M#wrals Engineer#tg, Vol. 9, No. 10, pp. 1033-1047.

1996

Pergamon
PI h S0892--6875(96)00096-9

Copyright 1996 Published by Elsevier Science Ltd Printed ill Great Britain. All rights reserved 0892-6875/96 $15.00+0.00

A C O M P A R I S O N OF ALKALI AND ACID M E T H O D S F O R THE E X T R A C T I O N OF GOLD F R O M L O W G R A D E ORES

S. VUKCEVIC A J Parker Cooperative Research Centre for Hydrometallurgy, Murdoch University, Murdoch WA 6150, Australia (Received 1 February 1996; accepted 12 July 1996)

ABSTRACT
Alternative alkali and acid methods for gold extraction from low grade copper-gold ores/tailings were studied. Several ores/tailings which originate from South and Western Australia were treated by cyanide, ammonia-cyanide, bromine and sulphuric acid, to achieve optimal reactant concentration for the selection of gold over copper. The validity of these systems was compared according to the gold leaching kinetics and other relevant criteria. It was found that different solubility of copper minerals and characteristics of predominant gangue minerals presented in the ores/tailings have a significant effect on both the concentration of copper in the solution and the consumption of the reactants. Selective copper precipitation occurs from ammonia-cyanide leach solutions, which explains the apparent selectivity of this system for gold.Leaching an ore consisting of 1.5% Cu as CuFeS2, Cu2S and Cu5FeS4 with 0.55 kg/t NaCN and 3 kg/t NH3allowed 89% gold extraction with only 200 ppm of copper remaining in solution. The same concentration of cyanide and a lower concentration of ammonia (2.2 kg/t NH3) were found to be optimum for achieving 85 % extraction of gold from tailings consisting of 1.15%Cu as Cu2S, Cu20 and CuS. The ammonia addition in the cyanide system leads to the production of Cu(II)NH 3 species during the oxidising of gold metal to Au(CN)2-. Copper precipitates mostly as Cu(OH)2, CuO, Cu20 and CuCN. Gold is leached as Au(CN) 2- by chemical reactions involving Cu(1) cyanides present in the system. Copper tailing containing 700-800 ppm Cu as CuFeS2 and CuS, was leached with sulphuric acid as a pre-treatment step. This step was found to be beneficial as only 30 ppm Cu remained in solution after ammonia-cyanide leaching. Leaching of the tailing in an acid bromine solution showed much faster kinetics of gold extraction with no worse copper selection compared to the alkali systems. Copyright 1996 Published by Elsevier Science Ltd

Keywords
Gold ores; tailings; leaching; process optimisation; cyanidation

INTRODUCTION
Cyanidation has been the standard process for gold recovery since cyanide was firstly applied as an optimal lixiviant for gold, nearly a century ago. However, there are a number of ores which contain cyanideconsuming constituents other than gold. Most important are the different sulphide minerals of iron, copper, arsenic and antimony. In spite of the work that has been done in the area of valorisation of these ores,

1033

1034

S. Vukcevic

particularly in attempts to reduce the reactivity of certain copper minerals in cyanide solution, little success has been achieved. The only method of ensuring consistently good gold recovery in these situations was to employ high cyanide concentration and to tolerate high cyanide consumption. The alternative process of selective gold leaching from copper-gold ores, using the ammonia-cyanide system, offers low cyanide consumption. This process was first patented in 1901 [1]. Since then, a literature review of the application of ammonia-cyanide for gold leaching reveals two widely separated periods of activity, the first before the 50's [2-4] and the second in the last ten years [5-13]. While the chemistry of the ammonia-cyanide system has been better understood in more recent times [13] the literature shows there is still some disagreement about gold dissolution [14]. Moreover, there is a lack of systematic research into different ore processing methods using the ammonia cyanide leach system. Slightly different kinetics and mechanism of gold leaching are caused by specific geo-physical and geochemical characteristics of natural minerals which follow gold. They are also caused by the tailings characteristics influenced by the type of mineral dressing employed for copper concentration of copper-gold ores. The adsorption characteristics of the gangue minerals in the applied gold ore also affect the kinetics and mechanism of gold leaching. There are only two operating plants using the ammonia cyanide leach system. One is a successful small scale tailing treatment plant on the Paris Dump near Kalgoorlie, Australia, which started in 1986 [15] and the other is the first major commercial operation at Ajkjoujt in Mauritania [16], which is now undergoing technological improvement [ 17]. Another process is the acid process in gold metallurgy, using bromine gold extraction. The results of research into this process (reviewed during the last ten years [18-21]) show much faster kinetics of gold leaching than in classical cyanidation. Gold recoveries from Br pregnant solutions using different separation methods (carbon adsorption, ion exchange, solvent extraction) can be 99.99 % [ 19]. One more advantage of this alternative process lies in the fact that the toxicity of cyanide is now raising some environmental concerns and thus alternative lixiviants for gold are of increasing interest. The present work studies both alkali and alternative acid methods for gold extraction from low grade copper-gold ores. The applicability of the ammonia cyanide system on low grade copper-gold ores is researched on several ores/tailings which originate from South and Western Australia. The possibility of bromine gold extraction in low copper soluble copper-gold ore has been investigated and compared to alkali leaching. In addition, sulphuric acid leaching as a pre-treatment step due to copper selection was studied. This is of special interest for the employment of classical cyanidation as the next step in CIP and/or RIP processes. MATERIALS AND METHODS Raw materiaL, Raw material 1 (RM 1). A copper-gold tailing which is deposited into dams and originates from copper flotation of several ores. Its chemical composition was (% weight): 50 % Fe, 4.3 % Si, 3.1% S and 1.5 ppm Au and 700-800 ppm Cu. Mineralogically the tailing consisted predominantly of magnetite (70-80%), silicates (10%), sulphides, haematite, goethite and siderite (10%). Copper is present predominantly as a chalcopyrite (CuFeS2) and to a much lesser extent as a covellite (CuS). Much of the gold occurred as inclusions of native gold in chalcopyrite. Raw material 2 (RM 2). A copper-gold ore. The chemical composition was 5 to 10 ppm Au and 1.5% Cu. Mineralogically the sample consists mainly of quartz with smaller amounts of kaolinite, haematite and goethite. The copper minerals appeared as chalcopyrite (CuFeS2), chalcocite (Cu2S) and bornite (CusFeS4). The gold distribution consisted of native gold, mostly liberated.

