Acid balance in a chloride heap leach

Abstract

A method of controlling the acid balance in a high chloride heap leach process tomaximise the copper dissolution in a cure step and to increase overall copper recovery which include an agglomeration stage in which acid and process solutions are combined with the ore prior to stacking to form a heap followed by a cure phase to leach a portion of the copper in the ore in the heap followed by an irrigated leach phase in which the remaining copper minerals are leached and copper is recovered from a pregnant leach solution by a solvent extraction step followed by an electrowinning step wherein the acid concentration in the pregnant leach solution which reports to the solvent extraction step is less than 10 g/L to allow effective copper recovery from the pregnant leach solution in the solvent extraction step.

Claims

1. A method of controlling acid balance in a high chloride heap leach process carried out at ambient temperature, wherein a chloride concentration is between 100 g/L and 180 g/L to ensure that copper dissolution in an agglomeration stage is not limited by acid to maximize the copper dissolution in a cure phase and thereby increase an overall copper recovery, wherein the method comprises: an agglomeration stage in which acid and process solutions are combined with an ore prior to stacking to form a heap; an aerated, but non-irrigated, cure phase to leach a portion of copper in the ore in the heap, wherein the copper dissolution in the aerated, but non-irrigated, cure phase is at least 30% by mass; and an irrigated leach phase during which remaining copper minerals are leached and copper is recovered from a pregnant leach solution by a solvent extraction process followed by an electrowinning process, and wherein the heap comprises a plurality of heap sections in which excess acid in the irrigated leach phase is reduced by circulating leach-liquor to the plurality of heap sections counter-current to the ore loading onto the plurality of heap sections and removal of ore from the plurality of heap sections, thereby increasing acid consumption by gangue mineral dissolution in proportion to a number of the plurality of heap sections irrigated during the irrigated leach phase and acid concentration in the pregnant leach solution, which reports to the solvent extraction process, is less than 10 g/L, to allow effective copper recovery from the pregnant leach solution in the solvent extraction process.

2. The method according to claim 1, where overall copper dissolution in the aerated, but non-irrigated, cure phase and in the irrigated leach phase is greater than 40% by mass.

3. The method according to claim 1, wherein an acid concentration in the pregnant leach solution is lower than 7 g/L.

4. The method according to claim 3, wherein the acid concentration in the pregnant leach solution is lower than 2 g/L.

5. The method according to claim 1, where a raffinate generated during the solvent extraction process comprises a copper content that is less than 1 g/L.

6. The method according to claim 5 wherein the copper content is less than 0.5 g/L.

7. The method according to claim 1, wherein, after completion of the irrigated leach phase, the heap is washed.

8. The method according to claim 1, wherein a quantity of acid added during the method is calculated from acid consumed by gangue minerals and acid required to leach the copper minerals.

9. The method according to claim 8, wherein acid required for copper leaching is added to the ore during the agglomeration stage.

10. The method according to claim 8, wherein acid addition to a raffinate solution which is used to irrigate the heap is done to meet increased acid demand by mineral leaching in the irrigated leach phase.

11. The method according to claim 8, which further comprises a preceding process of conducting tests to determine the acid consumed by the gangue minerals for a specific type of ore as a function of at least one of the following: solution pH, acid concentration, temperature, and ore particle size.

12. The method according to claim 1, wherein an optimal addition of acid added during the method is determined by content of acid-soluble gangue minerals and the copper minerals in the ore.

13. The method according to claim 12, wherein the pregnant leach solution collected from initial irrigation of the heap following the aerated, but non-irrigated, cure phase is added to the ore during the agglomeration stage so as to utilize acid content in the pregnant leach solution during a subsequent cure phase.

14. The method according to claim 12, wherein acid added to the ore during the agglomeration stage is determined by demand for copper mineral and gangue mineral dissolution in the aerated, but non-irrigated, cure phase.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) Two embodiments of the invention are further described herein, respectively with reference to FIGS. 2 to 7, and FIGS. 8 to 12, of the accompanying drawings wherein:

(2) FIG. 2 is a generalized diagram of a reactor;

(3) FIG. 3 shows a standard circuit in a heap leach process;

(4) FIG. 4 schematically depicts a multi-stage heap leach process operated in accordance with a first embodiment of the invention;

(5) FIG. 5 reflects curves of free acid profiles against time for the parameters of PLS, ILS and rafinate;

(6) FIG. 6 illustrates a process flow according to the invention with counter-current circulation;

(7) FIG. 7 is similar to FIG. 6 but with co-current circulation;

(8) FIG. 8 depicts a general flow diagram for a process operated in accordance with a second embodiment of the invention;

(9) FIG. 9 shows the process of FIG. 8 in more detail;

(10) FIG. 10 graphically reflects PLS concentration profiles showing acid, copper and iron concentrations as a function of the PLS irrigation ratio at an irrigation rate of 3 L/h.Math.m.sup.2;

(11) FIG. 11 illustrates a test reactor for determining gangue acid consumption at a constant pH;

(12) FIG. 12 graphically depicts gangue acid consumption for a hypogene ore type, as a function of pH, against time;

(13) FIGS. 13 to 27 relate to circuits used in test work and data arising from such test work.

DESCRIPTION OF PREFERRED EMBODIMENTS

(14) A first embodiment of the invention is hereinafter described with reference to FIGS. 2 to 7 while a second embodiment of the invention is described hereinafter with reference to FIGS. 8 to 12.

Embodiment 1—Multistage Heap Leach Operation

(15) FIG. 2 shows a typical reactor 10. A mass balance for a reactant C can be carried out over the reactor. For simplicity, it is assumed that volumetric flows in (12) and out (14) are equal. In addition, as real heaps are surprisingly well-mixed, it is assumed for simplicity that the concentration of reactant within the reactor 10 is the same as in a discharge from the reactor (i.e. a well-mixed reactor).

(16) The mass balance over reactant C is as follows:
In=out+lost in reaction
F.Math.Ci=F.Math.Co+rV

(17) Where: F is the flow rate; C.sub.i is the inlet concentration; C.sub.o is the outlet concentration; V is the reactor volume; and r is the rate of acid use, which in this case, as defined earlier, is proportional to the acid concentration C.sub.o.

(18) Thus r=kC.sub.o, where k is a rate constant for the mineral concerned.

(19) The equation can be re-written as:
F.Math.Ci=F.Math.Co+k.Math.Co.Math.V

(20) V/F has a unit of time and is known as the average retention time, or τ.

(21) The equation can be rewritten as follows:

(22) $\begin{array}{cc}\frac{C_o}{C_i}=\frac{1}{\left(1+k\tau \right)}& \left(A\right)\end{array}$

(23) The factor k is a constant and τ is a constant for a fixed heap bed at fixed irrigation rate per unit area. This means the percentage conversion (Co/Ci) of the inlet concentration of acid is fixed irrespective of the inlet concentration.

(24) FIG. 3 is a flowsheet of a standard heap leach circuit 18 wherein about 50% of the PLS is bypassed for CuSX optimisation. In FIG. 3 a single heap 20 is used. By way of contrast, in the process 24 shown in FIG. 4, there are two heaps 20A and 20B respectively.

(25) In both processes (FIG. 3 and FIG. 4) the same amount of copper is transferred to the CuSX stage (30)—this transfer of copper elevates the acid tenor by 7 g/L.

