hydrometallurgy

ELSEVIER Hydrometallurgy39 (1995) 11-23

Development of ammoniacal lixiviants for the

in-situ leaching of chalcopyrite
Shawn L. Bell *, Glenn D. Welch, Paul G. Bennett
U.S. Departnzent of the Interior, Salt Lake City Research Center, 729 Arapeen Drive, Salt Lake City, UT 84108,
USA

Accepted 8 June 1995

Abstract

Researchers at the U.S. Bureau of Mines are investigating the ammonia--oxygen leaching of
chalcopyrite at conditions anticipated in an in-situ environment. Two major problems were identified
in a review of the literature: (1) providing sufficient oxidant to drive the leaching reaction, and (2)
decreased leaching kinetics due to the build-up of a ferric oxide reaction product layer at the mineral
surface. Preliminary characterization studies were performed in a 2-1, well-mixed autoclave system
incorporating automated sampling and data acquisition. A statistical experimental design was utilized
to determine which parameters were most influential in the dissolution of copper from relatively pure
chalcopyrite specimens. The most significant leaching parameters for the ammoniacal leaching of
copper from chalcopyrite were determined to be temperature, oxidant concentration, ammonium
hydroxide concentration, and an interaction between temperature and the ammonium hydroxide
concentration. Preliminary leaching studies indicate that further research must be undertaken to
evaluate oxidant delivery to an in-situ orebody and that the addition of organic compounds, such as
simple sugars or polyvinyl alcohols, stabilize at least some of the reacted iron in solution, which could
result in decreased passivation due to the formation of an iron oxide coating. In order to determine
the practicality and effectiveness of this approach, researchers have been investigating several types
of organic additives, the extent to which iron is sequestered, and methods to control the sequestered
iron.

1. Introduction

As copper oxide and near-surface copper sulfide deposits are depleted, the need to exploit
more deeply buried, refractory copper sulfide deposits will increase. Typically, sulfide ores
are mined, transported to the surface, concentrated, and treated by pyrometallurgical tech-

* Correspondingauthor.

0304-386X/95/$09.50 © 1995 Elsevier ScienceB.V. All righLsre~rved

SSDI 0 304- 3 86 X ( 9 5 ) 0002 2-4
12 S.L. Bell et al. / HydrometaUurgy 39 (1995) 11-23

niques. Conventional mining techniques are becoming less feasible, however, due to increas-
ing labor and energy costs involved in mining deep deposits as well as more severe
environmental constraints being placed on the mining industry. For the domestic copper
industry to remain competitive, innovative technologies must be developed for the recovery
of copper from otherwise uneconomical deposits. As a result, alternative hydrometallurgical
processing schemes are being explored.
In-situ solution mining has been identified as a possible alternative for copper recovery
from deeply buried sulfide deposits. The concept of in-situ leaching is well established for
copper oxide orebodies [ 1-3 ], and a considerable amount of information regarding in-situ
leaching of copper oxides and uranium has been documented [4-9]. However, for in-situ
leaching of copper sulfides to become a reality, a suitable lixiviant must be identified.
Based on the literature and contacts with industry [ 10], the most promising lixiviant
systems for commercialization have been identified as ( 1) sulfuric acid/oxygen, (2) ferric
and cupric chlorides, and (3) ammonia/oxygen. The sulfuric acid/oxygen system has good
potential for commercialization; however, the kinetics are relatively slow at typical in-situ
conditions. Although the cupric-ferric chloride system shows promise, severe corrosion
problems associated with pumping the liquor at high pressures have resulted in limited
industrial interest. By contrast, the ammonia/oxygen system has some unique advantages
which make it of more interest to industry. The advantages are that the basic leach solution
alleviates several corrosion problems observed with the acidic systems, reagent consumption
by carbonaceous gangue mineralization is minimal, and cleaner leach liquors are produced,
thus facilitating subsequent metal recovery [ 11 ].
A considerable amount of research has been conducted on the ammoniacal leaching of
copper-bearing ores. Past research has focussed on three main areas: ( 1 ) native copper ore
leaching, (2) sulfide concentrate leaching, and (3) simulated sulfide ore heap leaching. A
brief summary of each of these applications follows:
1. Native copper ores ---Benedict was granted a patent for leaching native copper from
ores with oxygenated ammoniacal solutions [ 12]. The technology was commercialized by
Kennecott [ 13,14] and Calumet [ 15] in the 1920's. Metallic copper dissolution in the
ammonia--oxygen system has been investigated by several researchers [ 16-22].
2. Sulfide concentrates - - A number of oxidants have been utilized in the ammoniacal
leaching of copper sulfides, including bromates, chlorates, oxygen, peroxides, and persul-
fates. Oxygen, being the least expensive, is the most widely studied of the oxidants [20].
Oxidation chemistry in the ammoniacal system is complex and has been shown to be
influenced by a number of factors. The leaching stoichiometry of chalcopyrite, the most
prevalent copper sulfide, has been well documented [ 11,23-29] and is indicated below in
Eqn. 1.
CuFeS2 + 4NH3 + 17/402 + 2 O H - ~ Cu(NH3) 2+ (1)
+ 1/2FezO3 +2SO 2- + H 2 0
3. Simulated heap leaching o f copper sulfide ores - - O f all the research conducted on the
ammoniacal leaching of copper sulfides, the most germane is the work by Dutrizac on
ammoniacal percolation leaching of chalcopyrite ore [ 11 ]. Experimental conditions in the
study are very similar to what would be encountered in an in-situ leaching environment,
namely, ambient temperature and pressure, with air as the oxidant. In an in-situ environment,
 S.L. Bell et al. / Hydrometallurgy 39 (1995) 11-23 13