Extraction of gold from low grade ores

1035

Raw material 3 (RM 3). A copper-gold tailing from the flotation concentration of copper ore. Its chemical composition was 1.15 % Cu and 4 to5 ppm Au. Mineralogically the sample consisted mainly of quartz and kaolinite with smaller amounts of ferruginous oxides and pyrites. The copper minerals appeared as chalcocite (Cu2S), cuprite (Cu20) and to a much lesser extent as covellite (CuS) and malachite (CuCO3xCu(OH)2).
The particle size of raw materials was 90 % less than 74/~m.

EXPERIMENTS
The slurry, 50% w/v, was treated in both systems using bottle rolling and agitation tanks (300 rpm), under ambient temperature. In the case of gold leaching by cyanide, aeration occurred through the use of a perforated lid. pH, Eh and the solution composition were controlled during all the processes. The processes which were researched are as follows: gold and copper cyanide extraction, selective gold and copper ammonia-cyanide extraction, copper leaching by sulphuric acid and gold and copper extraction in bromine solution. The alkali processes started at pH 11 with spontaneous decrease to about 10 (or less when processes in agitation tanks were run) due to various reactions such as cyanide oxidation or carbon dioxide adsorption from the atmosphere. The acid processes were run under pH 1.5 to 2.5. RM I- water slurry has natural acidity of pH =2.4, while RM 2 has pH 7.5 and RM 3 has pH 5.4.

Chemical analysis of the components of the slurry Solution analysis. Gold from the leached solution was determined by Atomic Absorption Spectrometry using organic selective extraction in DIBK solution. The change of copper concentration was determined by the measurement of total copper by Atomic Absorption Spectrometry.
Residue analysis. Gold analysis was carried out by treatment of the residue after leaching, using digestion in aqua regia. This was done parallel to the solution analysis. These parallel analyses were especially important in the ore samples in which a coarse grade effect was emphasised, as in RM 2.

The calculation and presentation of gold and copper recovery. The results of gold extraction are presented in both forms directly as concentration in leaching solution (in ppm units) and/or in % of gold extraction. The last form presents the efficiency of the leaching process, calcualted using both solution and residue gold analyses to achieve the highest possible accuracy.
The analysis of copper extraction is based on copper concentration in the leaching solution. This concentration shows directly the applicability of the solution for selective gold recovery. RESULTS AND DISCUSSION This work is aimed at presenting and discussing gold extraction from three raw materials as well as copper removal from leach solutions. Alkali and acid leaching processes are employed. The optimisation of the processes and a comparison of them according to validity criteria are studied.

Cyanide leaching
A fundamental study on heterogenous equilibrium, kinetics and mechanism of gold leaching in the Au-Cu-NaCN-H20 system was undertaken recently using the HSC(enthalpy-entropy-heat capacity)

1036

s. Vukcevic

chemistry computer program produced by Outokumpu Oy Research. This study explains the production of gold-cyanide by the reaction of gold with free cyanide: 2Au + 4 C N - + 1/202 + H20 = 2Au(CN)2+ 2OH5 G = - 4 6 . 8 6 kcal/mol (1)

Copper in cyanide solution produces Cu(I) cyanides with the stabilities as follows: Species AG, kcal/mol CuCN 25.88 Cu(CN)2 83.11 Cu(CN)32 129.90 Cu(CN)43 180.71

