low-grade manganese ore

Manganese was extracted from leaching low-grade manganese ore in sulfuric acid medium. The effects of granule diameter, leaching time, liquid/solid ratio (V/W) and the concentration of sulfuric acid were investigated through orthogonal and single factor experiments. The experimental results showed that the optimal leaching conditions are, size of 0.054mm, 120 minutes of reaction time, 3(V/W) of liquid/solid ratio and 30% of the concentration of sulfuric acid (g/g). Under those conditions, the leaching efficiency is 96.73%. The kinetics of the leaching process is in accordance with the characteristics of fractal reaction.     

陈家岭钒矿选矿工艺试验

采用钙法氧化焙烧——酸浸的方法从钒矿石中浸出钒,克服了钠化焙烧过程中产生的H2S、Cl2,实验了矿石物料粒度、氧化钙添加量、焙烧温度、焙烧时间、漫出温度、浸出时间、酸的浓度、浸出液固比对浸出率的影响,获得了88％的浸出率。实验表明,焙烧温度、酸的浓度、浸出温度、浸出时间、液固比是影响钒浸出率的重要因素。     

Preparation of chemical manganese dioxide from low-grade rhodochrosite ore

The preparation of chemical manganese dioxide(CMD) from low-grade rhodochrosite ore(LGRO) in Xiushan,Chongqing,was studied and improved,including leaching with sulfuric acid,purifying,crystallizing and decomposing of MnCO3,and refining of primary MnO2.The product was characterized by X-ray diffraction.The results showed that the extraction ratio,the manganese recovery ratio of purifying,crystallization and refining reached 96.8%,93.9%,97.7%and 85.4%,respectively.The optimum conditions of refining were described as follows:liquid(H2SO4)/solid(primary MnO2) ratio was 3 L/g,the concentrations of NaClO exceeded 20%,and reaction time was 3 hours.Under the above conditions,the contents of MnO2and Mn in the obtained manganese dioxide were respectively 85.1%and 53.9%.The refined MnO2can be used as the super grade manganese dioxide mine powder in chemical industry.The XRD indicated that the structure of the product wasγ-MnO2.     

碱熔融-电感耦合等离子体发射光谱法测定高硫铝土矿中的硫

应用电感耦合等离子体发射光谱法(ICP-OES)测定高硫铝土矿(硫含量≤8%)中的硫时,由于硫存在-2、+4和+6等多种价态,常用的酸溶法和碱熔法处理高硫铝土矿时往往无法完全氧化硫而导致硫测定结果偏低。本文用过氧化钠熔融、热水浸取和盐酸酸化提取高硫铝土矿中的硫,使用基体匹配法绘制校准曲线补偿铝和钠对硫测定的光谱干扰,以S182.034 nm(184 nm)作为分析谱线,采用ICP-OES对硫进行测定。结果表明:3 g过氧化钠在700℃下熔融10 min,可以较好地氧化高硫铝土矿中的硫;校准曲线的线性相关系数为0.9999,方法检出限为0.025μg/m L,相对标准偏差(RSD,n=6)小于5%;与碳硫仪的测定结果相比较,两种方法无显著性差异。本方法溶样彻底,无样品损失,为今后实现应用ICP-OES同时测定高硫铝土矿中的硫和其他元素奠定了基础。     

New Process for Preparation Alumina and Silica White from Coal Fly Ash

Fly ash was used to prepare alumina and silica white, The 3 stages of the process are as follows: ammonium sulfate calcining, acid leaching and alkali dissolution. The optimum conditions for the experiments to determine are as follows: molar ratio of (NH4)2SO4/Al2O3 is 6, the calcining time is 2h, he H2SO4 concentration is 20%, the leaching temperature is 80℃ and dissolution duration is 2h, the ratio of solution and solid reaction material is 6 for ammonium sulfate calcining and acid leaching stage, reaction time 30min, ratio of liquid to ore 5∶1, alkali concentration 45% and reaction temperature 95 ℃for the alkali dissolution stage. Under these conditions, the total leaching efficiencies of Al2O3 and SiO2 are 78.86% and 95%, respectively. The quality of the main products alumina and silica white can meet the national standards of GB/T24487-2009 and GB10517-89, respectively.     