pressures and temperatures may be higher, as high as 6900 kPa and 100°C, respectively,
resulting in improved reaction kinetics. The results of Dutrizac's work indicate that reason-
ably fast reaction rates (on the order of 20% extraction of copper in as little as 50 days)
similar to those obtained with the commercially used acidic ferric sulfate system were
achieved with ammoniacal leaching. However, a ferric oxide product layer inhibited the
reaction. Analysis of the leach residue showed significant quantities of elemental sulfur,
indicating that the oxygen requirement may be much lower than expected, since sulfate is
not produced exclusively.
Dutrizac drew several conclusions pertinent to in-situ leaching:
1. The feasibility of percolation leaching of copper sulfides utilizing an ammoniacal-oxygen
lixiviant was demonstrated.
2. Ammoniacal percolation leaching is oxygen transport limited as is commercial perco-
lation leaching with acidic ferric sulfate.
3. The solubility of oxygen in aqueous media is only a few mg/1 and such amounts are
small relative to the oxygen demand given by Eqn. 1. Hence, the amount of oxygen
dissolved in the leaching medium itself is of minor importance and the significant
parameter is the transport of oxygen gas to the ore and the subsequent dissolution of
oxygen into the leaching medium.
4. Volatile ammonia losses during 3 months of leaching amounted to 5% to 20% of the
input NH 3.
5. Copper recovery from the dilute ammoniacal liquor was straightforward utilizing com-
mercial solvent extractants.
Dutrizac's work with percolation leaching of broken ore indicates that the ammoniacal
in-situ leaching of copper sulfide ore has potential for success providing that a means to
supply sufficient oxidant for leaching is developed. In addition, the leaching rate appears to
be reasonable for a situation where the lixiviant slowly travels through a sulfide ore body.
Volatile ammonia losses that were observed in the percolation leaching research are not
expected to be a factor in in-situ leaching environments, because the lixiviant will be
contained within the ore body and not exposed to the atmosphere.
An extensive review of the literature has identified two major problems which need to
be addressed in the in-situ ammoniacal leaching of copper sulfide ores. The first is providing
enough oxidant to drive the leaching reaction. As indicated above, Dutrizac [ 11 ] concluded
that the solubility of oxygen in aqueous media at ambient pressure is only a few nig/1 and
such amounts are small relative to the oxygen demand of the leaching reaction. Conse-
quently, a technique must be developed for delivering sufficient oxidant to drive the chemical
reaction.
The second problem that needs to be addressed is the decrease in leaching kinetics due
to the build-up of the ferric oxide product layer. One possible solution may lie in the addition
of saccharides or related organic compounds to the leach liquor. Multiple OH groups
attached to the long chain molecules may function as sequestering agents, which aid in
keeping iron in solution as it leaches and prevent ferric oxide formation. The sequestered
iron could then be removed from the leachate as part of the metal recovery operation.

