锰矿浸渣中水溶性锰的回收

采用水洗—生石灰沉淀法回收锰矿浸渣中的水溶性锰,考察了液固比、水洗时间对锰矿浸渣中水溶性锰洗出率（洗出液与锰矿浸渣中水溶性锰的质量比）的影响,并探讨了n（生石灰）∶n（水溶性锰）、聚丙烯酰胺絮凝剂加入量、反应温度和反应时间对洗出液中水溶性锰回收率（沉淀与洗出液中锰的质量比）的影响。实验结果表明：水洗工段,在去离子水体积（mL）与锰矿浸渣质量（g）比为5∶1、水洗时间5 min的条件下,水溶性锰洗出率达到92%;生石灰沉淀工段,n（生石灰）∶n（水溶性锰）对水溶性锰回收率的影响最大,其次为反应温度、絮凝剂加入量和反应时间,在n（生石灰）∶n（水溶性锰）=1.8、絮凝剂加入量0.2 mg/L、常温、反应时间10 min的条件下,水溶性锰回收率达90%以上;锰矿浸渣中水溶性锰的总回收率达83%以上。     

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 by citric acid from fly ash generated in municipal waste incineration plants

The leaching behavior of heavy metals from municipal waste incineration (MWI) fly ash was investigated in this study. The leaching process includes two steps, i.e., fly ash was firstly washed with water, and then subjected to citric acid leaching. The main parameters of the washing process such as liquid/solid ratio, washing time, and number of washing were tested. The optimum conditions for water washing were found as follows: washing time 5–10 min, liquid/solid ratio 10:1 (ml:g), and number of washing was twice; under these conditions, 86% Na, 70% K, 12% Ca, 1.2% Al, and 0.5% Pb were removed from the fly ash in the prewashing. From the results of screening tests of leaching lixiviants, citric acid was found to be the most effective leaching agent, taking account of its environmentally benign characteristics. Optimum metal extraction can be achieved with citric acid under the following conditions: pH 3.0, liquid/solid ratio 40 (ml:g), citric acid concentration 0.10 mol/dm³, contact time 20 min at room temperature.     

Immobilisation of beryllium in solid waste (red-mud) by fixation and vitrification

The objective of this study was to obtain information on the immobilization of beryllium (Be) in solid waste generated in the extraction process of beryllium from its ore, Beryl. This solid waste, termed red-mud, contains oxides of iron, aluminium, calcium, magnesium and beryllium. The red-mud waste contains beryllium at levels above the permissible limit, which prevents its disposal as solid waste. The total beryllium content in the red-mud analysed showed value ranging from 0.39 to 0.59% Be The studies showed that 50% of the total beryllium in red-mud can be extracted by water by repeated leaching over a period of 45 days. The cement mix, casting into cement blocks, was subjected to leachability studies over a period of 105 days and immobilization factor (IF factor) was determined. These IF values, of the order of 102, were compared with those obtained by performing leachability study on vitrified red-mud masses produced at different temperature conditions. Direct heating of the red-mud gave the gray coloured, non-transparent vitreous mass (as 'bad glass') showed effective immobilisation factor for beryllium in red-mud of the order of 10(4).     

Treatment process for MSW combustion fly ash laboratory and pilot plant experiments

Fly ash from combustion of municipal solid waste sometimes contains large amounts of soluble salts, such as NaCl, even though the content of soluble toxic metal compounds is relatively low. Removal of the salts by washing with water has been suggested as a method to increase the stability of this type of ash. In the work presented here, a simple washing process was studied and evaluated. The process includes three steps: leaching with water, filtration and displacement washing. Basic data were obtained in laboratory experiments and used in the construction of pilot plant equipment at a full size fluidized bed boiler, where a side-stream of the cyclone ash was treated. The process was designed to minimize the water consumption while obtaining an effective removal of salts and a stable ash residue. In order to achieve this, recirculation of leaching liquor was used and the displacement washing was adjusted to become close to ideal. The results showed that an ash/water slurry with a liquid to solid ratio as low as 3 could be handled without difficulty in the mixing, pumping and filtration units. Washing of the filter cake at a liquid to solid ratio of 0.5 removed the major part of the remaining dissolved salts in the pore liquid. About 90% of the chloride content was removed from the ash, whereas the contents of Na, K, Ca, Cd, Pb and a number of other minor elements were removed by 10-30%. Before treatment, the results of ash leaching tests were sometimes too high for chloride (2003/33/EC), but the treatment reduced the amount of soluble chlorides to far below the limit values. The leachability of most metals was reduced or unaffected by the ash treatment. For Na, K and Cl, it was less than 10% of the value for the untreated ash. However, the results showed that some ash components may be mobilized by the washing. Antimony is the most important due to its toxicity.     

