Recovery of base metals, silicon and fluoride ions from mobile phone printed circuit boards after leaching with hydrogen fluoride and hydrogen peroxide mixtures.

The recovery of copper, nickel, zinc, silicon, iron, aluminum, tin and fluoride ions from fluoride leach liquors of non-ground printed circuit boards (PCBs) from mobile phones is described in detail. These PCBs were leached with HF + H2O2 mixtures after previous treatment with 6 mol L-1 NaOH (removal of the solder mask). A combination of solvent extraction (SX) and precipitation techniques was used. 99.5 wt% zinc, copper and nickel, in this order, were extracted in one stage (Zn, Ni) or two stages (Cu) with di-2-ethylhexylphosphoric acid (D2EHPA) diluted in kerosene (25 °C, A/O = 1 v/v) after adjusting the pH of the leachate. They were easily stripped by aqueous H2SO4. Iron, aluminum and tin did not interfere because they were masked by fluoride ions. Iron and aluminum were precipitated together as Na3FeF6 + Na3AlF6 by careful addition of aqueous NaOH. Silicon, tin and fluoride ions were recovered together (Na2SiF6 + Na2SnF6 + NaF) by careful evaporation of the aqueous solution after SX of nickel. The tin salt was leached from this solid by absolute ethanol. High HF concentration (10 mol L-1) in the leachant affected SX of Cu(II) and precipitation of iron/aluminum flurocomplexes since some NaF partially precipitated at acidic pH.

Determination of low-molecular-weight amines and ammonium in saline waters by ion chromatography after their extraction by steam distillation.

A new method was developed for the determination of ammonium ion, monomethylamine and monoethylamine in saline waters by ion chromatography. Steam distillation was used to eliminate matrix interferences. Variables such as distillation time, concentration of sodium hydroxide solution and analyte mass were optimized by using a full two-level factorial (2(3) ) design. The influence of steam distillation on the analytical curves prepared in different matrices was also investigated. Limits of detection of 0.03, 0.05 and 0.05 mg/L were obtained for ammoniumion, monomethylamine and monoethylamine, respectively. Saline water samples from the Brazilian oil industry, containing sodium and potassium concentrations between 2.0-5.2% w/v and 96-928 mg/L, respectively, were analyzed. Satisfactory recoveries (90-105%) of the analytes were obtained for all spiked samples, and the precision was ≤ 7% (n = 3). The proposed method is adequate for analyzing saline waters containing sodium to ammoniumion, monomethylamine and monoethylamine concentration ratios up to 28 000:1 and potassium to ammonium, monomethylamine and monoethylamine concentration ratios up to 12 000:1.

Recovery of platinum, tin and indium from spent catalysts in chloride medium using strong basic anion exchange resins.

This work describes a route for platinum recovery from spent commercial Pt and PtSnIn/Al(2)O(3) catalysts using strong basic mesoporous and macroporous anion exchange resins (Cl(-) form). The catalysts were leached with aqua regia (75 °C, 20-25 min). Platinum adsorption was influenced by the presence of other metals which form chlorocomplexes (tin, indium) and also base metals (aluminum). However, it was possible to overcome this fact by a sequential desorption procedure. Aluminum was selectively removed from the resins by elution with 3 mol L(-1) HCl. Platinum was desorbed passing 1 mol L(-1) Na(2)S(2)O(3) (pH 9). Tin was removed by elution with 0.1 mol L(-1) ascorbic acid. Indium was removed using 0.1 mol L(-1) EDTA as eluent. Desorption efficiency exceeded 99% for all metals. Metals were recovered in high yields (>98 wt%).

Processing of spent platinum-based catalysts via fusion with potassium hydrogenosulfate.

This work describes a route for processing spent platinum-based commercial catalysts (Pt and PtSnIn/Al(2)O(3)) via fusion with potassium hydrogenosulfate (KHSO(4)). Samples were previously ground. The optimized experimental parameters were: temperature, 450°C; time, 3h; sample/flux mass ratio, 1/10. The fused mass was dissolved in water and the elements present were isolated by a multi-step separation procedure. Platinum was recovered as the only water-insoluble residue. About 45 wt% of aluminium was recovered as KAl(SO(4))(2)·12H(2)O (alum), whereas the remaining element was recovered as Al(OH)(3). Tin and indium were recovered together as sulfides at pH 1. About 72 wt% of potassium was recovered as K(2)SO(4) when the final effluent was treated with sulfuric acid (pH 1) and slowly evaporated. Generation of final wastes was greatly reduced. More than 98 wt% of the elements present in the catalysts examined was recovered.

Recovery of platinum from spent catalysts by liquid-liquid extraction in chloride medium.

