粉煤灰防治煤矸石酸性与重金属复合污染

采用柱状淋溶模拟试验,分析添加粉煤灰防治煤矸石酸性和重金属污染的效果及机理.结果表明：煤矸石淋溶液具有典型的酸性矿山废水特征.在粉煤灰处理中,淋溶液的pH值呈中性或微碱性,重金属浓度显著下降.这主要是因为：① 粉煤灰促进了Fe等氢氧化物沉淀和多种重金属的共沉淀;② 生成的Fe沉淀具有包被作用,阻隔黄铁矿的氧化;③ 碱性环境抑制了氧化亚铁硫杆菌的生长和对黄铁矿的微生物催化氧化.研究表明,粉煤灰直接覆盖可以明显地抑制煤矸石中硫化物的氧化并提高煤矸石淋溶液的水质.     

Fate of sulphate removed during the treatment of circumneutral mine water and acid mine drainage with coal fly ash: Modelling and experimental approach

The treatment of acid mine drainage (AMD) and circumneutral mine water (CMW) with South African coal fly ash (FA) provides a low cost and alternative technique for treating mine wastes waters. The sulphate concentration in AMD can be reduced significantly when AMD was treated with the FA to pH 9. On the other hand an insignificant amount of sulphate was removed when CMW (containing a very low concentration of Fe and Al) was treated using FA to pH 9. The levels of Fe and Al, and the final solution pH in the AMD–fly ash mixture played a significant role on the level of sulphate removal in contrast to CMW–fly ash mixtures. In this study, a modelling approach using PHREEQC geochemical modelling software was combined with AMD–fly ash and/or CMW–fly ash neutralization experiments in order to predict the mineral phases involved in sulphate removal. The effects of solution pH and Fe and Al concentration in mine water on sulphate were also investigated. The results obtained showed that sulphate, Fe, Al, Mg and Mn removal from AMD and/or CMW with fly ash is a function of solution pH. The presence of Fe and Al in AMD exhibited buffering characteristic leading to more lime leaching from FA into mine water, hence increasing the concentration of Ca²⁺. This resulted in increased removal of sulphate as CaSO₄·2H₂O. In addition the sulphate removal was enhanced through the precipitation as Fe and Al oxyhydroxysulphates (as shown by geochemical modelling) in AMD–fly ash system. The low concentration of Fe and Al in CMW resulted in sulphate removal depending mainly on CaSO₄·2H₂O. The results of this study would have implications on the design of treatment methods relevant for different mine waters.     

Start-up,adjustment and long-term performance of a two-stage bioremediation process,treating real acid mine drainage,coupled with biosynthesis of ZnS nanoparticles and ZnS/TiO2 nanocomposites

Acid mine drainage (AMD) generation is a widespread environmental problem in Europe, including Portugal. Previous experience has shown that a combined process consisting of an anaerobic sulphate-reducing bioreactor, following neutralization with calcite tailing, produces water complying with legal irrigation requirements from synthetic AMD. Aiming the treatment of real AMD a new bioreactor was inoculated with a SRB enrichment obtained from sludge from a local WWTP anaerobic lagoon. In the initial batch phase, sulphate supplementation was needed to achieve high sulphate-reducing bacteria counts before continuous feeding of AMD was started. The system quickly achieved good performance, proving it is easy to start-up. However, this time the neutralization step failed to keep bioreactor affluent pH higher than 5 for longer than three weeks. This was due to armouring of calcite by precipitates of various metals present in AMD. A new configuration, replacing a packed-bed column by a shallow contact basin, proved to be more robust, avoiding clogging, short-circuiting and providing long-term neutralization. The treated effluent, with excess of biologically generated sulphide, was successfully used to synthesize zinc sulphide nanoparticles, both in pure form and as a ZnS/TiO₂ nanocomposite, thus proving the feasibility of coupling an AMD bioremediation system with the synthesis of metal sulphide nanoparticles and nanocomposites.     

