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.     

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.     

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.     

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.     

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.     

Survey of mercury,cadmium and lead content of household batteries

The objective of this work was to provide updated information on the development of the potential impact of heavy metal containing batteries on municipal waste and battery recycling processes following transposition of the new EU Batteries Directive 2006/66/EC. A representative sample of 146 different types of commercially available dry and button cells as well as lithium-ion accumulators for mobile phones were analysed for their mercury (Hg)-, cadmium (Cd)- and lead (Pb)-contents. The methods used for preparing the cells and analysing the heavy metals Hg, Cd, and Pb were either developed during a former study or newly developed. Several batteries contained higher mass fractions of mercury or cadmium than the EU limits. Only half of the batteries with mercury and/or lead fractions above the marking thresholds were labelled. Alkaline–manganese mono-cells and Li-ion accumulators, on average, contained the lowest heavy metal concentrations, while zinc–carbon batteries, on average, contained the highest levels.     

废旧电池回收利用产业化的若干思考

对废旧电池处置不当既污染环境又浪费资源,我国在废旧电池处理方面,应走产业化回收利用的道路,提出了一些具体的建议.     

Nickel and cobalt recycling from lithium-ion batteries by electrochemical processes

The presence of LiCoO(2) and LiCo(x)Ni((1-x))O(2) in the cathodic material of Li-ion and Li-polymer batteries has stimulated the recovery of Co and Ni by hydrometallurgical processes. In particular, the two metals were separated by SX method and then recovered by electrochemical (galvanostatic and potentiostatic) processes. The metallic Ni has been electrowon at 250 A/m(2), pH 3-3.2 and 50 degrees C, with 87% current efficiency and 2.96 kWh/kg specific energy consumption. Potentiostatic electrolysis produces a very poor Ni powder in about 1 h with current efficiency changing from 70% to 45% depending on Ni concentration in the electrolyte. Current efficiency of 96% and specific energy consumption of 2.8 kWh/kg were obtained for Co at 250 A/m(2), pH 4-4.2 and 50 degrees C, by using a solution containing manganese and (NH(4))(2)SO(4). The Co powder, produced in potentiostatic conditions (-0.9 V vs. SCE, pH 4, room temperature) appears particularly suitable for Co recycling as cobaltite in new batteries.     

废干电池中锌和汞的分布及其处理

由于民众缺乏环境意识和国家没有相应法规,大多数废干电池都随手丢弃,回收的废电池处于不同程度的腐蚀状态.介绍了锌、汞在废干电池中的分布状态以及腐蚀对其分布的影响,并根据它们的分布特点提出用真空法回收废干电池中的锌、汞.     

Current situation of used household batteries in Iran and appropriate management policies

Used household batteries are considered as hazardous wastes in many countries due to the potential environmental and human health risks associated with the heavy metals present in batteries. This article presents the current situation of waste household batteries and policies in Iran. Iran with more than 70 million people is a developing country where latest technologies like cell phones and laptops are in widespread use and battery consumption increases accordingly. The household battery demand in Iran has rapidly grown since 2001 and it is expected to increase more quickly in next years, due to increasing technological development. Based on the available data, more than 9800 metric tons of household batteries were imported into Iran in recent decade, with the market value of about US$ 42.6 million. At present, there is no program available in Iran regarding to collection, separation, recycling or safe disposal of used batteries. Therefore, almost all of the spent household are discarded into municipal solid waste (MSW) and sent to sanitary landfills. Appropriate policies to meet safe disposal of household batteries in Iran is also discussed in this investigation.     

Recovery of nickel, cobalt and some salts from spent Ni-MH batteries

This work provides a method to help recover nickel, cobalt metals and some of their salts having market value from spent nickel-metal hydride batteries (SNiB). The methodology used benefits the solubility of the battery electrode materials in sulfuric or hydrochloric acids. The results obtained showed that sulfuric acid was slightly less powerful in leaching SNiB compared to HCl acid. Despite that, sulfuric acid was extremely applied on economic basis. The highest level of solubility attained 93.5% using 3N sulfuric acid at 90 degrees C for 3h. The addition of hydrogen peroxide to the reacting acid solution improved the level of solubility and enhanced the process in a shorter time. The maximum recovery of nickel and cobalt metals was 99.9% and 99.4%, respectively. Results were explained in the light of a model assuming that solubility was a first order reaction. It involved a multi-step sequence, the first step of which was the rate determining step of the overall solubility. Nickel salts such as hydroxide, chloride, hexamminenickel chloride, hexamminenickel nitrate, oxalate and nickel oleate were prepared. With cobalt, basic carbonate, chloride, nitrate, citrate, oleate and acetate salts were prepared from cobalt hydroxide Cost estimates showed that the prices of the end products were nearly 30% lower compared to the prices of the same chemicals prepared from primary resources.     

Heat-treatment recycling of waste toner and its applications in lithium ion batteries

Journal of Material Cycles and Waste Management - With the growing demand of print and copy in modern society, the number of abandoned toner cartridges has increased year by year. Unfortunately,...     

Removal of batteries from solid waste using trommel separation

This paper describes the design and testing of a trommel for separation of batteries from solid waste. A trommel is a cylindrical separation device that rotates and performs size separation. It has also been used in areas such as municipal solid waste (MSW) processing, classifying construction and demolition debris, screening mass-burn incinerator ash and compost processing. A trommel has been designed based on size separation to separate household batteries from solid waste, which can then be used as feedstock for alternative applications of solid waste combustion, particularly where the metal content of the product is also a critical parameter, such as the Co-Co process for integrated cement and power production. This trommel has been tested with batches of university office and restaurant wastes against various factors. The recovery efficiency of batteries increases with decreasing inclination angle of the trommel and decreasing rotational speed. A physical characterization of the university solid waste has been performed with a 20-kg sample of the tested waste. It was found that there is a trend of decreasing recovery of batteries with increasing paper composition, and a trend of increasing recovery of batteries with increasing organic materials composition.     