These cyanides are responsible for the gold leaching in the absence of tree cyanide in the solution, under conditions similar to industry using 0.01 to 0.03 mol NaCN, as the following reactions show: Au+2Cu(CN)43- + 1/402 + 1/2H20 = Au(CN) 2- +2Cu(CN)32- + O H 2Au + 4Cu(CN)32- + 1/202 + H20 = 2Au(CN) 2AG = - 4 2 . 6 8 kcal/mol (2) AG=-69.32kcal/mol

+ 4Cu(CN) 2- + 2 O H -

(3)
Au + Cu(CN) 2 - +1/402 + 1/2H20 = Au(CN) 2- + Cu + + O H A G = - 4 8 . 8 9 kcal/mol(4)

Figure 1 presents the log(mol)-mol stability diagram. The concentration of products at (theoretical) equilibrium states, expressed in mol, is calculated using the amount of raw materials in the system. After achieving a state of equilibrium, copper starts to precipitate from the solution, as this experimental work showed, according to the following reactions: Cu(CN) 2 - + 1/402 + O H - = CuO + 2 C N - + 1/2H20 2Cu(CN) 2- + 2 O H - = Cu20 + 4 C N - + H20 Cu(CN) 2- + 1/2 02 = CuCN + O C N Log(ntol)
-2.7

A G = - 2 2 . 1 2 kcal/mol

(5) (6) (7)

AG=-18.29kcal/mol

A G = - 8 0 . 5 2 kcal/mol

f~ -7.7

Otq-a)

CuCN

Au(CN) 2(-a)

-12.7 -17.7 -22.7 -27.7 -32.7

_Z
y-.
6.0E-03 1.1E-02

_.c

~,(CN)3(-2a)

I
[
1.6E-02 2.1E-02 2.6E-02

cN(-.)
3.1E-02 tool

1.0E-03

Fig. 1 Log(mol)-mol diagram for the Au-Cu-NaCN-H20 at 25C; [Au] =5x10 -5 mol; [Cu] =2x10-1 tool; [NaCN] = 10 -3 tool; [0 2] = 10 -3 tool

Extraction of gold from low grade ores

1037

The experimental optimisation of the NaCN concentration was aimed at achieving gold extraction at a level more than 60%. This led to very high Cu concentration in the solution of 1000 ppm Cu and low Cu precipitation,when an initial 1.5% Cu was present in the system [22]. Thermodynamically, when Cu-minerals are cyanised, Cu(CN)2- is produced with more negative AG value than Au(CN) 2-. Also, copper concentration in the system is much higher than gold and kinetics of copper cyanidation is faster. It is understood that concentration of Cu in solution plays a significant role in g o l d extraction. This concentration depends on the type of Cu mineral used and its solubility. When 1.5 % of the initial Cu in the form of different minerals was diluted together with 10 ppm of Au powder, the highest concentration in solution was produced when Cu20 and Cu2S minerals were treated. The solubility of Cu from CuO and especially CuFeS 2 is much lower (Table 1). Consequently, the lowest gold extraction occurred when Cu20 was leached.

TABLE 1 Solubility of copper from different minerals, leached with 1.6 g/! NaCN in presence of gold
Cu

mineral CuFeS2

"C~O"
Cu2S

Cu, ppm , Au, % after 4 hours 237 ' 40 65T - - 4 30 812 ~ 10

iOn]--+---TO' I

' Cu, ppm , Au, % after 24 hours 425 ' 100 757 I-- 70 8"1-5 - - 4 27 8-6-2 - - 4 25
I

The preliminary tests of leaching of ores in cyanide solutions for 24 hours showed low solubility of copper (25%) from RM 1, but high solubility (73%) from RM 2 and 80% from RM 3, under highly concentrated NaCN solution (Table 2). The reason for this is that RM 1 consists mostly of CuFeS 2 with low Cu concentration and the RM 2 and RM 3 have high Cu concentration with more soluble minerals appearing (Cu2S, Cu20, CuS). High gold leaching is explained by the presence of high free cyanide in the system, according to reaction (1).

TABLE 2 Copper and gold leaching from ores using cyanide solutions
NaCN, kg/t 50 30 10 RM 1 Au, % RM 2 Cu, % ' Au, % 73 ~ 99 RM 3 Au, %

Cu, %

'

Cu, %

'

]3---+--Tff6
t
25 73 70 ]3 - ' - q 25 4

4
4---. 80

~5 - - - +

4-

4 4

80

1.65

T ---qI

17

The same copper solubility from RM 1 was found by leaching with other reactants, such as weaker cyanide solutions (Table 2), sulphuric acid and bromine solutions. Most of the dissolved copper comes from minerals in the ore other than chalcopyrite. A decrease of NaCN concentration resulted in a decrease of Cu and Au. Below 1.65 kg/t NaCN, only 17 % Au and 4 % (650 ppm) of Cu were extracted from RM 2. When metallic Cu was leached under the same conditions, 500 ppm of Cu in solution and less than 20 % of Au were found. This indicates that high copper concentration achieved by leaching RM 2 and RM 3, and consequently low level of gold extraction, cause high cyanide consumption. To analyse selective gold leaching at lower reactant consumption, alternative leaching methods are considered in the following section.

