Characterization of spent AA household alkaline batteries

The aim of this work is identification of the structural components of actual domestic spent alkaline AA batteries, as well as quantification of some of their characteristics. Weight, humidity, ash content, zinc and zinc oxide on anode, manganese on cathode and other metals, potassium hydroxide on the internal components and heating values for papers, anode and cathode were determined in several batteries. As expected, cathode, anode and the steel can container are the main contributors to the 23.5 g average weight of the batteries. Cathode is also the major contributor to the positive heating value of the batteries as well as to the heavy metals content. Mercury was detected in very low levels in these mercury-free batteries. Zinc and zinc oxide amounts in the anodes are highly variable. Results obtained were compared to information on alkaline batteries in the literature from 1993 to 1995; and a positive evolution in their manufacture is readily apparent. Data from the producer of batteries shows some small discrepancies relative to the results of this experimental work.     

Thermal treatment for recovery of manganese and zinc from zinc-carbon and alkaline spent batteries

The aim of this paper is the recovery of manganese and zinc from a mixture of zinc-carbon and alkaline spent batteries, containing 40.9% of Mn and 30.1% of Zn, after preliminary physical treatment followed by removal of mercury. Separation of the metals has been carried out on the basis of their different boiling points, being 357°C and 906°C the boiling point of mercury and zinc and 1564°C the melting point of Mn(2)O(3). Characterization by chemical analysis, TGA/DTA and X-ray powder diffraction of the mixture has been carried out after comminution sieving and shaking table treatment to remove the anodic collectors and most of chlorides contained in the mixture. The mixture has been roasted at various temperatures and resident times in a flow of air to set the best conditions to remove mercury that were 400°C and 10min. After that, the flow of air has been turned into a nitrogen one (inert atmosphere) and the temperatures raised, thus permitting the zinc oxide to be reduced to metallic zinc by the carbon present in the original mixture and recovered after volatilization as a high grade concentrate, while manganese was left in the residue. The recovery and the grade of the two metals, at 1000°C and 30min residence time, were 84% and 100% for zinc and 85% and 63% for manganese, respectively. The recovery of zinc increased to 99% with a grade of 97% at 1200°C and 30min residence time, while the recovery and grade of manganese were 86% and 87%, respectively, at that temperature. Moreover, the chlorinated compounds that could form by the combustion of the plastics contained in the spent batteries, are destroyed at the temperature required by the process.     

Waste battery treatment options: Comparing their environmental performance

Waste consumer batteries are recycled using different routes based on hydrometallurgical and pyrometallurgical processes. Two hydrometallurgical and two pyrometallurgical treatment scenarios are compared starting from an average composition of Belgian waste batteries. The environmental performance is compared using life cycle analysis (LCA). The recycling rate is studied through mass balance calculation.Each treatment scenario results in a specific recycling rate. The environmental impact and benefits also vary between the treatment options. There is no such thing as a typical hydrometallurgical or pyrometallurgical treatment. When applying a hydrometallurgical treatment scenario, the focus lies on zinc and iron recycling. When allowing manganese recycling, the energy demand of the hydrometallurgical process increases considerably. Both pyrometallurgical options recycle zinc, iron and manganese. According to the LCA, none of the treatment scenarios performs generally better or worse than the others. Each option has specific advantages and disadvantages. The Batteries Directive 2006/66/EC sets out a recycling rate of 50% for consumer waste batteries. Based on metal recycling alone, the mass balances show that the target is difficult to obtain.     