Mine water quality deterioration due to acid mine drainage

Water quality deterioration due to acid mine drainage is of concern in the northeastern coalfield of India as the water in this area is severely polluted. The mine drainage water emanating from various collieries are highly acidic in character and contain high hardness, sulphate, total dissolved solids and iron coupled with low pH values—which further results in contamination of trace (heavy) metals at significant levels. Trace metals are highly toxic and undesirable and are injurious to human health. These acidic waters are also typically hard in character because of iron sulphate content rather than common Ca?Mg bicarbonate type hardness.     

Acidic sulphate leaching of chalcopyrite concentrates in presence of pyrite

Copper concentrates with mineralogy dominated by chalcopyrite have slow leaching kinetics at atmospheric pressure in sulphate media because of the formation of passivation layer on its surface during the leaching. To enhance the leaching rate of the copper concentrate, pyrite was added to act as a catalyst. Pyrite and copper sulphide minerals then form a galvanic cell which increases both the copper leaching rate and yield. Effect of parameters such as solution redox potential, temperature, initial acid concentration, solids content, total initial iron concentration and pyrite to copper sulphide minerals mass ratio were investigated. Mineralogical analyses by XRD were performed on selected leach residues and the feed materials. A copper recovery higher than 80% in 24 h was achieved at a redox potential of 410 mV vs Ag, AgCl, a temperature of 85 °C, 15 g/L of initial acid concentration, a solid content of 7.8% (w/v), a total initial iron concentration 5 g/L and pyrite to copper sulphide minerals mass ratio 2:1. XRD patterns on leach residues showed that candidates for surface passivation, i.e. jarosite and elemental sulphur, were formed at high total initial iron concentrations.     

A study of the drainages of the pyrite mines of Aljustrel (Portugal)

Characterization of the pollution charge of drainages from pyrite mines of Aljustrel (Portugal) was made. Laboratory experiments were performed in order to recover copper by cementation and remove iron, zinc and acidity by neutralization with lime. It was found that the removal of the metal ions is completed when pH reaches a step at 5.0–5.5, whichever the ratio between Fe(II) and Fe(III).     

Phosphate coating on pyrite to prevent acid mine drainage

Abstract

Acid mine drainage (AMD) is a serious environmental problem that preoccupies the Canadian Mineral Industry. Considerable amounts of money are spent every year in an effort to prevent or reduce the acid mine drainage phenomenon. AMD occurs when sulfide minerals (ex. pyrite) contained in rock are exposed to air and water and subsequently oxidize to produce low pH water. This acid effluent has the potential to mobilize any heavy metals contained in the rock. Coating the sulfide minerals with iron phosphate is a new promising technology to reduce AMD.Pyrite is treated with a solution containing H₂O₂, KH₂PO₄ and sodium acetate (NaAc). H₂O₂ oxidizes a small part of pyrite producing ferric iron (Fe³⁺) anions. These cations subsequently react with the PO₄ ^3? anions to produce FePO₄ that precipitates on the pyrite surface producing a passive coating. This iron phosphate coating can protect the grains of pyrite from oxidation. This paper presents a series of experiments that confirm that iron phosphate coating can considerably reduce AMD.     

A Bench-scale Assessment of a Combined Passive System to Reduce Concentrations of Metals and Sulphate in Acid Mine Drainage

Abstract  Passive treatment of acid mine drainage (AMD) requires a combined strategy to minimize the effect of climatic variability on the treatment performance of the system. A vertical-flow combined passive treatment system was developed and evaluated in a bench-scale laboratory test for a 290-day period. The combined system consisted of four components with specific treatment functions: an oxidation/precipitation basin for excess iron removal; a peat biofilter for heavy metal sorption and the establishment of anoxic conditions; a bioreactor for alkalinity generation and sulphate reduction; and an anoxic limestone drain for alkalinity addition. The benchscale system was dosed with moderate strength synthetic AMD at a surface loading of 95 L/m²/d, and operated under continuous flow conditions. Removal efficiencies were 99.7%, 99.9%, 99.9%, 98.6%, 98.2%, and 99.9% for Fe, Al, Zn, Mn, Ni, and Cu, respectively, while Cd remained more mobile with a removal efficiency of 66.5%. Sulphate concentrations were reduced from 3030 mg/L to 814.9 mg/L and the acidic drainage was neutralized to an effluent pH of 7.2 and an alkalinity of 1353.6 mg/L (as CaCO₃).     