蛇纹石微波辐照硫酸浸出的实验研究

通过蛇纹石微波辐照硫酸浸出新方法的实验，研究了微波辐照强度、辐照时间、硫酸浓度、液固比及矿石粒度等因素对蛇纹石中氧化镁浸出率的影响，结果表明：与传统加热方式相比，微波辐照加热可显著提高蛇纹石酸浸速率；在最佳工艺条件下，氧化镁浸出率可达97％以上；蛇纹石酸浸渣的主要成分为无定形SiO2，化学成分与沉淀白炭黑相同。     

安徽沿江锰矿开发利用的一种新途径

用黄铁矿作还原剂 (燃料 )与低品位高锰矿混合 ,在立窑中焙烧 ,经水和溶液浸出、净化、合成、过滤等工序生产人造碳酸锰等矿产品。用软锰矿浆吸收废气中二氧化硫     

Magnesium recovery from magnesite tailings by acid leaching and production of magnesium chloride hexahydrate from leaching solution by evaporation

The recovery of magnesium from magnesite tailings in aqueous hydrochloric acid solutions by acid leaching was studied in a batch reactor using hydrochloric acid solutions. Subsequent, production of magnesium chloride hexahydrate (MgCl₂.6H₂O) from leaching solution was also investigated. The effects of temperature, acid concentration, solid-to-liquid ratio, particle size and stirring speed on the leaching process were investigated. The pseudo-second-order reaction model seemed to be appropriate for the magnesium leaching. The activation energy of the leaching process was estimated to be 62.4 kJ mol^− 1. Finally, MgCl₂.6H₂O in a purity of 91% was produced by evaporation of leaching solution obtained at a temperature of 40 °C, 1.0 M acid, solid-to-liquid ratio of 10 g/L, particle size of 100 µm, stirring speed of 1250 rpm and leaching time of 60 min.     

高压密闭消解-电感耦合等离子体质谱法测定锰矿石中的稀土元素前处理方法研究

高压密闭消解因称样量小、用酸量少、空白低等优点成为测定稀土元素前处理的主要方法。但锰矿石组分复杂,锰含量差别较大且具有多种不同价态,常含有伴(共)生金属和其他杂质,该方法采用常规酸溶体系很难将其消解完全,造成ICP-MS测试结果不准确。本文从样品前处理消解效果出发,选择锰矿石标准物质GBW07261、GBW07263、GBW07266和一个锰矿石样品,试验了三种酸溶前处理方法对锰矿石稀土元素测试的影响。结果表明:方法一(氢氟酸-硝酸密闭消解,硝酸复溶提取)不能将锰矿石样品完全消解,测定值偏低0. 28%～61. 31%;方法二(氢氟酸-硝酸-双氧水密闭消解,硝酸-双氧水复溶,硝酸提取)和方法三(氢氟酸-硝酸密闭消解,盐酸复溶,硝酸提取)均可将锰矿石样品消解完全,用ICP-MS测定稀土元素的数据较为接近,与传统的过氧化钠熔融ICP-MS法测定值吻合。但实验过程中发现对于锰含量较高的样品,方法三需多次重复加入盐酸复溶后方可将样品消解完全,而方法二复溶一次即可。因此,方法二对锰矿石样品的消解效率更高,精密度好(0. 96%～2. 68%),加标回收率在95. 0%～107. 0%之间,更适用于锰矿石中稀土元素的分析。     