Recovery of manganese oxides from spent alkaline and zinc–carbon batteries. An application as catalysts for VOCs elimination

Manganese, in the form of oxide, was recovered from spent alkaline and zinc–carbon batteries employing a biohydrometallurgy process, using a pilot plant consisting in: an air-lift bioreactor (containing an acid-reducing medium produced by an Acidithiobacillus thiooxidans bacteria immobilized on elemental sulfur); a leaching reactor (were battery powder is mixed with the acid-reducing medium) and a recovery reactor. Two different manganese oxides were recovered from the leachate liquor: one of them by electrolysis (EMO) and the other by a chemical precipitation with KMnO₄ solution (CMO). The non-leached solid residue was also studied (RMO). The solids were compared with a MnO_x synthesized in our laboratory.The characterization by XRD, FTIR and XPS reveal the presence of Mn₂O₃ in the EMO and the CMO samples, together with some Mn⁴⁺ cations. In the solid not extracted by acidic leaching (RMO) the main phase detected was Mn₃O₄.The catalytic performance of the oxides was studied in the complete oxidation of ethanol and heptane. Complete conversion of ethanol occurs at 200 °C, while heptane requires more than 400 °C. The CMO has the highest oxide selectivity to CO₂.The results show that manganese oxides obtained using spent alkaline and zinc–carbon batteries as raw materials, have an interesting performance as catalysts for elimination of VOCs.     

Reclaiming the spent alkaline zinc manganese dioxide batteries collected from the manufacturers to prepare valuable electrolytic zinc and LiNi0.5Mn1.5O4 materials

A process for reclaiming the materials in spent alkaline zinc manganese dioxide (Zn–Mn) batteries collected from the manufacturers to prepare valuable electrolytic zinc and LiNi_0.5Mn_1.5O₄ materials is presented. After dismantling battery cans, the iron cans, covers, electric rods, organic separator, label, sealing materials, and electrolyte are separated through the washing, magnetic separation, filtrating, and sieving operations. Then, the powder residues react with H₂SO₄ (2 mol L^?1) solution to dissolve zinc under a liquid/solid ratio of 3:1 at room temperature, and subsequently, the electrolytic Zn with purity of ?99.8% is recovered in an electrolytic cell with a cathode efficiency of ?85% under the conditions of 37–40 °C and 300 A m^?2. The most of MnO₂ and a small quantity of electrolytic MnO₂ are recovered from the filtration residue and the electrodeposit on the anode of electrolytic cell, respectively. The recovered manganese oxides are used to synthesize LiNi_0.5Mn_1.5O₄ material of lithium-ion battery. The as-synthesized LiNi_0.5Mn_1.5O₄ discharges 118.3 mAh g^?1 capacity and 4.7 V voltage plateau, which is comparable to the sample synthesized using commercial electrolytic MnO₂. This process can recover the substances in the spent Zn–Mn batteries and innocuously treat the wastewaters, indicating that it is environmentally acceptable and applicable.     

Laboratory study on the leaching potential of spent alkaline batteries

Four different leaching tests were carried out with spent alkaline batteries as an attempt to quantify the environmental potential burdens associated with landfilling. The tests were performed in columns filled up with batteries either entire or cross-cut, using either deionized water or nitric acid solution as leachant. In a first set of tests, the NEN 7343 standard procedure was followed, with leachant circulating in open circuit from bottom to top through columns. These tests were extended to another leaching step where leachant percolated the columns in a closed loop process.Leachate solutions were periodically sampled and pH, conductivity, density, redox potential, sulphates, chlorides and heavy metals (As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, Tl and Zn) were determined in the samples.The results showed that the total amount of substances leached in tests with cross-cut batteries was higher than with entire ones; zinc and sulphates were the substances found the most in the leachate solutions. In general, the amount of substances dissolved in open circuit is higher than in closed loop due to the effect of solution saturation and the absence of fresh solution addition.Results were compared with metal contents in the batteries and with legal limits for acceptance in landfill (Decision 2003/33/CE and Decree-Law 152/2002). None of the metals were meaningfully dissolved comparatively to its content in the batteries, except Hg. Despite the differences in the experiment procedure used and the one stated in the legislation (mixing, contact time and granulometry), the comparison of results obtained with cross-cut batteries using deionized water with legal limits showed that batteries studied could be considered hazardous waste.     