2. Experimental
Two chalcopyrite samples were obtained through Ward's Scientific for use in the study,
the first a high purity Transvaal chalcopyrite, and the second a less pure sample from
14 S.L. Bell et al. / Hydrometallurgy 39 (1995) 11-23

Table 1
Screen size analysis o f c h a l c o p y r i t e specimens

Screen size (Tyler) Transvaal ( % ) Arizona ( % )

+ 100# 0.0 0.0

- 100+ 150# 23.9 31.3
- 150+200# 20.6 15.3
- 200 + 2 7 0 # 20.6 15.1
-270+400# 17.3 15.1
- 400# 17.4 22.7

Arizona. Both chalcopyrite samples were crushed and pulverized to minus 100 mesh ( 150
micron). Data from the screen size analyses are shown in Table 1 for each sample.
Head samples of the chalcopyrite specimens were obtained and sent in for analysis. The
samples were analyzed by X-ray fluorescence, X-ray diffraction (XRD), atomic absorption
(AA), and inductively coupled plasma (ICP), in order to identify mineral phases, as well
as impurity elements present. Pure chalcopyrite, by stoichiometry, contains 34.6% copper,
30.4% iron, and 34.9% sulfur. The Transvaal chalcopyrite specimen contained about 26.2%
copper, 26.7% iron, and 31.3% sulfur, corresponding to about 76% CuFeS2. XRF analysis
of the Transvaal sample identified that the specimen contained a minor amount of calcium
and XRD analysis indicated that the balance was SIO2. No other sulfide mineralization was
identified in the sample. The Arizona sample was much less pure, however, containing
17.9% copper, 24.3% iron, and 23.8% sulfur, which corresponds to approximately 52%
CuFeS2. XRF analysis indicated that minor amounts of calcium, magnesium, nickel, and
zinc were present, in addition to trace amounts of arsenic, selenium, molybdenum, lead,
silver, and tin. Mineral species identified by XRD were SIO2, FeS2, FeS, ZnS, and small
amounts of multi-metal silicates.
Leaching experiments were performed in a stirred, 2-1, Incone1600 autoclave with internal
baffles. The autoclave was externally heated and incorporated an internal cooling coil
arrangement for precise temperature control. Autoclave pressure was monitored with an
electronic pressure transducer. Internal and heating jacket temperatures were monitored
using Type K thermocouples. All sensors were routed to a PC data acquisition computer,
which continuously displayed the data on a monitor as well as periodically saving the
averaged data to a text file. A series of pneumatic valves were controlled by the computer
in such a way as to allow for slurry samples to be taken remotely at specified intervals and
piped to a sample fractionator, which was also controlled by the computer. These samples
were immediately filtered and collected for later analysis.
The autoclave reactor was charged with chalcopyrite, deionized water, and the appropriate
amounts of 55.6% pure reagent grade ammonium hydroxide and 97% pure reagent grade
ammonium sulfate. The pulp density was maintained at 1% solids, resulting in a final copper
concentration, assuming complete reaction, of about 3 g/1. Due to problems encountered
by Beckstead [ 26 ] with premature reaction during heat-up, a mechanism was used to prevent
introduction of solids until after the test temperature was reached. The solid charge was
placed into a borosilicate glass test tube which was then capped and placed into the bottom
of the reactor. The mixer, which was started only after the reactor had reached the test
temperature and pressure, shattered the glass vial to introduce the solids into the solution.
 S.L. Bell et al. / Hydrometallurgy 39 (1995) 11-23 15

Oxygen was allowed to enter the vessel continuously, following heat up, to maintain a
constant pressure for the duration of the experiment.

3. Results and discussion

3.1. Activation energy studies

Initial experimentation was directed at determining the activation energy of each of the
chalcopyrite specimens. Several tests were conducted on each of the two chalcopyrite
samples at the following conditions:
1.5 1 of solution,
3.0 M ammonium hydroxide,
0.3 M ammonium sulfate,
2070 kPa oxygen overpressure,
1% solids (chalcopyrite only),
2000 rpm mixing speed,
4 h leach time,
temperatures of 20, 40, 60, 80, and 100°C.
Fig. 1 and Fig. 2 show typical copper extraction versus time plots for the Transvaal and
Arizona chalcopyrite, at different temperatures. As may be seen from the two figures, copper
extraction is highly dependent upon temperature. As the temperature increases, the rate of
reaction increases significantly, and final copper extractions vary from about 10% to 95%
over the 4-h tests. The Transvaal chalcopyrite, as seen in Fig. 1, leaches at a slightly higher
rate than was observed with the less pure Arizona chalcopyrite, shown in Fig. 2.

