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.     

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 °C, 5 h) in order to eliminate coke and other volatile species present. Pre-oxidized catalysts were dissolved in H₂SO₄ (9 mol L⁻¹) at 90 °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 (>98 wt.%).     

Sorption of Cr(VI) ions on two Lewatit-anion exchange resins and their quantitative determination using UV-visible spectrophotometer

The sorption of Cr(VI) from aqueous solutions with macroporous resins which contain quarternary amine groups (Lewatit MP 64 and Lewatit MP 500) was studied at varying Cr(VI) concentration, adsorbent dose, pH, contact time and temperature. Batch shaking sorption experiments were carried out to evaluate the performance of Lewatit MP 64 and Lewatit MP 500 anion exchange resins in the removal of Cr(VI) from aqueous solutions. The concentration of Cr(VI) in aqueous solution was determined by UV-visible spectrophotometer. The ion exchange process, which is dependent on pH, showed maximum removal of Cr(VI) in the pH range 3-7 for an initial Cr(VI) concentration of 1x10(-3) M. The optimum pH for Cr(VI) adsorption was found as 5.0 for Lewatit MP 64 and 6.0 for Lewatit MP 500. The maximum Cr(VI) adsorption at pH 5.0 is 0.40 and 0.41 mmol/g resin for Lewatit MP 64 and Lewatit MP 500 anion exchangers, respectively. The maximum chromium sorption occurred at approximately 60 min for Lewatit MP 64 and 75 min for Lewatit MP 500. The suitability of the Freundlich and Langmuir adsorption models was also investigated for each chromium-sorbent system. The uptake of Cr(VI) by the anion exchange resins was reversible and so it has good potential for the removal of Cr(VI) from aqueous solutions. Both ion exchangers had high bonding constants but Lewatit MP 500 showed stronger binding. The rise in the temperature caused a slight decrease in the value of the equilibrium constant (K(c)) for the sorption of Cr(VI) ion.     

Studies of removal of platinum(IV) ion microquantities from the model solutions of aluminium, copper, iron, nickel and zinc chloride macroquantities on the anion exchanger Duolite S 37

Platinum has been widely applied in catalytic industry and the recovery of noble metals from industrial wastes becomes an economic issue. The laboratory studies of platinum(IV) microquantities removal from 1M aluminium, copper, iron, nickel and zinc chloride solutions in 0.1M hydrochloric acid solutions on the anion exchanger Duolite S 37 of the functional secondary and tertiary amine groups were carried out. For this anion exchanger the fraction extracted values (%E, Pt(IV)) as well as the sorption isotherms were determined depending on the kind of aqueous phase and phase contact time. Moreover, the bed and weight distribution coefficients as well as working and total ion-exchange capacities were calculated from the platinum(IV) breakthrough curves. Kinetic parameters were determined.