活性污泥焚烧过程中镍的迁移分布特性

采用管式炉对污水厂活性污泥焚烧过程中Ni的迁移分布特性进行研究。实验结果表明：当污泥掺烧量（污泥质量与煤和污泥总质量的比）为25%时，Ni的挥发率（飞灰与气体中Ni质量的总和与污泥中Ni质量的比）几乎为零，且污泥与煤混合试样的综合燃烧效果最好；当污泥焚烧加入硫化物时，各种硫化物对Ni的残留率（炉渣中Ni的质量与污泥中Ni质量的比）提高能力大小顺序为Na₂S>S>Na₂SO₃>Na₂SO₄；当污泥焚烧加入氯化物时，促使Ni向烟气中迁移，且加入无机氯更易使Ni向烟气中迁移。     

Review of biosolids management options and co-incineration of a biosolid-derived fuel

This paper reviews current biosolids management options, and identifies incineration as a promising technology. Incineration is attractive both for volume reduction and energy recovery. Reported emissions from the incineration of biosolids were compared to various regulations to identify the challenges and future direction of biosolids incineration research. Most of the gaseous and metal emissions were lower than existing regulations, or could be met by existing technologies. This paper also presents the results of an experimental study to investigate the potential use of biosolids for co-incineration with wood pellets in a conventional wood pellet stove. Pilot scale combustion tests revealed that co-incineration of 10% biosolids with 90% premium grade wood pellets resulted in successful combustion without any significant degradation of efficiency and emissions.     

Optimal utilization of waste-to-energy in an LCA perspective

Energy production from two types of municipal solid waste was evaluated using life cycle assessment (LCA): (1) mixed high calorific waste suitable for production of solid recovered fuels (SRF) and (2) source separated organic waste. For SRF, co-combustion was compared with mass burn incineration. For organic waste, anaerobic digestion (AD) was compared with mass burn incineration. In the case of mass burn incineration, incineration with and without energy recovery was modelled. Biogas produced from anaerobic digestion was evaluated for use both as transportation fuel and for heat and power production. All relevant consequences for energy and resource consumptions, emissions to air, water and soil, upstream processes and downstream processes were included in the LCA. Energy substitutions were considered with respect to two different energy systems: a present-day Danish system based on fossil fuels and a potential future system based on 100% renewable energy. It was found that mass burn incineration of SRF with energy recovery provided savings in all impact categories, but co-combustion was better with respect to Global Warming (GW). If all heat from incineration could be utilized, however, the two alternatives were comparable for SRF. For organic waste, mass burn incineration with energy recovery was preferable over anaerobic digestion in most impact categories. Waste composition and flue gas cleaning at co-combustion plants were critical for the environmental performance of SRF treatment, while the impacts related to utilization of the digestate were significant for the outcome of organic waste treatment. The conclusions were robust in a present-day as well as in a future energy system. This indicated that mass burn incineration with efficient energy recovery is a very environmentally competitive solution overall.     

酸浸—萃取—沉淀法回收废锂离子电池中的钴

采用酸浸—萃取—沉淀法回收废锂离子电池中的钴。实验结果表明:废锂离子电池在600℃下煅烧5 h可将正极材料上的有机黏结剂与正极活性物质分离;正极活性物质在Na OH溶液浓度为2.0 mol/L、n(Na OH)∶n(铝)=2.5、碱浸温度为20℃的条件下碱浸反应1 h后,铝浸出率达99.7%;已除铝的正极活性物质在硫酸浓度为2.5 mol/L、H_2O_2质量浓度为7.25 g/L、液固比为10、酸浸温度为85℃的条件下酸浸反应120 min,钴浸出率高达98.0%;酸浸液在p H为3.5、萃取剂P507与Cyanex272体积比为1∶1的条件下,经2级萃取,钴萃取率为95.5%;采用H_2SO_4溶液反萃后在硫化钠质量浓度为8 g/L、反萃液p H为4的条件下沉淀反应10 min,钴沉淀率达99.9%。     

Chemical and physical characterization of electrode materials of spent sealed Ni-Cd batteries

