Redox behavior and chemical species of arsenic in acidic aqueous system

Arsenic (As) removal from smelting acidic wastewater is an urgent task. The most common method is oxidation of trivalent As(III) to pentavalent As(V) subsequently precipitated by ferric (Fe(III)) salts. Foundations of redox behavior and chemical species are of great importance for understanding As removal. In this work, cyclic voltammetry (CV) and UV-Vis spectroscopy were used for laboratory observation; meanwhile HSC and MINTEQ software were employed for theoretical analyses. It is found that As(III) oxidation, a multiple electron transfer reaction, is diffusion-controlled. The oxidation over-potential is very high (about 0.9 V) in sulfuric acid solutions (pH 1.0). In addition, Fe(III)-As(V) complexes are evidenced by UV-Vis spectra and chemical species analyses in series of Fe(III)-As(V)-H₂SO₄-H₂O solutions. Therefore, the Fe(III) and As(V) species distribution against pH values are determined and a new φ–pH diagram with inclusion of Fe-As complexes is consequently compiled based on thermodynamic data predicted by other researchers.     

As(Ⅴ)-Fe(Ⅱ)体系常压臭葱石合成过程过饱和度对形貌和稳定性的影响

针对低溶液过饱和度是常压臭葱石合成过程的关键要素这一问题,本文在As(Ⅴ)-Fe(Ⅱ)体系下,通过Fe2+缓慢氧化来控制溶液过饱和度,研究了pH对Fe2+氧化速率的影响、Fe2+氧化速率与过饱和度的关系和过饱和度对砷铁沉淀率、臭葱石组分含量、颗粒粒径、形貌及其稳定性的影响。结果表明,Fe2+的氧化速率随初始pH值的降低而降低,而溶液过饱和度随Fe2+氧化速率的降低而降低。较低的初始过饱和度不利于砷铁的沉淀,对渣中砷铁含量影响不显著,但对渣中硫含量影响较大。初始过饱和度从7.86升至78.86时,砷、铁沉淀率分别从77.05%、53.9%升至88.66%、61.79%,渣中砷、铁和硫含量分别为30.74%、24.14%和0.58%~0.17%。臭葱石颗粒粒径随初始过饱和度的增加而先增加后减小,初始过饱和度值为11.7时,颗粒尺寸达到最大87.5μm。初始过饱和度为7.86~24时,形成类球型臭葱石颗粒;初始过饱和度值为24~78.86时,形成无规则型臭葱石颗粒。通过控制初始过饱和度在7.86~78.86下,合成的臭葱石稳定性高,其浸出毒性均小于1 mg/L。     

Novel technology of purification of copper electrolyte

The effects of arsenic with different valence states on the purification of copper electrolyte were studied and a novel technology of purification of copper electrolyte by copper arsenite was proposed. The results show that the purification performance of As（Ⅲ） compounds is better than that of As（Ⅴ） compounds. The purification technology by copper arsenite has the advantages of simple operation, high purification performance and low cost in comparison with other technologies and its appropriate purification conditions are that copper arsenite concentration is 18 g/L, reaction temperature is 65 ℃ and reaction time is 8 h. The removal rates of Sb and Bi are 53.22% and 58.67% respectively under these conditions. The purification principle show that a kind of yellow precipitate mainly composed of arsenic, antimony （ Ⅴ ）, bismuth and oxygen forms in electrolyte after copper arsenite is added, and consequently antimony and bismuth are removed from electrolyte.     

Adsorption of Arsenic on Activated Charcoal

This study explores the adsorption behavior of As(III) and As(V) on activated charcoal under the various conditions of solution pH and temperature. The adsorption loading of As(III) remains constant in the pH range from 0.16 to 3.5, while that of As(V) shows a maximum value at pH2.35 when the pH varies from 0.86 to 6.33. The isosteric heat of adsorption for As(III) varies from 4 to 0.75 Kcal/mole and that for As(V), from 4 to 2 Kcal/mole with varying surface loading. The magnitude of these values suggests that the adsorption of arsenic is by physisorption and due to weak forces such as Van der Waals forces. Activated charcoal adsorbs As(V) by 2.5% of its own weight while it absorbs As(III) by 1.2% of its own weight when the equilibrium concentration of each species is 22 × 10^?2 molar. Since arsenic has appreciable adsorbability on activated charcoal, this adsorbent may be a viable candidate to be used for removing arsenic from solution. Further studies to determine more information on the selectivity of arsenic over other valuable metal ions and the ones to determine the effects of other cations such as, ferric, calcium, and magnesium ions are suggested as a next step.     