(26) In the flowsheet of FIG. 3, the acid in the PLS 32 is set at y g/L. The raffinate 34 then contains y+7 g/L of acid. The bypass 36 and raffinate 34 are recombined (38) to give an average acid concentration of (2y+7)/2. This is passed over the heap 20 where the conversion is assumed to be 50%. This conversion would occur, irrespective of the acid concentration, as shown by equation A.

(27) At steady state the process 18 must balance, hence:
y (in PLS)=50%.Math.(2y+7)/2
Thus y=3.5 g/L of acid.

(28) The PLS is split in half in the example in FIG. 3. This is for ease of comparison to the example in FIG. 4. If the PLS were not split, it would still result in the same PLS acid concentration. However the acid increase in the raffinate would be 3.5 g/l.

(29) In the flowsheet of FIG. 4, the acid in the PLS (32) is also set at y g/L. The PLS is already ½ that of the example in FIG. 3. The PLS (32) reports to CuSX (30) and 7 g/L of acid is transferred to the liquor. The resultant liquor (raffinate) 34 then contains y+7 g/L of acid. This is passed over the heap 20B where the conversion is assumed to be 50%. It is then passed over the heap 20A where a further 50% conversion occurs.

(30) At steady state the process (24) must balance, hence:
y (in PLS)=50%.Math.50%.Math.(y+7), and
Thus y=2.3 g/L of acid
If the process were to be extended to 3 stages, then
y(in PLS)=50%.Math.50%.Math.50% (y+10.5), and
and y=1.5 g/L of acid.

(31) Thus, by operating the process with two or more ILS 42 stages, the amount of acid in the PLS 46 reporting to the copper solvent extraction stage can be significantly reduced without a detrimental impact on the process. An example of the effectiveness of the process can be seen by the change in free acidity for the hypersaline section (100 to 150 g/L chloride) of a pilot plant as shown in FIG. 5.

(32) The multistage implementation of the process of the invention can be configured such that the process flow is counter-current with the ore, or co-current thereto, as shown, respectively, in FIG. 6 and FIG. 7.

(33) The counter-current operation has an advantage over the co-current operation in that the final stage of the heap 20C is irrigated with the raffinate (34). The raffinate has the lowest copper tenor and hence this minimises soluble copper loss to the ripios.

Embodiment 2: Control and Optimisation of Acid Added During Agglomeration

(34) Excess Acid Control

(35) In any of the circuits shown in FIGS. 3 to 7, (as examples), PLS (32) or raffinate (34) can be circulated back to the agglomerator to provide soluble copper, iron and acid. The acid is required in the ore agglomeration to reduce the pH in the cure/rest phase, and to generate oxidant for copper sulfide leaching (rxn 1). Iron and copper are required as oxidants. The effectiveness of the oxidants increases with concentration.

(36) A typical simplified general flow diagram for the process is shown in FIG. 8. This depicts a two stage process wherein the solution for agglomeration is taken from the PLS.

(37) FIG. 9 shows the process of FIG. 8 in more detail.

(38) It has been found that upon irrigation of the ore bed, following the rest period and ore curing, the first drainage solution or initial PLS contains exceptionally high concentrations of copper, iron and acid. A further optimisation of the process is to utilise this initial PLS or “first flush” in the ore agglomeration step firstly, to increase the levels of oxidants (soluble copper and iron) in the subsequent cure/rest stage, and, secondly, in line with the acid strategy, if there is excess acid, then the amount of fresh acid added to the agglomeration of subsequent ore can be discounted by the acid. This helps to mitigate against excess acid in the leach phase.

(39) This is illustrated by the results which are presented in FIG. 10, for a 2 m×2 m×8 m crib test at a pilot plant used to treat a hypogene ore with a grade of 0.79% copper, with 70% copper as chalcopyrite and a crush size of about 80% passing 19 mm.

(40) The results presented in FIG. 10 show that the initial drainage solution or first PLS, leaving the ore bed of the crib (G10/2) contained exceptionally high concentrations of acid (80 g/L) (A), copper (55 g/L) (B) and iron (35 g/L) (C). This PLS solution can be efficiently used in the agglomeration of a new batch of ore, instead of raffinate, with the benefit of utilising the high acid, copper and iron concentrations to promote mineral leaching, allowing reduced fresh acid addition for that batch of ore. The volume of PLS used is based on the required moisture content for ore agglomeration. A typical value in this example is about 0.07 m.sup.3/t; which corresponds to the first 10 days of PLS drained from the ore bed, at an irrigation rate of 3 L/h.Math.m.sup.2. The iron in solution is oxidised to ferric during the ore agglomeration and subsequent curing process under aerated conditions, which contributes to copper mineral leaching. The high copper concentrations promote ferrous ion oxidation, increasing solution oxidation potentials, and increase copper mineral leaching rates during the curing period. It is also expected that excess ferric iron in solution will precipitate during this process as jarosites, or as metasideronatrite, as shown by reactions 3, 4 and 5, respectively. This would lower concentrations of iron in solution and maintain iron levels at the expected equilibrium concentration in the raffinate typically, but not limited to, about 5 g/L in solutions with 150 g/L chloride.

(41) The Determination of Gangue Acid Consumption (GAC) and Control of Acid Addition to Heap Leaching

(42) The acid required for chloride leaching is added as fresh concentrated acid during ore agglomeration or as make-up acid to the raffinate solution. In an operation with an ore agglomeration step, acid is thus provided by the addition of concentrated acid to the ore and, or only as, acid in the raffinate solution. The raffinate addition is controlled to achieve the final moisture content specified for the agglomerated ore.

(43) In the case of ore leaching without ore agglomeration acid is provided in the raffinate stream used to irrigate the heap.

(44) The acid required is calculated from the acid consumed by gangue minerals and the acid required to leach the copper minerals. The rate of acid consumption during mineral leaching is dependent on the acid concentration in solution and the temperature.

(45) Test methods have been developed to determine the acid consumed by gangue mineral leaching, so that for a specific ore type the gangue acid consumption (GAC) can be determined, as a function of solution pH, or acid concentration, and temperature. The results of these GAC tests have been used to determine model parameters which are used to calculate the acid demand for the leaching of fast, medium and slow-leaching, gangue minerals. Thus, for a specific ore type the GAC can be determined and the acid addition to ore agglomeration and to the raffinate controlled, in order to meet the acid demand without creating excess acid concentration in solution. The amount of acid required for copper dissolution can be calculated from the copper grade, expected copper dissolution determined by testing, and by considering the ore mineralogy and reaction stoichiometry defined by the leaching reactions, for example as shown by reaction 1. This data is then used to determine the acid addition required during ore agglomeration and the acid concentration required in the raffinate to sustain mineral leaching, and to maximise copper dissolution and to maintain an optimum concentration of acid in the PLS, in order to allow efficient copper extraction by SX.