This work examines a hydrometallurgical route for processing spent commercial catalysts (Pt and PtSnIn/A(2)O(3)) used in Brazilian refineries for recovery of the noble metal with less final wastes generation. Samples were initially pre-oxidized (500 degrees C, 5 h) in order to eliminate coke. The basis of the present route is the partial dissolution of the pre-oxidized catalyst in aqua-regia. Temperature and time necessary to dissolve all platinum were optimized in order to reduce the operation severity and aluminum solubilization. All platinum and 16-18 wt.% of aluminum were dissolved at 75 degrees C in 20-25 min. Separation of platinum from the acidic solution was accomplished by solvent extraction. The best extractant (> 99 wt.%) was Aliquat 336 (a quaternary ammonium salt) in one stage (A/O phase ratio = 1, v/v). Platinum was stripped (> 99.9 wt.%) in one stage (A/O phase ratio = 1, v/v) with aqueous sodium thiosulfate (> or = 0.75 mol L(-1)). Black platinum was obtained from this solution via reduction with magnesium or ascorbic acid.

Removal of ammonium ion from produced waters in petroleum offshore exploitation by a batch single-stage electrolytic process.

This work describes a batch single-stage electrochemical process to remove quantitatively the ammonium ion from produced waters from petroleum exploration of the Campos' Basin, seeking to fulfil the directories of the National Brazilian Environmental Council. The anode was made out of titanium covered by a layer of RuO(2)+TiO(2) oxides (Dimensionally Stable Anode), whereas the cathode was made out of pure titanium. Anodic and cathodic compartments were separated by a membrane. The applied current varied from 0.3 to 1.5A. As the current increased NH(4)(+) removal was faster and pH was rapidly decreased to 3. The pH of the anodic compartment increased to approximately 10. When the current was 0.92 A chlorine evolution was observed after 40 min or only 15 min when that current was 1.50 A. In this voltage a deposit containing alkali-earth metal hydroxides/sulphates was formed on the membrane surface of the cathode side, thus suggesting a diffusion process from the anodic to the cathodic compartment. The maximum current applied to the cell must not exceed approximately 0.70 A in order to avoid chlorine evolution. Ammonia removal was over 99.9 wt% at 0.68 A in about 75 min.

Hydrometallurgical route to recover molybdenum, nickel, cobalt and aluminum from spent hydrotreating catalysts in sulphuric acid medium.

This work describes a hydrometallurgical route for processing spent commercial catalysts (CoMo and NiMo/Al2O3), for recovering the active phase and support components. They were initially pre-oxidized (500 degrees C, 5h) in order to eliminate coke and other volatile species present. Pre-oxidized catalysts were dissolved in H2SO4 (9molL-1) at approximately 90 degrees C, and the remaining residues separated from the solution. Molybdenum was recovered by solvent extraction using tertiary amines. Alamine 304 presented the best performance at pH around 1.8. After this step, cobalt (or nickel) was separated by adding aqueous ammonium oxalate in the above pH. Before aluminum recovery, by adding NaOH to the acid solution, phosphorus (H2PO4-) was removed by passing the liquid through a strong anion exchange column. Final wastes occur as neutral and colorless sodium sulphate solutions and the insoluble solid in the acid leachant. The hydrometallurgical route presented in this work generates less final aqueous wastes, as it is not necessary to use alkaline medium during the metal recovery steps. The metals were isolated in very high yields (>98wt.%).

Recovery of valuable elements from spent Li-batteries.

This work examines two recycling processes for spent Li/MnO(2) and Li-ion batteries. The anode, cathode and electrolyte (LiPF(6)) were submitted to one of the following procedures: (a) calcination at 500 degrees C (5h) followed by solvent extraction to recover lithium salts (fluoride, phosphate) in good yield (90 wt%). The residual solid was treated with H(2)SO(4) containing H(2)O(2) and on evaporation gave high purity grade cobalt or manganese sulfate; (b) fusion with KHSO(4) (500 degrees C, 5h). The resulting aqueous solution was added dropwise to a solution of NaOH, giving cobalt or manganese as impure precipitate. Addition of KF precipitated high purity grade LiF in moderate yield (50 wt%). The final aqueous solution on treatment with calcium sulfate precipitated the corresponding phosphate and fluoride salts.

Processing of spent NiMo and CoMo/Al2O3 catalysts via fusion with KHSO4.

This work describes a route for processing spent commercial hydrorefining (HDR) catalysts (CoMo and NiMo/Al2O3), containing support additives, for recovering active phase and support components. Samples were used as catalysts in diesel hydrotreaters. They had neither been submitted to mechanical stresses nor overheating while under operation. The route is based on fusion of samples with KHSO4. Four experimental parameters were optimized: reaction time, sample/flux mass ratio, temperature, and sample physical characteristics (ground/non-ground). After fusion, the solid was dissolved in water (90-100 degrees C); the insoluble matter presented low crystallization. Several phases were identified: silicates, spinel-like compounds and aluminosilicates. Cobalt, nickel, molybdenum and aluminum were recovered by conventional precipitation techniques or selective solvent-extraction procedures, with at least 85 wt.% yield. Final liquid colorless effluents are obtained as neutral solutions of alkali sulfates or chlorides and a water insoluble solid after fusion, which can be either sent to industrial dumps or co-processed. Fusion with KHSO4 was shown to be applicable to the catalysts of the present study, and the optimized experimental parameters are much less drastic than the conventional pyrometallurgical routes proposed in the literature.