废弃SCR催化剂中钒和钨的浸出及回收

采用NaOH溶液一次性浸出废弃SCR催化剂中的钒和钨,并用硫酸对浸出液进行除杂,再利用NH4Cl和硫酸分步对浸出液中的钒和钨进行沉淀回收。在NaOH质量分数40%、液固比8、浸出时间4 h、浸出温度90℃的最佳碱浸条件下,钒和钨的浸出率分别达到90.44%和84.49%。除杂过程的铝去除率达到100%,硅去除率达到77.56%。在沉钒pH为8.0、n(NH_4~+)∶n(V)为4的最佳沉钒条件下,钒回收率达到82.79%。在n(SO_4~(2-))∶n(W)为2的最佳沉钨条件下,钨回收率达到76.41%。     

多组分电镀污泥酸浸出液中铁的分离

研究了采用Ｐ５０７－煤油－Ｈ２ＳＯ４萃取体系分离电镀污泥酸浸出液中Ｆｅ＾３＋的工艺，确定了从含有多种上金属组分的硫酸溶液中萃取铁的最佳工艺条件以及负载有机相反萃取较优工艺条件，研究结果表明，以Ｐ５０７为萃取剂，硫酸为洗涤剂，经３级萃取、２级洗涤的分馏萃取后，可以从含有多种金属组分的硫酸溶液中分离出９９．９％的铁，其他金属的流失量小于１％，不影响后者的回收，铁在工艺过程中以ＦｅＣｌ３·６Ｈ２Ｏ的形式     

Release of salts from municipal solid waste combustion residues

Residues from fluidized bed combustion of municipal solid waste were investigated with respect to their leaching behavior and possible extraction of salts. The total water extractable amounts of Na, K, Ca, Cl(-), Br(-), F(-) and SO(4)(2-) along with the total dissolved solids of bottom, hopper, cyclone and bag house filter ashes were determined. A simple multistage washing process (using water as the extraction medium) was tested in lab scale experiments. The effect of variations in parameters, such as water to ash weight ratio, contact time, temperature and number of extraction steps was investigated. The leaching behavior of untreated and washed cyclone and bag house filter ashes was evaluated by a two-step batch-leaching test, i.e. the CEN test. The ashes investigated in this study can be arranged according to their decreasing water extractable contents and total dissolved solids as follows: filter ash > cyclone ash > hopper ash > bottom ash. A triple extraction with water at liquid to solid ratio 2 and extraction time 5 min gave the best results for the extraction of Ca, Na, K, Cl(-) and SO(4)(2-) from the cyclone as well as from the filter ashes. The leached amounts of salts in the CEN test performed on the washed cyclone ash were considerably lower than the corresponding amounts released from the unwashed ash. Thus, the washed cyclone ash was made more stable with respect to salt leachability. On the other hand, large amounts of salts were leached from the washed filter ashes as well as from unwashed filter ashes. Therefore, it can be concluded that three stage water extraction is not a suitable stabilization method for this type of filter ashes.     

Washing of waste prior to landfilling

The main impact produced by landfills is represented by the release of leachate emissions. Waste washing treatment has been investigated to evaluate its efficiency in reducing the waste leaching fraction prior to landfilling. The results of laboratory-scale washing tests applied to several significant residues from integrated management of solid waste are presented in this study, specifically: non-recyclable plastics from source separation, mechanical-biological treated municipal solid waste and a special waste, automotive shredded residues. Results obtained demonstrate that washing treatment contributes towards combating the environmental impacts of raw wastes. Accordingly, a leachate production model was applied, leading to the consideration that the concentrations of chemical oxygen demand (COD) and total Kjeldahl nitrogen (TKN), parameters of fundamental importance in the characterization of landfill leachate, from a landfill containing washed wastes, are comparable to those that would only be reached between 90 and 220years later in the presence of raw wastes. The findings obtained demonstrated that washing of waste may represent an effective means of reducing the leachable fraction resulting in a consequent decrease in landfill emissions. Further studies on pilot scale are needed to assess the potential for full-scale application of this treatment.     

Distribution of remaining Cd in MSWI fly ash washed with nitric acid

Municipal solid waste incineration (MSWI) fly ash is by-product and hazardous waste produced from MSWI plant. In the MSWI fly ash there are high contents heavy metals, among which cadmium (Cd) is more active and toxic. Although inorganic acid leaching is an effective way to remove heavy metals out from the MSWI fly ash and nitric acid has great efficiency for Cd removal, little literature reported the redistribution of remaining Cd in the MSWI fly ash. This investigation focused on the change of different factions (exchangeable, bound to carbonates, bound to Fe–Mn oxides, bound to organic matter and residual) of Cd in treated (i.e. washed with nitric acid) MSWI fly ash. Sequence extraction procedures (SEP) have been used to derive different fractions of Cd, results indicated that fractions of Cd have changed significantly after nitric acid washing procedures. Due to the changes of main compounds and microstructures stable Cd (bound to organic matter and residual) had opportunity to leach out, which resulted in a higher potential risk (or higher bioavailability index) for living creatures, although the total amount of Cd decreased. X-ray diffraction (XRD) and images of scanning electron microscope (SEM) proved these changes in washed MSWI fly ash.     