The present work aimed at the chemical and physical characterization of spent sealed MONO-type Ni-Cd batteries, contributing to a better definition of the recycling process of these spent products. The electrode material containing essentially nickel, cadmium and some cobalt corresponds to approximately 49% of the weight of the batteries. The remaining components are the steel parts from the external case and the supporting grids (40%) containing Fe and Ni, the electrolyte (9%) and the plastic components (2%). Elemental quantitative analysis showed that the electrodes are highly concentrated in metals. The phase identification achieved by X-ray powder diffraction combined with chemical analysis and leaching tests allowed the authors to proceed with the composition of the electrode materials as following: cathode: 28.7% metallic Ni, 53.3% Ni(OH)2, 6.8% Cd(OH)2 and 2.8% Co(OH)2; anode: 39.4% metallic Ni and 57.0% Cd(OH)2. The morphology of the electrodes was studied by microscopic techniques and two phases were observed in the electrodes: (1) a bright metallic phase constituted of small nickel grains that acts as conductor, and (2) the main hydroxide phase of the active electrodes into which the nickel grains are dispersed. The disaggregation of the electrode particles from the supporting plates was easily obtained during the dismantling procedures, indicating that a substantial percentage of the electrodes can be efficiently separated by wet sieving after shredding the spent batteries.     

Management of municipal solid waste incineration residues

The management of residues from thermal waste treatment is an integral part of waste management systems. The primary goal of managing incineration residues is to prevent any impact on our health or environment caused by unacceptable particulate, gaseous and/or solute emissions. This paper provides insight into the most important measures for putting this requirement into practice. It also offers an overview of the factors and processes affecting these mitigating measures as well as the short- and long-term behavior of residues from thermal waste treatment under different scenarios. General conditions affecting the emission rate of salts and metals are shown as well as factors relevant to mitigating measures or sources of gaseous emissions.     

Tools for evaluation of impact associated with MSW incineration: LCA and integrated environmental monitoring system

The identification of significant pollutants emitted from the contamination source is the first step in evaluating the impact associated with anthropic activity. Municipal solid waste (MSW) incinerators are still generally perceived as great pollutant sources, in particular due to their gaseous emissions from the stack, which constitute the major effluent from the plant. In this work a life cycle assessment and an integrated environmental monitoring system were applied together, in order to obtain complete information about the incineration process and its environmental impact. The former is a proven methodology, but its application to waste management systems constitutes a relatively new field of application with a great developmental potential. The contribution of the incineration process to the different environmental impact categories was investigated, finding many avoided impacts due to energy recovery. The latter is an innovative approach that allows a remarkable understanding of impact due to a contamination source; interesting correlations were found between heavy metals both in gas emissions and in natural matrices in the surroundings.     

Impact of moisture on volatility of heavy metals in municipal solid waste incinerated in a laboratory scale simulated incinerator

In this work, the impact of moisture on the volatility of heavy metals present in municipal solid wastes (MSW) in a laboratory scale simulated incinerator was studied, using synthetic waste consisting of 5.4 g of wood powder, 2.6 g lava, 1.9 polythene, 0.19 g polyvinyl chloride, and a given quantity of water and heavy metals represented by lead, zinc and copper in forms of metallic, chlorides and oxides. It is found that the presence of high moisture in MSW will greatly reduce the volatilization of heavy metals in MSW in the incineration process. The volatilization behavior of chlorides, oxides and the metallic species with respect to the effect of moistures is quite different. For copper, the presence of moisture in MSW depresses the volatilization of oxides, and increases that of chloride and the metallic species, while in contrast, the volatilization of both lead and zinc is always depressed by the presence of moisture in MSW, regardless of the chemical forms used. The chemical mechanisms, which govern the volatilization behaviors of different chemical forms in the incineration process, are proposed. Hydrolysis, dewatering of hydrolyzed species, sublimation, chemical transformation of less volatiles to more volatiles or reverse, may participate in and affect the volatilization of heavy metals in MSW.     

