Hydrometallurgy, 12 (1984) 195--215 195

Elsevier Science Publishers B.V., A m s t e r d a m -- Printed in The Netherlands

D I S S O L U T I O N O F B O R N I T E IN S U L F U R I C A C I D U S I N G O X Y G E N A S
OXIDANT *

B. PESIC
Department of Metallurgy and Mining Engineering, University of Idaho, Moscow, ID
83843 (U.S.A.)
and F.A. O L S O N
Department of Metallurgy and Metallurgical Engineering, University of Utah, Salt Lake
City, UT 84112 (U.S.A.)
(Received April 15, 1983; accepted in revised form D e c e m b e r 28, 1983)

ABSTRACT

Pesic, B. and Olson, F.A., 1984. Dissolution of bornite in sulfuric acid using oxygen as
oxidant. Hydrometallurgy, 12: 195--215.

Leaching of natural bornite in a sulfuric acid solution with o x y g e n as o x i d a n t was in-

vestigated using the parameters: temperature, particle size, initial c o n c e n t r a t i o n of fer-
rous, ferric and cupric ions, and using microscopic, X-ray and e l e c t r o n p r o b e microanal-
ysis to characterize the reaction products. Additionally, stirring rate, pH and PO2 were
varied. Dissolution curves for percent copper extracted as a f u n c t i o n of time were sig-
moidal in shape with three distinct periods of reaction: induction, autocatalytic and post°
autocatalytic which levelled off at 28% dissolution o f copper. The length of the i n d u c t i o n
period was n o t reproducible, causing the dissolution curves to be shifted with respect to
time. The dissolution curves in the a u t o c a t a l y t i c and post-autocatalytic regions were re-
producible, and this p r o p e r t y was utilized to treat m u c h of the kinetic data. The iron dis-
solution curves had f o u r dissolution regions. An initial small but rapid release of iron to
solution preceded the three periods just given for copper dissolution. Aside f r o m this ini-
tial iron release, the iron and copper dissolution curves were almost identical.
Stirring rate had no effect on dissolution of copper above 400 min -~ nor did o x y g e n
flow rate in the range 20--40 cm 3/rain. Dissolution rate was slightly d e p e n d e n t on oxy-
gen partial pressure for PO- < 0.67. H y d r o g e n ion c o n c e n t r a t i o n had no effect e x c e p t that
sufficient acid was requirec~ to prevent hydrolysis and precipitation of iron salts.
The dissolution rate was directly d e p e n d e n t on the reciprocal of particle diameter in-
dicating possible surface chemical reaction control, but the activation energy of 35.9
k J / m o l (8.58 kcal]mol) for the a u t o c a t a l y t i c region of copper dissolution is slightly t o o
small for that, t h o u g h n o t unreasonable. Initial a d d i t i o n of Fe ~÷ had a rather c o m p l e x ef-
fect and m a r k e d l y e n h a n c e d dissolution of copper, as also did initial addition of Fe ~÷.
Microscopic analysis showed nuclei of two new phases, covellite and Cu3FeS4, in the in-
d u c t i o n region. The new phases grow rapidly in the autocatalytic stage, which is control-
led by nuclei f o r m a t i o n and chemical reaction. The post-autocatalytic region is charac-
terized by c o m p l e t e t r a n s f o r m a t i o n of bornite into covellite on the particle surfaces and
Cu3FeS 4 as an internal p r o d u c t with an X-ray s p e c t r u m very similar to that of chalco-
pyrite. The post-autocatalytic region is controlled by a u t o c a t a l y t i c growth o f newly

*This paper is based on M.S. Thesis w o r k of B. Pesic.

0304-386X/84/$03.00 © 1984 Elsevier Science Publishers B.V.

196

formed phases. Further reaction beyond the autocatalytic region (percent copper disso-
lution > 28%) occurs so slowly with oxygen as oxidant that it was not studied.
The rate of copper dissolution appears to be controlled by the rate of iron dissolution.
Using that and the other experimental evidence a mechanism for reaction is proposed in
which iron-deficient bornite, CusF%S4, is formed on the surface by initial preferential
iron dissolution. Labile Cu + diffuses into this from CusFeDSO 4 and unreacted bornite to
produce CuS on the surface. Depletion of labile Cu ÷ ions from CusFeS 4 produces Cu3FeS 4
in the interior of the mineral particles.

INTRODUCTION

A l t h o u g h leaching o f c o p p e r minerals has b e e n practiced for m a n y years,

