分步沉淀法处理酸性矿山废水

采用分步沉淀工艺处理酸性矿山废水,考察了工艺条件对废水中有价金属元素回收效果的影响。实验结果表明:Ca(OH)_2为适宜的废水pH调节剂;调节废水pH至4.00左右并投加0.05 mL/L的H_2O_2,可首先去除Fe~(2+)及Fe~(3+),得到富Fe渣(w(Fe)=51.00%);调节废水pH至6.00~6.50,先投加50 mg/L的Na_2S,去除废水中的Cu~(2+),获得富Cu渣(w(Cu)=10.89%),再将Na_2S的投加量增至100 mg/L,去除废水中的Zn与Mn,获得富Zn-Mn渣(w(Cu)=2.37%,w(Mn)=6.79%,w(Pb)=1.61%);进一步调节废水pH至8.40,可去除剩余的Zn、Mn及其他重金属。分步沉淀工艺处理后的废水可达标排放,产生的富Fe渣、富Cu渣及富Zn-Mn渣可直接出售或具有利用价值。分步沉淀工艺可实现有价金属元素的高效回收,大幅度降低废水处理的实际成本,值得工程应用与推广。     

Preliminary studies on potential remediation of acid mine drainage‐impacted soils by amendment with drinking‐water treatment residuals

Mining operations result in a wide range of environmental impacts: acid mine drainage (AMD) and acid sulfate soils being among the most common. Due to their acidic pH and high soluble metal concentrations, both AMD and acid sulfate soils can severely damage the local ecosystems. Proper post‐mining management practices are necessary to control AMD‐related environmental issues. Current AMD‐impacted soil treatment technologies are rather expensive and typically not environmentally sustainable. We conducted a 60‐day bench‐scale study to evaluate the potential of a cost‐effective and environment‐friendly technology in treating AMD‐impacted soils. The metal binding and acid‐neutralizing capacity of an industrial by‐product, drinking water treatment residuals (WTRs) were used for AMD remediation. Two types of locally generated WTRs, an aluminum‐based WTR (Al‐WTR) and a lime‐based WTR (Ca‐WTR) were used. Highly acidic AMD‐impacted soil containing very high concentrations of metals and metalloids, such as iron, nickel, and arsenic, was collected from the Tab‐Simco coal mine in Carbondale, Illinois. Soil amendment using a 1:1 Al‐ and Ca‐WTR mix, applied at 5 and 10 percent rates significantly lowered the soluble and exchangeable fractions of metals in the AMD‐impacted soil, thus lowering potential metal toxicity. Soil pH increased from an extremely acidic 2.69 to a near‐neutral 6.86 standard units over the 60‐day study period. Results from this preliminary study suggest the possibility of a successful scale‐up of this innovative, cost‐effective, and environmentally sustainable technology for remediating AMD‐impacted acid sulfate soils.     

Enhancement of Sedimentation Velocity of Heavy Metals Loaded Hydroxyapatite Using Chitosan Extracted from Shrimp Waste

In this study, synthesize hydroxyapatite (HA) suspensions sedimentation was used after usual terms as support for adsorption of heavy metals ions. Thus, the effectiveness of chitosan, produced from shrimp waste, in the flocculation of turbid suspensions resulting from the treatment of water contaminated with heavy metals was studied by adsorption on HA. Different particles sizes of HA were mainly controlled in this work (an average of granule size ranging from 1.6 to 63 μm). The results of Cu²⁺ and Zn²⁺ adsorption on HA showed relatively fast kinetics, with removal extent of 88–95 % by varying the initial total metal concentration. High removal rates were obtained for Cu²⁺. Chitosan was found to be able to eliminate by flocculation more than 98 % of turbid suspensions generated by metals adsorption on HA after only 30 min of sedimentation. Effects of pH and dose of chitosan on the coagulation–flocculation process were also studied. The optimal dose of chitosan was found between 0.2 and 2 mg/L which corresponds to an optimal pH ranging from 6 to 7.     

