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.     

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.     

The BATINTREC process for reclaiming used batteries

The Integrated Battery Recycling (BATINTREC) process is an innovative technology for the recycling of used batteries and electronic waste, which combines vacuum metallurgical reprocessing and a ferrite synthesis process. Vacuum metallurgical reprocessing can be used to reclaim the mercury (Hg) in the dry batteries and the cadmium (Cd) in the Ni-Cd batteries. The ferrite synthesis process reclaims the other heavy metals by synthesizing ferrite in a liquid phase. Mixtures of manganese oxide and carbon black are also produced in the ferrite synthesis process. The effluent from the process is recycled, thus significantly minimizing its discharge. The heavy metal contents of the effluent could meet the Integrated Wastewater Discharge Standard of China if the ratio of the crushed battery scrap and powder to FeSO4.7H2O is set at 1:6. This process could not only stabilize the heavy metals, but also recover useful resource from the waste.     

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.     

Laboratory study on the behaviour of spent AA household alkaline batteries in incineration

The quantitative evaluation of emissions from incineration is essential when Life Cycle Assessment (LCA) studies consider this process as an end-of-life solution for some wastes. Thus, the objective of this work is to quantify the main gaseous emissions produced when spent AA alkaline batteries are incinerated. With this aim, batteries were kept for 1h at 1273K in a refractory steel tube hold in a horizontal electric furnace with temperature control. At one end of the refractory steel tube, a constant air flow input assures the presence of oxygen in the atmosphere and guides the gaseous emissions to a filter system followed by a set of two bubbler flasks having an aqueous solution of 10% (v/v) nitric acid. After each set of experiments, sulphur, chlorides and metals (As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, Tl and Zn) were analyzed in both the solutions obtained from the steel tube washing and from the bubblers. Sulphur, chlorides and metals were quantified, respectively, using barium sulfate gravimetry, the Volhard method and atomic absorption spectrometry (AAS). The emissions of zinc, the most emitted metal, represent about 6.5% of the zinc content in the batteries. Emissions of manganese (whose oxide is the main component of the cathode) and iron (from the cathode collector) are negligible when compared with their amount in AA alkaline batteries. Mercury is the metal with higher volatility in the composition of the batteries and was collected even in the second bubbler flask. The amount of chlorides collected corresponds to about 36% of the chlorine in the battery sleeve that is made from PVC. A considerable part of the HCl formed in PVC plastic sleeve incineration is neutralized with KOH, zinc and manganese oxides and, thus, it is not totally released in the gas. Some of the emissions are predictable through a thermodynamic data analysis at temperatures in the range of 1200-1300K taking into account the composition of the batteries. This analysis was done for most of potential reactions between components in the batteries as well as between them and the surrounding atmosphere and it reasonably agrees the experimental results. The results obtained show the role of alkaline batteries at the acid gases cleaning process, through the neutralization reactions of some of their components. Therefore, LCA of spent AA alkaline batteries at the municipal solid waste (MSW) incineration process must consider this contribution.     

Laboratory study on the leaching potential of spent alkaline batteries using a MSW landfill leachate

Two leaching tests were carried out, one with whole batteries and another with cross-cut batteries. In both cases, NEN 7343 (a Nederland’s Standard) procedure was followed using a municipal solid waste (MSW) landfill leachate as extraction solution. Seven fractions were collected corresponding to cumulative liquid/solid (L/S) ratio from 0.1 to 10.0. Those fractions were separately characterized in terms of pH, conductivity, redox potential, density, sulphate, chloride, As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, Tl and Zn. Results showed that the influence of the alkaline batteries in the landfill leachate composition varies with their physical integrity and with the L/S ratio, and several variations were observed throughout the tests. The leachate pH and redox potential increased as result of the contact with batteries, particularly pH in the test with the cross-cut batteries. The leachate density and conductivity did not change significantly with the whole batteries, in contrast with the test with cross-cut batteries.     

Chemical characterisation of spent rechargeable batteries

A chemical characterisation of used batteries can give useful information to implement suitable recycling techniques and to estimate the flux of the different materials recovered. This work is aimed to provide quantitative data about the composition of mixed batteries (in particular, Ni–Cd, Ni-MH and Li-ion batteries) collected in a Northern Italian town in order to evaluate the feasibility of recovery processes applied to the selected material. The higher concentration of metals in the <3 mm fraction suggested that significant quantities of valuable elements could be recovered: in particular, for a kg of the <3 mm fraction deriving from disassembled batteries, about 390 g Ni and 330 g Cd can be recovered from Ni–Cd, 630 g Ni, 80 g Co from Ni-MH and 250 g Co, 110 g Ni, 120 g Cu from Li-ion ones. Leaching tests applied to the same fractions, to assess possible contaminant releases, resulted in low metal content in aqueous solutions (except for Al and Fe, the concentrations of all metals remained below 1 mg/kg). Even so, great care is required in all handling activities due to the high pH values of leachate solutions.     

