金属离子配位调控分子组装浮选理论及其研究进展

在矿物浮选过程中,金属离子发挥着重要的作用,特别是活化浮选作用。在氧化矿的金属离子活化浮选过程中,金属离子与浮选药剂形成的金属-有机/无机配合物在矿物浮选过程中发挥了极大的作用,并在捕收能力和选择性等方面体现出一定的优势。本文总结了苯甲羟肟酸铅配合物、油酸钙、盐化水玻璃、金属离子改性淀粉等在浮选领域的研究进展,并从金属离子配位调控分子组装的角度,提出金属离子在矿物浮选过程中的新作用机制。金属离子具有良好的模板效应,可以定向调控金属配合物结构实现功能组装,这一功能为新型浮选药剂的设计与开发提供了新的思路。     

A novel process for sorting fine-sized sulphide minerals by biocoagulation

Based on a process design idea, investigations at Technical University of Berlin confirm that the biocoagulation of microorganisms and solid particles would be a new method to generate coarser particles suitable for sorting. The procedure of selective biocoagulation of microorganisms, e.g. yeasts like Saceharomyces cerevisiae and Yarrowia lipolytica respectively, and micro-dispersed solids, e.g. minerals like galena and sphalerite, has been analyzed as a basis for a novel sorting process. Therefore, especially the characteristics of the cell surface of the microorganisms, e.g. the electrostatic charge and the composition of extracellular polymeric substances, as well as their influence on the selective biocoagulation were studied. Experimental investigations show that the microorganisms and the sulphide particles below 10 μm coagulate effectively. Furthermore, the flotation is suitable for the separation of the selectively formed biocoagulates. With the designed column flotation, satisfying recovery rates are reached.     

金属阳离子在锂辉石浮选中的活化行为及作用机理

在油酸浮选锂辉石体系中分别加入Ca^2+、Al^3+、Fe^3+离子,通过单矿物浮选试验、金属离子吸附量检测、金属离子水解组份浓度计算、矿物表面动电位测试、红外光谱检测以及量子化学模拟计算研究Ca^2+、Al^3+、Fe^3+离子对锂辉石浮选的活化行为和作用机理。结果表明:Ca^2+离子的最佳活化区间为pH大于12的强碱性条件,Al^3+离子的最佳活化pH为6.47,而Fe^3+离子的最佳活化pH为7.25;在这些pH区间内,锂辉石浮选回收率和金属离子吸附量均达到最大值。在锂辉石浮选过程中起活化作用的有效组份为它们分别对应的氢氧化物沉淀。Ca^2+、Al^3+、Fe^3+离子可使锂辉石表面动电位向正值方向显著偏移;Ca^2+离子在锂辉石表面双电层的外层发生静电吸附,Al^3+和Fe^3+离子在锂辉石表面双电层的内层发生特性吸附。钙原子与锂辉石矿物表面吸附后形成的Ca—O键的键强较小,以离子键为主;铁原子与矿物表面形成Fe—O化学键的键强较大,含有一定的共价键组份;而铝原子与矿物表面吸附后形成的Al—O键的键长、键强等参数介于钙、铁的参数之间。油酸在Ca^2+活化后的锂辉石表面发生了化学吸附和少量的物理吸附,而在Al^3+、Fe^3+活化后的锂辉石表面发生了较为强烈的化学吸附。     

氯化钠对铝硅矿物浮选的影响及其作用机理

采用季铵盐DTAL作捕收剂,研究了氯化钠对一水硬铝石和叶蜡石浮选的影响及其作用机理.随着氯化钠浓度的增加,叶蜡石的浮选回收率显著提高,而一水硬铝石的可浮性受其影响很小.机理研究表明:氯化钠对一水硬铝石的zeta-电位没有影响,而能显著降低叶蜡石的zeta-电位,增强捕收剂与叶腊石的静电作用,促进捕收剂的吸附而活化其浮选;叶蜡石表面电位的降低是因为氯离子对叶蜡石存在选择性吸附作用并对其结构进行插层,使得叶蜡石的层间距从0.93 nm增大至1.40 nm.溶液化学计算表明:氯化钠改变溶液的离子强度,显著降低了季铵盐阳离子表面活性剂的临界胶束浓度,使得吸附了捕收剂的矿物表面更容易疏水上浮.     

