A review of copper hydrometallurgy

by j. C. PAYNTER*, B.Sc. (Ch em. Eng.) (Visitor)

SYNOPSIS
Copper. hydrom~t~lIurgy is discus~ed with special reference to the treatment of chalcopyrite concentrates under
Sout~ African con~ltlons. The following processes are described and illustrated: Sherritt Gordon's ammonia pressure
leac~lng, t~e Arbiter Process, sulphuric acid pressure leaching, roasting processes, the Cymet Process, and the

.
ferric chloride process developed at the National Institute for Metallursy. These processes are then compared with
respect to the form of sulphur produced (elemental sulphur or sulphate), the character of the iron product and the
handling of different types of ore.

SAMEVATTING
~oper.hidrometallurgie wo~d bespreek met spesiale verwysing na die behandeling van chalkopirietkonsentrate in
Sul?-Afrl.kaanse. toestande. Die volgende prosesse word beskryf en geillustreer: Sherritt Gordon se ammoniakdruk-
logl~g, die. Arblter-pr~ses, sw~wels~urd~ukl?ging, roosterprosesse en die ferrichloriedproses wat by die Nasionale
Instltuut vir Metallurgle ontwlkkells. Hlerdle prosesse word dan vergelyk ten opsigte van die vorm van die swawel
wat geproduseer word (elementale swawel of sulfaat), die aard van die ysterproduk en die hantering van die ver-
skillende soorte ertse.

INTRODUCTION
In giving a review of the hydro-
metallurgical processes for copper,
I am conscious of its being a subject
that is widely discussedl-3. Not
being an expert, I shall not attempt
to provide a better review than those
already available. However, as a
result of discussion with my col-
leagues at the National Institute for
Metallurgy (NIM) and with metal-
lurgists in industry, I have come to
realize that, instead of having a clear
picture of the direction in which
copper processing is moving, par-
ticularly processes employing hydro-
metallurgical techniques, most
metallurgists are becoming increas-
ingly confused, myself included. It is
hoped that this paper, although
saying very little that is new, will
provide a suitable basis for dis-
cussion so that benefit can be ob-
tained from the wealth of experience
and judgment available and so that
the picture can be clarified just a
little.
I intend to discuss copper hydro-
metallurgy with special reference to
South African conditions because I
believe that conclusions drawn for
conditions elsewhere, for example in
Arizona, D.S.A., are unlikely to be
the same as those arrived at for a
plant situated in South Africa. Even
within Southern Africa, what applies
to a plant located in a remote desert
area does not necessarily apply to a
plant located in the Witwatersrand
"National Institute for Metallurgy,
nesburg.
area. I also hope to highlight those economic reasons, these ores often
areas in which research can probably cannot be processed by normal
lead to cheaper and improved pro- flotation and pyrometallurgical
cesses. techniques. Differential-flotation
processes for mixed sulphides
WHY HYDROMETALLURGY? seldom give as clean a separation
It is perhaps difficult to provide a as desired, and in some instances
conclusive reason for the upsurge of flotation is quite unpractical.
interest in hydrometallurgical pro- (b) The successful industrial appli-
cesses during the past five years. cation of the copper-selective
I expect that many persons would solvent LIX4. 5, even though used
cite the fact that, whereas the 1960s in the treatment of oxide ores,
felt the impact of the computer in provided the most significant
almost every sphere of life, the breakthrough in copper hydro-
1970s are destined to experience the metallurgy since that achieved by
impact of the environmentalist. Sherritt Gordon in their success-
'Clean environment' campaigns are ful development of pressure-
already a reality of life, and en- leaching techniques.
vironmental considerations have (c) Many of the basic chemicals re-
forced the cancellation of construct- quired for hydrometallurgical
ion plans for power stations, the processes are produced in large
closing down of copper and zinc tonnages at low prices (e.g.,
smelters, the wresting of power from oxygen, ammonia, chlorine, hy-
the motor giants of Detroit, and drochloric acid). Of course, if
last, but not least, the clean-up of your process requires sulphuric
the air in cities like London, which acid, a smelter may pay you to
visitors now say has air superior to take it away by the 1980s!
that we breathe in our own modern (d) Suitable materials of construc-
metropolis. Sulphur dioxide pol-
tion, e.g., titanium, fibreglass, and
lution from smelters has perhaps plastics, have been developed at
been the strongest driving force
reasonable prices.
behind the recent massive expendi- (e) The ever-increasing cost of trans-
ture on research and development in port and the tendency for con-
hydrometallurgy. However, there are
centrates to be processed locally
probably other factors that have possibly mean that smelters,
contributed towards this trend. whose processing costs are
(a) It has been predicted that an favoured by very large units, are
increasing percentage of new less competitive with hydro-
copper production will come from metallurgical plants for the small-
non-sulphuric sources and mixed- er tonnages often applicable to
sulphide ores (e.g., copper-zinc). new discoveries (e.g., 5000 to
Johan-
For a variety of technical and 30000 tonnes of copper