100
....--
90
80
I 70
60
/ jr- _..---------W--

50
40
30
20 ~ 0 0
.____o------o-
_,___w__-----o-
10
0
0 40 80 120 160 200 240
Elapsed lime, minut~
m

[-~o~20C -~o~40C . 60C * 80C s 100C1

Fig. 1. Copper extraction versus time for the ammoniacal/oxygen leaching of chalcopyrite, Arizona specimen.
16 S,L. Bell et al. / Hydrometallurgy 39 (1995) 11-23

100
9O

8O

"D 70
| -
f
0 411
S
S ---.---11-
J
10 rl [] d

0
40 80 120 t80 200 240
Elapsed Ume, m l n u t u

] -~o---- 20C • 40C * 60C A 80C • 100C

Fig. 2. Copper extraction versus time for the ammoniacal/oxygen leaching of Transvaal chalcopyrite, activation
energy studies.
-1.50

-1.70

-1.90

-2.10

.~ -2.3O
.a
,~E .2.50
-...4
oo~-2.70
-2.90
Arizona Chalcopyri~
--....
-3.10 • Tramvaal Chalcopyfita

-3.3O

-3.50 [ I I

2.50 2.00 2.70 2~0 2~0 3.00 3.10 3.20 330 3.40 3.50
lIT (K) " 1 0 0 0
Fig. 3. Plot of the logarithm of the initial reaction rate (log k) vs. the inverse of absolute temperature ( 1/T), for
both the Transvaal and Arizona chalcopyrite specimens.

The parabolic shape o f the c o p p e r extraction versus time curves at various temperatures
indicates that the reaction rate can be described by an Arrhenius plot. The Arrhenius equation
for d e p e n d e n c e o f the rate on temperature m a y be written as

E a
log k - log A (2)
2.303RT
 S.L. Bell et al. / HydrometaUurgy 39 (1995) 11-23 17

Table 2
Factors and factor levels utilized in statistical experimental design

Factors Low ( - ) Medium (0) High ( + )

Ammonium hydroxideconc. (moles/I) 0.5 0.75 1.0

Ammonium sulfate conc. (moles/l) 0.25 0.375 0.5
Oxygen overpressure (kPa) 690 3450 6200
Temperature (°C) 25 53 80

where, k = initial leach rate, A = pre-exponential factor, Ea = activation energy, R = universal

gas constant, T = absolute temperature.
Fig. 3 is a plot of log (k) versus 1 / T(K) values, showing initial rate data for both of the
chalcopyrite specimens in the study. As is predicted by the Arrhenius equation, both data
sets approximate a straight line on the plot. Activation energies were computed from these
plots as being 31.4 and 37.7 kJ/mole, for the Transvaal and Arizona chalcopyrite, respec-
tively. The Arizona chalcopyrite is slightly more refractory than that from Transvaal. Both
activation energy values indicate surface reaction rate control and show good agreement
with values reported in the literature [26].

3.2. Statistical experimental design studies

As was mentioned in the introduction, a considerable amount of research has been

conducted on the ammoniacal leaching of chalcopyrite. The approach of the current research
is to build upon existing research findings by characterizing the ammoniacal/oxygen system
at anticipated in-situ conditions. In an in-situ environment, temperature, pressure, and ore
characteristics vary depending on factors such as deposit depth, degree of water saturation
at that depth, geothermal activity, and mineralogy. Other factors, such as ammonium hydrox-
ide and ammonium sulfate concentrations in the leach solution, have an impact on the
economic viability of a particular ore body. Consequently, it was necessary to characterize
the variables and the effects of those variables on copper extraction, over a broad range to
ensure that the data obtained in the laboratory are applicable to a variety of field situations,
from a processing as well as an economic standpoint.
In order to study the effect of ammonium hydroxide, ammonium sulfate, temperature,
and oxygen overpressure on copper extraction from chalcopyrite, a two-level, four-factor
statistical experimental design with three center-point replicates was chosen. The factor
levels, shown in Table 2, were chosen to cover the broad ranges that are anticipated in an
in-situ environment. An experimental design was utilized to maximize factor effect infor-
mation while simultaneously minimizing the number of leaching tests conducted. A total
of nineteen tests ( 16 design experiments and 3 center-point replicates) were performed on
each of the chalcopyrite specimens. The experimental design allowed identification of linear
and interaction effects present in the system from which a multiple regression model was
estimated, having the form

percent Cu extraction = constant + linear effects + interaction effects (3)

