Martina Petranikova

Production of zinc and manganese oxide particles by pyrolysis of alkaline and Zn–C battery waste

Production of zinc and manganese oxide particles from alkaline and zinc-carbon battery black mass was studied by a pyrolysis process at 850-950°C with various residence times under 1L/minN2(g) flow rate conditions without using any additive. The particular and chemical properties of the battery waste were characterized to investigate the possible reactions and effects on the properties of the reaction products. The thermodynamics of the pyrolysis process were studied using the HSC Chemistry 5.11 software. The carbothermic reduction reaction of battery black mass takes place and makes it possible to produce fine zinc particles by a rapid condensation, after the evaporation of zinc from a pyrolysis batch. The amount of zinc that can be separated from the black mass is increased by both pyrolysis temperature and residence time. Zinc recovery of 97% was achieved at 950°C and 1h residence time using the proposed alkaline battery recycling process. The pyrolysis residue is mainly MnO powder with a low amount of zinc, iron and potassium impurities and has an average particle size of 2.9μm. The obtained zinc particles have an average particle size of about 860nm and consist of hexagonal crystals around 110nm in size. The morphology of the zinc particles changes from a hexagonal shape to s spherical morphology by elevating the pyrolysis temperature.

Separation of rare earths and other valuable metals from deep-eutectic solvents: a new alternative for the recycling of used NdFeB magnets

Deep-eutectic solvents (DESs) are used as a promising alternative to aqueous solutions for the recovery of valuable metals from NdFeB magnets. A deep-eutectic solvent based on choline chloride and lactic acid (molar ratio 1 : 2) was used for the leaching of rare earths and other metals from NdFeB magnets. A process for the separation of Fe, B and Co from Nd and Dy in the deep-eutectic solvent was developed by using the ionic liquid tricaprylmethylammonium thiocyanate (Aliquat 336 SCN, [A336][SCN]) diluted in toluene (0.9 M). The extraction parameters were optimized and stripping of B was efficiently carried out by HCl, while EDTA was employed for the recovery of Fe and Co. The separation of Nd and Dy was assessed by using two different types of extractants, a mixture of trialkylphosphine oxides (Cyanex 923) and bis(2-ethylhexyl)phosphoric acid (D2EHPA). Based on the distribution ratios, separation factors and the ease of subsequent stripping, Cyanex 923 was chosen as the most effective extractant. The purified Dy present in the less polar phase was easily recovered by stripping with water, while the Nd present in the deep-eutectic solvent was recovered by precipitation stripping with a stoichiometric amount of oxalic acid. Nd2O3 and Dy2O3 were recovered with a purity of 99.87% and 99.94%, respectively. The feasibility to scale up this separation process was corroborated by a setup of mixer-settlers and highlighted by the possibility to fully recover and reuse the deep-eutectic solvent and the less polar phases employed in the extractions. The new proposed system based on a deep-eutectic solvent combined with traditional organic extraction phases presented higher selectivities and efficiencies than the analogous aqueous system. Extended X-ray absorption fine structure (EXAFS) was employed to elucidate the different mechanisms for extraction of Co and Fe from the deep-eutectic solvent and from an aqueous solution.

Lithium Batteries Recycling

Spent lithium-ion (Li-ion) batteries are considered to be a secondary source of valuable metals, such as cobalt, nickel, aluminum, copper manganese, etc. Recently, the recovery of lithium has been considered to be needed not only to increase the material recovery rate of the existing process, but also to use the spent lithium-ion batteries (LiBs) as a source of the metal, of which almost one-third of the production is applied in the battery industry. In this chapter research activities and current recycling technologies for LiBs are described. The characterization of the waste shows that spent LiBs are heterogeneous waste not only because of the different materials used for battery construction, but also because of the differences in the active material composition. Discharging processes, followed by mechanical pretreatment and separation are necessary parts of the spent batteries treatment, especially when hydrometallurgy is implemented for metal recovery. This chapter describes current efforts in recycling using hydrometallurgical treatment applying inorganic and organic acids for leaching, as well as bioleaching methods. Processes of metal recovery using solvent extraction and precipitation are also described. Thermal pretreatments are introduced as an example for removing organic compounds and carbon in order to improve the metal recovery. Current industrial processes that apply mechanical treatment, pyrometallurgy, hydrometallurgy, or combined processes for LiBs recycling are described as well.

Investigation of zinc recovery by hydrogen reduction assisted pyrolysis of alkaline and zinc-carbon battery waste

Zinc (Zn) recovery from alkaline and zinc-carbon (Zn-C) battery waste were studied by a laboratory scale pyrolysis process at a reaction temperature of 950°C for 15-60min residence time using 5%H2(g)-N2(g) mixture at 1.0L/min gas flow rate. The effect of different cooling rates on the properties of pyrolysis residue, manganese oxide particles, were also investigated. Morphological and structural characterization of the produced Zn particles were performed. The battery black mass was characterized with respect to the properties and chemical composition of the waste battery particles. The thermodynamics of the pyrolysis process was studied using the HSC Chemistry 5.11 software. A hydrogen reduction reaction of the battery black mass (washed with Milli-Q water) takes place at the chosen temperature and makes it possible to produce fine Zn particles by rapid condensation following the evaporation of Zn from the pyrolysis batch. The amount of Zn that can be separated from the black mass increases by extending the residence time. Recovery of 99.8% of the Zn was achieved at 950°C for 60min residence time using 1.0L/min gas flow rate. The pyrolysis residue contains MnO and Mn2O3 compounds, and the oxidation state of manganese can be controlled by cooling rate and atmosphere. The Zn particles exhibit spherical and hexagonal particle morphology with a particle size varying between 200nm and 3µm. However the particles were formed by aggregation of nanoparticles which are primarily nucleated from the gas phase.

SUPPLY AND SUBSTITUTION OPTIONS FOR SELECTED CRITICAL RAW MATERIALS: COBALT, NIOBIUM, TUNGSTEN, YTTRIUM AND RARE EARTHS ELEMENTS

European industry is dependent on the import of raw materials. The European Commission has recognized that some raw materials are crucial for the function of the European economy and show a high risk of supply shortage. This communication addresses supply and substitution options for selected critical raw materials: cobalt, niobium, tungsten, yttrium, and the rare earth elements. For each element, the most relevant data concerning mining, abundance, recycling rates and possible substitutes are summarized and discussed.​