高磷铁矿石成分分析标准物质研制

高磷铁矿石的分析测试过程需要基体组分相似、含量适中、定值组分全的标准物质进行质量监控,目前我国没有高磷铁矿石标准物质,现有铁矿石标准物质因基体组分不尽相同,磷元素含量大部分低于0.25%,而高磷铁矿石中磷含量均高于0.25%,这些标准物质难以满足高磷铁矿石产品的分析测试质量监控要求。基于此,本文研制了3个高磷铁矿石成分分析标准物质,样品分别采集于鄂西地区湖北宜昌秭归县野狼坪矿区、湖北恩施长岭矿区(武钢矿区)、湖北宜昌长阳县火烧坪矿区(宝钢长阳矿区),磷和铁含量均呈一定梯度,基本覆盖高磷铁矿的含量范围。均匀性和稳定性对SiO_2、Al_2O_3、TiO_2、P、K_2O、Na_2O、Fe、MnO、CaO、MgO、FeO、LOI、S、Cu、Pb、Zn、Cr、Ni、Co、Cd、Sr、Ba、V、As、Hg共25个组分进行检验,均匀性检验采用方差分析F检验法和测试结果的相对标准偏差进行评价,稳定性检验采用直线拟合,t检验法进行评估。经检验,样品均匀性、稳定性良好;定值采用11家实验室协作,采用2种以上不同原理的方法进行测试,定值组分包括主量元素、微量元素共25项,其中24项提供认定值及不确定度,Hg提供参考值。磷的含量分别为0.285%、不确定度0.010%,0.735%、不确定度0.020%,1.73%、不确定度0.05%,总铁含量分别为35.18%、不确定度0.20%,41.46%、不确定度0.20%,51.44%、不确定度0.13%。本次研制的高磷铁矿石标准物质可用于高磷铁矿的勘查、评价和综合利用开发中对标准物质的需求。     

铜镍尾矿砂微波加热硫酸溶解实验研究

通过尾矿砂微波加热硫酸溶解新方法的实验,研究了硫酸浓度、液固比及反应时间等因素对尾矿砂酸蚀率的影响。结果显示,在无需搅拌的情况下,微波加热实验的最佳条件酸浓度5mol/L、液固比5.0mL/g都较传统水热法有优势,在反应时间上,微波加热15min就能达到传统水热法2～3h的效果。在酸蚀率相同的情况下,微波加热所用时间仅为传统水热法的1/6,而所用的酸浓度、液固比都较传统水热法小很多。先对尾矿砂直接微波辐照一段时间,然后再加入硫酸进行微波辐照加热溶解,能够促进尾矿砂的溶解,提高尾矿砂的酸蚀率。微波加热条件下,尾矿砂在硫酸浓度8mol/L、液固比5.0mL/g条件下无需搅拌,反应1h后,除透闪石没有完全溶解外,绝大部分的矿物被溶解。与传统加热方式相比,微波加热可显著提高尾矿砂酸溶解速率。     

贵州遵义二叠系茅口组锰矿成矿建造、盆地原型及锰矿相带特征*

为提高勘查效率,降低找矿勘查风险及成本,需建立贵州遵义二叠系锰矿深部找矿预测模型。近年来通过“贵州遵义锰矿整装勘查区矿产地质调查与找矿预测”项目4个1︰50000图幅专项地质填图工作,总结了贵州遵义二叠系茅口组锰矿成矿建造、盆地原型及锰矿相带特征及标志。根据不同的岩性组合和结构构造等,将锰矿成矿期沉积(茅口组三段)划分为6个建造类型,分别为富锰建造、贫锰建造、含锰建造、黏土岩建造、硅化岩建造、生物灰岩建造,并划分出中心相、过渡相和边缘相3个锰矿相带;依据地层厚度、硅化角砾岩、特殊沉积构造、AMT地球物理标志,对盆地原型进行了分析。以上述理论为指导开展找矿预测工作,在研究区圈定了3个全隐伏找矿靶区,为钻探工程部署提供依据。2018—2019年在谢家坝找矿靶区施工了4个验证钻孔,均揭露厚层富锰矿体,初步探获新增锰矿资源量逾2200×10⁴ t,显示该理论方法运用在遵义锰矿区深部找矿预测是有效的,对勘查工作指导效果显著。     

