Inhibition of acid rock drainage from uranium ore waste using a conventional neutralization and precipitation treatment

Glass columns (length 50 cm, i.d. 4 cm) containing 900 g of uranium ore waste were subjected to a three-step process: (1) acid drainage generation, (2) neutralization and precipitation treatment and, again, (3) acid drainage generation. In the first acid generation step, lasting about one year, different variables (pyrite addition, inoculation and irrigation solution) were tested by measuring effluent pH, redox potential, total iron and sulphate. Conditions of acid generation were satisfactorily reproduced, reaching stable pH values around 2.0 that were determined mainly by pyrite addition and the type of irrigation solution used (distilled water or ferrous sulphate). The neutralization and precipitation treatment consisted of alternating irrigations of a neutralizing solution (CaO saturated plus NaOH) and a precipitating solution (ferric sulphate saturated). This treatment caused accumulation of basic iron sulphate and iron oxide precipitates according to SEM studies. After this treatment, the barrier effect created by the reaction products was checked, using irrigation solutions similar to the first step. The effluents collected showed higher pH and lower redox potential, total iron and sulphate values than those observed before the treatment, evidencing inhibition of acid drainage generation.     

On-line corrosion monitoring in geothermal district heating systems. II. Localized corrosion

Corrosion monitoring in district heating systems has traditionally been performed by using off-line methods, such as weight loss. The disadvantage is that the method is very slow, especially in low-corrosive environments, and that it only provides information about the past corrosion (accumulated over period of time). The purpose of the work is to test on-line monitoring methods in geothermal hot water in the district heating system in Reykjavik, Iceland. Geothermal water poses certain problems with regards to corrosion monitoring due to low conductivity, high pH and the presence of sulphide. These conditions make the geothermal environment low corrosive. However, a quality control is needed, especially since the sulphide causes the steel pipes to be more vulnerable towards localized corrosion. The methods used in this study were: linear polarization resistance (LPR), harmonic analysis (HA), electrochemical noise (EN) and zero resistance ammetry (ZRA). The Pitting Factor was measured with EN and showed promising results for measuring-localized corrosion on-line. A crevice corrosion cell also gave good results but had a low lifetime. However, the results of a galvanic corrosion cell (Fe/Cu) proved more difficult to interpret since they were dependent both on the dissolved oxygen and the sulphide level.     

Catalytic oxidation of sulphide ions to elementary sulphur in aqueous solutions over transition metal oxides

The catalytic activity of a wide range of transition metal oxides in oxidation of sulphide ions by air in aqueous medium was studied. Some specific features of the reaction mechanism on some of the studied oxides were considered. The transition metal oxides are promising catalysts for practical application. Some of these oxides will allow the preparation of catalysts possessing activity comparable to that of the cobalt phthalocyanine based catalysts, popular in industrial practice.     

硫化矿床开采特高温炮孔的装药爆破安全技术

本文阐述了高温矿床火区开采特高温炮孔的装药爆破安全技术。提出了掌握炸药安全使用温度,采取隔离、隔热包装,降低孔温及提高临界温度等安全措施。     

Management of thiosalts in mill effluents by chemical oxidation or buffering in the lime neutralization process

Laboratory studies were conducted to investigate the removal or management of thiosalts within the lime-neutralization process, to prevent or minimize the adverse effects of thiosalts that cause delayed acidity to downstream environment. The oxidizing reagent hydrogen peroxide (H₂O₂) and the pH stabilizing (buffering) reagents carbon dioxide (CO₂), sodium bicarbonate (NaHCO₃) and sodium carbonate (Na₂CO₃) were examined for removal and management of thiosalts, respectively. Chemical oxygen demand (COD) was determined to be a proxy for thiosalts and was employed for their rapid assessment. The Target Level of thiosalts harmless to aquatic life was found to be 30 mg/L or less. The optimized lime-neutralization process required a pH level of 9.5–10 and aeration. Over-liming to pH levels >11 did not provide excess alkalinity, hardness, or a decrease in thiosalt levels.Addition of H₂O₂ to either the acid or lime-neutralized water at a molar H₂O₂:S₂O₃ ratio of 1–1.5 removed thiosalts to safe levels. About 10–15 min. at room temperature was ample time low temperatures slowed down the process but the dosages were not affected. Removal of thiosalts from 170 to 30 mg/L caused a decrease in pH from 9.6 to 6.5. Among the buffering reagents studied, both NaHCO₃ and Na₂CO₃ provided adequate buffering and a stable pH of 7 to the lime-neutralized water; whereas CO₂ resulted in poor buffering and an unstable pH that remained below 6. In cold temperatures, NaHCO₃ and Na₂CO₃ also outperformed CO₂ with higher alkalinity and hardness. Na₂CO₃ addition to lime neutralized water at pH 9.5 was found to be the most cost-effective option. Other methods could have niche applications, depending on seasonal variations and temperature.     