一水硬铝石型铝土矿铝硅浮选分离的溶液化学

分析了我国铝土矿中一水硬铝石和铝硅酸盐脉石矿物的晶体结构与表面性质,一水硬铝石与铝硅酸盐脉石矿物晶体结构的差异、表面断裂的Al-O和Si-O健及表面离子活性区的差别,可影响矿物表面的润滑性与可浮性,类质同象及各种晶格杂质离子也将影响浮选剂与矿物表面的相互作用和矿物可磨性,提出了正浮选、反浮吕硅分离的技术原型,用溶液化学与计算研究了其基本原理。结果表明,通过溶液化学计算可确定阴离子捕收剂正浮选脱硅时捕收剂,分散剂和PH三者之间的匹配关系,矿物的PZC与捕收剂的pKa值是阳离子捕收剂反浮选的主要控制参数,阴离子捕收剂反浮选时,铅盐和钙盐是浮选铝硅酸盐较理想的活化剂。     

FLOTATION BEHAVIOUR AND MECHANISM OF BASTNAESITE WITH N-HYDROXYL PHTHALICIMIDE

The flotation behaviour and mechanism of bastnaesite with N-hydroxyl phthalicimidewere investigated by ξ-potential measurement,infrared spectrum and quantum chemistrycalculation.The results show that 3 oxygen atoms from N-hydroxyl phthalicirnide chelatethe rare earth ions on the surface of bastnaesite to form double five-chain O=C-N-O-RE(Ⅲ)-O chelate which is chemically adsorbed on the surface of bastnasite,thus makingN-hydroxyl phthalicimide an effective collector for bastnaesite.     

混合捕收剂浮选锂辉石的应用及作用机理

通过浮选试验,研究十二烷基磺酸钠、十二烷基硫酸钠、油酸、731、环烷酸皂,以及油酸与十二胺的混合捕收剂对锂辉石、长石和石英单矿物浮选行为及锂辉石实际矿石浮选指标的影响。借助Zeta电位、红外光谱分析、吸附量测试及量子化学计算,探讨混合捕收剂的作用机理。结果表明:油酸与十二胺的混合捕收剂,兼有捕收性和选择性好的特点,在碱性条件下能实现锂辉石与长石和石英的浮选分离。混合捕收剂在锂辉石表面的吸附量大于长石和石英。混合捕收剂中油酸在矿物表面以化学吸附为主,十二胺则以物理吸附为主。油酸离子分别与十二胺离子(或分子)和油酸分子以缔合形态存在,油酸的头基COO^-与锂辉石表面的Al原子发生化学作用。     

ADSORPTION AND ACTIVATION OF METAL IONS ON KYANITE

ＡＤＳＯＲＰＴＩＯＮＡＮＤＡＣＴＩＶＡＴＩＯＮＯＦＭＥＴＡＬＩＯＮＳＯＮＫＹＡＮＩＴＥ￥ＤｏｎｇＨｏｎｇｊｕｎ；ＣｈｅｎＪｉｎ（ＤｅｐａｒｔｍｅｎｔｏｆＭｉｎｅｒａｌＥｎｇｉｎｅｅｒｉｎｇ，ＣｅｎｔｒａｌＳｏｕｔｈＵｎｉｖｅｒｓｉｔｙｏｆＴｅｃｈｎｏ...     

烷基羟肟酸对细粒锡石的浮选及其溶液化学性质(英文)

采用烷基羟肟酸作为捕收剂对细粒锡石进行浮选,并对其溶液化学性质进行研究。结果表明,3种烷基羟肟酸在碱性条件下对细粒锡石有较好的捕收能力,且适宜的浮选pH随着捕收剂碳链的加长而升高。金属离子对锡石浮选的影响主要由矿浆pH决定,金属离子浓度对锡石浮选也有影响。计算基团电负性得出烷基羟肟酸作为锡石捕收剂的适合烷基碳链长度大约为7。由溶液的组分浓度对数分布图(lgc—pH)分析可知,捕收剂以分子-离子共吸附模式作用于矿物表面。动电位测试及红外光谱分析表明,吸附反应中涉及到电荷作用力、氢键力和络合作用力,其最终产物可以表示为锡石的O,O-五元环结构的螯合物。     