m u c h still remains u n k n o w n c o n c e r n i n g t h e c h e m i s t r y o f dissolution o f the
various sulfide minerals, particularly the C u - - F e sulfides t h a t are o f great
c o m m e r c i a l i m p o r t a n c e . One o f these, b o r n i t e , is a widespread m i n e r a l and
is the s e c o n d m o s t i m p o r t a n t mineral at the Bingham Mine o f Utah, f o r in-
stance.
Leaching o f b o r n i t e in acidified solutions has been studied [ 1 - - 8 ] , and in
all cases t h e applied o x i d a n t was ferric ion. O x y g e n , although a m u c h slower
o x i d a n t , is attractive f r o m a practical p o i n t o f view. It is the actual o x i d a n t
in d u m p leaching, t h o u g h its role in m o s t cases is to oxidize ferrous to ferric
ion. O x y g e n has b e e n studied as an o x i d a n t for c h a l c o p y r i t e [ 9 - - 1 1 ] , chalco-
cite [ 9 , 1 2 , 1 3 ] and o t h e r c o p p e r sulfides [ 9 ] , b u t n o t for bornite.
Pesic and Olson [14] also studied the leaching o f b o r n i t e using FeC13 as
the lixiviant. T h e r e a c t i o n was f o u n d to be a b o u t t w o orders o f m a g n i t u d e
m o r e rapid t h a n f o u n d in this s t u d y using o x y g e n as o x i d a n t . In their ferric
chloride s t u d y t h e y observed t w o distinct stages o f r e a c t i o n with a t r a n s i t i o n
p e r i o d b e t w e e n these t w o stages. T h e first stage was v e r y rapid and t e r m i n a t e d
at 28% c o p p e r e x t r a c t i o n . It was c h a r a c t e r i z e d b y an activation e n e r g y o f
2 4 . 7 8 k J / m o l (5.92 k c a l / m o l ) , direct d e p e n d e n c e o f rate o n inverse o f particle
size, l/d0, first-order d e p e n d e n c e on [ F e 3+] and n o d e p e n d e n c e o n [Cu 2+] or
[Fe2+]. It was d e d u c e d t h a t like c h a l c o c i t e [15] the first stage was mixed-
kinetics c o n t r o l l e d , with b o t h ferric ion t h r o u g h the solution b o u n d a r y layer
and r e a c t i o n o n the surface to release Cu ~÷ into solution being i m p o r t a n t .
T h e c o n c e n t r a t i o n o f labile Cu+ in the b o r n i t e lattice was believed to govern
the p o t e n t i a l o f the surface reaction. O n c e Cu ÷ was d e p l e t e d f r o m the origi-
nal lattice Stage I t e r m i n a t e d . T h e transition p e r i o d (28 t o 40% dissolution)
was c h a r a c t e r i z e d with considerably slower r e a c t i o n and was c o n t r o l l e d b y
n u c l e a t i o n and g r o w t h o f active surface sulfur sites which were r e q u i r e d for
Fe 3÷ r e d u c t i o n to release Cu 2÷ and S f r o m the i n t e r m e d i a t e Cu3FeS4 f o r m e d
b y Stage I r e a c t i o n . R e a c t i o n o f Stage II was still slower and was c o n t r o l l e d
b y d i f f u s i o n ( p r e s u m a b l y o f Cu ÷) t h r o u g h the t h i c k e n i n g p r o d u c t sulfur
layer in a t o p o c h e m i c a l r e a c t i o n o f m i n u t e subcrystallites o f Cu3FeS4 f o r m -
ed b y Stage I reaction.
In this s t u d y with o x y g e n as o x i d a n t the r e a c t i o n rate is t w o orders o f
m a g n i t u d e or m o r e slower t h a n with ferric chloride, or o t h e r ferric ion solu-
 197

tions, in which Fe 3÷ is the oxidant. Because of the extreme slowness of the

reaction with 02 as oxidant it was feasible to study only the period of disso-
lution which presumably corresponds to the first stage of reaction, i.e., to
28% copper dissolution. There are significant differences, however, in Stage I
dissolution using 02 as oxidant in a sulfuric acid medium as presented in this
paper and Stage I leaching with Fe 3÷ as oxidant. As will be treated subse-
quently, the behavior with sulfuric acid is also rather different than with hy-
drochloric acid [16], where in each case 02 is oxidant.
In this study a rather controversial intermediate (Cu3FeS4) is considered.
Kopylov and Orlov [3] were the first who discovered formation of this new
phase during dissolution of natural bornite in ferric sulfate solution. Using
X-ray diffraction analysis, they deduced that the new phase was chalcopyrite
and modified Sullivan's representation [1] of bornite, CuS.2Cu2S. FeS~, to
CuFeS2" 2Cu2S. The more rapid dissolution of chalcocite when compared to
bornite was explained by the one atom of copper being in the form of poor-
ly soluble chalcopyrite.
Dutrizac et al. [4] studied kinetics of dissolution of bornite in acidified
ferric sulfate solutions using sintered discs of synthetic bornite. They found
that at temperatures above 40°C dissolution occurred in two stages. In the
first, a nonstoichiometric bornite with up to 25% deficiency of copper was
formed; in the second, the nonstoichiometric bornite was converted to chal-
copyrite and elemental sulfur. At temperatures below 40°C, only nonstoichi-
ometric bornite was formed.
Ugarte and Burkin [8] studied the rate of reaction of synthetic bornite
with aqueous ferric sulfate solutions. They identified two stages of dissolu-
tion in both temperature regions, above and below 40°C. Above 40°C.
Cu3FeS4 formed and dissolved in the second stage to produce copper, iron
sulfate and elemental sulfur. Below 40°C, in the first stage nonstoichiometric
bornite, Cus~x FeS4, formed and dissolved further in the second stage to pro-
duce Cu3FeS4.
Lowe [7] proposes a complex mechanism for dissolution of bornite in fer-
ric sulfate solutions. The mineral structure of bornite is changed by solid
state diffusion of cuprous ions, Cu÷, to an intermediate mineral, Cu3FeS4,
with further conversion to Cu2FeS3. Formation of these phases was not
proven.