交联阳离子淀粉的合成及其对重金属离子的吸附

通过正交实验合成了取代度为0．568的交联阳离子淀粉。考察了溶液pH、螯合剂用量、重金属离子初始浓度对交联阳离子淀粉去除重金属离子效果的影响。当重金属离子初始质量浓度为50mg／L、螯合剂投加量为0．5g／U时,Pb^2 ,Cu^2 ,Cr^3 在溶液pH为6时的去除率达到最高,分别为97．94％,99．46％,84．30％,而Cd^ 在溶液pH为7时的去除率达到最高,为99．36％。实验结果表明,交联阳离子淀粉是一种有效去除废水中重金属的处理剂。     

Adsorption characteristics of Cu2+ and Zn2+ from aqueous solution using carbonized food waste

The aim of the present study was to analytically provide adsorption characteristics of Cu²⁺ and Zn²⁺ using carbonized food waste (CFW); more specifically, batch tests were conducted using various concentrations of metal ions, contact times, and initial pH levels in an attempt to understand the adsorption removal of heavy metal ions in aqueous solution at concentrations ranging between 50 and 800 mg/l. The results confirmed that the adsorption equilibrium was established within a maximum of 80 min, and the maximum concentrations for adsorption of Cu²⁺ and Zn²⁺ were 28.3 and 23.5 mg/g, respectively. These adsorption levels indicate that CFW has better performance than many other adsorbents. In experiments using different pH conditions, the applicability to acid wastewater was found to be high, and an excellent adsorption removal ratio of 75%–90% was observed under acid conditions at pH 2–4. Furthermore, as the adsorption time increased, the calcium component in the CFW began to leach into the aqueous solution and raise the pH, accordingly causing the removal of heavy metal ions partially as a result of precipitation. When our results were analyzed using the Langmuir model and the Freundlich model for isothermal adsorptivity, the activity of CFW in this study was shown to be more consistent with the former; the adsorption speed of Cu²⁺ and Zn²⁺ according to a pseudosecond-order reaction model was found to be very fast for an initial concentration of not more than 100 mg/l. In a test in which an attempt was made to compare adsorption capacity values obtained from the experiments in this study with the aforementioned three models, the pseudosecond-order reaction model was found to provide results closest to the actual values.     

Treatment of waste containing EDTA by chemical oxidation

Ethylenediaminetetraacetic acid (EDTA) is a chelating agent that has been extensively used to enhance the solubilization of heavy metal cations and release of EDTA contributes to environmental problems. EDTA is recalcitrant to microbial metabolism and chemical oxidation is considered a possible method of remedial treatment. The use of the commercially available process of MIOX Corporation generates mixed oxidants on site and this solution is markedly effective in the destruction of the chelating characteristic and the decarboxylation of EDTA. When measuring the release of C-14 from carboxyl labeled EDTA, the mixed oxidant solution was comparable to the Fenton's reaction over a broad pH range. The presence of Mn²⁺, Cr³⁺, or Fe³⁺ at levels equal to that of EDTA stimulated the rate of EDTA decomposition; however, the rate of EDTA breakdown was inhibited when the concentration of Cr³⁺ or Mn²⁺ exceeded the concentration of EDTA. The treatment of Co²⁺–EDTA or Cu²⁺–EDTA with mixed oxidants in the presence of ultra violet light resulted in the loss of chelation ability of EDTA. In the absence of chelated metals, over 75% of the chelation property of a 70 mM EDTA solution was destroyed in 45 min. The reaction products resulting from the use of mixed oxidants added to EDTA were non-toxic to bacteria and should not contribute to additional environmental problems.     