18 S.L. Bell et al. / Hydrometallurgy 39 (1995) 11-23

Table 3
Regression coefficients for statistical design analysis, Transvaal chalcopyrite

Factors and interaction Regression coefficients at various times

Time ( h ) 1/2 1 2 4
Temperature (°C) 0.218 0.300 0.345 0.464
N H 4 O H concentration - 5.545 - 7.318 - 10.091 - 9.364
O x y g e n pressure ( k P a ) 0.0010 0.0013 0.0013 0.0015
N H 4 O H × temperature 0.282 0.373 0.464 0.555
Constant term - 4.064 - 4.859 - 0.089 - 0.013

Factor effects were estimated by running a multiple linear regression with linear and
interaction effects as the independent variables and percent copper extraction as the depend-
ent variable. Linear regression analyses were conducted at each time interval, and similar
effects were obtained at every point. Uncoded factor effect coefficients with respect to
copper extraction at 0.5, 1, 2, and 4 hours leach times are displayed in Table 3 and Table 4
for both the Transvaal and Arizona chalcopyrite specimens, respectively. Coded values are
not shown for the regression, however, coded values are normalized with respect to the
magnitude of the effect and provide an indication of the relative importance of each variable
allowing direct comparison to the others. In every case, temperature was by far the most
important leaching parameter, followed by oxygen pressure, ammonium hydroxide concen-
tration, and the ammonium hydroxide/temperature interaction. The temperature effect was
previously observed in the activation energy studies, as temperature increases, the leach
rate increases. Oxygen pressure and ammonium hydroxide concentration effects are to be
expected from the leaching reaction, Eqn. I. As either of these two factors are increased,
the reaction should be driven to the right, thus leaching copper. The temperature/ammonium
hydroxide interaction was not expected, but can be explained by the decomposition of
ammonium hydroxide to ammonia gas and water. As the temperature increases, the decom-
position rate increases, thus producing more ammonia, which is a direct participant in the
leaching reaction, Eqn. 1, resulting in a synergistic effect of the two factors. As either the
temperature or the concentration of ammonium hydroxide increases, the combined effect
produces more ammonia, thus driving the leaching reaction. The regression functions
recorded adjusted R 2 values ranging from 0.93 to 0.98 for all regression analyses conducted
with both the Transvaal and Arizona chalcopyrite. The high R 2 values indicate that the

Table 4
Regression coefficients for statistical design analysis, A r i z o n a chalcopyrite

Factors a n d interaction Regression coefficients at various times

Time ( h ) 1/2 1 2 4
T e m p e r a t u r e (°C) 0.286 0.430 0.640 0.639
N H 4 O H concentration - 0.167 - 0.392 2.058 - 3.528
O x y g e n press ure ( k P a ) 0.0010 0.0013 0.0012 0.0017
N H 4 O H X temperature 0.034 0.072 0.050 0.285
Constant term - 7.628 - 10.945 - ! 3.439 - 11.983
 S.L. Bell et al. / Hydrometallurgy 39 (1995) 11-23 19

regression equations fit the data very well with only the four factors listed being important
to copper leaching from chalcopyrite.
As an example, a sample of the Transvaal chalcopyrite is leached for 4 h at 80°C, 1.0 M
NHnOH, 0.25 M (NH4)2SO4, and 6200 kPa oxygen overpressure. At these conditions, the
regression equation predicts that 81.1% of the copper should be extracted as indicated by
Eqn. 4.
( - 0.013) + (0.464"80 - 9.364" 1.0 + 0.0015"6200)
constant linear effects

+(0.555"1.080)=81.1% (4)
interaction effect

A test was conducted at these conditions to verify the model. Test results showed that
80.8% of the contained copper was extracted, showing excellent agreement with the model.
Results of the statistical experimental design show that temperature, ammonium hydrox-
ide concentration, and oxygen pressure, along with a temperature/ammonium hydroxide
interaction, have the greatest effect on copper leaching from chalcopyrite. When these
variables are incorporated into the statistical model, virtually all the observed variation is
accounted for, as evidenced by the high R 2 values. In an in-situ leaching application,
ammonium hydroxide concentration and oxygen pressure are identified parameters which
may be controlled. It is unlikely that the ambient temperature could be significantly altered
in a deeply buried ore body, but temperature is the single most important parameter in the
ammoniacal leaching of chalcopyrite. Consequently, from a commercial standpoint, ammo-
nium hydroxide concentration and oxygen pressure appear to be the only adjustable leaching
parameters of importance in the in-situ ammoniacal leaching of chalcopyrite.