EXPERIMENTAL TECHNIQUES

Bornite preparation and characterization

The bornite mineral used in this study was obtained from Pinal, Arizona
as a coarse specimen of high-grade mineral. The mineral was crushed, ground
and screened to prepare monosize fractions in the range - 4 0 to +400 mesh
size. Gangue and diamagnetic minerals were removed from each size fraction
by using a Carpco Laboratory Model Magnetic Separator. The chemical corn-
198

position o f the prepared mineral and the theoretical value for bornite are
given in Table 1.
X-ray diffraction analysis indicated the presence of chalcopyrite and ten-
nantite in the sample (Fig. 13). A fluorescence spectrometric study also con-
firmed tennantite. A microscopic study of polished sections showed in addi-
tion chalcocite, though the latter was not indicated by X-ray diffraction.
Chalcocite was the major i m pur i t y and total impurities made up about 20%
o f the sample.

TABLE 1

Chemical composition of bornite

Experimental (%) Theoretical (%)

Copper 62.15 63.33

Iron 10.80 11.12
Sulfur 26.01 25.55

Apparatus and procedure

A schematic diagram of the experimental apparatus in Fig. 1 shows the

one-liter glass reactor with baffles used for the leaching tests. The reactor
cover had four ground-glass ports, which contained a Friedrich's condenser,
sampling device, oxygen dispersion tube, and a glass impeller. The impeller
was inserted through the center por t by means of a Chesapeake stirrer con-
nection and was driven by a Fisher mixer. The entire reactor assembly was
clamped into place in a water bath which was heated with a Haake tempera-
ture controller and held to within +0.1°C o f the desired temperature.
Prior to beginning an experiment, 0.5 1 of the H2SO4 solution was pre-
heated to the desired reaction t em pe r at ure with oxygen being constantly
purged through the solution using a fritted tube for good dispersion. Half a
gram o f bornite sample was introduced through one of the cover ports to
initiate the reaction. Aliquot samples of about 3 cm 3 were taken with a
sampling device about every hour and analyzed using an atomic absorption
s p e c t r o p h o t o m e t e r . Medical-grade oxygen was used, and it was passed
through glass wool and water before entering the reaction system.

Stirring speed, oxygen flow rate and acid concentration

Variation of stirring speed in the range 400--1100 min -~ had no effect on

leaching rate results. At lower impeller speeds the mineral had a t e n d e n c y to
float on the surface of the solution, so 1100 min -1 was used for the leaching
measurements.
Three different oxygen flow rates, 10, 20 and 40 cm3/min, were used, and
no variation o f leaching rate was observed. An oxygen flow rate of 20 cm 3
was used for o the r measurements.
 199

In the range 0.05--0.4 N sulfuric acid concentration, no change in the

rate of dissolution of bornite was observed; 0.1 N H2SO4 was used. Table 2
gives the standard conditions for the results presented unless otherwise indi-
cated in the figures.

"1-

i - -

i -

i -
i - -
i - -
i--

3 Cover Clamp
4- B a f f l e d Reaction Vessel
5-Sampler
6 - C h e s a p e a k e Connector
1 Friedrich's 7 Water Bath
Condenser
8 G l a s s T u r b i n e Impeller
2 H a a k e - C o n stant
Temperature
C,rculator

Fig. 1. Leaching apparatus.

TABLE 2

Standard leaching conditions

Temperature 90 ° C
Po 1.0
Sulfuric acid concentration 0.1N
Particle size - 3 2 5 +400 mesh
Solution 500 cm 3
Bornite sample size 0.5g
200

RESULTS

Reproducibility
Figure 2 shows that plots of percentage of copper extracted as a f u n c t i o n
of time are sigmoidal in shape with three distinct periods of reaction or
regions of the curve: induction, autocatalytic, and post-autocatalytic. The
latter had slow reaction rate which tended to level off at about 28% Cu ex-
tracted. Shown in Fig. 2 is a reproducibility problem with respect to induc-
tion, as the results are for four supposedly identical experiments. The auto-
catalytic and post-autocatalytic regions are reproducible, however.

i I I r ~ I T I

25

~20

w
P

- /
/ . / /,, /
X /
/ %2
size ~2s~4oo
J
5

1 2 3 4 5 6 7 8
TIME, h

Fig. 2. Leaching curves showing variation of induction time using supposedly identical
experimental conditions.