基于地球化学的水热还原矿化稳定砷的技术思路

砷作为有色金属矿物的共伴生元素,在有色金属冶炼过程中以含砷“三废”形式大量产出。由于砷具有强致癌性及毒性,导致砷的安全处置问题严重困扰着有色金属冶炼企业。本文通过阐述含砷废水中砷的两种稳定化工艺的研究进展,对比了现有稳定化工艺的优缺点,结合药剂稳定化和矿物稳定化的优点,借鉴砷元素在地球化学中的成矿规律,提出了硫化沉砷?水热还原矿化稳定砷的技术思路。首先采用硫化法脱除含砷废水中的砷,砷的沉淀率高达99.65%,硫化沉淀物在TCLP毒性检测中砷的浓度达到212.9 mg/L。然后采用As-S系一元水热还原矿化法和As-Fe-S系二元水热还原矿化方法稳定砷,稳定化产物分别为雌黄和雌黄?铁硫系(黄铁矿、硫化亚铁)混合物,在TCLP毒性检测中砷的浸出浓度分别为3.86 mg/L和2.65 mg/L。水热还原矿化工艺实现了含砷废水中砷的脱除及稳定化的目的,为水溶液中砷的脱除和稳定化提供了新的思路。     

Selective removal of As from arsenic-bearing dust rich in Pb and Sb

The selective removal of arsenic from arsenic-bearing dust containing Pb and Sb in alkaline solution was studied. The influence of NaOH concentration, temperature, leaching time, liquid to solid ratio, and the presence of elemental sulfur on the dissolution of As, Sb and Pb in NaOH solution was investigated. The results indicate that the presence of elemental sulfur can effectively prevent leaching of lead and antimony from arsenic. The Sb₂O₃, As₂O₃ and Pb₅(AsO₄)₃OH in the raw material convert to NaSb(OH)₆ and PbS in the leaching residue, while arsenic is leached out as As(III) or As(V) ions in the leaching solution. Arsenic leaching efficiency of 99.84% can be achieved under the optimized conditions, while 97.82% of Sb and 99.97% of Pb remain in the leach residue with the arsenic concentration of less than 0.1%. A novel route is presented for the selective removal of arsenic and potential recycle of lead and antimony from the arsenic-bearing dust leached by NaOH solutions with the addition of elemental sulfur.     

二段脱铜液还原结晶法脱砷新工艺

对铜电解液脱砷方法进行研究,提出以二段脱铜液为原料,采用SO2还原结晶法脱砷新工艺。在二段脱铜液中通入SO2,将其中的As(Ⅴ)还原成As(Ⅲ),还原后的溶液通过蒸发结晶析出As2O3,达到二段脱铜液脱砷的目的。结果表明:当As(Ⅴ)浓度为12.41 g/L、H2SO4浓度为253.00 g/L、反应温度为60℃时,向二段脱铜液中通入SO290 min后静置90 min,二段脱铜液中As(Ⅴ)的还原率达到94.54%。还原后的溶液进行蒸发结晶,当蒸发前与结晶后的体积比(V0:V1)为3.5时,砷的脱除率达到91.33%,结晶产物为As2O3。与传统脱砷工艺相比,新工艺具有操作简单、成本低廉及砷的脱除效果明显等优势。     

难处理高砷金矿的细菌氧化-提金研究

采用经过驯化的HQ0211菌对高砷金矿进行氧化预处理-氰化提金实验研究.该矿石含金128.5 g/t,含砷16.84%(质量分数,余同),含硫21.72%,含铁26.62%,氰化浸出率只有29.35%,是典型的高砷难处理矿.经过细菌氧化预处理,金矿脱砷率达到96.2%,失重率达到43.9%.矿石的金氰化浸出率由原来的29.35%提高到92.57%,效果十分显著.     

A new mixed-valent iron arsenate black crystal

Scorodite (FeAsO₄·2H₂O) is the most popular phase for arsenic (As) immobilization while the reductive dissolution of Fe(III) to Fe(II) will promote As release. In the present study, an equilibrium between Fe(III) and Fe(II) was achieved in scorodite preparation system by introducing certain alcohol (methanol, ethanol, isopropanol or tert-butanol), and thus a new mixed-valent iron arsenate black crystal formulated as Fe(II)_5.2Fe(III)_8.8(HAsO₄)₄(AsO₄)₈·H₂O was prepared. In comparison with scorodite, the black crystal has higher As content (36.4%, mass fraction) and lower crystal water content (0.73%, mass fraction). Additionally, the leaching concentration of As can be lower than the threshold value (5 mg/L) regulated by identification standards for hazardous wastes of China (GB 5080.3–2007). Therefore, this new mixed-valent iron arsenate crystal could be classified as a non-hazardous and promising As-bearing phase in environmental applications.     