Transmission electron microscopy (TEM) investigations of Mn-oxide rich cathodic material from spent disposable alkaline batteries

Transmission electron microscopy (TEM) techniques were used to investigate the spent cathodic material of a single common brand of disposable alkaline batteries. Mn-oxide particles are anhedral and irregular in shape and compose an estimated 99-95% of the <10mum size fraction of sample material. Diameters of particles vary widely and typically are between 50nm and 3mum; however, most particles are approximately 200-400nm in diameter. Chemical composition varies for Mn-oxide particles with concentrations being SiO(2) (0.00-1.52wt%), TiO(2) (0.49-4.58wt%), MnO (65.85-92.06wt%), ZnO (1.00-7.53wt%), K(2)O (4.97-20.48wt%) and SO(3) (0.43-2.21wt%). Discrete prismatic zinc crystals occur and vary from a maximum of approximately 0.8mum longx0.15mum wide, to 100nm longx20nm wide. Titanium metal was also observed in samples and composes approximately 0.25-1.0% of the <10mum size fraction of sample material. Results of this study suggest that battery components may be recycled in some special applications. Examples are low energy-low material requirement products such as paint pigments and Zn nanoparticles. This investigation provides detailed constraints on the nature of spent cathodic materials to improve existing recycling methods and develop new technologies.     

Management of spent solvents by alkaline hydrolysis process

This paper deals with the treatment method for the management of spent solvents of reprocessing origin (30% tri-n-butyl phosphate in n-dodecane) using the ‘alkaline hydrolysis process’. The consolidated work reported herein has established total conversion of TBP to aqueous soluble reaction products and transfer of near total radioactivity associated with the waste into this aqueous phase. It was also observed that n-dodecane (diluent) did not take part in the reaction and separated out as the top layer. Repeated runs have established the process on engineering scale (up to 200 l/batch) with regard to conversion of TBP into sodium salt of HDBP, butanol and recovery of the diluent practically free of TBP. The measured parameters, specifically, temperature and pressure did not deviate from set limits during the entire reaction time indicating safe operation. Experiments were also carried out on immobilization of the aqueous phase resulting from hydrolysis which contains almost all the radioactivity associated with the original spent solvent. These immobilization studies have established compatibility of the process generated aqueous stream with cementitious matrix.     

Recycling of spent nickel-cadmium batteries based on bioleaching process

Only 1-2 percent of discarded dry batteries are recovered in China. It is necessary to find an economic and environmentally friendly process to recycle dry batteries in this developing country. Bioleaching is one of the few techniques applicable for the recovery of the toxic metals from hazardous spent batteries. Its principle is the microbial production of sulphuric acid and simultaneous leaching of metals. In this study, a system consisting of a bioreactor, settling tank and leaching reactor was developed to leach metals from nickel-cadmium batteries. Indigenous thiobacilli, proliferated by using nutritive elements in sewage sludge and elemental sulphur as substrates, was employed in the bioreactor to produce sulphuric acid. The overflow from the bioreactor was conducted into the settling tank. The supernatant in the settling tank was conducted into the leaching reactor, which contained the anode and cathodic electrodes obtained from nickel-cadmium batteries. The results showed that this system was valid to leach metals from nickel-cadmium batteries, and that the sludge drained from the bottom of the settling tank could satisfy the requirements of environmental protection agencies regarding agricultural use.     

废旧锂离子电池回收利用的研究现状

目前废旧锂离子电池的回收利用,重点是电极材料中有价金属的回收,主要是应用酸浸和溶剂萃取相联合的湿法冶金技术,其次将电化学技术用于浸出液中金属的沉积和对失效电极材料的直接修复也有相关的研究报导.根据锂离子电池的发展和未来的环境要求,今后的回收利用将朝综合处理和多元化处理技术的方向发展.     

Environmental friendly leaching reagent for cobalt and lithium recovery from spent lithium-ion batteries

We investigated an environmentally friendly leaching process for the recovery of cobalt and lithium from the cathode active materials of spent lithium-ion batteries. The easily degradable organic acid DL-malic acid (C₄H₅O₆) was used as a leaching reagent. The structural, morphology of the cathode materials before and after leaching were characterized by X-ray diffraction (XRD) and scanning electronic microscopy (SEM). The amount of Co and Li present in the leachate was determined by atomic absorption spectrophotometry (AAS). Conditions for achieving a recovery of more than 90 wt.% Co and nearly 100 wt.% Li were determined experimentally by varying the concentrations of leachant, time and temperature of the reaction as well as the initial solid-to-liquid ratio. We found that hydrogen peroxide in a DL-malic acid solution is an effective reducing agent because it enhances the leaching efficiency. Leaching with 1.5 M DL-malic acid, 2.0 vol.% hydrogen peroxide and a S:L of 20 g L^?1 in a batch extractor results in a highly efficient recovery of the metals within 40 min at 90 °C.     