3.3. Iron sequestering agents

Preliminary leaching tests conducted on the Arizona chalcopyrite specimen indicate that
the addition of organic compounds, such as simple sugars or polyvinyl alcohols, stabilize
at least some of the reacted iron in solution, thus preventing it from passivating the mineral
surface. This finding could be very significant for in-situ leaching systems which are
inherently limited by a number of diffusion processes. To determine the practicality of this
approach, several types of organic additives have been studied with regard to the extent to
which the additives sequester iron.
Leaching test series were conducted with mannitol and dextrose (sequestering agents)
added to the leaching solution at concentrations ranging from 0.0 to 0.1 M. The tests were
conducted at atmospheric pressure in a stirred reactor at temperatures ranging from 25 to
80°C, with 2.5% solids, and 1.8 M ammonia. Hydrogen peroxide was used as the oxidant.
Copper and iron extraction results are presented in Table 5 and Table 6 for the addition of
dextrose, and Table 7 and Table 8 for the addition of mannitol. The following general trends
can be observed from the data:
Iron extraction (into solution) increases with increasing sequestering agent concentration.
Copper extraction decreases with increasing temperature and increasing sequestering agent
concentration.
The trend with respect to iron extraction is considered positive and desirable; however,
20 S.L. Bell et al. / Hydrometallurgy 39 (1995) 11-23

Table 5
Copper extraction (ppm) at varying temperatures and dextrose additions

Additive concentration (mol/l) Temperature (°C)

25 45 65 80

0.0 254 200 84 20

0.05 187 175 0.6 0.3
0.1 145 117 0.6 0.3

Table 6
Iron extraction (ppm) at varying temperatures and dextrose additions

Additive concentration (mol/l) Temperature (°C)

25 45 65 80

0.0 0.08 0.13 0.03 0.03

0.05 0.28 1.14 1.33 9.64
0.1 16.8 24.3 9.09 24.3

Table 7
Copper extraction (ppm) at varying temperatures and mannitol additions

Additive concentration (mol/1) Temperature (°C)

25 45 65 80

0.0 254 200 84 13

0.05 201.5 159 49.5 0.03
0.1 256 159 0.03

Table 8
Iron extraction (ppm) at varying temperatures and mannitol additions

Additive concentration (mol/l) Temperature (°C)

25 45 65 80

0.0 0.08 0.13 0.03 0.03

0.05 145.8 72.2 18.4 0.51
0.1 182.8 97.6 22.8

the decreasing copper extraction trends are undesirable. It is currently hypothesized that the
observed decrease in copper extraction is related to the reductive nature of the organic
sequestering agents, coupled with problems commonly observed with the use of hydrogen
peroxide as an oxidant. Two well-known chemical reactions support the first hypothesis.
Reactions between sugars and metallic ions reduce silver (I) ions to metallic silver (Tollens
solution) and cupric ions to cuprous oxide (Fehlings reagent) [30]. In addition, when
 S.L. Bell et al. / HydrometaUurgy 39 (1995) 11-23 21

hydrogen peroxide is used as an oxidant, decomposition of the compound occurs with

increasing temperature and high pH. As a result, the decrease in copper extraction with
temperature could be solely due to the much more rapid decomposition of hydrogen peroxide
at the higher temperatures and high pH associated with ammoniacal lixiviants. Additional
research will be conducted in order to further characterize and optimize the sequestering
chemistry and determine the effects upon the subsequent processing of the leach liquor.