Effect of the milling conditions for nanocrystalline iron powders on their corrosion behavior in neutral electrolytes

The corrosion behavior of nanocrystalline iron powders obtained by milling in oxygen-containing organic media (isopropyl alcohol, acetic acid, oleic acid, and its solutions in heptane) was studied. The high corrosion resistances of iron powders obtained by mechanoactivation in oleic acid were associated with a protective surface layer formed by iron oxide and chemisorbed oleic acid or products of its partial degradation. Nanocrystalline iron-based systems that contain oxide phases without forming protective layers were less resistant to corrosion. Original Russian Text ? S.F. Lomayeva, A.V. Syugaev, S.M. Reshetnikov, A.S. Shuravin, O.M. Nemtsova, V.V. Aksenova, 2007, published in Zashchita Metallov, 2007, Vol. 43, No. 2, pp. 207–215.     

Abnormal Nitride Morphologies upon Nitriding Iron-Based Substrates

Nitriding of iron-based components is a very well-known surface engineering method for bringing about great improvement of the mechanical and chemical properties. An overview is presented of the strikingly different nitride morphologies developing upon nitriding iron-based alloy substrates. Observed abnormal morphologies are the result of intricate interplay of the thermodynamic and kinetic constraints for the nucleation and growth of both alloying element nitride particles in the matrix and iron nitrides at the surface of the substrate. Alloying elements having strong Me-N interaction, such as Cr, V, and Ti, precipitate instantaneously as internal Me-nitrides, thus allowing the subsequent nucleation and growth of “normal” layer-type iron nitride. Alloying elements having weak Me-N interaction, such as Al, Si, and Mo, and simultaneously having low solubility in iron nitride, obstruct/delay the nucleation and growth of iron nitrides at the surface, thus leading to very high nitrogen supersaturation over an extended depth range from the surface. Eventually, the nucleation and growth of “abnormal” plate-type iron nitride occurs across the depth range of high nitrogen supersaturation. On this basis, strategies can be devised for tuned development of specific nitride morphologies at the surface of nitrided components.     

高砷难处理硫精矿氰化浸出提银实验研究

某硫精矿中的银矿物嵌布粒度非常细小,包裹于硫化物中的银约占50.46%,属于难处理高砷含银硫精矿。采用细磨后化学预处理氰化浸出,银浸出率仍然低于80%;硫精矿经氧化焙烧后,As、S的脱除率都达到90%以上,但银浸出率却较低;对该含银硫精矿添加钠盐焙烧预处理,再采用常规氰化法浸出,银浸出率显著提高,达到85.15%,同时氰化钠耗量降低至2.0 kg/t。     

Fundamentals of Selective Laser Melting of alloyed steel powders

The successful fabrication of dense iron-based parts by selective laser melting (SLM) is still limited to a narrow range of materials. This study aims at gaining an understanding of the effect of elements such as oxygen, carbon, silicon, titanium and copper on the quality of two-dimensional and three-dimensional iron-based objects. The results are related to the effect of the elements on physical phenomena such as laser absorption, heat transfer, wetting and spreading of the melt, oxidation, Rayleigh instability and Marangoni convection.     

铜闪速熔炼渣中砷的赋存状态和浸出毒性（英文）

铜冶炼含砷炉渣的高效安全处置取决于对其含砷物相及其浸出毒性的准确认识。采用X射线荧光光谱、X射线衍射、电子探针显微分析、扫描电子显微术和选择性逐级提取法对铜熔炼渣中的含砷物相进行鉴定,并基于对炉渣中不同含砷物相的选择性逐级提取结果探讨渣中砷浸出毒性的可能来源。结果表明,砷以水溶性砷、铜砷金属间化合物、铜砷硫化物以及固化在铁橄榄石和硅酸盐玻璃相中的砷等形式赋存在熔炼渣中。浮选过程可以去除熔炼渣中的水溶性砷并回收铜砷金属间化合物,降低渣尾矿的砷浸出毒性,使其符合USEPA和SEPA标准要求。     

高熵合金电解水电极的研究进展

开发合适的催化材料,制备出高性能、大规模、低成本的催化电极,可减少电解水过程的能量消耗、提升制氢效率。高熵合金由于具有高催化活性,在催化电极应用方面受到广泛关注。综述了应用于电解水过程中析氢反应和析氧反应的高熵合金催化电极的研究进展。首先简述了电解水制氢的工业背景和电化学原理;分析了高熵合金催化活性的来源,即杂化能带结构带来的更为合理的表面吸附能和更多的表面活性位点,以及其特有的高熵效应与“鸡尾酒”效应对整体催化活性的影响;接着讨论了高熵合金的成分设计理念,即通过非贵金属元素的替代来降低成本,同时通过改变合金化元素含量提高高熵合金的内禀活性、增加表面活性位点数量;介绍了第一性原理计算在高熵合金催化机理研究、催化表面吸附能调控、合金成分高通量筛选中的应用;总结了高熵合金平板、多孔、负载纳米颗粒催化电极制备的工艺特点,以及其中的问题与挑战;最后对未来高熵合金电催化电极的发展前景和研究方向进行了展望。     

铁基高密度烧结材料的摩擦磨损性能研究

采用烧结热锻工艺获得高密度和高硬度的铁基粉末烧结冶金材料,研究了铁基粉末中的铬含量和施加在烧结材料上的载荷对材料摩擦磨损性能的影响,并借助于扫描电镜观察和分析了粉末冶金烧结材料的磨损形貌、探讨其摩擦磨损机制.结果表明,在铁基粉末中加入0.6%铬时,该粉末材料的硬度、密度和耐磨性最好.主要磨损机制为氧化磨损、粘着磨损和磨粒磨损.     