Vitrification for reclaiming spent alkaline batteries

The object of this study is to stabilize spent alkaline batteries and to recover useful metals. A blend of dolomite, limestone, and cullet was added to act as a reductant and a glass matrix former in vitrification. Specimens were vitrified using an electrical heating furnace at 1400 °C and the output products included slag, ingot, flue gas, and fly ash. The major constituents of the slag were Ca, Mn, and Si, and the results of the toxicity leaching characteristics met the standards in Taiwan. The ingot was a good material for use in production of stainless steel, due to being mainly composed of Fe and Mn. For the fly ash, the high level of Zn makes it economical to recover. The distribution of metals indicated that most of Co, Cr, Cu, Fe, Mn, and Ni moved to the ingot, while Al, Ca, Mg, and Si stayed in the slag; Hg vaporized as gas phase into the flue gas; and Cd, Pb, and Zn were predominately in the fly ash. Recovery efficiency for Fe and Zn was >90% and the results show that vitrification is a promising technology for reclaiming spent alkaline batteries.     

LCA to choose among alternative design solutions: The case study of a new Italian incineration line

At international level LCA is being increasingly used to objectively evaluate the performances of different Municipal Solid Waste (MSW) management solutions. One of the more important waste management options concerns MSW incineration. LCA is usually applied to existing incineration plants.In this study LCA methodology was applied to a new Italian incineration line, to facilitate the prediction, during the design phase, of its potential environmental impacts in terms of damage to human health, ecosystem quality and consumption of resources. The aim of the study was to analyse three different design alternatives: an incineration system with dry flue gas cleaning (without- and with-energy recovery) and one with wet flue gas cleaning. The last two technological solutions both incorporating facilities for energy recovery were compared. From the results of the study, the system with energy recovery and dry flue gas cleaning revealed lower environmental impacts in relation to the ecosystem quality.As LCA results are greatly affected by uncertainties of different types, the second part of the work provides for an uncertainty analysis aimed at detecting the extent output data from life cycle analysis are influenced by uncertainty of input data, and employs both qualitative (pedigree matrix) and quantitative methods (Monte Carlo analysis).     

Thermal conversion of municipal solid waste via hydrothermal carbonization: comparison of carbonization products to products from current waste management techniques

Hydrothermal carbonization (HTC) is a novel thermal conversion process that may be a viable means for managing solid waste streams while minimizing greenhouse gas production and producing residual material with intrinsic value. HTC is a wet, relatively low temperature (180-350 °C) thermal conversion process that has been shown to convert biomass to a carbonaceous residue referred to as hydrochar. Results from batch experiments indicate HTC of representative waste materials is feasible, and results in the majority of carbon (45-75% of the initially present carbon) remaining within the hydrochar. Gas production during the batch experiments suggests that longer reaction periods may be desirable to maximize the production of energy-favorable products. If using the hydrochar for applications in which the carbon will remain stored, results suggest that the gaseous products from HTC result in fewer g CO(2)-equivalent emissions than the gases associated with landfilling, composting, and incineration. When considering the use of hydrochar as a solid fuel, more energy can be derived from the hydrochar than from the gases resulting from waste degradation during landfilling and anaerobic digestion, and from incineration of food waste. Carbon emissions resulting from the use of the hydrochar as a fuel source are smaller than those associated with incineration, suggesting HTC may serve as an environmentally beneficial alternative to incineration. The type and extent of environmental benefits derived from HTC will be dependent on hydrochar use/the purpose for HTC (e.g., energy generation or carbon storage).     

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.     

溶剂萃取法提取废旧碱性电池中的有价成分

为回收利用废旧电池，进行了溶剂萃取法提取碱性废弃电池中锌、锰金属的试验研究。选择南孚（AA）碱性废电池为处理样品，通过粉碎、水浸、酸浸等步骤，获得含锌、锰离子的稀溶液，并利用模拟体系得到的萃取结果进行浸出液的萃取性能试验研究。结果表明，每个废电池填充物中含锌和锰分别为0.25g和0.36g，具有可观的回收价值；采用完全皂化的二（2－乙基己基）磷酸（D2EHPA）／煤油为萃取剂提取含锌锰的酸浸出液，一级萃取就可获得60％以上的提取率。