PROCESSING OF SPENT ULTRA-DEEP HYDRODESULFURIZATION CATALYSTS. This work discusses the recycling of spent NiMo/Al2O3 catalysts from ultra-deep hydrodesulfurization (HDS) units. They contain a refractory coke and fouling elements from the processed feedstocks. Samples were preoxidized (600 ºC) for 12 h using a very slow heating rate to eliminate coke and volatiles. Experiments were performed in the presence of HF + H2O2 mixtures under stirring at 25-60oC for 1-4 h. The amount of insoluble matter was the lowest (< 1 wt.% of the initial mass) after leaching for 2 h at 60oC using an excess of 50 vol.% HF and 20 vol.% H2O2. Leached molybdenum and vanadium were extracted together with Alamine 304 (tri-dodecylamine) in n-heptane at pH below 2. Aluminum and iron were precipitated from the raffinate as Na3AℓF6 (+ Na3FeF6) by adjusting pH at ~4 using 6 mol L-1 NaOH. Nickel was either recovered by solvent extraction using D2EHPA (bis-(2-ethylhexyl)phosphoric acid) in n-heptane at pH 6 or precipitated at pH 8 using 6 mol L-1 NaOH. The first method proved better as less contaminants were present. After slow evaporation of the final aqueous solution, a mixture of Na2SiF6 and NaF was recovered. Fluoride losses were very low (~0.10 wt.%).

The recovery of precious and base metals of a metal concentrate from ground waste printed circuit boards (PCBs) is described in detail. Samples were treated with NaOHaq. to remove the soldering mask. Experiments were performed in acidic medium (HF, H2SO4, CH3COOH or H3PO4) using H2O2 as oxidant. Base metals were leached in high yields (>99 wt.%) at ~40 ºC after ~1 h (HF), ~2 h (H2SO4), ~4 h (H3PO4) and ~5 h (CH3COOH). Lead precipitated in the presence of H2SO4 and HF. Precious metals were not oxidized. Ceramic/fiberglass components were dissolved in the presence of HF. Silver, palladium and gold were recovered from the insoluble solid, in this order, by a sequential oxidative treatment in aqueous medium. Recovery of leached elements was possible by a combination of solvent extraction and precipitation. The choice of the extractant and the precipitant were essential to recover them with high yields. The leachates from H3PO4 + H2O2 experiments could not be processed above pH 2.5. Leaching of waste PCBs in the presence of a weak organic acid is possible but a multistage separation scheme for elements recovery is unavoidable as PCBs is a complex material in terms of composition.

This work examines the leaching of printed circuit boards (PCBs) from cell phones in aqueous solutions containing HF + H2O2 or HF + NaClO under mild experimental conditions. The PCBs were not ground but were previously treated with 6 mol L-1 NaOH at 50 ºC for 1 h to remove their soldering mask. The HF + H2O2 mixtures leached copper and base metals (except lead) at 35-40 ºC, leaving a solid residue containing lead and noble metals. Leaching was fastest (1 h) when HF and H2O2 concentrations were at least 5 mol L-1 and 3 mol L-1, respectively. The processing of the solid residue is also described in detail. It was leached with water at ~90 ºC followed by HNO3aq. at 25 ºC. Lead, palladium and silver were recovered in this order, leaving gold as final solid. After 1 h at 35-40 ºC, 5 mol L-1 HF + 0.3 mol L-1 NaClO mixtures leached the base metals, copper, gold and palladium. Gold was recovered by liquid-liquid extraction with methyl isobutyl ketone. Silver precipitated as chloride. This salt was isolated by leaching with NH3aq. Loss of fluoride ions (as HF) was below 0.5 wt.% after leaching and handling the solid residue.

This paper describes a route for recovering manganese and zinc from spent zinc-MnO2 dry cells via acid leaching using sulfuric or hydrochloric acids as leachants. Hydrogen peroxide was added as reductant. Experiments were run at 25-40 °C for 1-3 h. Under the best optimal conditions, over 97.5 wt.% of zinc and manganese were leached by both acids. Zn(II) was best extracted at high free acidity (≥ 1 mol L-1) with tributylphosphate (TBP) or trialkylphosphine oxides (Cyanex 923) diluted in n-heptane. Cyanex 923 was a better extractant than TBP, and the extraction was better performed in hydrochloric leachates. Mn(II) was more co-extracted from hydrochloric leachates and when Cyanex 923 was the extractant, but was easily scrubbed with dilute leachant (~1-2 mol L-1). Zn(II) striping was possible using 5 mol L-1 HCl or H2SO4. Manganese was precipitated as oxalate (MnC2O4.2H2O), free of leached contaminants. High-purity sodium salts of the anions of the leachants were recovered after slow evaporation of the final solution.

This paper describes a route for recovering manganese and zinc from spent zinc-MnO2 dry cells via acid leaching. Sulfuric, hydrofluoric and formic acids were used as leachants. Hydrogen peroxide was added as reductant, except for formic acid since it is itself a reductant. Experiments were run at 25-40 ºC for 1-3 h. Under the best optimal conditions, over 95 wt.% of zinc and manganese were leached irrespective of the leachant. Leaching of contaminants was strongly dependent on the leachant due to the insolubility of salts or complexing reactions. Zn(II) was best extracted with D2EHPA diluted in n-heptane at pH > 1, particularly from the leachates of weak acids. Mn(II) was much more co-extracted from sulfuric leachates, but was easily scrubbed with dilute leachant (~2 mol L -1). Zn(II) striping was possible using 5 mol L -1 H2SO4. Manganese was isolated as MnO2 carrying the leached contaminants. High-purity sodium salts of the anions of the leachants were recovered after slow evaporation of the final solution.