高镁低品位铜镍矿氧压硫酸浸出液综合回收研究

针对高镁低品位铜镍矿氧压硫酸浸出液特点,提出“Lix984萃取提铜-MgO中和黄钠铁矾法沉淀除铁-MgO中和沉镍”综合回收工艺。结果表明,采用Lix984可选择性萃取99.79%的铜,其他金属离子基本不萃取,经模拟工业贫铜电解液反萃,铜反萃率达98.13%,得到富铜电解液,可电积制备金属铜; 萃铜余液通过MgO中和黄钠铁矾法沉淀除铁,铁沉淀率达99.20%,镍损失率仅0.60%; 沉铁后液通过MgO中和沉淀回收镍,镍沉淀率为99.91%,并得到镍含量24.13%的氢氧化镍粗产品; 沉镍后的高浓度硫酸镁沉淀后液,可用于回收镁。     

锌精矿氧压浸出过程伴生硫铁矿的转化行为

针对锌精矿氧压浸出过程伴生硫铁矿的氧化转化行为,以硫铁矿为研究对象,研究了不同初始硫酸浓度、温度、氧分压、矿物粒度、反应时间对硫铁矿氧压浸出行为的影响。研究表明：硫铁矿氧压浸出过程反应初期为耗酸反应,硫酸的消耗速率大于硫酸的生成速率,反应后期主要是元素硫氧化转化生成硫酸;反应初期浸出液中的铁主要为二价铁离子,反应后期发生铁离子的氧化,且在高温酸性溶液中三价铁离子可水解沉淀为赤铁矿和铁钒;硫铁矿中的硫元素在氧压浸出过程大部分转化为硫酸并以硫酸根的形式存在溶液中,而少部分以单质硫形式存在于浸出渣中,附着于浸出渣表面,形成包裹层。     

Mineralogical and Geochemical Characterization of Mine Tailings and Pb, Zn, and Cd Mobility in a Carbonate Setting (Northern Tunisia)

Millions of tonnes of Pb–Zn ore flotation tailings and waste rock have been discharged at sites in northern Tunisia without concern for environmental issues. The tailings are dominantly fine grained (<125 μm), with high porosity and permeability. The tailings were characterized to assess base metal (Pb, Zn, and Cd) mobility. The relatively low percentage of iron sulphide and the dominance of carbonates in the matrices of the tailings indicated that only neutral mine drainage is likely. Batch sequential testing showed that the calcium and sulphate, which are the major ionic species in solution, are derived mainly from the dissolution of gypsum and not from neutralization of acidity generated by pyrite oxidation. Yet, despite the carbonate setting, the resultant neutral to slightly alkaline pH, and prolonged weathering, the studied flotation tailings maintain their capacity to release contaminants, notably Zn and Cd, into the environment. The amount of Zn that dissolves (2,400 μg L^?1, on average), though significant, is below the background concentrations in the Mejerda River and the environmental norms established for surface waters. Pb concentrations come close to the standards, but only Cd (18 μg L^?1, on average) sometimes exceeds current river water concentrations and environmental standards.     