Considerable time was devoted to at t em pt s to obtain reproducible induc-

tion periods. Sequencing of the experimental procedure, and in particular
any aspect that might effect the mineral surface, was carefully considered.
It was found that purging the solution with 02 for up to 2 hours before in-
troducing the sample reduced the induction period to about I h from 4--8 h
otherwise, but still results were not reproducible. As a consequence it was
decided for some of the results to analyze the data in a different way and
take advantage of the reproducibility of post-induction results. The tech-
nique decided u p o n was to use the inflection points of the curves as in Fig. 2
as reference points for bot h percent copper extraction and time. These
parameters were defined as follows:
A Time = (Time)t - (Time)i (1)
where (Time)t = reaction time of interest, and (Time)i = reaction time at the
inflection point of the sigmoidal rate curve
 201

ACu = (Cu)t- (Cu)i (2)

where: (Cu)t = copper extracted at reaction time of interest, and (Cu)i =
copper extracted at inflection point.
In Fig. 3 the data of Fig. 2 are replotted using this approach; excellent re-
producibility has been achieved.

I X
Lu
I-

I.-
x 10
LU

~3

AT I M E,h

Fig. 3. Data of Fig. 2 replotted to show reproducibility with inflection point as reference
(conditions as in Fig. 2).

Effect of oxygen partial pressure

Oxidative leaching of sulfides in acid solutions is not thermodynamically

favored unless oxygen (or other oxidant) is present. The driving force of the
leaching reaction is substantially increased by the free energy of water for-
mation (AG = - 2 3 5 . 1 kJ/mol (-56.2 kcal/mol)) when oxygen is present.
Oxygen partial pressure was varied from PO2 = 0.21 to 1.0 and there was
a slight direct dependence of the leaching rate of bornite on oxygen partial
pressure for PO 2 < 0.67.

Effect of particle size

Figure 4 shows a rather strong direct dependence of leaching rate on reci-

procal of particle size. Plotting the leaching rate at the inflection point
against the reciprocal of particle diameter, do, gave a linear dependence as
shown in Fig. 5. This effect m a y be analyzed using the interpretive relation
as presented by Wadsworth [ 1 7 ] :
Ida\ kA0 6kf 1
- + (3)
i ~ ~ do
202

w h e r e : a = p e r c e n t o f c o p p e r extracted; t = t i m e ; k = c o n s t a n t w h i c h in-
cludes specific rate c o n s t a n t , all r e a c t a n t c o n c e n t r a t i o n terms, and a conver-
sion factor; A0 = internal area per unit v o l u m e {cm2/cm3); ~ = particle den-
sity (g/cm3); and f = e x t e r n a l surface r o u g h n e s s factor.
Figure 5 s h o w s in a d d i t i o n to t h e linear relationship as e x p e c t e d f r o m eqn.
(3) a n o n - z e r o intercept suggesting the p r e s e n c e o f internal surface area at
t h e stage o f r e a c t i o n associated w i t h the i n f l e c t i o n p o i n t . As will be s h o w n

~ ,-32~+~oo //~,I.-- "-'~

/ ///

I
1 2 3 4 5 6 7 8
T I M E, h

Fig. 4. Effect of initial particle size (conditions as in Fig. 2).

i i i

12

10

8
:g

~6

J- 4

n.- ~ e,l

8 112 116 210 24

I oo~
do
Fig. 5. A plot of linear rate constants (slopes at inflection points in Fig. 4) versus inverse
initial particle size.
 203

later on the basis of microscopic examination of the leaching residues this is

reasonable, and it is also in agreement with ferric chloride leaching of bornite
[ 14]. Initially, the mineral particles had no internal area, so internal surface
area resulted because of leaching to the inflection point, i.e., autocatalytic
region.

Effect o f temperature

Figure 6 shows that the leaching rate increased with increase in tempera-
ture in the range 50--90°C. This was evaluated for the autocatalytic region
(slopes at inflection points) of Fig. 6 to obtain an Arrhenius plot as shown in
Fig. 7. The activation energy, Ea = 35.9 kJ/mol (8.58 kcal/mol), is too high
for the reaction to be controlled by mass transfer through the boundary
layer and is slightly too low but possible for chemically controlled reactions.

J I l T I 0 °C

5 ,.._ I I I I I I I I
1 2 3 4 5 6 7 8
T I M E,h

Fig. 6. Effect of temperature (conditions as in Fig. 2).

Effect o f ferrous ion

The possibility of a back reaction or effect of increased ionic strength due

to Fe z÷ p r o m p t e d a study of the effect of ferrous ion on leaching rate, and
the result was rather surprising. Initial addition of ferrous ion p r o m o t e d the
leaching reaction rate to a great extent (Fig. 8). Also, the induction time de-
creased and the a m o u n t of copper dissolved greatly increased. Leaching bey-
ond the first stage, 28% dissolution, also occurred. The possibility of a trace
of ferric sulfate in analytical grade ferrous sulfate used for the leaching tests
was considered and eliminated. Analytical grade ferrous ammonium sulfate
was used and these same results were obtained. As shown by H u f f m a n and
Davidson [18] and by Matseevskii and Dokuchaeva [19], homogeneous oxi-
204

d a t i o n of ferrous ion by o x y g e n to p r o d u c e ferric ion is very slow, m u c h t o o

slow to explain the marked increase in dissolution o f bornite f o u n d in this
case. A possibility is that ferrous ion is o x i d i z e d by o x y g e n catalytically on
the surface o f the bornite particles. A d d i t i o n a l experimental i n f o r m a t i o n is
required for a definite answer as to the role o f ferrous ion in the leaching re-
action.

c
0o.
2

l e. ~

o.
o

v 3

' 2'.8 ~ 2'., ' 3'.0 ' 3!,

1000 , k-1
T

Fig. 7. Arrhenius plot. Rates were taken as slopes at inflection points in Fig. 6.
f [

5O

4C
a
tu
I.-

I-
X
~20

~0

T I M E, h

Fig. 8. Effect o f initial addition of ferrous sulfate (conditions as in Fig. 2).

