Technical Report

R080929JVDL

Mining of valuable metals: in situ and heap leaching

Jan van der Lee Paris School of Mines Geosciences Department Reactive Hydrodynamics Group

This report provides background information on leaching processes applied in the mining industry, with focus on in situ leaching of uranium and copper.

September, 2008

 2008 ARMINES Mines Paristech Geosciences Department 35 rue Saint-Honor 77305 Fontainebleau Cedex France.

Reference: J. van der Lee (2008). Mining of valuable metals: in situ and heap leaching Technical Report Nr. R080929JVDL, Paris School of Mines, Fontainebleau, France.

September 2008 J. van der Lee <jan.vanderlee@mines-paristech.fr>

A This document has been typeset with L TEX using GNU-Emacs.

Contents
1 Introduction 1.1 1.2 About the Reactive Hydrodynamics Group . . . . . . . . . . . . . . . . In situ leaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 1 1 3 3 5 7 7

2 Copper leaching 2.1 2.2 Copper ore mineralogy . . . . . . . . . . . . . . . . . . . . . . . . . . . . Leaching . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

3 Solvent extraction 3.1 Solvent extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1 Introduction

1.1

About the Reactive Hydrodynamics Group

The Reactive Hydrodynamics Group is one of the six research groups of the Geosciences department of the Paris School of Mines. Proting from the general knowledge base of the department (geology, geophysics, geostatistics, hydrogeology and geomechanics), this group has built an expertise in geochemistry, leaching and degradation of (geo)materials coupled with hydrodynamic ow of uids (reactive transport). The group strongly focusses on modeling of coupled processes. This specic scientic branch covers a wide variety of industrial problem domains, including waste and acid-gas storage, environmental science, contaminant hydrology and leaching. Modeling of in-situ leaching is a fast growing activity since the increase of the value of geological ressources. So far, most of leaching studies have been focussed on uranium mining. More information can be found on the website of the research group1 .

1.2

In situ leaching

Leaching is employed to extract chemicals from a material using an aqueous solution (lixiviant or leach-uid). The technique is commonly applied in mining to recover valuable metals (silver, gold, copper, uranium) from geological materials. The three basic leaching techniques applied in the mining industry are heap leaching, vat (or tank) leaching and in situ leaching. In situ leaching (ISL), sometimes referred to as solution mining or in situ recovery (ISR), is a process of dissolving minerals such as copper or uranium directly in the ore deposit. Using a series of boreholes, a ow of leach solution is established allowing to wash the ore and to recover the uid for processing. In situ leaching is originally developed in the early 1960s for uranium. It contributes to 15% of the world uranium production. The major advantage of in situ leaching is that metals or valuable minerals can be recovered without the need for conventional mining techniques, involving drilling, blasting, opencut or large and expensive underground facilities. Consequently, there is only little surface disturbance and no tailings or waste-rock generated. In order to apply ISL, the ore-body must be permeable with respect to the leaching uid. Typically, ores contained in permeable sedimentary formations such as sandstones or highly fractured rocks are suitable candidates for ISL. Furthermore, the ores should be sandwiched between relatively impermeable layers, so-called aquitards, in order to canalize the leaching agent through the ore and to avoid leakage. Leakage leads to environmental contamination and reduces the eciency of the method as the pregnant solution is lost. Figure 1.1 illustrates an often-described hydrogeological conguration with ideal conditions for in situ leaching. Furthermore, the following conditions should
1

http://hr.geosciences.ensmp.fr

Figure 1.1: In situ leaching of an ore-body present in a deep-underground sandstone aquifer.

be met: with respect the ore mineralogy: favorable dissolution kinetics of the valuable minerals; low buer capacity with respect to pH and Eh, especially a low carbonate content since carbonates are notorious acid-consumers; with respect to the hydrodynamic environment: conned medium, to avoid leakage and to guide the leaching uid through the ore permeable ore-body, with an optimum accessibility of the grains A perfect combination of all these conditions is rarely met. Each leaching installation has its specic conguration, mineralogy, geology and hydrogeological environment. The task of the Reactive Hydrodynamics group is to understand the local, site-specic behavior of the system from both geochemical and hydrodynamic view points, and to help in providing specic advice to improve the overall process from an economic and/or environmental perspective.