废旧锂离子电池资源化技术研究

通过介绍废旧锂离子电池的组成成分及近年来废旧锂离子电池资源化处理技术的研究进展,提出目前主要回收方法有溶解分离法和直接回收正极材料的新型方法等,并对现有研究中存在的二次污染、安全性问题进行了初步探讨。     

Characterization and leaching of NiCd and NiMH spent batteries for the recovery of metals

Since NiMH and NiCd batteries are still used in the electronic devices market, a treatment and recycling plant has many advantages both from the environmental and the economic points of view. Unfortunately, there is no relationship between shape, size and chemical composition of spent batteries, consequently the characterization and the leaching method of the starting material becomes an important step of the overall treatment process in choosing the best conditions for the selective separation of the metals by hydrometallurgy. Leaching at 20 degrees C with H(2)SO(4) 2M for about 2h seems to be a good solution in terms of cost and efficiency for both battery types. The hydroxide compounds can be readily leached while Ni present as metallic form requires more aggressive conditions due to kinetic constraints. In this paper, the characterization of NiMH and NiCd spent batteries and the results of leaching tests in different conditions are reported.     

Ni-MH spent batteries: a raw material to produce Ni-Co alloys

Ni-MH spent batteries are heterogeneous and complex materials, so any kind of metallurgical recovery process needs a mechanical pre-treatment at least to separate irony materials and recyclable plastic materials (like ABS) respectively, in order to get additional profit from this saleable scrap, as well as minimize waste arising from the braking separation process. Pyrometallurgical processing is not suitable to treat Ni-MH batteries mainly because of Rare Earths losses in the slag. On the other hand, the hydrometallurgical method, that offers better opportunities in terms of recovery yield and higher purity of Ni, Co, and RE, requires several process steps as shown in technical literature. The main problems during leach liquor purification are the removal of elements such as Mn, Zn, Cd, dissolved during the leaching step, and the separation of Ni from Co. In the present work, the latter problem is overcome by co-deposition of a Ni-35/40%w Co alloy of good quality. The experiments carried out in a laboratory scale pilot-plant show that a current efficiency higher than 91% can be reached in long duration electrowinning tests performed at 50 degrees C and 4.3 catholyte pH.     

Physical separation,mechanical enrichment and recycling-oriented characterization of spent NiMH batteries

Nickel–metal hydride (NiMH) batteries contain high amount of industrial metals, especially iron, nickel, cobalt and rare earth elements. Although the battery waste is a considerable secondary source for metal and chemical industries, a recycling process requires a suitable pretreatment method before proceeding with recovery step to reclaim all valuable elements. In this study, AA- and AAA-type spent NiMH batteries were ground and then sieved for size measurement and classification. Chemical composition of the ground battery black mass and sorted six different size fractions were determined by an analytical technique. Crystal structures of the samples were analyzed by X-ray diffraction. Results show that after mechanical treatment, almost 87 wt% of the spent NiMH batteries are suitable for further recycling steps. Size classification by sieving enriched the iron content of the samples in the coarse fraction which is bigger than 0.25 mm. On the other hand, the amounts of nickel and rare earth elements increased by decreasing sample size, and concentrated in the finer fractions. Anode and cathode active materials that are hydrogen storage alloy and nickel hydroxide were mainly collected in finer size fraction of the battery black mass.     

Bioleaching of metals from spent lithium ion secondary batteries using Acidithiobacillus ferrooxidans

Bioleaching of spent lithium ion secondary batteries, containing LiCoO2, was attempted in this investigation. The present study was carried out using chemolithotrophic and acidophilic bacteria Acidithiobacillus ferrooxidans, which utilized elemental sulfur and ferrous ion as the energy source to produce metabolites like sulfuric acids and ferric ion in the leaching medium. These metabolites helped dissolve metals from spent batteries. Bio-dissolution of cobalt was found to be faster than lithium. The effect of initial Fe(II) concentration, initial pH and solid/liquid (w/v) ratio during bioleaching of spent battery wastes were studied in detail. Higher Fe(II) concentration showed a decrease in dissolution due co-precipitation of Fe(III) with the metals in the residues. The higher solid/liquid ratio (w/v) also affected the metal dissolution by arresting the cell growth due to increased metal concentration in the waste sample. An EDXA mapping was carried out to compare the solubility of both cobalt and lithium, and the slow dissolution rate was clearly found from the figures.     

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.     

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%。