Jéssica Frontino Paulino

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.%).

NEW STRATEGIES FOR TREATMENT AND REUSE OF SPENT SULFIDIC CAUSTIC STREAM FROM PETROLEUM INDUSTRY

This work examines traditional and new routes for removal of H2S and other sulfur compounds from spent sufidic caustic (SSC). SH- (hydrogenosulfide) and S2- (sulfide) ions were quantitatively oxidized at 25 oC using H2O2, NaOCl or a spent sulfochromic mixture. SH-/S2- ions were also removed via reaction with freshly prepared iron or manganese hydroxides, or after passing the SSC through strong basic anion exchange resins (OH- form). The treated caustic solution, as well as iron/manganese hydroxides, removed H2S from diesel samples at 25 oC. SSC treatment via strong basic anion-exchange resins produced the treated caustic solution with the highest free alkalinity.

Rota hidrometalúrgica de recuperação de molibdênio, cobalto, níquel e alumínio de catalisadores gastos de hidrotratamento em meio ácido

This work describes a hydrometallurgical route for processing spent commercial catalysts (CoMo and NiMo/Al2O3). Samples were preoxidized (500 oC, 5 h) in order to eliminate coke and other volatile species present. The calcined solid was dissolved in concentrated H2SO4 and water (1:1 vol/vol) at 90 oC; the insoluble matter was separated from the solution. Molybdenum was recovered by solvent extraction using tertiary amines at pH around 1.8. Cobalt (or nickel) was separated by addition of aqueous ammonium oxalate at the above pH. Phosphorus was removed by passing the liquid through a strong anion exchange column. Aluminum was recovered by neutralizing the solution with NaOH. The route presented in this work generates less final aqueous wastes because it is not necessary to use alkaline medium during the metal recovery steps.

Processamento de pilhas Li/MnO2 usadas

This work presents two recycling processes for spent Li/MnO2 batteries. After removal of the solvent under vacuum the cathode + anode + electrolyte was submitted to one of the following procedures: (a) it was calcined (500 oC, 5 h) and the calcined solid was submitted to solvent extraction with water in order to recover lithium salts. The residual solid was treated with sulfuric acid containing hydrogen peroxide. Manganese was recovered as sulfate; (b) the solid was treated with potassium hydrogeno sulfate (500 oC, 5 h). The solid was dissolved in water and the resulting solution was added dropwise to sodium hydroxide. Manganese was recovered as dioxide. The residual solution was treated with potassium fluoride in order to precipitate lithium fluoride.

Evaluation of cryolite from pitinga (Amazonas-Brazil) as a source of hydrogen fluoride

This paper reports the use of cryolite from the Pitinga Mine (Amazonas state, Brazil) as raw material in hydrogen fluoride production. Samples were initially characterized by chemical and mineralogical analyses. They presented low silica content (< 4 wt.%). After milling, cryolite samples were digested with concentrated sulfuric acid under stirring (200 rpm) and variable temperature, time and liquid to solid ratio conditions. Under the best experimental conditions (140 °C, 3-5 h), 96 wt.% of fluorine was recovered as hydrogen fluoride. The application of a 23 full factorial design showed that temperature and reaction time were relevant parameters during leaching, whereas liquid to solid ratio was not statistically significant.

Processing of spent NiW/Al2O3 catalysts

Spent oxidized (500 oC, 5 h) commercial NiW/Al2O3 catalysts were processed using two different routes: a) fusion with NaOH (650 oC, 1 h), the roasted mass was leached in water; b) leaching with HCl or H2SO4 (70 oC, 1-3 h). HCl was the best leachant. In both routes, soluble tungsten was extracted at pH 1 with Alamine 336 (10 vol.% in kerosene) and stripped with 2 mol L-1 NH4OH (25 oC, one stage, aqueous/organic ratio = 1 v/v). Tungsten was isolated as ammonium paratungstate at very high yield (> 97.5%). The elements were better separated using the acidic route.

Isolamento do tungstênio da volframita da mina de Igarapé Manteiga (Rondônia - Brasil) por lixiviação ácida

We report results of the efficiency of tungsten extraction from wolframite concentrate (containing 61.5 wt % WO3) from the Igarape Manteiga mine (state of Rondonia, 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).