(46) Determination of Optimal Acid Addition During Agglomeration

(47) Copper-bearing ores contain a wide range of minerals. Sulfide minerals, such as pyrite and chalcopyrite, are not leached under the low Eh conditions of the GAC test. Gangue minerals leached by sulfuric acid typically include metal oxides and carbonates and various potassium-ferrous-magnesium-aluminium silicates. The acid reaction with a gangue mineral is assumed to result in stoichiometric dissolution of the mineral, for example:
Calcite: CaCO.sub.3+2H.sup.+.fwdarw.Ca.sup.2++CO.sub.2+H.sub.2O
Chlorite: Mg.sub.3Fe.sub.2Al.sub.2Si.sub.3O.sub.10(OH).sub.8+16H.sup.+.fwdarw.3Mg.sup.2++2Fe.sup.2++2Al.sup.3++3SiO.sub.2+12H.sub.2O
K-Feldspar: KAlSi.sub.3O.sub.8+4H.sup.+.fwdarw.K.sup.++Al.sup.3++3SiO.sub.2+2H.sub.2O
Kaolinite: Al.sub.2Si.sub.2O.sub.5(OH).sub.4+6H.sup.+.fwdarw.2Al.sup.3++2SiO.sub.2+5H.sub.2O

(48) The chemical reaction between acid and gangue mineral in the ore releases ions into solution. When the solution is relatively dilute and sulfate mineral precipitation can be neglected then the amount of acid consumed by reaction with gangue can be calculated from the sum of the total charge released as ions, expressed mathematically as:
Δ[H.sup.+]=Δ[K.sup.+]+2Δ[Fe.sup.2+]+2Δ[Mg.sup.2+]+3Δ[Al.sup.3+]+. . . −Δ[Cl.sup.−]  (1)
where Δ[H.sup.+] is the amount of H.sup.+ (protons) consumed (mol/L) and Δ[K.sup.+], Δ[Fe.sup.2+], Δ[Al.sup.3+] etc are the changes in ion concentrations (mol/L) during the reaction. The summation is over all cations released during the reaction. The change in chloride concentration, Δ[Cl.sup.−], is included in the calculation to correct for dissolution of NaCl in the ore, which releases Na.sup.+ cations (and Cl.sup.− anions) into solution but does not consume acid, and possible leakage of KCl from the pH probe, which releases K.sup.+ cations (and Cl.sup.− anions) into solution and does not consume acid.

(49) The acid consumption is 49 Δ[H.sup.+] in g-H.sub.2SO.sub.4/L, or 49 Δ[H.sup.+] VIM in kg-H.sub.2SO.sub.4/t-ore, where V is the volume of solution in the reactor and M is the weight of the ore (kg). When the solution composition is known at various times during the course of the gangue-acid reaction then the acid consumption can be calculated as a function of reaction time.

(50) The concentration of acid in solution during the reaction can be calculated from an overall charge balance, expressed mathematically as:
[H.sup.+]=2[SO.sub.4.sup.2−]+[Cl.sup.−]−[K.sup.+]−2[Fe.sup.2+]−2[Mg.sup.2+]−3[Al.sup.3+]−. . .  (2)
where [H.sup.+] is the proton concentration or total concentration of H (as H.sup.+ and HSO.sub.4.sup.−) in solution (mol/L). The sulfate concentration [SO.sub.4.sup.2−] is known from the sulfur concentration [S] in solution.

(51) The concentration of acid in solution is y 49 [H.sup.+] in g-H.sub.2SO.sub.4/L. The acid concentration can be calculated as a function of time during the reaction.

(52) The pH of the solution in the reactor is maintained constant during the gangue-acid reaction by the addition of concentrated acid to the reactor. The acid added to maintain pH is recorded as a function of time and expressed as kg-H.sub.2SO.sub.4/t-ore.

(53) The acid added to maintain a constant pH is not equal to the acid consumed by the reaction with the gangue. In fact, the acid added to maintain a constant pH is generally greater than the acid consumed by the reaction with the gangue, increasingly so at low pH, which can be explained as follows. The acid H.sub.2SO.sub.4 dissociates in solution to produce the acidic chemical species H.sup.+ and HSO.sub.4.sup.−, but only H.sup.+ (through its activity) influences the solution pH. Because HSO.sub.4.sup.− has no effect on pH, the amount of acid that must be added to maintain pH is greater than the amount of acid that is consumed. The geochemical model EQ3/6 predicts that the proportion of HSO.sub.4.sup.− in solutions of H.sub.2SO.sub.4 at pH1 and pH2 is around 40% and 20%, respectively. The release of cations into the solution during the gangue-acid reaction is predicted to increase the percentage HSO.sub.4.sup.−. These results suggest that at pH1 the quantity of acid added to maintain a constant pH can be twice the quantity of the acid consumed by the reaction thereof with the gangue.

(54) As noted, the acid added to maintain a constant pH is measured directly during the course of the gangue-acid reaction. The acid added can also be calculated from the solution composition data and doing so provides a check on the consistency of that data. The acid added during a given reaction period is calculated as the sum of the acid consumed in that period, calculated from equation (1), and the difference between the concentrations of acid in solution at the end and beginning of the period, calculated from equation (2), which can be expressed as:
Δ[H.sup.+].sub.pH=2Δ[SO.sub.4.sup.2−]  (3)

(55) The acid added to maintain constant pH is 49 Δ[H.sup.+].sub.pH V/M in kg-H.sub.2SO.sub.4/t-ore.

(56) From equation (3), the amount of acid added to the reactor can be calculated from the change in sulfate concentration in solution. This simple relationship is a consequence of the fact that the reaction between acid and gangue does not change the sulfate concentration in solution.

(57) For modelling purposes, the specific reaction rate for acid consumption by gangue minerals is given by:

(58) $\begin{array}{cc}{R}_{\mathrm{Ga}}=g_{\mathrm{Ga}1}\frac{d{\alpha }_{\mathrm{Ga}1}}{\mathrm{dt}}+g_{\mathrm{Ga}2}\frac{d{\alpha }_{\mathrm{Ga}2}}{\mathrm{dt}}+g_{\mathrm{Ga}3}\frac{d{\alpha }_{\mathrm{Ga}3}}{\mathrm{dt}}& \left(4\right)\end{array}$
where R.sub.Ga is the specific reaction rate (kg-acid/t-ore.s) expressed as the sum of three terms, representing fast, medium and slow reaction, with gangue conversions α.sub.Ga1, α.sub.Ga2 and α.sub.Ga3 and ultimate acid consumptions g.sub.Ga1, g.sub.Ga2 and g.sub.Ga3 (kg-acid/t-ore), respectively. For each of the three types of acid consumption, the gangue conversion varies from zero to one and the acid consumption varies from zero to g as the reaction proceeds. The three types of acid consumption can be regarded as being representative of various gangue species: for example, fast (calcite), medium (chlorite and biotite), and slow (kaolinite, K-feldspar and sericite).

(59) The acid consumption by gangue is obtained by integrating the reaction rate given by equation (4) over the elapsed time of the reaction:
GAC=g.sub.Ga1α.sub.Ga1+g.sub.Ga2α.sub.Ga2+g.sub.Ga3α.sub.Ga3  (5)
where GAC is the acid consumption in kg-acid/t-ore.

(60) For each of the three types of acid consumption, the rate of gangue conversion during reaction is expressed in Arrhenius form as:

(61) $\begin{array}{cc}\frac{d{\alpha }_{\mathrm{Ga}}}{\mathrm{dt}}={\frac{k_{\mathrm{Ga}}}{{\left(d_p/d_0\right)}^{n_p}}\left[H^{+}\right]}^{n_H}\exp \left(-\frac{E_{\mathrm{Ga}}}{R}\left(\frac{1}{T}-\frac{1}{298}\right)\right){\left(1-{\alpha }_{\mathrm{Ga}}\right)}^{n_{\alpha }}& \left(6\right)\end{array}$
where k.sub.Ga is the rate constant ((L/mol).sup.nH/s), E.sub.Ga is the activation energy (cal/mol), d.sub.p is the ore particle size (mm), d.sub.0 is a characteristic ore particle size (taken as 10 mm), [H.sup.+] is the proton concentration (mol/L), T is the temperature (K), R is the universal gas constant (1.986 cal/mol.Math.K), and n.sub.p, n.sub.H and n.sub.α are exponents for particle size, acid concentration and gangue conversion, respectively. As shown in equation (5), the rate of acid consumption by gangue is expressed in terms of the proton concentration rather than the proton activity or pH.