2 Copper leaching

2.1

Copper ore mineralogy

Often encountered copper ore mainly consists of bornite (Cu5 FeS4 ) and chalcopyrite (CuFeS) in a poorly sorted matrix of sand, silt and clayey grains (graywacke), containing principally quartzite with some feldspar and carbonaceous facies. The ore also contains minor amounts of chalcocite (Cu2 S), covellite (CuS) and very minor amounts of native copper. Oxidation of chalcocite in acidied ferric sulfate seems to proceed in two distinct stages: chalcocite is oxidized to covellite and that the covellite oxidizes further to form free sulfur. The dissolution of the intermediate product is assumably slower than that of the original chalcocite. The conversion rate of chalcocite to covellite was found to be about 10 times as high as the dissolution rate of covellite (Konishi et al., 2001). The time required for complete dissolution of covellite is directly proportional to the initial particle size, hence exposed surface area. Oxidic ore is composed of a poorly sorted matrix of sand, silt and clayey grains (graywacke), containing principally quartzite with some feldspar and carbonaceous facies. Common oxidic copper minerals are malachite (Cu2 CO3 (OH)2 ), lesser amounts of azurite (same formula) and chrysocolla (CuSiO3 ), tenorite (CuO) and cuprite (Cu2 O). Oxidic copper ore may contain certain amounts of copper suldes either composed of secondary minerals chalcocite and covellite, or the primary minerals bornite and chalcopyrite.

Figure 2.1: Typical examples of ore containing malachite (left) and chrysocolla (right).

The solubility of the dierent minerals is conveniently illustrated with help of so-called Pourbaix diagrams. They display the expected predominant species or solids as a function of two important variables, pH and Eh (redox potential). Figure 2.2 shows a pH-Eh diagram (Pourbaix) for copper, in presence of iron, sulphide and silicate. We can see that in reducing conditions, mineral chalcopyrite is the expected predominant iron species, together (although less dominant) with bornite, chalcocite, metallic Cu and covellite. In more oxidizing and intermediate and high pH conditions, cuprite, malachite and possibly Antlerite (Cu3 (SO4 )(OH)4 ) or Brochantite (Cu4 (SO4 )(OH)6 ) seem to be able to form, at least from a thermodynamically view point (absence of kinetics). 3

Figure 2.2: Pourbaix diagram for Cu in prensence of Fe, S and Si. Copper oxides readily dissolve in acid conditions, in contrast to suldes which required oxidizing to dissolve conditions. An optimum acidity region is found at pH 4. Diagram calculated by the CHESS software using the CTDP thermodynamic database.

Whatever the exact mineral phases, the diagram shows an increase of the expected solubility in the upper-left corner of the diagram, i.e. in acidic and oxidizing conditions. Copper dissolves below pH of 5, provided an increase in oxidation state (Eh > 300 mV, approximately). Although they provide a quick overview of possible predominant phases, care must be taken with using pH-Eh diagrams for predictive purposes. This type of diagrams is based on simple hypotheses. First, the diagrams assume instantaneous thermodynamic equilibrium, as only rarely observed in heterogeneous natural systems. Second, Pourbaix diagrams are calculated using a strongly simplied background geochemistry (no speciation) with only a few major phases imposed by a constant activity or concentration. More precise predictions are provided using full speciation, which can be performed using the tools developed by the Reactive Hydrodynamics Group, CHESS1 and HYTEC2 .

2.2

Leaching

The leach process is governed by the attack-uid composition and the mineralogy of the ore. The main parameters of the leach uid are the pH and oxidation state (redox potential), although the auxiliary chemicals of the uid may play a role as well (e.g. carbonate content, ferric iron concentration,. . . ). The type of mineral species of the metal of interest present in the ore is of key-importance for leaching. The host-rock and auxiliary minerals are important as well, since they can act as acid-consumers and therefore reduce the eciency of the leach uid. Leaching aims at dissolving all copper-containing minerals of the ore. The commonly accepted Cu-oxide dissolution reactions are formulated as follows: Cu2 CO3 (OH)2 + 4H+ + 2SO4 2 CuSiO3 + 2H + SO4
+ 2 2

2CuSO4 (aq) + CO2 (aq) + 3H2 O CuSO4 (aq) + SiO2 (aq) + H2 O CuSO4 (aq) + H2 O

CuO + 2H + SO4
+

All three reactions require two moles of H+ to produce one mole of Cu2+ . The generally accepted Cu-sulde dissolution reactions are something like these: Cu2 S + 2H+ + SO4 2 + 0.5O2 (aq) CuS + 2 O2 (aq) CuSO4 (aq) + CuS + H2 O CuSO4 (aq)