Effect of ferric ions

Leaching o f s y n t h e t i c bornite using ferric ion as an o x i d a n t has been

studied before [ 1 - - 8 ] . It was n o t the purpose o f this s t u d y to repeat that
 205

work, b u t an e x p e r i m e n t was p e r f o r m e d to check if t he natural bornite used

in this s t u d y was peculiar, i.e., to see if there was also an induction period
using ferric sulfate. Figure 9 shows t hat there is no induction period. It also
shows how mu c h stronger ferric ion is as an oxidant than oxygen. Lack of
the induction period using ferric ion (Fig. 9) and presence o f an induction
period using ferrous ion (Fig. 8), with bot h having 02 present, is a further
p r o o f that h o m o g e n e o u s oxidation of Fe 2÷ to Fe 3+ by 02 was n o t the reason
for the enhanced oxi da t i on rates o f Fig. 8.
[ I t i i i i t + i

Fe 3+ m o l a r
70
• 0.11 §
• 0.0 3
60
• 0.0 0

~ 5o

x
m 30

10

I I
I 2 3 4 5 6 7 8 9 10
T I M E,h

Fig. 9. Effect of initial addition of ferric sulfate (conditions as in Fig. 2).

Effect of product ions

To see if species already dissolved in solution are responsible for the auto-
catalytic stage of the reaction, an experiment was p e r f o r m e d in which the
reaction was quenched in the autocatalytic region (aCu ~- 15%) and the
leaching residue was removed and placed in another reactor with the solu-
tion u n d er the same initial standard conditions. The residue then cont i nued
reaction with the fresh solution. The results in Fig. 10 show that the reac-
tion p r o ceed ed as if it were not disrupted. An additional induction period
was not present, indicating that pr oduc t s in solution are not i m port ant in
the reaction. This result was i m por t ant because initial addition of cupric sul-
fate to the level of 0.012 M had indicated a slight retardation of reaction.

Effect of replacement of oxygen with nitrogen

Figure 11 shows extraction o f bot h copper and iron in which oxygen flow
into the solution was replaced with nitrogen. Copper dissolution not only
stopped when this was done, but some copper was removed from solution.
206

Iron continued to go into solution. This result shows that o x y g e n in solution

controls the dissolution rate of copper from bornite.
Cupric ion itself can be an oxidant as shown by Parker et al. [20] and by
Muir et al. [ 2 1 ] , but in the process it would be converted to cuprous ion,
and in this case copper disappeared from solution. Copper depletion from
solution is no d o u b t due to ion exchange with Fe 3+ in the mineral. This con-
clusion is supported by a stoichiometric calculation and the fact that H:S
was n o t detected, eliminating Cu :÷ precipitation.
I T I 1 1 I i 1 I ~

30
P c oVP e~.... -''4r~

°,,~20 i /-, ,oo

I.->< .

~ ~ I I i I I I i I I
1 2 3 4 5 6 7 8 9 10
TIME, h

Fig. 10. Leach interruption e x p e r i m e n t in which residue o f reaction after part I was in-
troduced into fresh leach s o l u t i o n at same initial c o n d i t i o n s as at the beginning o f part II
( c o n d i t i o n s as in Fig. 2).

i f T r r I i

°~15

(9
e r
1--10 8
X
UJ

~5
C.)

J i I i J
1 2 3 4 5 6 ? 8
T I M E, h

Fig. 11. R e p l a c e m e n t o f o x y g e n with nitrogen at a u t o c a t a l y t i c region o f reaction, nitro-

gen i n t r o d u c e d at asterisk ( * ) ( c o n d i t i o n s as in Fig. 2).
 207

Iron dissolu tion

Bornite leaching with respect to iron dissolution is characterized with four

distinct reaction periods or regions of the dissolution rate curve as shown in
Fig. 12 for b o th Fe and Cu dissolution. Initially, about 5% Fe dissolved, but
no co p p er dissolved in this time period. Subsequently, iron dissolution level-
ed off. These two regions o f iron dissolution correspond to the induction
region o f copper dissolution. After this part of the reaction iron and copper
dissolved at about the same rate in both the catalytic and autocatalytic re-
gions. Finally, iron dissolution reached a plateau, though just ahead o f cop-
per and at a b o u t the same level of extraction as with the copper plateau ter-
minating the autocatalytic region. It appears as though the rate of copper
dissolution is based on the rate o f iron dissolution.
A n o t h e r p h e n o m e n o n observed is that the plateau for iron dissolution was
n o t constant as was f ound for copper dissolution. The final percent of iron
dissolution was a direct function of the length of the induction period of
copper dissolution and varied between 20 and 40%.