四川盆地东部茅口组白云岩成因: 来自岩石学、矿物学和地球化学的证据*

四川盆地中二叠统茅口组白云岩中蕴藏丰富的天然气资源,但是这套白云岩的成因多年来一直存在争议。盆地东部茅口组白云岩储集层多发育在茅三段中下部,纵向上厚度介于3.0~46.8 m之间,平面上沿北西—南东向基底断裂呈带状展布。野外和钻井岩心观察发现,白云岩内发育交织状张性裂缝,将岩石切割呈角砾状,裂缝多被粗晶方解石、白云石充填或半充填。根据围岩和裂缝中白云石晶体形貌和产出状态,在显微镜下识别出4类不同组构的白云石: 第1类为灰泥基质中“星散状”自形粉晶—细晶白云石; 第2类为半自形面状组构细晶白云石,呈他形—半自形镶嵌状; 第3类为具“雾心亮边”的自形晶面状组构细晶—粗晶白云石,具糖粒状结构,晶间孔隙发育; 第4类为脉体充填的粗晶鞍状双晶白云石。背散射照片显示前3类白云石的“雾心”部分晶面混浊、表面分布方解石残斑及微孔, 而第3类白云石的“亮边”部分与第4类鞍状粗晶白云石脉则晶体明亮、洁净、致密,属新生矿物。上述4类白云石的成分均具有富Ca和贫Fe、Mn、Sr的特点,MgO含量变化较大,其中前两类白云石MgO含量总体低于白云石标准计量,而后两类白云石的MgO含量则接近或略高于标准计量。岩石学、矿物学和地球化学特征表明:茅口组白云岩主要经历了2期白云化作用,初次白云化作用形成第1类、第2类白云石及“雾心”白云石,二次白云化作用形成“亮边”白云石和粗晶白云石脉体; 2期白云化作用均发生得很早,可能始于同沉积期至浅埋藏期。白云石原位微量元素和原位锶同位素分析表明,白云化作用流体具有混源的特点,流体可能由富Ca地下水以及与火山活动有关的热液混合而成。推测中二叠世末期峨眉山地幔柱的喷发引起四川盆地内基底断裂再次活动,造成茅口组内张性构造裂缝发育,这为白云化流体混合及运移提供了通道。     

矿石之微生物脱磷机理的初步研究

以生尘芽孢杆菌进行了微生物脱磷机理与应用的探索性研究。试验结果表明：生尘芽孢杆菌脱磷必须经过两个步骤：（1）通过产生有机酸降低溶液pH值使磷矿石中的磷溶出;（2）当溶液中的磷达到一定浓度后微生物形成胞内聚磷酸盐。     

Leaching of manganese residue for the preparation of trimanganese tetroxide with a high surface area

The accumulation of electrolytic manganese residue (EMR) has become a serious problem and its recycling will be of great benefit to protect the environment and assist sustainable development. The reusing method was conducted by leaching EMR with sulfuric acid and the optimal leaching condition was 1:3 (g/g) as the ratio of solid to liquid with 20% (g/g) H2SO4 , heating at 90 ℃ for 3 hours, which aims at extracting Mn in a sulfuric acid medium. The produced MnSO4 solution was precipitated by adding alkali and oxidized in aqueous phase. The oxidized products were characterized by various techniques, including X-ray powder diffraction (XRD), Fourier transform infrared (IR) spectrometry, vibrating sample magnetometry (VSM), with Brunauer-Emmett-Teller (BET) specific surface area instrument and laser particle size analyzer. The final products were confirmed to be a single-phase Mn3O4 .     

钾长石粉酸浸除铁废液资源化的实验研究

钾长石粉经过硫酸或盐酸酸浸除铁后, 废液中含有大量的金属离子和游离酸.对废硫酸进行循环利用实验, 钾长石粉铁的浸出率达到88.3%.对酸浸废液进行蒸发结晶, 分别制备得到了纯度为94.1%的绿钾铁矾和74%的三氯化铁.用硫酸酸浸废液蒸发结晶后, 铁的回收率为70.0%, 钾的回收率为96.5%, 整个工艺无需高温, 无需加压, 操作简单, 具有高效、低能耗、低污染的特点, 表明用本项技术处理酸浸废液行之有效.分析认为, 废液呈强酸性、溶液中存在大量Fe2+、碱金属离子含量偏低是蒸发结晶过程中形成绿钾铁矾而不是黄钾铁矾的主要原因.      