Vanadium recovery from oil fly ash by leaching, precipitation and solvent extraction processes

In order to reduce the environmental impact due to land disposal of oil fly ash from power plants and to valorize this waste material, the removal of vanadium was investigated using leaching processes (acidic and alkaline treatments), followed by a second step of metal recovery from leachates involving either solvent extraction or selective precipitation. Despite a lower leaching efficiency (compared to sulfuric acid), sodium hydroxide was selected for vanadium leaching since it is more selective for vanadium (versus other transition metals). Precipitation was preferred to solvent extraction for the second step in the treatment since: (a) it is more selective; enabling complete recovery of vanadate from the leachate in the form of pure ammonium vanadate; and (b) stripping of the loaded organic phase (in the solvent extraction process) was not efficient. Precipitation was performed in a two-step procedure: (a) aluminum was first precipitated at pH 8; (b) then ammonium chloride was added at pH 5 to bring about vanadium precipitation.     

Leaching of heavy metals in acid mine drainage.

Acid mine drainage is one of the most serious environmental problems that the coal and metal mining industry is currently facing. The generation of low pH drainage enhances the dissolution of heavy metals in water. The samples used in this research originated from three pits at mine dumps. In a study reported in this paper, three types of tests; namely static test, kinetic test and column test were conducted to estimate acid generation and acid neutralization reaction rates, and to predict the solubility of metals and their release rates. Static test showed that all samples had a pH of net acid generation (NAG pH) <4, a net acid producing potential (NAPP) >10 kg H2SO4tonne(-1), and a S-content >3%, which can be classified as a high acid-forming capacity. Simulated runoff in the column tests was equivalent to 5-year average rainfall in Indonesia, the resultant leachates showed acidic behaviour (pH < 3.5). Based on the results, it was found that high mobilization of heavy metals (Cr, Cu, Zn, Cd and Pb) takes place under strong acidic conditions (pH approximately equal 2).     

Passive Treatment Alternatives for Remediating Abandoned‐Mine Drainage

Abandoned‐mine drainage (AMD) is drainage flowing from or caused by surface mining, deep mining, or coal refuse piles that is typically highly acidic with elevated levels of dissolved metals. AMD results from the interactions of certain sulfide minerals with oxygen, water, and bacteria. Passive treatment systems have been used to remediate AMD at numerous sites throughout the United States. The theory behind passive treatment is to allow naturally occurring chemical, biological, and physical reactions that aid in AMD treatment to occur in the controlled environment of the system, not in the receiving water body. The advantages of passive treatment over active treatment include lower operation and maintenance costs, virtually no use of chemicals, and minimal energy consumption. The disadvantages are that smaller volumes of water are treated than with active systems, and discharges with high concentrations of dissolved metals and extremes of pH may have to be treated several times within one system to treat the discharge. AMD passive treatment systems include aerobic treatment systems and anaerobic treatment systems. It is estimated that it will take 50 years and between $5 billion and $15 billion to remediate all AMD problems in Pennsylvania. © 2001 John Wiley & Sons, Inc.     

Preparation of Alginic Acid and Metal Alginate from Algae and their Comparative Study

Alginic acid and metal alginates are prepared from fresh algae using extraction method. A FTIR spectrum indicates that alginic acid is converted into the metal alginate. Comparing calcium and cobalt alginates, asymmetric stretching of free carboxyl group of calcium alginate at 1630 cm⁻¹ is shifted to 1585 cm⁻¹ in cobalt alginate, due to the change of charge density, radius and atomic weight of the cation, creating a new environment around the carbonyl group. The strong exothermic peak of alginic acid in DSC thermogram indicates the decomposition of biopolymer, whereas strong exothermic peak of metal alginate in DSC thermogram attributed to the decomposition of biopolymer and formation of respective carbonate. Based on DSC study, the decomposition of cobalt alginate occurs at higher temperature comparing to those of sodium and calcium alginate, which may conclude into the higher stability of cobalt alginate. TGA results reveal that, cobalt alginate is more stable than calcium and sodium alginate at 300 °C temperature. Surface morphology (at same magnification), as well as porosity (%) and pore size distribution results change with metals present in different metal alginates.     

