Recovery of nockel and cobalt from nickel laterite leach solution using chelating resins and pre-reducing process.

Author(s)

Amilton Barbosa Botelho Junior

• Document type: Master's Dissertation
• Press: São Paulo.
• Institution: Universidade de São Paulo (USP). Escola Politécnica (EP/BC)
• Defense date: 2018-12-13

Examining board members

Jorge Alberto Soares Tenório; Juliana de Carvalho Izidoro; André de Albuquerque Vicente

• Advisor: Jorge Alberto Soares Tenório; Denise Crocce Romano Espinosa

Abstract

Nickel laterite ores represent 70% of the available metal reserves. The nickel production from these reserves represents 40%, where it is also possible extract copper and cobalt. It occurs due to the high impurities content, mainly iron. With the growing demand of these metals, the use of nickel laterite reserves became more deeply investigated, as well as hydrometallurgical process development. In this case, the ferric iron difficult the nickel and cobalt recovery, once in ion exchange processes this metal competes in the occupation of the cationic sites. In solvent extraction processes the same effect is observed. Besides that, during the eventual iron precipitation there is a co-precipitation. Therefore, for ion exchange, ferrous iron may be less damaging than ferric iron. The aim of this work was to study the reducing process of ferric iron in aqueous solution, and also the subsequent obtaining of cobalt and nickel through chelating resins. It was studied the reducing process of ferric iron and the effect of it in metals adsorption by ion exchange. Experiments of chemical reduction of ferric iron in solution were studied using sodium dithionite, sodium metabisulfite and sodium sulfite. Experiments with reducing agents sodium dithionite and metabisulfite were performed in São Paulo, and experiments with sodium sulfite were performed in The University of British Columbia. Reducing agents were added in ferric iron mono-elementary solution to decrease the redox potential. The variables potential redox, between 860mV and 240mV; pH, between 0,5 and 3,5; temperature, between 25°C e 60°C; and time, between 30min and 96 hours were studied in erlenmeyer flasks under constant stirring. Then, analyzed ferric iron reduction in multielementary solution of nickel laterite. In ion exchange experiments, performed in batch and column, it was used chelating resin Lewatit TP 207, with iminodiacetate functional group, and resin Lewatit TP 220, with bis-picolylamine functional group. Three solutions were studied: prepared with Fe(III), other with Fe(III) and the third with Fe(III) after pre-reducing process. Experiments in batch system were performed using erlenmeyer flasks, under constant stirring, with 100mL of solution to 1mL of resin. It was studied the effect of pH, between 0,5 and 3,5, time, between 30min and 480min, and temperature, between 25°C e 60°C. In experiments in continuous system, the three solutions were fed in glass columns filled with resin. The solution was fed using peristaltic pumps at constant flow rate. For column elution, sulfuric acid 1mol.L-1 was fed to the column using peristaltic pumps. The second part of this work, performed at The University of British Columbia, was the study of sodium sulfite application at prereducing process. It was studied two resins: Lewatit TP 207, selective for copper, and Lewatit TP 220, selective for nickel and cobalt. Sodium sulfite was added to the solution to decrease the potential, in flasks and it was placed under constant stirring. After reaction, the solution was placed in contact to the chelating resin, which was placed under stirring. Batch experiments were performed, and the effect of pH was studied between 0,5 and 3,5. In column process, the Column 1, filled with Lewatit TP 207, was used for copper removal, and output solution was feed in Column 2, filled with Lewatit TP 220. For the elution, it was studied sulfuric and hydrochloric acids in two different concentrations, 1mol.L-1 e 2mol.L-1. Sodium hydroxide was used for iron removal from solution obtained in Column 2 output. Cobalt separation was performed using solvent extraction technique (Cyanex 272 20%), studying the effect of pH, 4,0 and 5,0, and temperature, 25°C e 65°C. Results shows that ferric iron reduction using sodium dithionite was 100% in mono-elementary solution and 70% in multi-elementary solution with other metals. In ion exchange experiments performed in batch using resin TP 207, 62% of copper was adsorbed by the resin after pre-reducing process. For solution with Fe(II), the copper adsorption was 61%, and for solution with Fe(III), 49%. In ion exchange experiments after pre-reducing process using sodium sulfite, the copper adsorption was 69% at pH 2,0 by the resin TP 207. The resin TP 220 was more selective for nickel and cobalt at pH 2,0, where these metals adsorptions were 32,5% and 69%, respectively. In experiments performed in column, the Column 1 was used for copper removal, however there were losses of nickel (17%) and cobalt (7%). In the feeding of Column 2, it was found that 98% of nickel and 84% of cobalt were adsorbed. Solution obtained in Column 2 had concentration of iron 618mg.L-1, nickel was 13231mg.L-1 and cobalt 179mg.L-1. The iron removal was 100% at pH 4,0. For cobalt separation in nickel-rich solution, it was used the solvent extraction with Cyanex 272 20% with kerosene, where 99% of cobalt was separated from solution at 65°C and pH 5,0, without nickel loss. For future studies, the copper removal in the beginning of the process can be explored using other techniques, in order to avoid nickel and cobalt losses. Another point that can be explored is the maximum use of ion exchange columns in the same conditions of this work - solution with Fe(III), with Fe(II) and after the pre-reducing process - mostly on a pilot scale, to study the effect of iron oxidation state on possible resin poisoning. (AU)

• FAPESP's process: 16/05527-5 - Separation of metals from sulfuric liquor of mining waste using chelating resins
• Grantee: Amilton Barbosa Botelho Junior
• Support Opportunities: Scholarships in Brazil - Master