A hydrometallurgical process applicable to printed circuit boards of small electrical and electronic devices was developed. This involved three leaching steps (60 ºC, 2 h): 6 mol L-1 NaOH, 6 mol L-1 HCl and aqua regia. NaOH removed the resin and flame retardant that covered the circuit boards. HCl dissolved the most electropositive metals and a small amount of copper (~0.3 wt%). Aqua regia dissolved the noble metals. Silver precipitated as AgCl. Gold and platinum were quantitatively extracted with pure methyl-isobutylketone and Alamine 336 (10 % vol. in kerosene), respectively. Slow evaporation of the raffinate crystallized CuCl2.4H2O (89% yield).

We report results of the efficiency of tungsten extraction from wolframite concentrate (containing 61.5 wt % WO3) from the Igarapé Manteiga mine (state of Rondônia, Brazil) through acid leaching with strong mineral acids at 100 ºC and 400 rpm for 2-4 h. HCl yielded insoluble matter containing the highest WO3 content (90 wt %). This solid was dissolved in concentrated NH3(aq) at 25 ºC and the insoluble matter filtrated. The filtrate was slowly evaporated. 70 wt % of the tungsten present in the starting concentrate material was recovered as ammonium paratungstate (APT).

This work presents a route for processing spent ink-jet cartridges in an experimental course. The disassembly of the cartridges requires several steps and the recognition of their different components is essential to define the best final destination (recycling, co-processing). The plastic strips were chemically processed so as to recover gold and copper. The students recognized the difficulty of processing multicomponent wastes and the importance of the chemical work under the best safety conditions; they also experienced many laboratory techniques and recognized the value of the selective collection and the reverse logistics to reach a viable commercial scale recycling.

This work describes a three-step pre-treatment route for processing spent commercial NiMo/Al2O3 catalysts. Extraction of soluble coke with n-hexane and/or leaching of foulant elements with oxalic acid were performed before burning insoluble coke under air. Oxidized catalysts were leached with 9 mol L-1 sulfuric acid. Iron was the only foulant element partially leached by oxalic acid. The amount of insoluble matter in sulfuric acid was drastically reduced when iron and/or soluble coke were previously removed. Losses of active phase metals (Ni, Mo) during leaching with oxalic acid were compensated by the increase of their recovery in the sulfuric acid leachate.

This work describes a recovery process of cadmium from spent nickel-cadmium batteries by a new hydrometallurgical route based on the selective extraction in hydrochloric acid medium with tributylphosphate (TBP), alone or dissolved in kerosene. The best results were obtained when TBP concentration was at least 75 vol%. Nickel extraction was negligible under these conditions. It was isolated after processing the rafinate through an anionic ion-exchange column. Final wastes generated are basically sodium chloride solutions, with no turbidity, color or heavy metals present in significant amounts.

A extração de metais com solventes orgânicos é uma poderosa ferramenta para ajudar a separação de complexas misturas de metais presentes em baterias usadas e dispositivos eletroeletrônicos, evitando assim o uso de produtos tóxicos ou de rotas experimentais geradoras de uma grande quantidade de resíduos finais. Este trabalho descreve um processo de recuperação de cobalto presente em baterias níquel metal-hidreto (Ni-MH) usadas por meio de uma nova rota hidrometalúrgica. O elemento foi extraído de uma solução em meio clorídrico com Cyanex 272 (ácido 2,4,4-trimetil-pentil fosfínico) dissolvido em querosene. Os melhores resultados foram obtidos quando o pH estava ligeiramente alcalino (7,2) e a concentração de Cyanex em querosene era 5% vol. A recuperação do cobalto atingiu 99% m/m. Foi também possível recuperar um precipitado contendo lantanídios (La, Ce, Pr) e ítrio, que foi purificado pela dissolução em ácido clorídrico seguido de adição de oxalato de amônio. O níquel também foi isolado como um precipitado impuro após a recuperação do cobalto e dos lantanídios. Os residuos finais gerados ao longo do processo são principalmente soluções de cloreto de sódio, sem coloração, turbidez ou metais pesados em quantidades significativas.

Metals extraction with organic solvents is a powerful tool to aid separation of complex mixtures of elements present in spent batteries and electronic devices, thus avoiding the use of toxic chemicals or experimental routes which generate high amounts of final wastes. This work describes a recovery process for cobalt present in spent Ni-MH batteries by a new hydrometallurgical route. The element was extracted in a chloride-bearing medium with Cyanex 272 (2,4,4-trimethyl-pentyl fosfinic acid) dissolved in kerosene. The best results were obtained when pH was slightly alkaline (7,2) and Cyanex concentration in kerosene was 5% vol. Cobalt recovery reached 99 wt%. It was also possible to recover a crude precipitate containing lanthanides (La, Ce, Pr) and yttrium, which was purified by dissolving it in HCl followed by addition of ammonium oxalate. Nickel was also isolated as an impure precipitate after cobalt and lanthanides recoveries. Final wastes generated along the separation processes are mainly sodium chloride solutions with no color, turbidity or heavy metals present in significant amounts.