(62) The concentration of a cation released into solution during the gangue-acid reaction is expressed as:
[C]=(g.sub.Ga1α.sub.Ga1Y.sub.C1+g.sub.Ga2α.sub.Ga2Y.sub.C2+g.sub.Ga3α.sub.Ga3Y.sub.C3)/98 (M/V)  (7)
where [C] is the cation concentration (mol/L) and Y.sub.C1, Y.sub.C2 and Y.sub.C3 are the cation release factors for each of the three classes of acid consumer, expressed as the number of moles of the cation released per mole of acid consumed (mol-C/mol-acid). For example, if calcite is the only fast reacting gangue species then the release factor for cation Ca.sup.2+ is Y.sub.Ca1=1. Similarly, if chlorite is the only medium reacting gangue species then the release factors for cations Mg.sup.2+, Fe.sup.2+ and Al.sup.3+ are Y.sub.Mg2=0.375, Y.sub.Fe2=0.25 and Y.sub.Al2=0.25, respectively.

(63) The ultimate weight of an element liberated by reaction between acid and gangue minerals is constrained to be less than the weight of the element in the ore:
(g.sub.Ga1Y.sub.C1+g.sub.Ga2Y.sub.C2+g.sub.Ga3Y.sub.C3)W.sub.C/98<G.sub.C  (8)
where W.sub.C is the atomic weight of the element and G.sub.C is the grade (kg-C/t-ore) of the element in the ore.

(64) The cation release factors are constrained by charge balance considerations:
Y.sub.K+2Y.sub.Fe(II)+2Y.sub.Mg+3Y.sub.Fe(III)+3Y.sub.Al+. . . =2  (9)

(65) The model parameters in equations (4) to (7), namely k.sub.Ga, E.sub.Ga, g.sub.Ga, Y, n.sub.p, n.sub.H and n.sub.α, are determined by fitting the model calculated acid consumption and solution composition to the measured data from the GAC tests.

(66) The experimental GAC determination is carried out using an arrangement 100 as is shown in FIG. 11. The arrangement includes a 5.5 L reaction vessel 102 equipped with an overflow outlet 104 at 4.5 L, in which vessel is placed 2750 g of an ore sample 106 (the size of the sample is increased with larger size fractions). The reaction vessel 102 is connected via tubing to a 3 L side reactor 110. A major portion of the lixiviant (5300 mL) is introduced into this connected system and circulated via a pump 116 from the side reactor 110 to the reaction vessel 102 at a fixed rate, flowing back via gravity into the side reactor 110.

(67) Once the 5300 mL of lixiviant is in the system, the lixiviant is brought to temperature, by means of heaters 118 underneath the reactors 102, 110. The pH (120) and final volume (122) are adjusted to the required starting values by the addition of 200 mL of an iron-containing acid solution 124 to give a final volume of 5500 mL.

(68) A reducing atmosphere is maintained over the reaction surfaces by excluding air from the reactors 102 and 110 and by introducing a flow of nitrogen 126 into the reactors 102, 110. The reactors are sealed allowing for the positive displacement of nitrogen from the reactors 102, 110. Solution samples are taken at stipulated time intervals from the side reactor 110 and analysed for a selection of elements using a computer 130. The pH and solution redox potential values are recorded over time in the computer 130.

(69) FIG. 12 graphically depicts the results obtained from the test arrangement 100 shown in FIG. 11. Acid consumption over time is illustrated for pH values pH1 (C), pH1.5 (B) and pH2 (A). It is evident that acid consumption is strongly affected by the solution pH i.e. the acid concentration in solution.

(70) It is also possible to use the reactor 100 to determine the effect of temperature and the effect of different crush sizes of the ore samples on acid consumption rates

(71) Typical results obtained using the method GAC test reactor are shown in FIG. 12. The results show how acid consumption is strongly affected by the solution pH or acid concentration in solution. As indicated the effect of temperature and the testing of ore samples at different crush sizes may be done to determine acid consumption rates as a function of particle size and temperature.

(72) The following description, with reference to FIGS. 13 to 23, relates to tests done in respect of aspects of the invention, as described hereinbefore.

Example 1: Description of an Integrated Pilot Plant Technical Evaluation of the Method of the Invention

(73) An integrated pilot plant incorporating 9 cribs and a solvent extraction plant has been established to replicate the commercial application of the process of the invention at pilot scale. This process is designed to treat various low grade chalcopyrite ores using a dynamic “race track” style heap leach operation. A “race track” style heap comprises of multiple sectors. New sectors get stacked and oldest most leached sectors are removed from the pad. The pad is re-used.

(74) Each crib contains approximately 40T of ore, has a cross sectional area of 4 m.sup.2, an operating height of 7.5 m and an overall height of 10 m. The cribs are operated to simulate a commercial operation with 9 sectors. Like the commercial heap, the process is dynamic with periodic removal of leach residue from a completed crib and replacement of residue with fresh ore in a vacant crib.

(75) Three separate phases of operation were undertaken. The range in composition of the principal copper sulfide minerals and gangue minerals contained in the ore samples tested, and a brief description of the operation are summarised in Table 1.

(76) TABLE-US-00005 TABLE 1 Brief Description of Pilot Plant Technical Evaluation Operational Phases Item Phase I Phase II Phase III Ore Crush size 80% 19.05 19.05 19.05 passing (mm) Copper Grade (%) 0.49-0.75 0.38-0.79 0.3-0.6 CSR* >10 10-20 10-20 chalcocite (%) CSR* covellite (%) 10-20 <10 <10 CSR* 40-75 65-75 40-75 chalcopyrite (%) Pyrite (%) 2-6 2-4 3-7 Chlorite (% 0.1-1.sup.  0-1 0-9 Biotite (%) .sup. 0-0.3   0-0.03 0-2 Kaolinite (%)  8-16 10-45 10-30 Description of Start up and Test variation Operate in Phase Operation initial data of leach closed collection conditions and circuit ore type. *CSR-Copper Source Ratio (Percentage of the total copper that is contained in this mineral)

(77) The ore samples are crushed in a 3 stage crushing circuit. The crushed ore is agglomerated before being loaded into the cribs. Sodium chloride (salt), acid and raffinate (or other copper, iron & acid containing process liquor) are added to the ore in the agglomeration process. The agglomerated ore is then placed inside an empty crib; cured for a period, following which irrigation commences. At the end of the irrigation cycle, each crib is drained, irrigated with water to wash, drained again and finally emptied out. The empty crib is then prepared to accept fresh agglomerated ore.

(78) Phase I and phase II involved start-up of the operation and gathering initial data and as well as construction of additional cribs for the phase III closed circuit operation.

(79) In the phase III operation low grade ores were included with copper grades as low as 0.3% Cu and with up to 75% of the contained copper associated with chalcopyrite (CSR chalcopyrite of 75%). The operation consisted of a 45 day curing period, 20 day wetting period, 360 days irrigation, 20 days washing and 30 days draining (total 475 days), before unloading and sample processing.