静电除尘技术在铬盐生产中的应用

简单介绍了静电除尘器的结构、工艺参数及在铬盐生产中的应用情况。讨论了尘粒的性质和气体性质对除尘效率的影响。铬矿回转窑尾气采用沉降－离心－静电三级除尘技术、酸化尾气采用静电除雾技术均取得了较好的效果。     

Process development for recovery of copper and precious metals from waste printed circuit boards with emphasize on palladium and gold leaching and precipitation

A novel hydrometallurgical process was proposed for selective recovery of Cu, Ag, Au and Pd from waste printed circuit boards (PCBs). More than 99% of copper content was dissolved by using two consecutive sulfuric acid leaching steps in the presence of H₂O₂ as oxidizing agents. The solid residue of 2nd leaching step was treated by acidic thiourea in the presence of ferric iron as oxidizing agent and 85.76% Au and 71.36% Ag dissolution was achieved. The precipitation of Au and Ag from acidic thiourea leachate was investigated by using different amounts of sodium borohydride (SBH) as a reducing agent. The leaching of Pd and remained gold from the solid reside of 3rd leaching step was performed in NaClO-HCl-H₂O₂ leaching system and the effect of different parameters was investigated. The leaching of Pd and specially Au increased by increasing the NaClO concentration up to 10 V% and any further increasing the NaClO concentration has a negligible effect. The leaching of Pd and Au increased by increasing the HCl concentration from 2.5 to 5 M. The leaching of Pd and Au were endothermic and raising the temperature had a positive effect on leaching efficiency. The kinetics of Pd leaching was quite fast and after 30 min complete leaching of Pd was achieved, while the leaching of Au need a longer contact time. The best conditions for leaching of Pd and Au in NaClO-HCl-H₂O₂ leaching system were determined to be 5 M HCl, 1 V% H₂O₂, 10 V% NaClO at 336 K for 3 h with a solid/liquid ratio of 1/10. 100% of Pd and Au of what was in the chloride leachate were precipitated by using 2 g/L SBH. Finally, a process flow sheet for the recovery of Cu, Ag, Au and Pd from PCB was proposed.     

Study of the treatment effectiveness of a solidification/stabilization process for waste bearing heavy metals

The sludge from a steel processing unit bearing zinc, lead, iron, and manganese was solidified with ordinary Portland cement. The waste was stabilized in the specimens with a waste/binder ratio range of 0.16–4.0. On the basis of the available leaching and unconfined compressive strength, the performance of the solidified/stabilized waste was compared for different numbers of curing days. It was found that curing up to 28 days resulted in a performance improvement, as shown by less leaching of heavy metals and the increased unconfined compressive strength of the specimen. The treatment effectiveness of the solidification/stabilization process was assessed for the metals Pb, Zn, Fe, and Mn, and was found to be 89%, 95%, 74%, and 90%, respectively, for an optimum ratio of 4.0 after 28 days of curing.     

Research & development methodology for recycling residues as building materials--a proposal

This article presents a proposal of methodology for conducting such research and development. The data/statistics waste collection statistics phase must cover geographical distribution, seasonal variations on production rates, waste management practices, current applications and their related costs and revenues. Waste characterisation must be comprehensive with physical, environmental and chemical aspects, including waste variability and waste contamination from shipping, handling and storage activities. Based on the previous results a broad forecast of potential applications must be developed based on very simple rules like minimisation of transportation distances and energy consumption, etc. Marketing evaluation is a very important step, frequently neglected when choosing the best applications for a particular waste. Other steps are product development and performance evaluation. Environmental evaluation of the new technology is very important because not all recycling is environmentally sound. This evaluation must be based on the life cycle assessment (LCA) and has to consider the environmental benefit of avoiding landfill disposal of the waste, and could include leaching or other specific tests or simulations. Also, the technological transference phase must be carefully planned and developed. Each proposed step is discussed, examples are given and needs for further research emphasised.     