加压酸浸过程中铟与铁的关系研究

用硫铁矿与硫酸铟模似高铟高铁闪锌矿的加压酸浸,对影响浸出的始酸浓度、温度、时间、压力等因素进行考察,得出铟会随黄钾铁矾、氢氧化铁胶体、赤铁矿的生成而随铁一起进入渣中,其中赤铁矿晶形较好,铟随其进入渣量最少。为了使浸出过程中铟尽可能少入渣,应减少浸出过程中铁的沉淀,铁的沉淀最好以赤铁矿的形式存在。      

Production of a poly-alumino-iron sulphate coagulant by chemical precipitation of a coal mining acid drainage

The aim of this work was to produce a poly-alumino-iron sulphate coagulant from acidic coal mine drainage. Precipitating the iron and aluminium at pH 5.0, followed by dissolution in sulphuric acid, produced a coagulant consisting of 8.7% iron and 3.3% aluminium. Water treatment tests proved that this coagulant was as efficient as the coagulant chemicals conventionally used in water treatment plants. The process can be easily incorporated into conventional AMD treatment plants, thereby reducing sludge waste issues and producing a valuable chemical reagent.     

Iron precipitation kinetics in synthetic acid mine drainage

To evaluate the design and operation of a new active treatment system for acid mine drainage (AMD), the behavior of ferric iron solutions after the addition of bicarbonate ions was investigated. The effects of various other factors common to AMD on the precipitation rate of iron were also studied. It was found that the rate of Fe III precipitation in synthetic AMD was not affected by the presence of Al or Mn, within the concentration ranges investigated (for Al, 0-0.01 M, for Mn, 0-0.002 M). Our experiments showed that the induction time (t_md),i.e., the time elapsed between the addition of base ions and the detection of iron precipitation, decreased with increasing iron concentration and pH but increased with increasing sulfate concentration: log t_ind=6.7(±0.30)?1.29 (±0.10) pH+0.94(±0.07) log [SO₄]?0.36 (±0.05) log [Fe] Our results suggested that sulfate sorbed to the surface of growing iron oxyhydroxides, inhibiting their growth. This effect offers an important tool that can be used to control the precipitation of iron in AMD treatment facilities.     

Waste Glycerol Addition to Reduce AMD Production in Unsaturated Mine Tailings

A 20?month long column study was conducted to evaluate the surface application of waste glycerol (WG) to reduce release of acid mine drainage constituents from mine tailings. Beneficial characteristics of the WG include high aqueous solubility, high organic content, and high alkalinity. Four columns were packed with fine-grained sulfide rich tailings and incubated in the field under ambient temperature and precipitation conditions. In the two replicate untreated control columns, diffusion of oxygen into the tailings resulted in large increases in dissolved iron, sulfate, manganese, magnesium, aluminum, zinc, and hot acidity with an associated drop in pH. In the two replicate treated columns, WG was blended into the top 0.18?m of tailings 7?months after the columns were established, resulting in large reductions in iron, sulfate, hot acidity, aluminum, copper, and manganese. Observed pollutant reductions resulted from a combination of processes including: (a) neutralization of acidity by the KOH present in the WG (b) reduction of SO₄ to H₂S with subsequent precipitation of dissolved metals, and potentially (c) consumption of oxygen, slowing oxidation of the tailings.     

Grain Size Effects on Mine Water Quality and Acid/Neutral Rock Drainage Production in Kinetic Testing Using Recsk Porphyry Skarn Cu–Zn Deposit Rocks

The quality of mine drainage from sulphide-containing waste rock dumps is controlled by several factors. To characterize the effects of grain size on acid/neutral rock drainage production, kinetic tests were performed on samples from the Recsk porphyry skarn Cu–Zn deposit in Hungary, an area known to generate ARD. Five columns were used, each containing specific grain size ranges (1–2, 2–4, 4–8, 8–16, and 16–32 mm). Prior to the kinetic tests, a static test was performed for each grain size range to obtain total and available neutralizing potential (NP) and acid potential (AP). Total NP and AP values were roughly similar for all grain size ranges, while available NP increased as grain size decreased. The neutralization potential ratio for all grain size ranges was <1, which suggests a potentially acid-producing material. The kinetic tests, however, had contrasting results; a grain size of 1–4 mm produced a circumneutral pH, while grain size groups >4 mm produced pHs from 5.1 down to 3.6. Higher alkalinity values in the leach water were linked to the finer grain samples, primarily producing circumneutral pH. Grain size correlated with the sulphate release rate during the stable release period: the sulphate release rate was less at larger grain sizes. In contrast, sulphide oxidation calculated from oxygen consumption was highest for the intermediate grain size range, followed by the coarser and then the finer grains. The leaching of metals established an increasing concentration with increasing acidity without a very clear relationship to grain size. The established concept of increased metal mobility with decreasing pH applies, regardless of grain size.     