(80) The phase III operating schedule was designed to allow for the loading and unloading of a crib every 45 days, thereby simulating a commercial dynamic pad operation and industrial liquid handling. This closure was imperative in order to obtain steady state impurities concentrations and identification of possible operational problems. The operation was maintained in a closed circuit, reintroducing the wash water to generate the new raffinate that was lost due to residue moisture and evaporation. The water addition rate was maintained at 0.11 m.sup.3/T ore. The fresh make-up water was used for washing loaded organic to remove chloride and for washing residue ore according to the method of invention described hereinbefore.

(81) The pilot plant is operated as a closed system with outputs and inputs carefully controlled to mimic a commercial heap leach operation. That is, the inputs and outputs are controlled so that fresh water added is limited to exactly balance water lost by evaporation, loss as moisture in leached residue (or rippos) and replacement of water lost in process solution purge (if required to lower impurities). The process flowsheet of the pilot plant is shown in FIG. 13. The main components and operation of the pilot plant are summarised as follows: Raffinate Tank 1: Storage of return raffinate from solvent extraction (SX) 7. Provides feed to separate 1 m.sup.3 raffinate feed tanks 2A-I to each crib, 3A-I. Make-up acid may be added to the raffinate tank as required to meet the operational acid demand of the process. Pregnant Leach Solution (PLS) 4 & 5: The PLS solution from each crib (3A-I) is collected in 1 m.sup.3 PLS tanks 4A-I. The PLS is transferred from tanks 4A-I to PLS holding tank 5. High Cu PLS 6: The first PLS collected from initial irrigation of the cribs following ore curing has a high copper content. This initial PLS is collected in holding tank 6. Make-up acid may be added to the high copper PLS in tank 6. Purge water from SX may be added to the high copper PLS in tank 6. Ore agglomeration 8: Ore is agglomerated in an agglomeration drum. Raffinate from Tank 1 is added to ore. Acid and solid salt are added to meet target acid addition and total salt addition as required. The high copper PLS 6, may be used in ore agglomeration to allow direct return of copper and acid (contained in the high Cu PLS) to ore agglomeration. A high copper content in agglomerated ore with acid may improve copper dissolution during ore curing in the initial rest step. Agglomerated ore is transferred to load cribs (3A-I) when required. Ore is leached in cribs 3A-I: The agglomerated ore is stacked in the cribs. It is allowed to cure (initial rest period). Irrigation is then commenced. Irrigation starts slowly to ensure wetting of the ore. Irrigation is carried out by pumping the low copper raffinate from the solvent extraction process to the top of the cribs. The liquor is distributed over the crib surface by application through a dripper network. The solution permeates down through the ore within each crib. Simultaneously air is introduced into the base of each crib. Copper is solubilised by the combination of the acid in the process liquor and oxygen in the air. The irrigation liquor reports to the base of the crib. It now has an elevated copper content and is called PLS (pregnant leach solution). This is collected and reports to the solvent extraction process. Following ore leaching the irrigation of the ore with raffinate is stopped. The ore bed is allowed to drain and then the ore is washed with wash water to recover entrained chloride (salt) and dissolved copper. Washed leached ore residue is then removed from the crib to waste. Solvent Extraction (SX) 7: The copper is recovered from the PLS by solvent extraction. The copper is loaded onto the organic in two extraction stages, E1 and E2. The loaded organic is then washed with water in a two stage wash L1 and L2. The wash is required to remove entrained aqueous solution, so that the chloride content of advanced electrolyte after stripping of loaded organic is <50 ppm. Following the wash stage, loaded organic is then stripped in S1 to recover copper to the advance electrolyte 7b. Spent electrolyte for loaded organic stripping is provided from holding tank 7c. If required, make-up acid may be added to the spent electrolyte in holding tank 7c to increase the acid concentration to the amount required for complete stripping of the loaded organic. Advance electrolyte is removed from the circuit for copper recovery and spent electrolyte is returned to the circuit. The wash efficiency of loaded organic may be improved by increasing the number of wash stages to three, as referred to in the preceding description. Increased wash efficiency reduces the wash water volume required for washing loaded organic, allowing increased water for washing of leached ore residue resulting in increased recovery of chloride and copper, by displacement of entrained solution in the ore residue.
The operating parameters for phase I, phase II and phase III are summarised in Table 2.

(82) TABLE-US-00006 TABLE 2 Pilot Plant Operating Parameters for Phase I, Phase II and Phase III Operations Parameter Units Phase I Phase II & III Crib irrigation area m.sup.2 4 4 (per crib) Ore bed height m 5.4 7.5 Ore loaded (per crib) T 36 44 Acid in ore kg/T 12 12 agglomeration Target moisture in ore mass % 8.5 8.6 agglomeration Bulk density ore T/m.sup.3 1.65 1.60 Initial rest or days 45 45 curing period Ore bed temperature ° C. 15-30 15-30 Aeration rate Nm.sup.3/h/m.sup.2 0.13 0.13 & 0.325 Raffinate — 9 h on at 12 h on at application rate 6 L/h/m.sup.2 6 L/h/m.sup.2 on period Leach cycle operation days Irrigation 20 days low 200-500 irrigation (ore wetting) 360 6ays irrigation, 20 days wash cycle. Flowsheet operation — Closed Closed with with SX SX and wash stage Closed circuit raffinate — 5 g/L Cu, 0.5 g/L Cu, solution 15 g/L Fe, 1-3 g/L Fe, 8 g/L H.sub.2SO.sub.4, 8 g/L H.sub.2SO.sub.4, 150 g/L Cl 150 g/L Cl
The simplified mass balance diagram for the pilot heap showing the inputs and outputs is shown in FIG. 14. Typical values for the ore, acid and water balance are shown in Table 3.

(83) TABLE-US-00007 TABLE 3 Pilot Plant Mass Balance Summary Showing Inputs and Outputs for Phase II Operation Phase II Pilot Plant Mass Balance In Out In Out (kg/T) (kg/T) Ore and Copper Total Ore loaded dry (T)-9 cribs 348.6 — Total copper loaded (0.5% CuT) (T) 1.7 5.00 Total copper recovered @ 60% 1.0 3.00 recovery average (T) Total copper lost in residues (T) 0.7 2.00 Total residues un-loaded (T) 348.6 — Acid Balance Agglomeration acid 4183.2 12.0 added @ 12 kg/t (kg) Acid loss in residue moisture @ 18.0 0.05 10.5% moisture (kg) Gross Acid consumption 6274.8 18.00 (by gangue and metals dissolution) (kg) Acid generated by EW (kg) 1708.1 Make-up acid added (kg) 401.4 1.15 Water Balance SX organic wash water (m3) 4.3 Wash water @ 0.1 m3/t (m3) 34.9 Moisture in residues @ 36.6 10.5% average-(m3) Water loss due to evaporation @ 2.8 5.4 L/day (m3) Purged water (m3) Zero

(84) The configuration of the leach area pilot plant flowsheet is shown in FIG. 15. This is an acceptable flowsheet because the ore used in the pilot plant operation was predominantly chalcopyrite and has a low copper head grade. The kay aspect of the flowsheet is that a low acid raffinate is generated through solvent extraction. This low acid raffinate is distributed over all sectors (cribs in this case). The low acid tenor minimises rates of gangue leaching.