1038

S. Vukcevic

Sulphuric acid leaching with cyanide post-treatment RM 1 was treated with sulphuric acid solution concentrations from 2.5 to 10% H2SO 4. The concentration of copper found in the solution can be seen in Table 3. In the next process--cyanidation, only 15-30 ppm Cu was leached. After acid pre-treatment, gold was leached with several units less extraction (68%), than when the acid treatment was not employed. Therefore, higher cyanide consumption for gold leaching of acid pre-treated material can be offset with very good selectivity of gold over copper as a final result. TABLE 3 Effect of pre-treatment of RM1 with H2SO 4 on leaching of copper with 1.65g/I NaCN Cu in solution, ppm, 5% ' 10% 2.50% ' 140 I 160 I 170 4. 4. 165 178 4. 4 4 4. 4.
I

hrs 0.16 0.66 0.5 1.16 4.8 5.42 5.66

Cu without 161 182

168 4. 190 4 4 4
I

173 197 180

in solution, ppm, ' 2.5% ' 5% I 24 I 28 4. 4. 4. 44. 4 4. 4. 32 29 44. 4. 4 27 30

C y a n i d e - a m m o n i a leaching Kinetics and mechanism. The study of the kinetics and mechanism of selective gold leaching in the cyanide ammonia system shows different models for gold selection over copper [13]. Research has shown that ammonia appears to catalyse the anodic dissolution of gold with cyanide [ 13] and other electrochemical research has shown that ammonia greatly suppresses the anodic half reaction [14]. These, and other results [8,9,13,14], are based on the thermodynamic consideration of only ten species, and some are obtained using concentrations of reactants not appropriate to application in industry. A recent study [22] was aimed at considering the kinetics and mechanism of selective gold leaching under conditions appropriate to industrial application. This study is also based on the thermodynamic analysis of 120 different species, which were chosen from a data base consisting of 5600 species,using the HSC chemistry computer program made by Outokumpu Research Oy. The Eh-pH diagrams of the stability of Au and Cu species are shown in Figures 2 and 3. The area of the highest stability of Au(CN) 2 - exists up to pH =6.5, and at lower Eh areas compared to the system without ammonia [22]. The most important role of ammonia is the production of Cu-NH 3 species. The priority of the existence of relevant species in the A u - C u - C N - N H 3 - H 2 0 system and the effect of CN and NH 4 concentration were analysed by the method explained above and it was tbund that after CuCN and Au(CN) 2 - the most thermodynamically probable species in this system are Cu-NH 3 species. The C u - N H 3 ions are produced by the addition of ammonia during the oxidation of gold metal to Au(CN)2- by chemical reaction including Cu(I)cyanide from the system: A u + C u ( C N ) 2 - + 4 N H 3 + 1 / 2 0 2 + H 2 0 = Au(CN)2- +Cu(NH3)42+ + 2 O H AG= - 3 4 . 6 7 kcal/mol (8)

They are also included in Cu precipitation by decomposition of Cu(NH3)42+ according to the reaction: Cu(NH3)42+ + 2 O H - = Cu(OH) 2 + 4NH 3 A G = --9.34 kcal/mol (9)

This study confirms, therefore, the positive role of ammonia in the cyanide system, as it helps both copper precipitation and gold leaching. Process optimisation was undertaken here to find the best reactant

Extraction of gold from low grade ores

1039

composition for the selection of gold over copper by the leaching of natural ores RM1 to RM3. Although this system is much more complicated, with the involvement of many other elements, the basic model developed in [22] is relevant. / Eh (Volts) 2.0

1.0
o.s 0.0

----~

............ ~
~ ......

_
" - "

~
.........

~,,~

r,)

NaO2 .......... -0.5 Na(+a) Nail

An

"~ ~ AuCl2(-a)

------.-'-~Au(CN)2(-a)"'~ ~ ~

---.--

-1.0 -1.5
-2.0 I I I f i f f i i I I ~ I

I0

12

14

pH Fig.2 Au species in Eh-pH diagram for the Au-Cu-NaCN-NH4CI-H20 system at 25C; [Au] =5x10 -5 mol; [Cu] =2.4x10-1 mol; [NaCN] = 10 -2 tool; [NH4C1 ] =4x10 -2 mol Ell (Volts) 0.3 I " --~

Cu2(OH)2CO3

02 I ~ "-~:........ .
o,
-

I
.

c,,(+2a)
. . . . .

0.1

~u(NH3)Z(+2a) [" % .

"-"~

co(+.)