Hydrometallurgical recycling of cobalt from zinc plants residue

A large amount of hot filter cake (HFC) is annually generated in Iranian zinc plants. It contains 1% zinc, 16–30% manganese, 5–25% calcium and 1–4.5% cobalt. Usually, zinc is selectively leached by an alkaline medium and its residue is known as alkaline leached HFC (ALHFC). In the present study, the possibility of cobalt extraction from ALHFC was investigated using a creative hydrometallurgical process. At the first stage, zinc and cadmium were selectively removed with sulfuric acid. At the second stage, it was deeply focused on the possibility of selective reductive leaching of cobalt by H₂O₂ as a reductant in the presence of manganese. As results, several differences were found between the mechanism of cobalt and manganese leaching. Accordingly, cobalt leaching was more affected by acid concentration and manganese leaching was more affected by reductant concentration. Consequently, with manipulating these important parameters, it was made possible to selectively separate cobalt from manganese. Based on the obtained results, 90.9% of cobalt and only 10.04% of manganese were leached with 1% of H₂O₂. At the third stage, pregnant cobalt solution was successfully purified through a solvent extraction process with D2EHPA. Finally, cobalt hydroxide as our final product with a purity of more than 99% was precipitated from the pure pregnant solution at 70 °C.     

Thermal and hydrometallurgical recovery methods of heavy metals from municipal solid waste fly ash

Heavy metals in fly ash from municipal solid waste incinerators are present in high concentrations. Therefore fly ash must be treated as a hazardous material. On the other hand, it may be a potential source of heavy metals. Zinc, lead, cadmium, and copper can be relatively easily removed during the thermal treatment of fly ash, e.g. in the form of chlorides. In return, wet extraction methods could provide promising results for these elements including chromium and nickel. The aim of this study was to investigate and compare thermal and hydrometallurgical treatment of municipal solid waste fly ash. Thermal treatment of fly ash was performed in a rotary reactor at temperatures between 950 and 1050 °C and in a muffle oven at temperatures from 500 to 1200 °C. The removal more than 90% was reached by easy volatile heavy metals such as cadmium and lead and also by copper, however at higher temperature in the muffle oven. The alkaline (sodium hydroxide) and acid (sulphuric acid) leaching of the fly ash was carried out while the influence of temperature, time, concentration, and liquid/solid ratio were investigated. The combination of alkaline-acidic leaching enhanced the removal of, namely, zinc, chromium and nickel.     

Removal of manganese and zinc from Kahrizak landfill leachate using daily cover soil and lime

The possibility of in situ removal of heavy metals found in leachate generated at municipal solid waste landfills was studied through amendment of daily cover soil. Kahrizak landfill, which receives the waste generated at Tehran, was selected as the source of leachate and soil samples. Manganese and zinc were selected in this study. The soil sample taken from the Kahrizak site contained about 17% clay, which was presumed to have significant capability for removing manganese and zinc. This capability was assumed to be enhanced further through the addition of lime and consequently to improve the potential for chemical precipitation of the selected metals. The in situ removal experiment was accomplished through a set of seven columns filled with the sampled soil with varying contents of lime (i.e., from 0% to 6% by dry weight). Fresh leachate of low pH was added to the columns on a daily basis. Concentrations of manganese and zinc were measured in the influent and effluent during 40 days when biological clogging resulted in a condition of almost no outflow in the columns. The results indicated a substantial increase in removal efficiency through the addition of lime to the daily cover soil. Desorption resulting from the low pH of fresh leachate occurs at later stages compared to the column with no lime addition.     

铁矿石烧结烟气脱硫灰处理含铬废水

在分析铁矿石烧结烟气脱硫灰成分的基础上,利用脱硫灰中的亚硫酸盐还原废水中的Cr(Ⅵ),再加碱中和,通过沉淀去除铬。在初始废水pH 1.0、脱硫灰加入量0.06 g/mg(以Cr(Ⅵ)计)、振荡转速160 r/min、振荡时间25 min、中和pH 7.5的最佳工艺条件下处理模拟含铬废水,Cr(Ⅵ)质量浓度由10.00 mg/L降至0.18 mg/L,去除率达98.2%。最佳工艺条件下处理3种实际含铬废水,处理后出水的Cr(Ⅵ)和总铬的质量浓度及pH均满足GB 8978—1996《污水综合排放标准》。实现了对脱硫灰的综合利用、化害为利和以废治废的目标。     

Exploitation of iron ore tailing for the development of ceramic tiles

India ranks as the sixth largest producer of iron ore in the world. The current practice of washing iron ore in India generates as high as 18 million tonnes of tailings per year. These tailings are stored in massive ponds and pose environmental hazards. Safe disposal or utilisation of these materials thus remains a challenging task for the iron ore industry in India. The present paper describes a new development in managing these tailings by converting them into value added products such as ceramic floor and wall tiles for building application. These tiles have high strength and hardness compared to conventional tiles and conform to most of the EN standards. Energy economy and lower production costs are some other benefits.