生物吸附在染料废水处理中的应用

生物吸附是微生物细胞和其它物质发生的一系列非发酵关联的吸附过程,其主要作用包括物理和化学吸附、静电作用、离子交换、络合、螯合、微量沉淀等。与生物降解相比,生物吸附不会产生有毒的代谢产物,为染料废水的处理和回收提供了一条经济可行的途径。综述了微生物对染料吸附的作用机制及影响因素如pH、温度、染料初始浓度等,介绍了生物吸附的发展现状及前景。     

重金属螯合剂TMT-15处理高含汞气田废水

选用重金属螯合剂TMT-15处理高含汞气田废水(COD=1 560 mg/L,SS=210 mg/L,pH=2.5~3.0,汞质量浓度为340 mg/L),考察了TMT-15投加量,废水pH,与氢氧化物、硫化物联用等因素对汞去除效果的影响,分析了TMT-15与汞的螯合产物的稳定性。实验结果表明:TMT-15能与汞强力螯合并沉淀,投加量低,pH适用范围广;絮凝剂聚合硫酸铝与TMT-15的联用可提高除汞效果,但作用有限;TMT-15与氢氧化物联用时的汞的去除效果提升显著,在氢氧化钠、三聚硫氰酸、汞元素的摩尔比为0.5:0.5:1和废水pH为3.0的条件下,汞去除率可达99.99%,剩余汞浓度低于GB 8978—1996中规定的汞排放浓度;螫合产物具有很高的热稳定性,且在较高浓度的酸碱环境中溶解率低,对环境造成二次污染的风险小。     

Water extraction with CO2 bubbling as pretreatment of melting-furnace fly ash for metal recovery

In Japan, melting-furnace fly ash (MFA) generated from ash melting and gasification/melting plants is considered an “urban mine” due to its high metal content. This study aimed to develop a novel approach to pretreating MFA for metal recovery. Water extraction with CO₂ bubbling was investigated because MFA mainly consists of water-soluble salts containing elements such as Cl, Ca, Na, and K. Instead of acid addition, CO₂ bubbling was applied to maintain the optimal pH for minimizing the release of target metal elements and maximizing the removal of undesirable elements during water extraction. The results revealed that CO₂ bubbling effectively decreased the release of Pb, Zn, and Cd into the treatment water. This was mainly due to coprecipitation with CaCO₃, which was primarily formed by the reaction of Ca²⁺ from the MFA with CO₃ ²⁻ from the CO₂ gas. The bubbling process also helped accelerate the removal of Cl from MFA. Furthermore, the study showed that it is possible to lower the water-to-solid ratio to 5 with only a slight reduction in water extraction effect. Finally, approximately four times the concentration of target metals (rare metals and Cu, Pb, and Zn) was achieved by removing 90% of Cl, 70%–90% of Na and K, and 30%–40% of Ca through water extraction with CO₂ bubbling, resulting in a concentration of target metals that was nearly equal to that of ore.     

Treatment of Stormwater using Fibre Filter Media

In this study, a high-rate fibre filter was used as a pre-treatment to stormwater in conjunction with in-line flocculation. The effect of operating the fibre filter with different packing densities (105, 115 and 125 kg/m³) and filtration velocities (20, 40, 60 m/h) with and without in-line flocculation was investigated. In-line flocculation was provided using 5, 10 and 15 mg/L of ferric chloride (FeCl₃·6H₂O). The filter performance was studied in terms of pressure drop (ΔP), solids removal efficiency, heavy metals (total) removal efficiency and total organic carbon (TOC) removal efficiency. It is found that the use of in-line flocculation at a dose of 15 mg/L improved the performance of fibre filter as measured by turbidity removal (95%), total suspended solids reduction (98%), colour removal efficiency (99%), TOC removal (reduced by 30–40 %) and total coliform removal (93%). The modified fouling index reduced from 750–950 to 12 s/L² proving that fibre filter can be an excellent pre-treatment to membrane filtration that may be consider as post-treatment. The removal efficiency of heavy metal was variable as their concentration in raw water was small. Even though the concentration of some of these metals such as iron, aluminium, copper and zinc were reduced, others like nickel, chromium and cadmium showed lower removal rates.     