(85) If the ore had higher grades and especially if the contained copper were predominantly secondary copper minerals such as covellite, chalcocite or bornite then, a flowsheet that favours increased gangue acid consumption in leach may have been employed as described hereinbefore. Such a flowsheet is shown in FIG. 16.

(86) The option in FIG. 16 could be operated as shown, or with the solvent extraction operating on the liquor from the second 4 cribs as opposed to the 1.sup.st four cribs as shown. The number of stages can be expanded from two to three, or as many as may be deemed necessary.

Example 2: The Acid Balance

(87) The preceding description specifies the need to balance the acid across the process. Acid is required as a reagent in agglomeration to effect copper dissolution during the cure phase. Acid is also required as a reagent during the leach phase for copper dissolution. Acid is generated by electrowinning the dissolved copper into copper metal. This acid is passed back into the process via solvent extraction and it all reports into the process during the leach phase.

(88) In the leach phase of the process, the amount of acid generated by EW needs to be offset by the amount of acid that is still consumed by reaction with gangue and copper sulphide minerals, as well as that left in the moisture after the leached ore is washed.

(89) In an ideal operation the amount of acid required by the leach and that generated by EW match and the leach phase of the operation is acid neutral. In this case the acid consumption and supply are balanced so that an acid balance is achieved. It is also acceptable if some acid is required to be added in the leach phase. What needs to be avoided is the situation where, in the leach phase, there is more acid returned by EW than is consumed by gangue and copper sulphide mineral leaching. This is because this is a closed circuit operation with a final wash stage and so the excess acid will accumulate. The elevated concentration of acid in the process liquors would become detrimental to the solvent extraction process, as this relies on having a low acid tenor in the feed to assist with copper loading onto the organic (proton/copper equilibrium).

(90) In Example 1, Table 3 shows the balance around the cribs for the phase II operation. Firstly, it can be seen that the amount of acid that leaves the leach process in moisture after washing the leached ore is very small (0.05 kg/t.sub.ore) and hence this will be discounted from further discussion. Secondly, it can be seen that on average the leach phase was acid negative. A small amount of acid was added to control pH during the leaching (1.15 kg/t.sub.ore). This is ideal and if this combination of ore were to be fed to a process and treated in this manner, there would no issues from an acid perspective.

(91) Table 4 shows the acid consumption and copper dissolution for each crib.

(92) TABLE-US-00008 TABLE 4 Individual CRIB copper and acid data for phase II CRIB code G5/2 G9/2 G10/2 G3/2 G6/2 G4/2 G1/2 G2/2 G8/2 Acid used in cure (kg/t of ore) 10.19 9.07 12.84 12.62 11.84 11.53 12.25 12.26 11.89 Total acid (kg/t of ore) 20.73 16.41 19.47 20.26 16.38 16.43 21.63 16.09 18.66 Copper leached in cure 11%  6%  7% 15%  8% 16% 18% 3%  9% Copper leached total 60% 55% 55% 75% 61% 65% 69% 56%  61% Copper Head grade 0.62%.sup.  0.66%.sup.  0.79%.sup.  0.45%.sup.  0.37%.sup.  0.37%.sup.  0.59%.sup.  0.36%   0.43%.sup.  Mass acid used in cure (kg/t of ore) 10.19 9.07 12.84 12.62 11.84 11.53 12.25 12.26 11.89 Mass acid used in leach (kg/t of ore) 10.55 7.34 6.63 7.64 4.54 4.90 9.37 3.83 6.77 Mass Cu leached in cure (kg/t of ore) 0.71 0.40 0.58 0.66 0.31 0.58 1.06 0.09 0.39 Mass Cu leached in leach cycle 2.99 3.26 3.74 2.72 1.96 1.82 3.02 1.94 2.22 (kg/t of ore) Acid produced through EW during 5.71 5.64 6.66 5.22 3.50 3.71 6.29 3.14 4.02 leach cycle (kg/t of ore) Is the leach phase acid posistive? No No Yes No No No No No No Percentage of Cu leached in 19% 11% 13% 20% 13% 24% 26% 4% 15% Cure to total leached

(93) The data in Table 4 shows the copper leached as well as acid used in both the cure phase and the leach phase for each crib. It also shows the amount of acid that would be generated and transferred back to the process by EW.

(94) The data shows that in general nearly all cribs were acid negative during leach, the exception being crib G10/2. If a commercial operation were to treat this particular ore, in this manner for an extended time, there would be a build of acid in the circuit. The operation would either need to reduce the acid supplied into the agglomeration phase to bring the circuit to an acid-neutral state, or employ a flowsheet such as that shown in FIG. 16 as opposed to the flowsheet used (FIG. 15) as this would assist to increase gangue acid consumption and bring the process back to acid neutral or acid deficit. The latter would be preferable as it would maintain the copper leach performance of the cure step.

(95) There are two key differences between the G10/2 ore and the other ores. The first is the head grade. This ore has a higher than average copper content and that, combined with a reasonable dissolution, means that EW produces higher than average acid. Secondly, the amount of acid consumed in the leach phase by gangue and copper minerals was only 6.6 kg/t. This is less than amount of acid that is likely to have been required to leach the 3.7 kg/t of copper generated in this period. This suggests that the gangue minerals had a low reactivity with acid and possibly there was a precipitation of acid generating compounds such as jarosite.

(96) This example shows that control may be required to ensure the process does not become acid generating and that an understanding of gangue mineral leach behaviour is key to predicting acid needs. This understanding then needs to be coupled with the appropriate flowsheet configuration for the leach period for optimal value. “Optimal value” is typically the maximum amount copper that can be leached because the value of the copper is significantly higher than the cost of the acid.

Example 3: The Acid Balance—Interaction Between Cure Phase and Final Extent of Copper Dissolution

(97) If extra acid were to be added to the agglomeration stage of phase II and that acid effected a proportional increase in chalcopyrite leaching, it could be estimated at what point the acid balances for the phase II cribs would become acid positive.

(98) TABLE-US-00009 TABLE 5 Individual crib copper and acid data for phase II assuming a 30% increase in acid consumption in the cure phase relating to copper. CRIB code G5/2 G9/2 G10/2 G3/2 G6/2 G4/2 G1/2 G2/2 G8/2 Adjustment acid consumed in cure phase 30% 30% 30% 30% 30% 30% 30% 30% 30% Acid used in cure (kg/t of ore) 13.24 11.79 16.69 16.41 15.40 14.99 15.93 15.94 15.45 Total acid (kg/t of ore) 20.73 16.41 19.47 20.26 16.38 16.43 21.63 16.09 18.66 Copper leached in cure 27% 19% 23% 42% 39% 46% 38% 36% 36% Copper leached total 60% 55% 55% 75% 61% 65% 69% 56% 61% Copper Head grade 0.62%.sup.  0.66%.sup.  0.79%.sup.  0.45%.sup.  0.37%.sup.  0.37%.sup.  0.59%.sup.  0.36%.sup.  0.43%.sup.  Mass acid used in cure (kg/t of ore) 13.24 11.79 16.69 16.41 15.40 14.99 15.93 15.94 15.45 Mass acid used in leach (kg/t of ore) 7.49 4.62 2.78 3.85 0.98 1.44 5.70 0.15 3.21 Mass Cu leached in cure (kg/t of ore) 1.70 1.28 1.82 1.89 1.46 1.70 2.25 1.28 1.55 Mass Cu leached in leach cycle 2.00 2.38 2.49 1.49 0.81 0.70 1.83 0.75 1.06 (kg/t of ore) Acid produced through EW 5.71 5.64 6.66 5.22 3.50 3.71 6.29 3.14 4.02 during leach cycle (kg/t of ore) Is the leach phase acid posistive? No Yes Yes Yes Yes Yes Yes Yes Yes Percentage of Cu leached in Cure 46% 35% 42% 56% 64% 71% 55% 63% 59% to total leached

(99) Table 5 shows that if the acid consumed in the cure phase were to be increased by 30%, the net result would be that 8 of the 9 cribs would become acid positive in the leach phase. This would require a change in flowsheet to a multistage approach. It is possible that, in addition to the change in flowsheet configuration some reduction of the amount of acid added in the cure phase would be necessary to prevent that occurrence and to limit the copper dissolution.