Recent advances in electrochemistry of sulfide mineral flotation

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Influence of metal cations on cassiterite flotation

1　ＩＮＴＲＯＤＵＣＴＩＯＮＣａｓｓｉｔｅｒｉｔｅｆｌｏｔａｔｉｏｎｈａｓｂｅｅｎｔｈｅｓｕｂｊｅｃｔｏｆｃｏｎ ｓｉｄｅｒａｂｌｅｒｅｓｅａｒｃｈｓｉｎｃｅｔｈｅｆｏｒｔｉｅｓｏｆ 2 0ｔｈｃｅｎｔｕｒｙ .Ｔｈｅｓｔｕｄｉｅｓａｒｅｃｏｎｃｅｎｔｒａｔｅｄｏｎｔｈｅａｓｐｅｃｔｓｏｆｒｅａｇｅｎｔｓ,ｆｌｏｔａｔｉｏｎｃｈｅｍｉｓｔｒｙａｎｄａｄｖａｎｃｅｄｔｅｃｈｎｏｌｏ ｇｙ ,ｗｈｉｃｈｌｅｄｔｏｔｈｅｉｎｔｒｏｄｕｃｔｉｏｎｏｆｆｌｏｔａｔｉｏｎｔｏｍｏｓｔｔｉｎｏｒｅｃｏｎｃｅｎｔｒａｔｏｒ…     

Bioleaching: A microbial process of metal recovery; A review

The present review describes the historical development and mechanisms of bioleaching. Recent development has shown commercial application of the process and, concurrently, details pertaining to the key microorganisms involved in these processes have been described. Bioleaching of metal sulfides is caused by diverse groups of bacteria. The dissolution biochemistry signifies two types of pathways, which are specifically determined by the acid-solubility of the sulfides, the thiosulfate and polysulfate pathways. This sulfide dissolution can be affected by ‘direct’ and ‘indirect’ mechanisms. In the ‘indirect’ mechanism bacteria oxidize only dissolved iron (II) ions to iron (III) ions and the latter can then attack metal sulfides and then be reduced to iron (II) ions. The ‘direct’ mechanism requires the attachment of bacteria to the sulfide surfaces. In the case of thiobacilli, bacteria secrete exopolymer that facilitates attachment of the bacteria to a metal surface, thus enhancing the leaching rate. In terms of eco-friendliness and process economics, within the field of biohydrometallurgy the technology is considered robust.     

铜离子在黄铜矿表面的吸附及活化作用：一个自活化的新观点

通过Zeta电位分析、X射线光电子能谱分析、铜离子吸附试验、第一性原理计算及Hallimond浮选试验综合揭示了铜离子在黄铜矿表面同样存在着吸附行为,铜离子对黄铜矿同样具有活化作用,主要诱因是铜离子与表面活化位的硫作用,从而增加疏水性。这种吸附作用在一定条件下有利于黄铜矿自身的浮选。浮选矿浆中的铜离子主要来源于黄铜矿的表面氧化溶解和矿物内流体包裹体的释放,这些离子的存在及吸附使黄铜矿具有自活化特性。     

Interaction and flotation of diaspore with alkylamine hydrochlorides

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Hydrophobic flocculation flotation of rutile fines in presence of styryl phosphonic acid

The hydrophobic flocculation flotation of rutile fines in the presence of styryl phosphonic acid (SPA) was investigated by flotation tests, zeta-potential measurement, optical microscope observation, laser-based particle size analysis, adsorption measurements and DLVO theory. The flotation tests indicated that rutile fines could be flocculated by SPA, and pH, shear force (stirring speed) and stirring time played significant roles in flocculation. The isoelectric point (IEP) and zeta-potential in whole range all moved to negative values as SPA was added according to the results from zeta-potential measurement. It was demonstrated that the primary reason for above was chemical adsorption. The laser-based particle size results showed the particle size at a stirring speed of 1800 r/min and 1000 mg/L SPA was the largest in all experiments. Furthermore, using the optical microscope observation and flotation tests, it was important for flotation of rutile fines to produce the flocculant. In the light of above-mentioned facts, floc flotation of rutile fines could be induced in the form of chemical adsorption by SPA to increase particle size. The data calculated from DLVO theory also indicated that chemical adsorption was the main reason for the formation of flocculant.     