Chemical Composition and Acidity of Rain at the Gulf of Iskenderun,North-East Mediterranean

The purpose of the present work was to investigate the chemistry of rain in the Gulf of Iskenderun, North East Mediterranean, Turkey. The Gulf region has a large number of industries. Main industries existing in the region are iron and steel works, fertilizer plants, a cement plant, and several medium and mini size steel mills in addition to the international pipe line terminals. This study aims to apportion the local sources contributing to the overall pollution of the region. To this end a precipitation sampling program was started in January 2000, and over 48 precipitation samples were collected from each of 5 stations located at Iskenderun city center, Iskenderun industrial zone, Payas city center, the campus of Iskenderun Technical College and the campus of Mustafa Kemal University. Samples were analysed for pH, NO₃ ⁺, Cl^-. Ca, Al, Ba, Na, Cd, Co, Cr, Cu, Pb, Li, Mg, Mn, Ni, Zn, Fe, K. Concentrations of metal ions were determined by ICP-AES. NO₃ ^- ions and pH were determined by using NO₃ ^- selective electrode and pH meter, respectively.pH values of the collected samples at the industrial zone and at Payas city center, ranged between 5.02 and 7.38, respectively. NO₃ ^- and metal ions concentrations were highly variable. Concentrations of Ca and Fe ions were higher in the industrial zone and Payas city center. In the other three stations, concentrations of metal ions and NO₃ ^- ion were lower than that of industrial zone and the values of pH ranged between 6 and 7.4. The average pH values at Iskenderun Gulf showed that the precipitation was not acidic, because of the high concentration of Ca. The highest concentrations of Na and Cl ions were recorded in the University campus because the campus is located by the Mediterranean Sea.     

Kinetics of biochemically driven metal precipitation in synthetic landfill leachate

This study investigates the effectiveness of using metal sulphide and carbonate precipitation mechanisms combined with a landfill‐derived mixed bacterial population. The study was conducted under controlled substrate conditions in anaerobic batch reactors. High chemical oxygen demand (COD):sulphate ratios, butyrate, propionate, and acetate were used anaerobically by bacteria for growth with associated sulphate reduction as well as sulphide and carbonate generation. Propionate and butyrate degradation occurred during sulphate reduction by sulphate‐reducing bacteria while acetate degradation was associated with methanogenesis by methanogenic bacteria. Using low COD, sulphate ratios showed limited acetate utilization, but sulphate reduction still occurred. Precipitation of Cd, Cu, Zn, Ni, and Fe sulphides occurred quickly and was completed in 15 to 30 days, while Ca, Mn, and Mg carbonates formed after 40 to 50 days and some soluble metal remained even after 120 days. The rate of metal precipitation was in the order of Cd>Cu>Zn>Ni>Fe>Mn>Mg>Ca. Bacterially mediated metal precipitation occurred slower than that recognized for chemical precipitation. These findings suggest that contaminant transport models based on chemical equilibrium metal behaviors may over‐predict metal removal by bio‐precipitation. © 2002 Wiley Periodicals, Inc.     

Limitations for heavy metal release during thermo-chemical treatment of sewage sludge ash