Note that the oxidation of chalcocite (Cu2 S) requires an intermediate step through the formation of covellite. It is often mentioned that dissolution of covellite is enhanced by an increase in ferric iron, probably related to bacterial activity. Using ferric iron instead of oxygen: Cu2 S + Fe2 (SO4 )3 (aq) CuS + Fe2 (SO4 )3 (aq) S + 1.5O2 (aq) + H2 O
1 2

CuSO4 (aq) + CuS + 2FeSO4 CuSO4 (aq) + 2FeSO4 + S 2H+ + SO4 2

http://chess.ensmp.fr http://hytec.ensmp.fr

The latter mole-balances assume that ferric iron is abundantly present in solution. Ferric iron is highly insoluble, however, and present as e.g. hematite or magnetite. Dissolution of these phases also requires acidity. The loaded leach-solution is often called the Pregnant Leach Solution or PLS. Copper is recovered from the PLS by solvent extraction, a well-established technique and briey outlined below.

3 Solvent extraction

3.1

Solvent extraction

Solvent extraction (SX) is required to concentrate the Pregnant Leach Solution (PLS) in copper content before electrowinning (EW). The method is based on the use of an extractant (e.g. LIX 984) complexed with an organic solvent (generally an inert kerosene based hydrocarbon, called diluent ) and mixed with the PLS. Due to the lower density of the organic solvent (about 15 % lighter than PLS), the latter oats on the top of the aqueous phase and can be separated. The remaining, stripped solution is called the ranate and is recycled for use in the leaching process. The chemical process of SX is simple and can be described by the following mass balance equation: 2 LIX(H ) + Cu2+ LIX2 (Cu ) + 2 H+ (3.1) Of course, in a sulfuric acid solution the free copper is readily complexed to form the aqueous species CuSO4 (aq), not considered here to simplify notations. Applying a classical law of mass-action and expressed in logarithmic terms we obtain a reaction of the following type: log[LIX2 (Cu )] = log[K ] + 2 log[LIX(H )] + log[Cu2+ ] + 2 pH (3.2)

This relationship readily shows that the amount of complexed copper increases with pH. Inversely, less copper is recovered at low pH. Industrial providers sell LIX 984 reagents on the internet as moderately strong copper extractants which operate best at a pH of 2 or higher and relatively high temperatures (> 20 C). However, the reactant starts to complex ferric iron at pH 1.8 and other metals (Ni2+ , Co2+ , Zn2+ , . . . ) at pH above 3.5. In order to avoid competition with other metals in the PLS, an optimum pH of 1.8 is often proposed.
Note: the minimum pH for ecient SX based on LIX 984 (Mufulira case) is 1.8.

Note that this information is based on commercial advertisement and not on scientic literature. In absence of signicant amounts of ferric iron, however, extraction is expected to works best at higher pH, between 2 and 3. pH lower than 1.8 will decrease the SX eciency: lime can be added to increase the pH before entering the SX process. Mufulira PLS contains ferric iron (oral information): we therefore recommend a pH between 1.8 and 2. Once the metal is complexed by the reagent after the mixing stage, the loaded organic layer is separated from the aqueous phase using a settler as illustrated by Figure 3.1. A stripping stage is applied separate the copper from the organic phase, a process described Eqn. 3.1 but reversed: the pH is signicantly decreased and Cu2+ ions are 7

Figure 3.1: Settler of the solvent extraction procedure in Mufulira (Zambia) of the Mopani Copper Mines, the largest copper mine in Africa.

outcompeted by H+ , thus leaving the reagent. This process of extraction and stripping is repeated one or several times until a convenient concentration of copper is obtained, suitable for electrowinning. This concentration is generally something like 40 g/l. It is clear that acidity (pH) and copper concentration of the PLS are critical parameters for SX. If the pH is too low, lime has to be added to the PLS to increase the pH. Very low concentrations of copper require many iterations in the process, thus increasing the costs. Another problem is crud formation, i.e. coagulation of nes and suspended solids in the PLS. Crud hinders the extraction process and special settling tanks are required to eliminate the crud, which increases the complexity and costs of SX. Speciation modeling, using speciation tools like CHESS, provides insight in the processes and allows for optimizing the solvent extractant process, with respect to key-variables like pH, copper content and dissolved solids (TDS). This kind of applications require specic databases containing the characteristics of the reagent.