Relaxation processes and kinetics of the thermal oxidation of Ni-Mo-B alloys obtained by chemical catalytic reduction

Kinetics of the high-temperature oxidation of Ni-Mo-B alloys containing 11 wt. % Mo (obtained by means of chemical catalytic reduction with the use of dimethylamine borane) is investigated. A strong dependence between the oxidation rate and the sublimation of volatile compounds on the prehistory of deposits is disclosed. Freshly obtained deposits exhibit an anomalous short-term weight loss caused by the “explosive” character of the removal of water vapors, evolved as a result of the reduction of molybdenum and boron oxides with hydrogen at heightened temperatures. Preliminarily heating the specimens in a vacuum decreases the intensity of or completely eliminates the anomalous phenomenon. When oxidizing the coatings in air at 600°C, two processes take place, namely, the oxidation of the coating components (a growth of the oxide layer) and the sublimation of volatile compounds. Original Russian Text ? V.A. Arslambekov, A.B. Drovosekov, M.V. Ivanov, V.M. Krutskikh, E.N. Lubnin, B.F. Lyakhov Yu.M. Polukarov, 2006, published in Zashchita Metallov, 2006, Vol. 42, No. 1, pp. 13–20.     

Integrated waste and water management in mining and metallurgical industries

Extractive operations usually co-produce large quantities of unmarketable materials （mineral wastes）, most of which are conventionally discarded to dumps （coarse material） and tailings ponds （fines）. Escalating cost and regulation worldwide highlight an increasing need for reduction and re-use of such wastes. The present paper introduces a new integrated waste management scheme for solids and water. The scheme was exemplified by novel treatment of synthetic waste and process water linked to the biohydrometallurgical processing of metal sulphide flotation concentrates. Bioleaching of sulphide concentrate leads to two types of solid waste： a ferrihydrite/gypsum precipitate from neutralisation of the bioleach liquor and un-leached gangue. The paper indicates that, depending upon the minor components involved, the solid phases in admixture might be usefully distributed among three types of product： conventional underground backfill, cemented civil engineering backfill （particularly controlled low strength material or CLSM） and manufactured soil. It emphasizes CLSM containing simulated mineral waste, showing that such material can exhibit the required characteristics of strength, porosity and permeability. When toxic components, e.g., arsenic from refractory gold ore, are present, encapsulation will be required. Process water is typically recycled as far as possible, although any excess should be treated before re-use or discharge. The paper also highlights treatment by reverse osmosis （one of the few methods able to generally remove dissolved components）, particularly showing that arsenic in oxidation state ＋6 can be readily removed for discharge （〈50× 10^-12 As）, although additional ion exchange is needed for potable water （〈 10 × 10^-12 As）.     

Thermodynamic and kinetic consideration on the corrosion of Fe, Ni and Cr beneath a molten KCl-ZnCl2 mixture

Thermogravimetric (TG) experiments have been carried out to study the kinetics of hot corrosion of Fe, Cr and Ni, covered by a molten KCl-ZnCl₂ mixture of a composition close to the eutectic (50 mol% KCl-50 mol% ZnCl₂). Furthermore binary and ternary phase diagrams were calculated in order to describe the corrosion process. The tests were conducted at a temperature of 320 °C in an atmosphere consisting of argon and oxygen. For iron different stages are observed in a TG curve. They can be attributed to the different reaction steps of iron chloride formation (incubation phase), oxide precipitation (linear stage) and scale formation (parabolic or logarithmic stage). Based on these observations a model, described by Spiegel [A. Spiegel, Molten Salt Forum 7 (2003) 253], is confirmed. For Cr and Ni these stages are not observed. At 8 vol% O₂ only slight oxidation of Cr and Ni was observed accompanied by evaporation of the salt deposit. At 16 vol% O₂ the rate of oxidation increases and the experiments yield a curve that is either parabolic or logarithmic for both Ni and Cr. As a result it is shown that the solubility of iron chloride in the KCl-ZnCl₂ melt is higher than the solubility of nickel chloride and chromium (III) chloride in the KCl-ZnCl₂ melt. This enables a higher diffusibility of iron chloride to the upper region of the melt where a higher oxygen partial pressure (p(O₂)) is present leading to a higher oxidation rate of iron.