3O I I r r I I T I 1 I I

d
I,-
X20
14J

Z
0
fie

Og
mlO
rt
O.
J
0

I I I E r I
1 2 3 4 5 6 7 8 9
T I M E,h

Fig. 12. T y p i c a l d i s s o l u t i o n curves w i t h r e s p e c t to c o p p e r a n d iron ( c o n d i t i G n s as in Fig.

2).

Microscopic study

The initial residue with less than 5% iron extraction (no copper dissolu-
tion) showed no change either on the surface of the particles or inside of
crushed particles. The particles showed the optical properties characteristic
of bornite.
The latter part of the induction region showed the presence of a new
phase on the surface when less than 5% of the copper was dissolved and iron
208

dissolution was a b o u t 10%. The indigo-blue color of the new surface phase
with extremely high bireflectance features indicated covellite, CuS. This
could only be seen clearly in colored photomicrographs, and hence, due to
lack of this detail in black and white reproductions, this and other photomi-
crographs are not given in this paper.
In the autocatalytic region (15.8% Cu extracted), the covellite phase was
prominent on the outside of the grains. Inside of the particles the vivid green
color of the inner product matched the description given for "idaite", by
Uytenbogaart and Burke [ 2 2 ] , which under polarized light has a vivid green
color, in contrast to chalcopyrite, which has a greenish-yellow color.
The photomicrograph from the final reaction stage (28% Cu extracted)
showed covellite completely covering the surface and thicker than previous-
ly, as well as an inner reaction product of which identification on the basis
of microscopy was doutbful; however, the optical properties, though similar
differed slightly from those for chalcopyrite.

X-ray analysis

In Fig. 13 (a--d) X-ray diffraction patterns of the feed material and of

leaching residues from the induction, autocatalytic and post-autocatalytic
regions are presented. The pattern for the feed material, Fig. 13(a), shows
characteristic peaks for bornite, along with two major additional peaks,
chalcopyrite, CuFeS2 (28 = 29.44) and tennantite, (CuFe)12As4S13 (20 =
30.36). No chalcocite peak can be seen, although its presence was identified
microscopically. The chalcopyrite peaks serve as an internal standard for
qualitative comparison purposes. The tennantite peak in Fig. 14 is unchanged
during reaction as tennantite is rather refractory especially under the mild
oxidizing conditions of this study.
Figure 13(b) (3.5% Cu extracted) still shows the peaks characteristic of
the initial bornite. Figure 13(c), for the autocatalytic stage (15.8% Cu ex-
tracted), is characterized not only by the new phase, covellite, but also by
disappearance of the peaks due to bornite.
Figure 13(d), for the final residue (33% Cu extracted), shows peaks char-
acteristic of covellite and the rather controversial intermediate which has
peaks very similar to, if not in fact, those of chalcopyrite. The latter peaks
have steadily increased in size.
Figure 13(e) is the X-ray diffraction pattern for leaching of bornite with
initial addition of ferrous sulfate. No covellite peaks are seen, so apparently
no covellite was formed in this case. Leaching of bornite with ferric chloride
also did not produce covellite as an intermediate [14].

Electron microprobe microanalysis

The same residue samples as discussed in the preceding were used for
chemical analysis using the electron microprobe. Very pure bornite served as
 209

an analytical standard. Because the outside reaction product, covellite, was

known from the previous microscopic study, only the inner phase was anal-
yzed. Table 3 gives the theoretical compositions of expected reaction prod-
ucts. Species id, id-1, id-2 and nm are variants of idaite, as will be discussed
later. Table 4 gives the microprobe compositions actually obtained, and they
fit the formula Cu3FeS4 best of all the proposed species in Table 3. Analysis
of the results in Table 4 shows that the reaction product in the centers of the
particles seems to be converging with time towards 50.9% Cu, 14.9% Fe and
34.2% S (Cu3FeS4), which is fitted almost exactly by the residue leached in a
solution with added ferrous ion.

bn

bn
bn tn ~bn [

cp

cp

CV
CV

[d]

[e]

I t I I I L I I I
60 55 50 45 40 35 30 25
29 o

Fig. 13. X-ray diffraction pattern of: (a) initial bornite; (b) residue at induction period
(3.5% Cu dissolution); (c) residue from autocatalytic reaction region; (d) final leaching
reaction residue;and (e) leaching residue from initial ferrous sulfate addition.
210

TABLE 3

Theoretical compositions of expected reaction products

Cu (wt.%) Fe (wt.%) S (wt.%) Total (wt.%)

CusFeS4, bn 63.33 11.12 25.55 100

CuFeS~, cp 34.64 30.42 34.94 100
Cu~FeS4, id 50.87 14.90 34.23 100
CusFeS6, id-1 56.14 9.87 34.00 100
Cus. s FeS~. s , id-2 56.94 9.11 33.95 100
Cu3.37Fe0.66S2.~7 , n m 56.51 9.64 33.51 100
Cu2. s FeS, 46.35 16.30 37.35 100

TABLE 4

Electron probe microanalysis of the reaction product present in the centers of the residue
particles

% Cu, dissolved Cu (wt.%) Fe (wt.%) S (wt.%) Total (wt.%)

0.00 62.26 12.32 26.27 100.85

3.50 63.49 10.83 26.64 99.96
9.00 61.80 12.06 27.2 100.88
15.80 59.60 12.67 27.33 99.60
33.00 52.94 13.80 31.79 98.53
a 50.15 15.04 33.30 98.49

aExperiment with initial addition of ferrous sulfate.