(100) These ores have a reasonably high proportion of chalcopyrite. It is known that chalcopyrite leaches at a slower rate than the other copper sulphide minerals, such as chalcocite and covellite. It is reasonable to assume that it is predominantly chalcopyrite that is leached at the end of the leach phase. Leaching chalcopyrite requires 4 protons (H.sup.+) for every Cu.sup.2+ that is liberated into solution. However, in EW only 2 protons (H.sup.+) are generated for every Cu.sup.2+ that is plated out as copper metal (Cu). This means that if the final extent of copper leaching that occurs in the leach phase increased for these ores, there would be a point where the process returned to being acid negative in leach, despite a higher copper dissolution having been achieved in the cure phase, with a low gangue acid consuming ore and the leach operating according to the flowsheet shown in FIG. 15.

(101) Table 6 shows some column leach results for these same ores. These columns performed better than the cribs partly because of operating conditions and partly because columns get better solution distribution. The details of the reasons for the performance change is not relevant to this discussion. What is relevant though is that these columns show that despite getting much higher copper dissolution in the cure phase, all would have been acid negative in their leach phase, including the ore used in crib G10/2 (see column MK104), the reason is because of the additional leaching achieved in the leach phase and consequent acid demand as discussed in the previous paragraph.

(102) TABLE-US-00010 TABLE 6 Individual column leach copper and acid data for column leaching of the same ores used in the phase II crib program Column Code MK117 MK102 MK104 MK115 MK113 MK114 MK104 MK119 MK120 Acid used in cure (kg/t of ore) 10.3 10.6 14.5 13.1 8.4 11.6 14.5 12.5 12.5 Total acid (kg/t of ore) 26.2 23.8 25.9 24.9 18.7 20.9 25.9 26.7 18.9 Copper leached in cure 21% 26% 27% 29% 10% 12% 27% 36% 27% Copper leached total 77% 76% 68% 79% 51% 46% 68% 85% 74% Copper Head grade 0.62%.sup.  0.66%.sup.  0.79%.sup.  0.45%.sup.  0.68%.sup.  0.81%.sup.  0.37%.sup.  0.59%.sup.  0.36%.sup.  Mass acid used in cure (kg/t of ore) 10.34 10.64 14.52 13.08 8.41 11.64 14.52 12.53 12.50 Mass acid used in leach (kg/t of ore) 15.85 13.18 11.40 11.87 10.27 9.23 11.40 14.22 6.36 Mass Cu leached in cure (kg/t of ore) 1.29 1.74 2.11 1.31 0.69 0.94 0.99 2.11 0.98 Mass Cu leached in leach cycle 3.49 3.26 3.30 2.22 2.79 2.82 1.55 2.93 1.67 (kg/t of ore) Acid produced through EW 7.37 7.72 8.35 5.46 5.38 5.79 3.91 7.78 4.09 during leach cycle (kg/t of ore) Is the leach phase acid posistive? No No No No No No No No No Percentage of Cu leached in Cure 27% 35% 39% 37% 20% 25% 39% 42% 37% to total leached

Example 4: Extrapolation of Phase II CRIB data

(103) It is possible to extrapolate the phase II crib data to get an indication of what the ideal split would be between cure and leach phase copper dissolution for theses ores at a maximum performance. A maximum target for copper dissolution from these ore type would be ˜85%. If that were to occur and the gangue acid requirements remained the same, it would be possible to estimate the maximum percentage of the total copper that could be leached in the cure phase but still allow the process to remain acid neutral in the leach phase. This is depicted in FIG. 17 which shows that there is a strong trend regarding proportion of cure phase copper dissolution to the ore copper head grade. At low head grades all the copper can be leached in the cure phase and the leach phase would still remain acid neutral. This makes sense as the amount of acid generated by the EW is directly proportional to mass of copper leached. Thus, at low head grades only a small amount of acid is generated by EW and this acid is consumed by residual acid soluble gangue minerals in the leach phase. When the grade increases there is insufficient gangue acid demand to offset the acid from EW and hence an increasing amount of chalcopyrite needs to be leached in the leach phase.

(104) Although a trend line has been fitted to the data, the data is scattered because the gangue mineral composition of the ore varies between the samples, and hence so does the point at which the acid balance converges. This is important as it underlines that the knowledge and understanding of the leach behaviour of the gangue minerals are critical to optimising the process.

(105) This plot would look different if the majority of the copper minerals were bornite, chalcocite or covellite. For these minerals the number of protons (H.sup.+) required for leaching is 2.4, 2 and 2 respectively. Thus, there is little or no differential between the protons required to leach the copper and the protons that are generated in EW. Hence the process would be more reliant on continued gangue acid demand during the leach phase to prevent it becoming acid positive. Alternatively, cure phase copper leaching would need to be lower.

(106) The trend line of this plot would shift upward if a multistage leach process were to be employed.

Example 5: Estimation of Gangue Acid Consumption

(107) The results in FIG. 18 show the total acid consumption from operation of cribs G5 (B) and G7 (A) in the phase III pilot plant operation, treating two different ore types. The mineralogy of the two ore types loaded in the cribs are noted in Table 7. The results show the higher biotite and chlorite content of the ore type C (crib G5 phase III) compared to ore type D (crib G7 phase III). Biotite and chlorite have been found to be the main contributors to GAC, typically leaching at a faster rate compared to other silicate minerals.

(108) TABLE-US-00011 TABLE 7 Mineralogy of Ore Types C and D Highlighting Gangue Mineral Content Ore Type C Low Acid Ore Type D Very Low Mineral Consumption Acid Consumption Chalcocite 0.13 0.08 Covellite 0.08 0.06 Chalcopyrite 1.07 1.15 Bornite 0.00 0.00 Other Cu Mins 0.13 0.11 Pyrite 6.25 2.93 Other Sulphides 0.05 0.05 Fe Oxides 0.53 0.15 Quartz 26.56 22.16 Feldspars 24.29 28.29 Muscovite/Sericite 18.51 19.85 Kaolinite/Clays 10.36 23.38 Biotite 8.26 0.03 Chlorite 2.07 0.08 Jarosite 0.21 0.00 Other Sulphates 0.47 0.62 Others 1.01 1.09 Total 100 100

(109) The total acid consumption includes acid for copper mineral leaching, and acid for gangue mineral leaching (GAC). The acid demand for copper mineral leaching is shown in FIG. 19, along with the mass of copper leached. The copper extraction achieved over the same period is shown in FIG. 20, for reference.