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.     

Recovery of lithium and cobalt from waste lithium ion batteries of mobile phone

In view of the stringent environmental regulations, availability of limited natural resources and ever increasing need of alternative energy critical elements, an environmental eco-friendly leaching process is reported for the recovery of lithium and cobalt from the cathode active materials of spent lithium-ion batteries of mobile phones. The experiments were carried out to optimize the process parameters for the recovery of lithium and cobalt by varying the concentration of leachant, pulp density, reductant volume and temperature. Leaching with 2 M sulfuric acid with the addition of 5% H₂O₂ (v/v) at a pulp density of 100 g/L and 75 °C resulted in the recovery of 99.1% lithium and 70.0% cobalt in 60 min. H₂O₂ in sulfuric acid solution acts as an effective reducing agent, which enhance the percentage leaching of metals. Leaching kinetics of lithium in sulfuric acid fitted well to the chemical controlled reaction model i.e. 1 ? (1 ? X)^1/3 = k_ct. Leaching kinetics of cobalt fitted well to the model ‘ash diffusion control dense constant sizes spherical particles’ i.e. 1 ? 3(1 ? X)^2/3 + 2(1 ? X) = k_ct. Metals could subsequently be separated selectively from the leach liquor by solvent extraction process to produce their salts by crystallization process from the purified solution.     

Enhancement of the recycling of waste Ni-Cd and Ni-MH batteries by mechanical treatment

A serious environmental problem was presented by waste batteries resulting from lack of relevant regulations and effective recycling technologies in China. The present work considered the enhancement of waste Ni-Cd and Ni-MH batteries recycling by mechanical treatment. In the process of characterization, two types of waste batteries (Ni-Cd and Ni-MH batteries) were selected and their components were characterized in relation to their elemental chemical compositions. In the process of mechanical separation and recycling, waste Ni-Cd and Ni-MH batteries were processed by a recycling technology without a negative impact on the environment. The technology contained mechanical crushing, size classification, gravity separation, and magnetic separation. The results obtained demonstrated that: (1) Mechanical crushing was an effective process to strip the metallic parts from separators and pastes. High liberation efficiency of the metallic parts from separators and pastes was attained in the crushing process until the fractions reached particle sizes smaller than 2 mm. (2) The classified materials mainly consisted of the fractions with the size of particles between 0.5 and 2 mm after size classification. (3) The metallic concentrates of the samples were improved from around 75% to 90% by gravity separation. More than 90% of the metallic materials were separated into heavy fractions when the particle sizes were larger than 0.5 mm. (4) The size of particles between 0.5 and 2 mm and the rotational speed of the separator between 30 and 60 rpm were suitable for magnetic separation during industrial application, with the recycling efficiency exceeding 95%.     

Field Evidence of Dissolution and Degradation Rates Enhancement During ISCR and ENA Treatments of Chlorinated Solvents

This article presents field tests comparing two methods of treatment of chlorinated solvents undertaken at the same site. The site is an automobile factory where two chlorinated solvents (CS) plumes were identified. At the first source, in situ chemical reduction (ISCR) was applied, while at the second one, enhanced natural attenuation (ENA) was used. A set of specific multilevel sampling wells were installed approximately 20 m downgradient of the sources to estimate the efficiency of the treatments. The presence of a low‐permeability layer (source 1) or a thick oil lens (source 2) in the top part of the aquifer prevented the CS from reaching the bottom of the aquifer. These layers led to difficulties treating the contamination. At the ISCR and ENA treatment zones, the concentrations of tetrachloroethene (PCE) and trichloroethene (TCE) did not change significantly, while the concentration of metabolites (cis‐1,2‐DCE, vinyl chloride, and ethene) significantly increased 50 to 150 days after treatment. Due to high concentration of CS in the source zone, a mass balance calculation, including chlorine, was possible. It showed that around 1 to 2 percent of the injected products were used to reduce the CS. A detailed analysis and 1D analytical modeling of CS concentrations showed that the treatment led to a large (two to three times) increase in dissolution of the organic phase. This explains why, despite an efficient treatment, the PCE and TCE concentrations remained virtually unchanged. Degradation rates also increased due to the treatment. Due to some differences in the source‐zone chemistry, it was not possible to differentiate between the ISCR and ENA efficiencies. © 2013 Wiley Periodicals, Inc.     

Dissolution of polystyrene into cyclic monoterpenes present in tree essential oils

We examined dissolution of polystyrene (PS) into cyclic monoterpenes present in tree essential oils, in order to develop an environmentally friendly shrinking agent for expanded polystyrene. The relationship between the chemical structure of the monoterpenes and their dissolution power for PS was studied through the solubility parameter (δ) and apparent activation energy (E _a) for dissolution. (R)-Limonene and its structural isomers on a C=C bond have high solvent power for PS. This favorable solubility was explained by their solubility parameters. The occurrence of hydroxyl group in a solvent molecule, such as in terpinen-4-ol, reduced affinity for PS. Bicyclic monoterpenes and 1,8-cineole, which have sterically bulky structure, showed limited dissolution power even though they have solubility parameters similar to that of (R)-limonene. Their bulky structures would interfere with permeation of solvent into the PS matrix. Cyclic monoterpenes and PS were recovered almost quantitatively by simple steam distillation of the PS solution.