Synthesis of copper oxy-chloride and iron oxide pigments using leachate from the bioleaching of a copper sulphide minerals

flotation concentrate
Authors: Carlos Souza, Luis Sobral, Dbora Monteiro, Paula Nascimento, Gabriel Peixoto Centro de Tecnologia Mineral - CETEM

Introduction

During the last and recent economic crisis the commodities

prices dropped down dramatically , which pushed the mining

sector to search for technological alternatives to produce

more cost effective final products. In the copper mine, in particular, the idea was to treat the leachate, out of the heap leaching process, to precipitate the iron oxide pigment (FeOOH), widely used in the ceramic and paint industries, followed by the precipitation of copper oxychloride, also widely used agriculture pesticide .

Bioleaching test
Copper concentrate particle size distribution Inner Diameter (mesh) 150 200 325 < 325 Particle Size (mm) 0.106 0.074 0.043 < 0.043 Retained Weight Fraction (%) 10.7 23.0 27.6 38.7

Copper content chalcopyrite (CuFeS2) 70% bornite (Cu5FeS4) 30%

- Support rock
-3mm +6mm - Microorganisms Mesophiles Up to 40C ModerateTermophiles ~40 - ~55C ExtremoTermophiles ~55 - ~80C

Bioleaching test
pH

Eh O2 CO2
Nutrients Temperature

Cell Concentrao
Elements Analysis

Outline of the column bioleaching reaction system

Experimental
Liquor : 18.0 g/L of copper 3.18 g/L of total iron [Fe3+] = 58.35% 1200 rpm
Fe3+/Fe2+ = 0.9

2Fe2

H 2O2

2H

2 Fe3

2 H 2O

Experimental
The filtrate pH was raised to 6.5 by adding 1 mol/L sodium hydroxide solution (NaOH), in the same stirred reactor, where copper hydroxide was precipitated [Cu(OH)2], and further separated from the aqueous phase containing, essentially, sodium sulphate (Na2SO4)

CuSO4

2 NaOH

Na2 SO4 Cu(OH ) 2

Cu(OH ) 2 4CuCl2

2HCl

CuCl2

2 H 2O 2 NaCl

2 NaOH

3CuCl2 .Cu(OH ) 2

Results and discussion

X-ray diffraction

Commercial pigment

Synthetic pigment aged for 24h at 50C

Natro-jarosite: NaFe3(SO4)2(OH)6

Results and discussion

Particle Size Analysis

Synthesized iron oxide pigment, have particle size below 20 m, below 62% of 5 mm and 42% are below 2 m. While the commercialised pigment, by the leader industry in the Brazilian market, 98% of the particles has size below 20 m, 94% below 5 m and 92% below 2 m

Results and discussion

Scanning Electron Microscopy

Synthetic pigment aged for 24h at 50C (nodular)

Commercial pigment (Acicular)

Conclusions
The iron oxide pigment obtained out of the leachate from the bioleaching of a copper sulphides flotation concentrate, consisting mainly of chalcopyrite (CuFeS2) and bornite (Cu5FeS4), is considered as a potentially attractive way for recovering iron as an iron oxide pigment without using organic reagents, as those used in solvent extraction processes, despite of high selectivity for copper, also present considerable flammability and toxicity risks. The pigment obtained in this test work, in the above mentioned experimental conditions, still have to be optimised so as to improve its crystallinity, compared with the one commercialised in the Brazilian market. The synthesized pigment showed particle size 94% below 20 m, which can be used in the ceramic industry, in the production of special bricks and cement or even as an adsorbent material.

Conclusions
The copper oxy-chloride, a widely used agriculture pesticide with broad spectrum for controlling of fungal diseases in several crops, mainly

horticulture and fruit production, may be obtained easily from the

remaining solution of the iron-base pigment precipitation process by raising the pH of the copper chloride solution using sodium hydroxide. As

previously mentioned, the copper content of that salt produced in this

study was of 50.7%, which is, to some extent, within the range of those commercialised in the market (from 30 to 50%).