(110) The gangue acid consumption (GAC), for a specific ore type and copper grade, may be estimated in the process of the invention by subtracting the acid demand for copper extraction from the total acid consumption. This result gives the net acid consumption (NAC) which in the case of the process of the invention is similar to the true GAC demand. The calculated gangue acid consumption for cribs G5 and G7 phase III is shown in FIG. 21.

(111) In the stripping stage S1 of the SX pilot plant (shown in FIG. 13) copper is stripped from the loaded organic using spent electrolyte with a high acid content. The copper reports to the aqueous advance electrolyte solution which is circulated to copper recovery by electrowinning. The copper in the organic phase is replaced by acid and the resulting stripped organic, with a high acid content, is re-circulated to the copper extraction stage E1, where copper is extracted from the PLS, as shown in FIG. 13. Therefore, the SX process returns acid to the raffinate solution following copper extraction from the PLS. The acid in the raffinate is utilised to leach more copper minerals and to meet the GAC demand during the leach cycle.

(112) The initial acid addition in ore agglomeration to crib G7 phase III (ore type D with a very low GAC) was 11.3 kg/T. In the case of crib G5 phase III (ore type C low GAC) the acid addition in ore agglomeration was 10.6 kg/T. In the case of crib G7 phase III, the initial acid concentration in solution was higher than crib G5 Phase III, due to the lower GAC rate of ore type D in the cure step. The higher initial acid concentration on irrigation of the ore in crib G7 phase III increased the acid consumption rate. However, once silicate gangue minerals became depleted the rate of acid consumption decreased. In the case of crib G5 phase III, the initial acid concentration was relatively low, and the initial rate of consumption was lower than crib G7 phase III, despite the higher GAC of ore type C in crib G5 Phase III. However, on irrigation with acid raffinate the GAC rate was clearly higher in the case of crib 5 phase III, such that towards the end of the leach at day 250, the GAC for crib G7 was 11.8 kg/T compared to crib G5 phase III at 12.9 kg/T. These trends are reflected in the corresponding PLS acid concentration profiles of both cribs shown in FIG. 22, and the corresponding PLS pH profiles in FIG. 23.

(113) The initial acid concentration in solution on irrigation is dependent on the acid addition in ore agglomeration and the GAC demand of the ore. Too low an addition will limit initial free acid available for copper mineral leaching. Too high an addition will result in excess acid in the PLS in the leach stage which will adversely affect copper extraction by solvent extraction. The variation in acid consumption and solution acid concentrations presented in FIGS. 21 and 22, are within acceptable operating parameters for the process of the invention. The results demonstrate how a small difference in the ore GAC and acid addition influence acid concentrations in the PLS and show the importance of understanding the GAC of the ore types leached and the acid required for copper mineral leaching.

Example 6: The Effect of Chloride Concentration on the PLS Solution pH at Different Acid Concentrations

(114) The effect of the chloride concentration on the solution pH as a function of acidity is shown in the results presented in FIG. 24. The results show that at a low chloride concentration (<5 g/L chloride) the free acid concentration is 4 g/L at a solution pH 1.5. The corresponding pH at a high chloride concentration (150 g/L) is about pH 0.8. The efficiency of solvent extraction is dependent on the PLS pH. An ideal PLS pH is about pH1.5 to achieve maximum copper extraction efficiency in the SX step. The copper extraction efficiency is impaired below a PLS pH1. Therefore, it is clear in a high chloride PLS the free acidity should be as low as possible, below 10 g/L acid, or preferably below 7 g/L, more preferably below 2 g/L and ideally at 1 g/L.

Example 7: The Effect of Acid Addition in Ore Agglomeration on Copper Recovery in a Cure Step

(115) A series of 1 m column tests show that, for example, with a specific ore type, where copper mineral dissolution in the cure step is high and limited by acid addition, that increasing the acid addition to ore agglomeration benefits the copper recovery. The results are shown in FIG. 25, where a fixed salt addition of 10 kg/T of ore was used and the sulfuric acid addition was varied from 10 kg/T to 21 kg/T of ore. The cure step following ore agglomeration was for a period of 50 days. The initial copper dissolution representing the copper leached in the cure step increased from about 30% to 80% with increased acid addition. The overall copper recovery increased from 78% to 98% in a 70 day total leach period, with a 20 day period of irrigation with raffinate solution.

Example 8: Example of Copper Dissolution Curves for Different Ore Types

(116) The copper dissolution by the method of high chloride (150 g/L chloride) heap leaching described herein is shown for different ore types in the results presented in FIG. 26. The results are for 6 m column tests using the method of high chloride (150 g/L) leaching described in the summary of invention. The acid addition to the ore in ore agglomeration, the overall acid consumption and NAC (total acid consumption less acid used to leach copper—this acid is returned from SX to the raffinate following copper extraction) is shown in Table 8. The results illustrate the high copper recovery that may be attained by the method of invention in the cure step when acid addition is not limiting. The results also show the significance of the copper recovery in the cure step compared to the overall copper recovery attained. The results apply to low grade high chalcopyrite ores (0.3% to 0.6% Cu) with a copper source ratio (CSR) as chalcopyrite in the range 40-75%.

(117) TABLE-US-00012 TABLE 8 Acid Addition, Acid Consumption and Copper Recovery for Various Ores in 6 m Column Tests Acid Net Acid Addition Overall Con- Copper Overall in Ore acid Con- sumption Recovery Copper Agglomer- sumption (NAC) in Cure Recovery Test ation (kg/T) (kg/T) (kg/T) Step (%) (%) A 11.3 23.0 16.2 50 85 B 10.9 22.5 16.8 45 67 C 10.3 14.4 11.9 40 62 D 10.6 22.0 17.5 25 53

Example 9: Moisture in Agglomeration—Effect on Cure Performance

(118) The preceding examples discuss optimisation of the amount of acid added to the cure phase and the relevance thereof to the optimisation of the flowsheet. It is important to note that it has been determined that the method of how this acid is added affects the performance of the cure as well.

(119) Process liquors are recycled to ore agglomeration to provide that moisture. This liquid volume in the ore bed represents the reactor solution volume where the generation of oxidant for mineral leaching occurs. The amount of oxidant produced per unit time is function of that volume of liquor. This oxidant is responsible for the oxidation of the copper sulfide minerals which leads to the solubilisation of the copper. If the amount of available liquid is restricted, then it is possible that insufficient oxidant will be produced, and this will limit the extent of mineral leaching. The effect is analogous to limiting acid addition to the ore such that insufficient acid is available to meet the requirement for metals dissolution considering the acid demand for both ore and gangue minerals. However, if too much process liquor is recycled to agglomeration, it can negatively impact on the agglomerate strength and thus the permeability of the heap to both gas and liquid flow. FIG. 27 shows the difference in leach performance for a column that has been supplied limited moisture (B) during agglomeration compared to a column that was supplied an ideal amount of moisture (A) during agglomeration. From the trends it is evident how insufficient moisture limits the copper dissolution.

(120) The importance of this example is that although it shows that the cure phase copper leach can be altered by reducing acid or moisture (as in this case), the leach phase is not as efficient at leaching copper and so it does not “catch up”. This is why, for the optimisation of the process, the modification of the flowsheet to counteract excessive acid in the leach is an optimal solution to ensure maximum copper recovery. Limitation of the cure phase should only be considered as an option of last resort.