晋东北地区银矿床类型及成矿机制

银矿床类型和矿床地质特征研究表明,晋东北地区银矿王要成因类型为与火山作用有关的中低温热液银矿床(包括石英脉型银矿、火山岩型银矿、(隐)爆破角砾岩型银矿),其次为接触交代矽卡岩型银矿、层控银锰矿床(包括氧化淋滤型锰银矿和铁锰帽型银锰矿).银的主要成矿期为燕山期.在沉积作用、火山一次火山热液作用和地表氧化淋滤作用条件下形成...     

北方低品位磷矿综合回收利用选矿研究及应用

我国北方内生磷矿主要集中在河北、辽宁、内蒙古,主要为赋存于绿岩带内的低品位晶质铁磷矿床,磁铁矿(含钛磁铁矿)-磷灰岩型矿石。矿石含磷低,易选,但选矿比大、成本高。利用研制出的适合北方低品位磷矿选矿的新型、高效的AW系列浮选捕收剂,解决了使用传统的脂肪酸类矿浆需要加温到35℃以上、需要加碱的问题。取得的科研成果已经应用于选矿实践,实现了工业化。     

Mode of Occurrence and Characteristics of Mn-ore Bodies in Iron Ore Group of Rocks, North Orissa, India and Its Significance in Resource Evaluation

Abstract. Several meso‐scale manganese ore bodies, scattered within Jone's horse‐shoe shaped synclinorium, in Bonai‐Keonjhar region of north Orissa are well known in the mineral map of India. Different grades of manganese ores are being exploited from this region by various agencies over a few decades. However, deceptive nature of ore bodies and complexity in control of mineralisation greatly confuse the exploration geologists for evaluation of these resources. In a recent study, the authors have classified Mn‐ore bodies of this region into three broad categories such as stratiform, stratabound (‐replacement) and lateritoid types based on mode of occurrence and their other chemical characteristics. Mn‐ore bands occur in close association with BIF and iron ores. Volcaniclastic shale in large geographic extension encloses these ore bodies. In the stratiform category of ore bodies (BMnF, analogous of BIF), manganese and shale bands, in variables thickness, alternate with each other and extend to a great depth. Such ore bodies generally constitute marginal to low‐grade ores, are characterised by low Mn/Fe ratio (～2) and have relatively lower abundance of trace (1500 to 2500 ppm) and relatively higher REE constituents. The stratabound‐replacement types of ore bodies are of intra‐stratal nature, occurring within tuffaceous shale. These are mostly shear‐controlled ore bodies extending along a zone of certain width. Increase in average Mn/Fe ratio (～6) and trace content (5000 to 8500 ppm) by 5 to 2.5 order of magnitude respectively or more above stratiform category are characteristic of these deposits. The lateritoid ore bodies have limited depth persistency. Such deposits are usually very low in Mn/Fe ratio (<1), trace (<2000 ppm) and REE contents. Different methods of exploration techniques are suggested for various categories of Mn‐ore bodies. In this context, the above findings would be the database for the exploration geologists to evaluate the potential of newer/existing Mn‐ore resources in this part of north Orissa.     

自动电位滴定测定锰矿石中锰的方法研究

多批次的锰矿石锰含量滴定分析消耗大量人工,随着自动化电位滴定仪的普及,利用仪器完成容量滴定成为可能,而将手工滴定向自动电位滴定移植是当前需要解决的课题。本文建立了一套自动电位滴定仪测定锰矿石中锰含量的方法,确定了相关滴定参数和等当点识别标准。锰矿石样品采用盐酸、磷酸分解,硝酸去除碳和有机物,高氯酸氧化,形成样品溶液。自动电位滴定仪先用硫酸亚铁铵标准溶液对预先移取的重铬酸钾标准溶液和标定空白溶液分别进行氧化还原滴定,用铂复合电极指示,计算得到硫酸亚铁铵标准溶液浓度,再对样品空白溶液和样品溶液进行氧化还原滴定,得到样品锰含量,方法检测范围为5%～60%。采用本法分析国家一级标准物质,测定结果的准确度和精密度高;分析多个产地不同水平的锰矿石样品,测定结果与手工方法进行对照,经t检验无显著性差异。建立的滴定方法自动化程度高、方法稳健,适用于冶炼企业、港口商检等行业,具有推广价值。