DISCUSSION

Of the two principal reaction products, the one, covellite, is readily char-
acterized on the basis of microscopy and X-ray studies, but the other is
rather difficult to characterize. X-ray evidence seems to indicate chalco-
pyrite, as has been previously reported [1,3,4], but optical microscopy and
electron probe microanalysis seem to indicate a different species, Cu3FeS4. It
might be argued that Cu3FeS4 is chemically the same as one CuFeS2 plus
two CuS molecules, but in the areas of the residue particles (centers) where
Cu3FeS4 was present there was no evidence of covellite. Covellite existed
only on the surface of the residues. The species Cu3FeS4 has been reported
by other researchers as idaite [23--30]. Levy [ 2 6 ] , Sillitoe and Clark [28]
and Constantinou [31] propose the formula for idaite of Cu3FeS4 on the
basis of microprobe data but give no X-ray data [26,28,31]. Rice et al. [32]
have reviewed the problem and conclude that idaite is inadequately defined,
and, using a mineral from a Fijian kuroko deposit previously defined as ida-
ite, propose a new name, " N u k u n d a m i t e " , with the formula Cu3.37Fe0.66S3.97.
This mineral is fully described [22].
 211

The authors on the basis of these microprobe results tend to favor idaite,
but the composition in the discussion to follow will not be called " i d a i t e "
but just Cu3FeS4. This is based primarily on the microprobe data.
The aspect of iron being dissolved before copper as previously discussed is
different than was found for leaching of synthetic bornite with ferric sulfate
by Dutrizac et al. [4] and also by Price and Chilton [33] for anodic oxida-
tion of synthetic bornite in an electroleaching study; on the basis of the stu-
dies with ferric sulfate [33] it has been suggested that two-stage leaching
occurs but with the intermediate being Cus-x FeS4. In this study, instead of a
copper-deficient nonstoichiometric compound being formed initially during
leaching, an iron-deficient c o m p o u n d is proposed. A difference exists when
comparing copper-deficient and iron-deficient bornite because only one Fe
exists in each bornite molecule. When a bornite molecule loses an iron atom,
an iron vacancy is left. The electrons also diffuse out leaving CusFe~ $4 where
FeB represents the iron vacancy. It is proposed that bornite molecules with
iron vacancies exist primarily on the surface, consistent with 5% initial iron
depletion but with retention of the bornite structure based on X-ray and
microscopic examinations.
Using the structural formula of bornite (Cu3FeS4) 2-- Cu + as proposed by
Manning [34], the oxidation half-reaction for iron-deficient nonstoichiom-
etric bornite can be represented as:
(Cu3 FeS4 )2-. 2Cu + = x (Cu3 Feo $4 )2-. 2Cu + + ( l - x ) (Cu3 FeS4 ) 2-. 2Cu ÷ +
x Fe 3+ + 3x e- (4)
At the end of the first step in iron dissolution, x = 0.05.
The cathodic half-reaction which consumed the electrons produced by
eqn. (4) is the well-known equation for reduction of oxygen to produce
water:
1/2 02 + 2 H + + 2 e - = H 2 0 (5)
According to Manning's structural formula, copper and iron are in the mo-
novalent and trivalent states, respectively, a conclusion supported by Bor-
shagovskii [35] and by Takeno et al. [36]. Both Fe 3+ and Cu + are con-
sidered as very labile, with Cu ÷ considered to be the faster-diffusing species
according to Grace [37] and Samalj and Gilevich [38]. On this basis, once
iron-deficient bornite is formed on the mineral surfaces, cuprous ions can
diffuse into this defect structure to occupy the iron vacancies and cuprous
ions can also diffuse out into the solution. Considering only the anionic half
of the reaction for iron-deficient bornite, diffusion of copper into the iron-
deficient species (Cu3FeoS4) produces four covellite (CuS) molecules. The
copper (labile Cu +) for this reaction may come from the iron-deficient bor-
nite molecule (Cu3FeD $4 "2Cu+), or from the unreacted bornite, or possibly
even from solution, though the latter is considered less likely. The suggested
reaction (anodic) for this is:
212

x [(Cu3Fe~S4) 2-- 2Cu ÷] + x [(Cu3FeS4) 2- • 2Cu ÷] = 4x CuS + x Cu3FeS4 +

3x Cu ÷ + 3x e- (6)
F o r the bornite in the particle interior which has n o t lost iron, the diffu-
sion o f the labile Cu ÷ ions into solution leaves Cu3FeS4 behind according to
the reaction (also anodic):
(Cu3FeSs) 2- • 2Cu ÷ = Cu3FeS4 + 2 Cu ÷ + 2 e- (7)
According to Frenzel [ 2 4 ] , when one-sixth of the copper atoms in the
covellite structure are replaced with iron, idaite is formed. Frenzel used
CusFeS6 as the formula for idaite which was later corrected by Levy [ 2 6 ] ,
who wr o te Cu3FeS4 as the formula. The opposite of this reaction, i.e., re-
placement of iron with copper in Cu3FeS4, would produce covellite. This
idea is used in the preceding for p r o d u c t i o n of covellite (eqn. 6).
Equations (4--7) represent sequential reactions up to the end of the in-
duction stage o f reaction. Thereafter, as the autocatalytic region is ent ered
and nucleation of the new species CuS and Cu3FeS4 is over, these sequential