Effect of mineral processing wastewater on flotation of sulfide minerals

The effects of mineral processing wastewater on sulfide minerals were investigated by flotation, infrared spectrometry and electrochemistry test. The results show that lead-concentrate water can improve the flotation of galena, while the sulfur-concentrate water has negative effect on flotation of galena compared with distilled water. The flotation behavior of pyrite is contrary to that of galena in three kinds of water. Infrared spectra indicate that the residual collector in the lead-concentrate water is beneficial to the formation of lead xanthate on the surface of galena. Electrochemistry results indicate that electrochemistry reaction on galena surface has apparent change. The anode polarization is improved and cathode polarization is depressed.     

First-principle investigation on mechanism of Ca ion activating flotation of spodumene

Different hypotheses of the activation mechanisms of metallic ions for silicate minerals flotation were stated in this work. Spodumene and Ca ion were taken to illustrate this issue. Flotation test results and diagram of Ca ion species distribution vs pH show that the dominant hydrolyzed species are Ca（OH）？and Ca（OH）2, which is in correspondence with the maximum flotation recovery of spodumene. Density functional theory（DFT） calculation results reveal further that the precipitation of calcium hydroxide on spodumene surface is the effective process to activate the flotation of spodumene.     

含铜、镍电镀污泥硫化烧结?浮选工艺

使用硫化烧结?浮选工艺处理含铜、镍的电镀污泥,采用MLA分析和扫描电镜分析等手段,研究污泥样品硫化烧结前后的性质变化;并通过Cu-S-O与Ni-S-O三元系等温优势区位分析,以及烧结的条件试验,确定了适宜的硫化烧结条件:硫化剂用量为20%,烧结温度为1100℃,烧结时间为90 min。通过烧结产品的闭路浮选试验,获得了铜、镍品位分别为10.14%和11.89%,铜、镍作业回收率分别为75.12%和70.02%的浮选精矿。通过浮选尾矿的浸出毒性鉴定,确定尾矿中有害金属元素的浸出毒性测试结果均小于国家标准。通过硫化烧结?浮选工艺,同步实现了含铜、镍电镀污泥的资源化和无害化处理。     

Monitoring the Diffusion Layer During Passive Film Breakdown on Alloy 800 with Digital Holography

The effects of chloride and thiosulfate ions on localized corrosion of alloy 800 are investigated through dynamical observation of the change in phase image of the diffusion layer during passive film breakdown using digital holography. The results indicate that solution chemistry has a significant effect on film breakdown and diffusion layer. The phase distribution changes at different applied potentials show that in the process of film breakdown, dissolution of metal ions from pitting is not remarkable in chloride-only solution, whereas dissolution of metal ions is significantly high in thiosulfate and chloride solution. Thiosulfate has a combined effect with chloride ions in passive film degradation.     

Adsorption behavior and mechanism of Bi(III) ions on rutile–water interface in the presence of nonyl hydroxamic acid

The adsorption behavior and mechanism of Bi(III) ions on the rutile–water interface were investigated through micro-flotation, Zeta potential measurement, adsorption amount measurement and X-ray photoelectron spectroscopy (XPS). According to the results of micro-flotation, Bi(III) ions could largely improve the rutile flotation recovery (from 62% to 91%), and they could increase the activating sites and reduce the competitive adsorption between nonyl hydroxamic acid negative ions and OH^? ions, which determined that Bi(III) ions were capable of activating rutile flotation. The adsorption of Bi(III) ions onto the rutile surface led to the shift of Zeta potential into the positive direction, which was good for the adsorption of nonyl hydroxamic acid anions. In addition, the results of XPS indicated that the chemical environment around Ti atom had not changed before and after the adsorption of Bi(III) ions. Based on the adsorption mechanism of Bi(III) ions, it was deduced that firstly Bi(III) ions occupied the vacancies of the original Ca²⁺, Mg²⁺ and Fe²⁺ ions on the rutile surface; secondly Bi(III) ions covered on the rutile surface in the form of hydroxides.