Phosphate recycling from sewage sludge can be achieved by heavy metal removal from sewage sludge ash (SSA) producing a fertilizer product: mixing SSA with chloride and treating this mixture (eventually after granulation) in a rotary kiln at 1000 ± 100 °C leads to the formation of volatile heavy metal compounds that evaporate and to P-phases with high bio-availability. Due to economical and ecological reasons, it is necessary to reduce the energy consumption of this technology. Generally, fluidized bed reactors are characterized by high heat and mass transfer and thus promise the saving of energy. Therefore, a rotary reactor and a fluidized bed reactor (both laboratory-scale and operated in batch mode) are used for the treatment of granulates containing SSA and CaCl₂. Treatment temperature, residence time and - in case of the fluidized bed reactor - superficial velocity are varied between 800 and 900 °C, 10 and 30 min and 3.4 and 4.6 m s⁻¹. Cd and Pb can be removed well (>95 %) in all experiments. Cu removal ranges from 25% to 84%, for Zn 75-90% are realized. The amount of heavy metals removed increases with increasing temperature and residence time which is most pronounced for Cu.In the pellet, three major reactions occur: formation of HCl and Cl₂ from CaCl₂; diffusion and reaction of these gases with heavy metal compounds; side reactions from heavy metal compounds with matrix material. Although, heat and mass transfer are higher in the fluidized bed reactor, Pb and Zn removal is slightly better in the rotary reactor. This is due the accelerated migration of formed HCl and Cl₂ out of the pellets into the reactor atmosphere. Cu is apparently limited by the diffusion of its chloride thus the removal is higher in the fluidized bed unit.     

Heavy metals removal/stabilization from municipal solid waste incineration fly ash: a review and recent trends

Waste treatment using thermal technologies, such as incineration, leads to the production of pollutants and wastes, including fly ash (FA). Fly ash contains heavy metals (HMs) and other contaminants and can potentially pose high risks to the environment and negatively impact health and safety. Consequently, stabilizing fly ash prior to either use or landfilling is crucial. The toxicity of fly ash through heavy metal leaching can be assessed using leaching tests. The leaching rates of heavy metals primarily depend on the surrounding conditions as well as fly ash properties and metal speciation. Physical separation, leaching or extraction, thermal treatment and solidification/chemical stabilization are proposed as suitable approaches for fly ash treatment. Economic considerations, environmental concerns, energy consumption and processing times can define the efficiency and selection of the treatment approach. This review considers the latest findings and compares the advantages and shortcomings of different fly ash treatment methods with the aim of highlighting the recent advances in the field. The review concludes that the simultaneous implementation of various methods can lead to highly efficient heavy metals removal/stabilization while simultaneously taking economic and environmental considerations into account.

     

Treatment of mixed contamination in water using cyclodextrin‐based materials

This study investigated the effectiveness of a cyclodextrin‐based solid material for the removal of mixed dissolved contaminants. The solid material was prepared by condensation of α‐cyclodextrin. The removal efficiency was found to be 70 percent for total heavy metals (cadmium, lead, chromium, iron, nickel, cobalt, and mercury) to 98 percent for polychlorinated biphenyls (PCBs). The optimum pH for heavy metal removal was approximately 5 and for PCBs it was in the range of 5–7. All of these heavy metals were successfully recovered from the spent cyclodextrin‐based material using nitric acid, allowing the material to be reused for further passes. The results also showed that the presence of alkaline and alkaline earth metals did not have a significant effect on the removal efficiency, indicating that the cyclodextrin‐based material could selectively remove the heavy metals of concern without being consumed by alkaline and alkaline‐earth metals. © 2006 Government of Canada.     

Electrochemical remediation of heavy metal contaminated soils

Over the years, many soils have been contaminated with toxic heavy metals as a result of a variety of industrial and military activities. Electrokinetic soil treatment is an emerging technology that could prove to be very effective in the remediation of these sites. “Real-world” heavy metal contaminated (Pb(II), Cd(II), and Cr(III)) soils from three military sites with varying soil properties were subjected to electrokinetic treatment in the laboratory. Metal extractants (chelating agents and acids) were studied and found to be effective in enhancing the electrokinetic process. Results indicated that heavy metal removal efficiencies varied in the three soils tested. In one case, removal efficiencies of 90 percent and 60 percent were obtained for Cd and Cr, respectively, for the nitric acid amended experiments. For another case, over 60 percent of the total Pb in the system was deposited near the cathode for the non-amended and the citric-acid amended tests. Conversely, in the third case, the electrokinetic soil-washing treatment process failed to produce significant removal of any metal contaminant. The discrepancies that exist between the metal removal results of the three soils were attributed to the different physiochemical characteristics of each soil.