4. Future plans

The automated, stirred autoclave system has proven to be a very useful tool for initial
characterization studies to evaluate the ammoniacal lixiviant system using pure chalcopyrite.
Several biased effects of laboratory autoclaving, however, obscure the simulation of in-situ
environments. In a true in-situ environment, the solution will percolate slowly through an
ore body, leaching chalcopyrite as it travels, whereas, in an autoclave, high speed mixing
results in very efficient mass transfer and consistent shearing of product layer from the ore
particle surface. The in-situ leach rate will be much lower, and hematite could precipitate
out and plug off the pores through which the solution is flowing. To permit a more realistic
assessment of these problems, a column leaching system for simulating an in-situ environ-
ment has been developed.
In the past, many researchers have successfully utilized columnar vessels with lixiviant
percolation through ore material to simulate heap and dump leaching of copper, as well as
gold ores. The columns were filled with ore, and solution was percolated through the ore

1 --®
I
0 0

0 0

® OxygenatedLiquid
o o
0 AmmoniacalLixiviant
o o
(~) ProductSolution o o
o o
o o

Fig. 4. Schematicof high pressurecolumn systemfor simulatingthe in-situ ammoniacalleachingof coppersulfide

ores.
22 S.L. Bell et al. / HydrometaUurgy 39 (1995) 11-23

body to leach the metal. Because of the success columnar leaching vessels have achieved
in simulating heap and dump leaching, a similar experimental setup was designed and
constructed for simulating in-situ leaching of chalcopyrite with ammoniacal lixiviants. The
system is shown in Fig. 4, and consists of a 1.83 m long, 15.2 cm diameter column which
may be operated at pressures up to 6900 kPa for simulating in-situ conditions. The column
will be packed with broken sulfide ore, and solution will be pumped at a low flow rate
through the column, utilizing a high pressure piston pump. The solution will be released
from the top of the vessel through a back pressure regulator.
Through the use o f the high pressure columnar leaching vessel, further research will be
conducted to evaluate alternative oxidant and oxygen delivery systems at conditions more
closely approximating those encountered in an in-situ environment. The system will also
be utilized to develop methods for minimizing the hematite product layer formation.

5. Conclusions

The activation energy was determined to be 31.4 and 37.7 k J / m o l e , for the basic a m m o n i a -
oxygen leaching of two chalcopyrite specimens, showing good agreement with values
reported in the literature.
• The most significant parameters for the ammoniacal leaching of chalcopyrite were deter-
mined to be temperature, oxygen pressure, and ammonium hydroxide concentration. A n
interaction between ammonium hydroxide and temperature was also identified as having
a significant effect on the extraction of copper, and is attributed to the breakdown of
ammonium hydroxide into water and ammonia. A m m o n i a is an active contributor in the
leaching reaction as shown in Eqn. 1.
• From an in-situ leaching standpoint, the only controllable parameters are ammonium
hydroxide concentration and oxygen pressure.
• Further research must be conducted to characterize the ammoniacal system at simulated
in-situ conditions with true copper sulfide ore. A column system has been designed and
constructed for this purpose.

References

[ 1] Aplan, F.F., McKinney, W,A. and Pemichele, A.D., Proceedings of Solution Mining Symposium, AIME
Annual Meeting, Dallas, TX (1974), 469 pp.
[2] Pugliese, J. and Larson, W., Bibliography on in-situ mining of metals. In Situ, 10(3) ( 1986): 277-311.
[ 31 Potter, G.M., Chase, C.K. and Chamberlain, P.G., Feasibility of in-situ leaching of metallic ores other than
copper and uranium. In: W.J. Schlitt (Editor), Proceedings of Second SME-SPE Inter. Solution Mining
Symp., Soc. Min. Eng., AIME, Denver, CO (1981), pp. 123-130.
[41 Ahlness, J.K., and Pojar, M.G., In-Situ Leaching in the United States: Case Histories of Operations. U.S.
Bureau of Mines, IC 8961 (1983), 37 pp.
151 D'Andrea, D.V., Larson, W.C., Flether, L.R., Chamberlain, P.G. and Engelmann, W.H., In Situ Leaching
Research in a Copper Deposit at the Emerald Isle Mine. U.S. Bureau of Mines, RI 8236 (1977), 43 pp.
[6] Groves, R.D., Jeffers, T.H. and Potter, G.M., Leaching Coarse Native Copper Ore with Dilute Ammonium
Carbonate Solution. Paper presented at the Annual AIME Meeting, Dallas, TX (February 23-28, 1974), 8
PP.
 S.L. Bell et al. / Hydrometallurgy 39 (1995) 11-23 23