-0.1

""-

-o.2
Cn(+a) -0.3
Na(+a)

\
\ ~__

~
__

~
__ __
Cu

-0.4 6

10

11

12

13 pH

Fig.3 Cu species in Eh-pH diagram for the Au-Cu-NaCN-NH4C1-H20 system at 25C; [Au] =5x10-Smol; [Cu] =2.4x10 -1 mol; [NaCN] =3.4xl0-2mol;[NH4C1 ] =4x10-2mol;[O2] = 10-2 tool

1040

S. Vukcevic

Optimisation. When RM 2 was leached with 1.65 kg/t NaCN, 17% of gold was extracted. The addition of 1.1 kg/t of NH 3 in this system increases gold leaching from 17 to 60% and decreases copper concentration in leach solution from 650 to 430 ppm due to precipitation. However, the addition of 0.79 to 1.1 kg/t of NH 3 in the same cyanide system for RM 1, increased gold extraction by only 10-20%. This was followed by a 17% decrease in copper concentration in the solution, from 180 to 150 ppm. To confirm the difference which ammonia causes in the cyanidation of these two materials, a systematic optimisation of both systems was developed. The results show that the influence of the cyanide concentration is superior, compared to the ammonia for RM 1 (Figure 4 and Figure 5, both obtained under eight different leaching conditions), while RM 2 leaching is characterised by a more significant influence of NH 3 (Figures 6 and 7, both obtained using eighteen different leaching conditions).

go.Ol 8 .oI so.ol

Fig.4 Effect of ammonia and cyanide on gold leaching from RM 1, after 24 hours

*~Io.o 1Oo,1~ ~ ~?o.(~ 1,~O.oo

Fig.5 Effect of ammonia and cyanide on copper leaching from RM 1, after 24 hours

Extraction of gold from low grade ores

1041

Fig.6 Effect of ammonia and cyanide on gold leaching from RM 2, after 24 hours

;"

Z_.///6

;'///~

S0().~

IIII

Fig.7 Effect of ammonia and cyanide on copper leaching from RM 2, after 24 hours The presence of 3 kg/t NH 3 allows 89% Au extraction from RM 2 ore, under only 0.55 kg/t NaCN ( Figure 6). The concentration of copper in solution under the same conditions is 200 ppm, which is a quarter of the copper found by leaching in 2 kg/t NaCN solution without ammonia (Figure 7). Although ammonia in this system has a significant role in enhancing gold leaching according to reaction (8) it also strengthens the precipitation of Cu(OH) 2 (reaction (9)).

1042

s. Vukcevic

Using the same amount of cyanide, 0.55 kg/t and 2.2 kg/t NH 3, the gold from RM 1 is leached with an extraction of not more than 73 %. Although this low cyanide concentration was desirable for low Cu concentration (111 ppm), gold could not be leached due to the high adsorption of gangue minerals and its low initial concentration (1.5 ppm). Also, the concentration of 2.2 kg/t of ammonia was not enough to drive reaction (8) to the right. Gold can be successfully leached (85-90%) only with a high level of cyanide concentration (1.65kg/t) from this ore. In this case, a low level of ammonia concentration is desirable ( < 1.1 kg/t). A higher level of ammonia dissolves Cu-compounds already precipitated and therefore increases the Cu concentration in solution (Figures 4 and 5). Copper removal. An analysis of the copper removed from the leaching solution in the ammonia cyanide system shows that ammonia has significant influence on it. Similarity in the shape of both diagrams, Figure 7 (the effect of ammonia and cyanide on copper leaching from RM 2, after 24 hours) and Figure 8 (the effect of ammonia and cyanide on copper leaching from RM 2, after 10 minutes, both obtained using eighteen different leaching conditions), is found. The parts of these two diagrams related to the area of low cyanide concentrations (0.55 kg/t NaCN), are nearly identical (about 200 ppm Cu present in the solution). However, it required 24 hours to achieve significant copper precipitation in the area of high concentration of leaching reactants (the "nearer right" area of the diagrams--Figure 7).

Fig.8 Effect of ammonia and cyanide on copper leaching from RM 2, after 10 minutes To rationalise these findings the influence of ammonia at the highest level of cyanide (2 kg/t), was investigated (Figure 9). Without ammonia, a high copper concentration was found in solution after 10 minutes. It is much higher after 24 hours. The use of ammonia to 1.5 kg/t decreases the final Cu concentration in solution, but it is still higher after 24 hours than after 10 minutes. Such a high initial level of cyanide (2 kg/t) caused high copper concentration in solution due to the high concentration of copper in RM 2 and the presence of Cu2S (high soluble mineral form). This requires more ammonia to achieve a solution composition suitable for decomposition of Cu(NH3) 4 2+ to Cu(OH)2 and a long process of oxidation of Cu(I) to CuO. These conditions are labelled as 5 and 6 in Figure 9 and correspond to the "nearer right" area in Figure 7 and Figure 8.