The application of wood ash as a reagent in acid mine drainage treatment

The paper deals with a possible utilisation of wood ash as a reagent in treating acid mine drainage (AMD) from opencast mining of brown coal. Wood ash samples were obtained having combusted deciduous and coniferous tree wood in a household furnace. The dominant mineral phases in wood ash are calcite, quartz, lime and periclase. The used AMD is characteristic of high contents of sulphates, iron, manganese, heavy metals and low pH. The AMD treatment process included dosing of wood ash to adjust pH values about 8.3 (a dose of 0.5 g l⁻¹) or calcium hydroxide (a dose of 0.2 g l⁻¹) for comparison. The reaction time was 20 min. Dosing of wood ash in AMD resulted in an increase of pH in solution from 3.5 to 8.3, which caused the removal of metal ions mainly by precipitation, co-precipitation and adsorption. Comparing the application of Ca(OH)₂ in AMD treatment, at an almost identical pH value the concentrations fell in both cases for Fe, Mn, As, Co, Cu, Ni, Zn, Mg, Al and Mo. Applying wood ash the drop was even more distinct in Mn, Zn and Mg. The results of sedimentation tests in an Imhoff cone confirm that the settling capacities of sludge using wood ash are significantly better than when using calcium hydroxide in acid mine drainage treatment.     

Production of a Poly-ferric Sulphate Chemical Coagulant by Selective Precipitation of Iron from Acidic Coal Mine Drainage

The aim of this work was to produce a ferric sulphate rich solution from acidic coal mine drainage that could be used as coagulant. Precipitating the iron at pH 3.8, followed by dissolution in sulphuric acid, produced a coagulant consisting of 12.4% iron and 1.3% aluminium. Water treatment tests proved that this coagulant was as efficient as the coagulant chemicals conventionally used in water treatment plants. The process can be easily incorporated into conventional AMD treatment plants, thereby reducing sludge waste issues and producing a valuable chemical reagent.     

Treatment of acid mine drainage through a ferrite formation process in central Hokkaido,Japan: Evaluation of dissolved silica and aluminium interference in ferrite formation

A two-step neutralization process, leading to the formation of ferrites has been developed for the treatment of acid mine drainage (AMD). In the first neutralization step magnesium oxide was used to raise the pH to around 4.5 to eliminate aluminium (Al) and to reduce the silica (Si) concentration. In the second neutralization step sodium hydroxide was used to complete the neutralization and to precipitate ferrous and ferric hydroxides, from which ferrite could be formed. The AMD of a closed gold mine in central Hokkaido, Japan was treated in a continuous-flow bench-scale plant of the process. During the first neutralization step the removal of Si was more difficult than the removal of Al; the presence of both Al and Si interfered in the ferritization of the sludge. When the Al removal decreased from 94.5% to 64.3% the magnetism per unit mass of the sludge was reduced by 36.7% and when the Al removal decreased to 21.8% the magnetism of the sludge was reduced by 51.5%. The interference of coexisting Si was even stronger: the sludge showed a 26% and 36.7% decrease in magnetism when the removal of Si was reduced by 15% and 18%, respectively.     

黄铁矿的可浮性研究及生产实践

文章综合了国内外有关资料,并结合生产实际对黄铁矿的可浮性进行了评述。纯矿物试验表明,表面氧化的黄铁矿,无论是增加捕收剂、添加活化剂硫酸铜,都不能使黄铁矿的可浮性得到很好的改善。本文重点研究了影响黄铁矿可浮性的各种因素,如氧化作用、pH值、抑制剂和调整剂种类、酸洗黄铁矿矿物表面和硫酸铜活化等。指出了生产实践中回收难选黄铁矿的技术途径。