(Cu3FeS4)2:'2CL~ = x(Cu3FeDS4)2-2Cu++(1-x)(Cu3FeS4)2-2Cu +

2H+;O

H2o

/' ~ '
2H + ~ O
H20
x(Cu3FeDS4)2;2Cu+-I -(1-x)(CU3FeS4)2":2CM + = 4 x C u S 4-

xCu3FeS 4 + (1-2x)(Cu3FeS4)2"2Cu + + 3xC 2+ + 6xe

Fig. 14. R e a c t i o n s c h e m a t i c .
 213

equations still apply. Thus iron depletion, eqn.(4), governs the rate of cop-
per dissolution, eqns. (6) and (7). Oxygen furnishes the oxidizing drive for
all three of these reactions according to eqn. (5).
Cuprous ion, once it reaches the mineral surface, is readily oxidized to
cupric ion, once again by 02 present (eqn.5). Also, any ferric ion present
would oxidize Cu ÷ to Cu 2+. The final state in solution of copper and iron is
Cu 2+ and Fe 2+.
The overall reaction on the basis of these sequential reactions (eqns. 4--7)
recognizing that Cu÷ in solution would be oxidized by Fe 3+ present is:

2[(Cu3FeS4) 2 - . 2 C u +] + 2 0 2 + 8 H + = C u 3 F e S 4 + 4 C u S + 3 C u 2 + + F e ~++
4 H20 (8)

This represents 30% copper dissolution and 50% iron dissolution, which is
good agreement for the former but slightly too high for the latter. A possible
explanation for the smaller a m o u n t of iron extraction than the predicted
value is iron adsorption on the surface of mineral particles, as found by
Majima [39]. Also, some iron could be trapped in the external covellite
phase. Microprobe analysis of this phase proved the presence of iron.
A schematic representation of these reactions is given in Fig. 14. Figure
14-I shows the formation of the bornite molecules with iron vacancies,
[(Cu3Fe~S4) 2-. 2Cu+], according to eqns. (4) and (5). Figure 14-II shows
the formation of the CuS and Cu3FeS4 nuclei involving reactions (5--7).
The role of ferrous ion in reducing the induction period for copper disso-
lution and in increasing both the rate and final amount of copper dissolu-
tion is still inconclusive. Fe 2÷ may undergo a surface oxidation reaction to
produce the powerful oxidant Fe 3÷ with 02 as oxidant (eqn. 5) for the other
half-reaction. The marked positive role of ferrous ion in leaching with oxy-
gen as oxidant as found in waste dumps is of possible considerable conse-
quence.

CONCLUSION

During oxidative leaching of bornite with oxygen in H2SO4 solutions, two

phases are formed. Covellite forms on the surface of the mineral particles,
and the inner phase is Cu3FeS4, on the basis of microprobe analysis and as
augmented by microscopic evidence which has been interpreted by some as
the mineral idaite. X-ray diffraction indicates a species very similar to, if not
in fact, chalcopyrite. Mineralogists are not in agreement as to the mineral
idaite, which is shown by some as Cu3FeS4, but w i t h o u t X-ray data. In this
paper the inner-phase product is defined only as Cu3FeS4.
Iron dissolution to produce a bornite species on the surface with iron
vacancies precedes the formation of covellite on the surface and Cu3FeS 4 in
the interior. The rate of iron depletion governs the rate of copper dissolution
as CuS and Cu3FeS4 are formed by reaction of the labile Cu ÷ present with
the iron-depleted molecules; Cu ÷ may originate from the iron-depleted or
214

original b o r n i t e molecules. N u c l e a t i o n o f the t w o new phases is believed to

be rate c o n t r o l l i n g in t h e i n d u c t i o n period. Their g r o w t h b y surface c h e m i c a l
r e a c t i o n (activation energy = 35.9 k J / m o l (8.58 k c a l / m o l ) ) c o n t r o l s the
a u t o c a t a l y t i c period.
F e r r o u s ion m a r k e d l y e n h a n c e s the leaching o f b o r n i t e and the residue
consists o f o n l y Cu3FeS4. The m e c h a n i s m for this r a t h e r m a r k e d and inter-
esting e f f e c t o f Fe 2÷ is n o t y e t u n d e r s t o o d and is w o r t h y o f f u r t h e r s t u d y .

ACKNOWLEDGEMENT

This s t u d y was s u p p o r t e d b y t h e U.S. Bureau o f Mines (Grant No.

G 0 2 8 4 0 0 1 ) and is fully a c k n o w l e d g e d . Published w i t h o u t prior review b y
the Bureau o f Mines.

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