Extraction of gold from low grade ores

1043

900 11O11 700 E liO0 50O 4110 3OO 2110 1 Oil

11
I i

2.5
2
"4

El.. O.

::5 0

1.5
I /

-17"

11.5 I1

Leaching condition
Fig.9 Effect of ammonia on copper removal under constant NaCN (2 kg/t); White bars: Cu in solution after 10 minutes; Black bars: Cu in solution after 24 hours; The line: change of the ammonia amount

Validity criteria. There are three important criteria for the assessment of the ammonia-cyanide process: the efficiency of gold extraction, the selectivity of gold over copper and the consumption of the reactants. According to these criteria, ammonia-cyanide leaching shows good possibilities for application with RM 2 and RM 3. High gold extraction for both RM 2 and RM 3 (85-90%) is achieved using only 0.55 kg/t, 2.2-3 kg/t NH 3 and 6-10 kg/t NaOH (to achieve the required pH 11). Good results in the removal of the copper are achieved and 100-200 ppm Cu remained in the final leaching solution after 24 hours.

Gold extraction from RM 1 is of the same high value (90%) and the remaining copper in the solution is 150 ppm, under 1.65 kg/t NaCN and 0.79 kg/t NH 3. These results basically satisfy the criteria. To analyse both copper removal and gold extraction from RM 1, the same optimised solution composition for RM 2 and RM 3, of 0.55 kg/t NaCN and 2.2 kg/t NH 3 was employed. The remaining copper in the solution is low, similar to the RM 3 leaching results. However, Au extraction efficiency for RM 1 under the researched conditions is about 70%, the same result being gained if using merely 1.65 kg/t NaCN (without the ammonia)! From the point of view of economy of reactant consumption for the leaching of RM"I, there is no crucial difference between using these two systems: cyanide and ammonia-cyanide. From the selectivity point of view, the involvement of ammonia in RM 1 cyanide" leaching is advantageous, as Cu in solution drops from 180 to 111 ppm. However, the high acidity of the RM 1-water slurry required 3-5 times more NaOH for leaching than for leaching of RM 2 or RM 3, whether cyanide or ammonia-cyanide was employed.
Gold and copper extraction with bromine

The main reason for employing bromine leaching is the high acidity of RM l-water slurry, pH 2.4. The leaching solution was prepared with a Br 2 and NaBr mixture.

1044

s. Vukcevic

The kinetics of both gold and copper leaching using acidic processes is slightly different compared to the alkali processes. Table 4 shows the first hour of gold leaching for three different compositions of bromine solution. The same values of gold extraction after 24 hours were found as after one hour. In fact, 90 % of extracted gold is achieved after 5 minutes.

TABLE 4 Gold extraction with bromine

Gold in solution, ppm, 0.75 ml/1 2.5 ml/1 0.47 0.88 0.55 0.87

Time, hrs 0.25 1

5 ml/1 1.1 1.1

The analysis of kinetics of copper leaching shows that for the lower concentrations of 0.75 and 2.5 ml Br2/1, copper concentration in the leaching solution increases during 24 hours to 180 ppm, but stagnates at the same value after only 5 minutes using 5 ml Br2/1. The optimal conditions for this system are when a bromine concentration of less than 2.5 ml/1 is employed to achieve an acceptable level of 140 ppm Cu after 5 minutes.

Comparing the leaching systems

When considering both alkali and acid leaching, additional validity criteria are required: gold leaching kinetics, resistance of the equipment to the corrosive action of the components and toxicity of cyanide. The fastest leaching is achieved by using the bromine solution, as 90% of gold is extracted after 5 minutes. A high gold extraction of 87% is achieved in the ammonia-cyanide system for RM 1. Compared to cyanidation only, a negligible higher reactant consumption of cyanide occurred with the use of a sulphuric acid pre treatment and resulted in 68 % of gold leaching in post-cyanidation. The kinetics of gold extraction for the researched material RM 3 is presented in Figure 10. Under optimised ammonia-cyanide leaching, 85 % of gold extraction is achieved, (upper curve). Au was leached by production of Au(CN) 2- according to reaction (8). Copper concentration in solution was low, < 100 ppm. Under non-optimised ammonia-cyanide leaching, 65 % of gold extraction is achieved (lower curve). A high level of cyanide concentration caused high concentration of Cu in solution and ammonia was not "powerful enough " during oxidation of Au metal to Au(CN)2-. Copper remaining in solution after 24 hours of leaching using different reactants is presented in Figure 11. Only cyanide leaching was employed under leaching conditions 1 and 9. Under condition 1, the concentration of Cu after 24 hours is extremely low (30 ppm) as H2SO 4 pre-treatment was employed. With the same amount of cyanide (condition 9), 180 ppm of Cu was determined. With addition of ammonia, lower levels of Cu concentration were determined, conditions 2 to 8, Figure 11. For the purpose of CIP or RIP gold leaching, the best system for RM 1 is cyanide leaching with sulphuric acid pre treatment. In existing gold technology, activated carbon for gold recovery is used. Carbon readily adsorbs ammonia and the Cu-cyanide species with little discrimination over Au-cyanide. Thus it is possible to selectively adsorb gold from solution using activated carbon provided the concentration of copper in solution is low, < 200 ppm approximately. Therefore, ammonia-cyanide leaching can be recommended for RM 2 and RM 3. To accept bromine leaching as an alternative process, crucial changes in industry are required. However, these results indicate significantly faster kinetics of gold leaching compared to cyanidation.