Rate controlling reactions for copper corrosion in anaerobic aqueous sulphide solutions

Abstract

The long term corrosion behaviour of copper in anoxic aqueous sulphide solutions has been studied using corrosion potential and electrochemical impedance spectroscopy measurements and scanning electron microscopy on corroded surfaces and cross-sections of surfaces prepared using a focused ion beam. Experiments were conducted in solutions containing either 5×10^?4 or 5×10^?5 mol L^?1 sulphide for 1691 and 4000 h respectively. In the more concentrated solution, a coherent, compact and crystalline chalcocite (Cu₂S) film accumulated on the corroding copper surface. A parabolic growth law was obtained, and the kinetics were controlled by Cu(I) ion transport either through the Cu₂S matrix or along crystalline grain boundaries in the film. In the more dilute solution, the growth of a less crystalline, porous chalcocite layer followed approximately the linear growth kinetics controlled by sulphide ion transport through the pores. If the sulphide was allowed to deplete in the dilute solution, rate control switched to sulphide diffusion in the bulk solution. The implications for waste container corrosion in a nuclear waste repository are discussed.     

Deterioration of Concrete by the Oxidation of Sulphide Minerals in the Aggregate

Cases of degradation of concrete associated to iron sulphides in aggregates were recently recognized in the Trois-Rivi6res area, Canada. The aggregate used to produce concrete was an anorthositic gabbro containing various proportions of pyrite, pyrrhotite, chalcopyrite and pentlandite. Quantitative microanalysis on sulphide minerals show that pyrrhotite contains small amount of Ni, Co, Cu and As substituting for Fe in the mineral structure. Considering element substitution, x value in the chemical formula （Fe~.xS） was calculated to 0.099 in the pyrrhotite studied. Petrographic examination of damaged concretes showed the presence of oxidized pyrrhotite. The observation of polished samples shows, in several cases, that the pyrite is intact while the pyrrhotite presents evident signs of oxidation. In the presence of water and oxygen, pyrrhotite oxidizes to form iron oxyhydroxides and sulphuric acid. The acid then reacts with the phases of the cement paste and provokes the formation of gypsum and ettringite. These minerals were observed by SEM-EDS （scanning electron microscope/energy dispersive x-ray spectrometer） and their precipitation causes a volume increase that creates expansion and cracking of the concrete.     

Corrosion and Cavitation Erosion Behaviours of Cast Nickel Aluminium Bronze in 3.5% NaCl Solution with Different Sulphide Concentrations

The effect of sulphide(Na_2S) concentration(SC) on the corrosion and cavitation erosion behaviours of a cast nickel aluminium bronze(NAB) in 3.5% NaCl solution is investigated in this study.The results show that when the SC exceeds 50 ppm,the hydrogen evolution reaction dominates the cathodic process,and a limiting current region appears in the anodic branch of the polarisation curve due to the formation of a copper sulphide film,which is a diffusion-controlled process.After longterm immersion,the increased mass loss rate of NAB with the sulphide additions of 20 and 50 ppm is attributed to the less protective films,which contains a mixture of copper oxides and sulphides.Moreover,NAB undergoes severe localised corrosion(selective phase corrosion,SPC) at the β' phases and eutectoid microstructure α+κ_Ⅲ.By comparison,NAB undergoes general corrosion and a copper sulphide film is formed in 100 and 200 ppm sulphide solutions.Cavitation erosion greatly increases the corrosion rate of NAB in all solutions and causes a negative potential shift in 3.5% NaCl solution due to the film destruction.However,a positive potential shift occurs in the solutions with SC higher than 50 ppm due to the accelerated mass transfer of the cathodic process.The cavitation erosion mass loss rate of NAB increases with the increase of SC.The occurrence of severe SPC decreases the phase boundary cohesion and causes brittle fracture under the cavitation impact.The corrosion-enhanced erosion is the most predominant factor for the cavitation erosion damage when the SC exceeds 50 ppm.     

硫化物对冷辗芯辊疲劳裂纹萌生的影响

硫化物夹杂对疲劳裂纹源萌生的影响有正负二重性。本文分析硫化物形状、尺寸、分布和力学性能对高速钢W6Mo5Cr4V2冷辗芯辊疲劳断裂的作用,认为质软硫化物能够减缓硬脆非金属夹杂物对基体产生的嵌镶应力,阻止疲劳裂纹的萌生。     

Mechanochemical sulfidization of a mixed oxide-sulphide copper ore by co-grinding with sulfur and its effect on the flotation efficiency

Mechanochemical sulfidization of a mixed sulfide/oxide copper ore by co-grinding with sulfur and additives including Mg(NO₃)₂ and Fe(NO₃)₃ salts and iron, aluminum and magnesium powders was investigated for the first time. Also, the influence of sulfidization during the wet-milling process was examined on the separation efficiency and recovery of copper in detail. The results demonstrated that co-grinding with sulfur solely had the best flotation performance at the value of 0.5 wt.% and it was attributed to the possible existence of S-O bonding on copper oxides surfaces. In addition, adding magnesium nitrate salt, magnesium powder, iron nitrate salt and aluminum powder as additive associated with 0.5 wt% sulfur into ball milling caused the flotation improvement at the amounts of 0.2 wt%, 0.2 wt%, 0.5 wt% and 0.5 wt%, respectively. Also, the effect of grinding time and sulfidization pH with 0.5 wt% sulfur solely was determined and pHs of 7.5 to 8.5 gave the best results. The highest recovery (75.76%) and separation efficiency (63.44%) were achieved at pH of 7.5 and 8.5, respectively.