[7] Hockings, W.A. and Freyberger, W.L., Laboratory studies ofin-situ ammonia leaching of Michigan copper
ores. In: J.C. Yannopoulus and J.C. Agarwal (Editors), Extractive Metallurgy of Copper. Proceedings Int.
Syrup. on Copper Extraction and Refining, Las Vegas, NV (February 22-26, 1976). TMS-AIME, ( 1976):
873-906.
[ 8 ] Isaacson, A.E. and Hill, S.D., U.S. Bureau of Mines Research on In-Situ Copper Leaching. Proceedings of
the Fourth National Congress on Nonferrous Extractive Metallurgy, Hermisillo, Mexico (May 26-30, 1992).
[ 9 ] Litz, L.M., In-situ uranium mining with oxygen. Min. Eng., January (1982): 52-56.
[ l 0 ] Copper Industry Participants Research Association (Tucson, AZ), In-Situ Mining of Copper Sulfides, March
(1991), 150 pp.
I I l ] Dutrizac, J.E., Ammoniacal Percolation Leaching of Copper Ores. Can. Metall. Q. (Canada), 20( 3 ) ( 1981 ) :
307-315.
112] Benedict, C.H., Extracting Copper from Cupriferous Sand, U.S. Pat. 1,131,986 (1915).
I 131 Eddy, L., Practical considerations in ammonia leaching of copper beating ores. Met. Chem. Eng., 20 ( 1917) :
328-334.
[ 14] Lawrence, H.M., Ammonia Leaching of Copper Tailings at Kennecott Alaska. Eng. Min. J., 104 ( 1917):
781-787.
I 15 ] B enedict, C.H., Ammonia leaching of calumet tailings. Eng. Min. J., 104 ( 1917 ) : 43-48.
1161 Yamasaki, E., On the rate of dissolution of metallic copper in aqueous ammonia. Science reports Tohoku
Univ. (Japan), Series I, v. 9. Abstract available. Chem. Abstr., 14, 3558 (1920): 160-220.
[171 Zeretskii, E. and Akimov, G., Corrosion of copper in aqueous solutions of ammonium compounds. I.
Mechanism. Zh. Pdkl Khim. v. I I. Abstract available, Chem. Abstr., 33, 4180 ( 1938): 1161-1172.
118] Lane, R.W. and MacDonald, H.J., Kinetics of the reaction between copper and aqueous ammonia. J. Am.
Chem. Soc., 68 (1946): 1699-1704.
1191 Lu, B.C.Y. and Graydon, W.F., Rates of copper dissolution in aqueous ammonium hydroxide solutions. J.
Am. Chem. Soc., 77 (1955): 6136-6139.
120] Halpern, J., Kinetics of the dissolution of copper in aqueous ammonia. J. Electrochem. Soc., 100 (1953):
421-428.
[ 21 ] Halpern, J., Milants, H. and Wiles, D.R., Kinetics of the dissolution of copper in oxygen-containing solutions
of various chelating agents. J. Electrochem. Soc., 106 (1959): 647-650.
[22] Fisher, J.l. and Halpem, J., Corrosion of copper gold alloys by oxygen-containing solutions of various
chelating agents. J. Electrochem. Soc., 103 ( 1956): 282-286.
[23] Evans, D.J.I., Romanchuk, S. and Mackiw, V.N., Treatment of copper-zinc concentrates by pressure
hydrometallurgy. Can. Min. Metall. Bull., 57 ( 1964): 857-865.
124] Beckstead, L.W. and Miller, J.D., Ammonia, oxidation leaching of chalcopyrite-reaction kinetics. Metall.
Trans,, 8b ( 1977): 19-29.
[ 25 ] Beckstead, L.W. and Miller, J.D., Ammonia, oxidation leaching of chalcopyrite-surface deposit effects.
Metall. Trans., 8b (1977): 31-38.
1261 Beckstead, L.W., Reaction mechanisms in the ammonia oxidation leaching of chalcopyrite. Ph.D. Thesis,
University of Utah, Salt Lake City, UT (1975), 194 pp.
{27 ] Fon seca, A.G., Ammonia-oxidative leach of chalcopyrite. ClM Bulletin, July (1974): 105-110.
[ 281 Roman, R.J. and Benner, B.R., The dissolution of copper concentrates. Miner. Sci. Eng., 5 ( 1) ( 1973 ) : 3-
23.
[ 29 ] Stanczyk, M.H. and Rampacek, C., Oxidation leaching of copper sulfides in ammoniacal pulps at elevated
temperatures and pressures. BuMines RI 6193 (1963).
[ 30] Morrison, R.T. and Boyd, R.N., Organic Chemistry. Allyn and Bacon, 5th ed., (1987) pp. 773-778 and pp.
1280-1285.