Extraction of gold from low grade ores

1045

4.5 4
3.5 3 ,,J

,I

E :. =.
<C

2.5

../
f

Y
v

2
1.5 1 0.5 0 0

&

RM 3 Ammonia-cyanide leach.,non-optim RM3 Ammonia-cyanide leach, optim.

I
L

I
i

10

15 time, hrs

20

25

30

Fig. 10 RM 3 leaching under different conditions

2.5 /

z~

2/

9
./

..~

=z= 1
=-

0.5 /

0-~
2 3 4 5 Leaching Condition
I

J 9

NH3, kq/t NaCN. kq/[ Cu,ppm, xl00

Fig. 11 Copper remaining in solution (black strip) after 24 hours of leaching under different conditions: condition number presents the amount of NaCN (black-white strip) and NH 3 (white strip)

CONCLUSIONS Validity criteria for both alkali and acid processes of gold leaching from non-conventional gold ores are: gold extraction, selectivity of gold over copper, reactants consumption, gold leaching kinetics, resistance of the equipment to the corrosive action of the components and toxicity of cyanide.

1046

S. Vukcevic

The application of a cyanide leaching system on the RM 2 and RM 3 acts to both extract 600 to 800 ppm Cu in solution and suppress gold leaching to a maximum of 17 %, at a cyanide concentration of 1.65 kg/t. This is because of the high level of Cu present in these ores, as well as the presence of high copper soluble minerals Cu20 and Cu2S. There is a higher thermodynamic possibility of production of Cu(CN) 2- from Cu-minerals than the Au(CN) 2- in the system. Also, the kinetics of Cu cyanidation is fast. RM 1 is characterised with lower copper concentration and less soluble copper sulphide minerals (mainly CuFeS2). Therefore, a lower copper concentration in a leaching solution of 180 ppm, and consequently higher gold extraction of 70% have been achieved under the same cyanide concentration of 1.65 kg/t NaCN. This concentration allowed an optimal concentration of Cu(I) cyanides responsible for oxidising of gold metal to Au(CN) 2 - . When sulphuric acid pre-treatment is employed for RM 1, followed by cyanidation with 1.65 kg/t NaCN, a highly satisfactory copper selection with 30 ppm Cu in solution is achieved. The gold is leached with 68% of extraction. The employment of an ammonia-cyanide system resulted in clear benefits for RM 2 and RM 3 and some benefit for RM 1, where there are better possibilities with the use of acid systems. As a result of the optimisation of the system composition of RM 2 leaching, a decrease in the concentration of cyanide in solution to 0.55 kg/t is achieved by using 3 kg/t of ammonia. This resulted in 89 % extraction of gold and a residual 200 ppm of copper in the solution. Using the same concentration of cyanide, RM 3 requires an even lower addition of ammonia, at 2.2 kg/t, to reach 85% extraction of Au and a better selection of Cu with 100 ppm remaining in solution. The ammonia addition in the cyanide system allows the production of Cu(II)NH 3 species, which are responsible for intensive copper precipitation and gold leaching. Copper precipitates mostly as Cu(OH) 2, CuO, Cu20 and CuCN. Gold is leached as Au(CN) 2 by chemical reactions including Cu(I) cyanides present in the system. The optimisation of RM 1 leaching in the ammonia-cyanide system, resulted in the requirement of a higher level of cyanide, 1.65 kg/t, but lower ammonia, 0.79 kg/t, which allows 90% Au extraction and 150 ppm Cu in solution. Leaching in bromine solution shows much faster gold extraction kinetics with no worse copper selection compared to the alkali systems. Therefore both researched acid systems (sulphuric acid pre-treatment and bromine leaching) are recommended as better technology for RM 1, compared to the alkali processes. On the other hand, the ammonia-cyanide system can be usefully employed for the leaching of RM 2 and RM 3 as they have similar mineralogy. ACKNOWLEDGMENTS The author gratefully acknowledges support from the Australian Research Council and the A J Parker Cooperative research Centre for Hydrometallurgy. The Parker Centre was established and is supported by the Australian Government under the Cooperative Research Centres' Program. The author wishes to acknowledge A/Prof. D. Muir, for his generous help and useful suggestions, and J. Biddle and T. Komosa for their technical assistance.

REFERENCES
i.

2.

Hunt, B., US Patent No. 689,190, (Dec. 17 1901). Jarman, A. & Brereton, E. Le Gay, Laboratory experiments on the use of ammonia and its compounds in cyaniding cupriferous ores and tailings, Trans.lnst. Min. and Metall. XIV, 289-334 (1905).

Extraction of gold from low grade ores

,

1047

4. 5.

7.

9.

10.

11.

12.

13.

14.

15.

!6.
17.

18. 19.

20.

21. 22.

Halferdahl, A.C., The problem of treating cupriferrous precious-metal ores by the cyanide process, Eng. Min. J., 128, 350-358 (1945). Putnam, G.L., Copper-ammonia process for cyanidation of complex ores, Chem. Engng. and Min. Review, 347-348 (June 10 1950). Costello,M.C., Ritchie, I.C., & Lunt, D.J., Use of ammonia cyanide leach system for gold-copper ores with reference to the retreatment of the TORCO tailings, Minerals Engineering, 5 (10-12), 1421-1429 (1992). Luo, R., Overall Equilibrium Diagrams for hydrometallurgical systems: copper-ammonia-water system, HydrometaUurgy, 17, 177-199 (1987). Han, K.N. & Meng, X., Extraction of gold/silver from refractory ores using ammoniacal solutions, Proc. Randol Gold Forum, Vancuver,Canada (Randol Intl. ,Golden, Co.), 213-218 (1992). La Brooy, S.R., Copper-goold ore treatment options and status, Proc. Randol Gold Forum, Vancuver, Canada (Randol Intl., Golden, Co.), 173-177 (1992). La Brooy, S.R., Komosa, T. & Muir, D.M., Selective leaching of gold from copper-gold ores using ammonia-cyanide mixtures, Proc. Extr. Metall. Conference, Perth, Australia (Aus. I. M. M., Melbourne), 127-132 (1991). Hayes, G.A. & Corrans, I.J., Leaching of gold-copper ores usingammoniacal cyanide, Proc. Extractive Metallurgy of Gold and Base Metals, Kalgoorlie, Australia (Aus. I.M.M., Melbourne), 349-352 (1992). Osseo-Asare, K., Xue, T. & Ciminelli, V.S.T., Solution chemistry of cyanide leaching systems, Precious Metals, Eds. Kudryk, V., Corrigan, D. A. & Lang, W. W., A. I. M. E., Warrendale, 173-198 (1984). Meng, X. & Hart, K.N., The dissolution behaviour of gold in ammoniacal solutions, Hydrometallurgy: Fundametals, Technology and Innovation, Proc.Milton Wadsworth Symposium on Hydrometallurgy, (Eds. Hiskey, J. B. &Warren, G. W.) A.I.M.E., Warrendale, 205-221 (1993). Muir, D.M., La Brooy, S.R., Deng, T. & Singh, P., The mechanism of the ammonia-cyanide system for leaching copper-gold ores, Hydrometallurgy: Fundamentals, Technology andlnnovation (Eds. Hiskey, J. B. & Warren,G. W.)A.I.M.E., Warrendale, Chapter 12, 191-204 (1993). Zheng, J., Ritchie, I.M., La Brooy, S.R. & Singh, P., Study of gold leaching in oxygenated solutions containing cyanide-copper-ammonia using a rotating quartz crystal microbalance, Hydrometallurgy, 39, 277-292 (1995). Ruane, M., Gold recovery from the Paris mine tailings using ammoniacalcyanide leachant, Proc. Symposium on Processing of Copper-Gold Ores, AMMTEC, Perth, Australia (1991). Esna-Ashari, M. & Beinhoff, C., Extraction of gold from Torco tailings, 15th Int. Min. Proc. Congress, Cannes, Vol 3 (GEDIM St Etienne, Cedex,France), 486-496 (1985). Butcher, D.J., Ammoniacal cyanide leaching for recovery of gold from Torco tailings--Akjoujt Mauritania, Proc. Randol Gold Forum, Perth, Australia (Randol Intl.,Golden, Co.), 231-238 (1995). Pesic, B. & Sergent, R., Reaction mechanism of gold dissolution with bromine, Metallurgical Transactions B, 24B, 419-429 (June 1993). Dadgar, A., Extraction and recovery of gold from concentrates by bromone process, Conference: Precious Metals '89, Las Vegas, Nevada, USA, 227-240 (Feb. 27-March 2 1989). Sergent, R.H., Dadgar, A., Shin, C.C. & Reid, K.J., A comparison of bromine and cyanide leaching for refractory gold concentrate, Conference: Precious and Rare Metal Technologies, Albuquerque, New Mexico, USA, 149-156 (April 6-8 1989). Mensah-Biney, R.K., Reid, K.J. & Hepworth, M.T., Kinetics of gold loading from bromide solution onto an anion exchange resin, Minerals Engineering, 7(7), 865-887 (1994). Vukcevic S., Unpublished Research, Murdoch University, CRC Parker, Perth WA (1995).

9-10-8