158 NOVEMBER 1973 JOURNAL OF THE SOUTH AFRICAN INSTITUTE OF MINING AND METALLURGY
 annually). Many local companies
have recently found that the
cost of transporting concentrates,
custom smelting, and refining has
risen so much that the need to
consider their own processing
facilities is becoming increasingly
pressIng.
(f) As the price of copper has ]isen,
the importance of working capital
tied up in copper inventory has
increased, and it is believed that
virtually all hydrometallurgical
processes will have a lower in-
ventory than that of conventional
pyrometallurgical processes.
Despite the enormous effort being
directed to research in hydrometal-
lurgical processes, an equal, if not
larger, effort is being devoted to the
following:
(i) improvements in existing pyro-
metallurgical processes, with
special emphasis on the control
of sulphur dioxide pollution, and
(ii) developments in new pyrometal-
lurgical processes in which the
smelting and converting steps
are integrated into one con-
tinuous operation (or sequence
of operations), and which pro-
duce a steady high-quality stream
of sulphur dioxide gases, thus
making the manufacture of sul-
phuric acid easier and cheaper
(e.g. Mitsubishi, Noranda, and
WORCRA processes).
The various new processes being
investigated are well summarized
in a recent issue of Engineering &
Mining Jourml6.
The cost of bringing sulphur
dioxide pollution under control will
vary from region to region, depend-
ing on the regulations in force, but,
for conditions in the U.S.A., the
cost has been estimated2 as anything
from 3,5 to 9,0 South African cents
per kilogram of copper. These costs
are significant when it is realized
that the custom processing of con-
centrates to refined copper in a
large smelter may cost about 15
South African cents per kilogram of
copper, direct operating costs being
as low as 7 to 10 cents.
The philosophy that, because
many smelters are situated in re-
mote areas, particularly in a country
like South Africa, the abatement of
sulphur dioxide pollution is not very
important is unlikely to carry much
JOURNAL OF THE SOUTH AFRICAN INSTITUTE OF MINING AND METALLURGY
support in the future. The erection of
smelters must involve the develop-
ment of a township for persons
working at the smelter, and such
persons are entitled to breathe
clean air when away from work,
even though they may have to
accept a certain discomfort while at
work. A partial solution to pollution
by sulphur dioxide does not seem to
be acceptable.
PRODUCTION OF SULPHURIC
ACID
It is interesting to consider what
increase in sulphuric acid production
from smelter gases could be ab-
sorbed by other industries during
the next decade. The 1972 pro-
duction of sulphuric acid in South
Africa was approximately 1 400 000
tonnes of 100 per cent H2SO4' of
which 22 per cent was used by the
mining industry (mainly in uranium
processing), 67 per cent in the
manufacture of fertilizers, and 11
per cent by other consumers.
The quantity of sulphuric acid
that could be recovered from smelter
gases currently going into the atmo-
sphere is approximately 120 000
tonnes per annum. The air-pollution
authorities are already taking certain
steps about persuading most of these
operators to recover and use this
sulphur dioxide.
It is estimated that, if all new
copper, zinc, lead, and platinum
mining operations smelt their own
concentrates and are required to
recover the sulphur dioxide from
their smelting operations, the pro-
duction of sulphuric acid in South
Africa would be an extra 1 000000
to 1 500 000 tonnes per annum by
1985. This is likely to be more than
the local mining and fertilizer in-
dustries would require, unless major
new uses for sulphuric acid are
found. Unfortunately, most of the
new smelter capacity is likely to be
located in the north-western Cape
and South West Africa, which are
near neither to the source of phos-
phates at Phalaborwa nor to the
main farming areas. It is fairly
generally accepted that it is un-
economic to transport acid more
than 100 to 200 miles.
There is a very good opportunity
for the export of fertilizers, especially
to South America, and the opening
up of Saldanha Bay may make it
worth while to site smelters near
Saldanha Bay so that the sulphuric
acid produced can be reacted with
phosphate from Foskor or from the
deposits at Langebaan, near Sal-
danha Bay. It is a well-known fact
that apatite (phosphate ore) is al.
most as cheap a neutralizing agent
for sulphuric acid as lime is.
These facts highlight the im.
portance of co-operation between the
mining and fertilizer industries in
co-ordinating, as far as possible,
future expansion in smelter and
fertilizer plants. The recently an-
nounced plans 7 of Impala and Omnia
to get together to produce phosphoric
acid using sulphuric acid produced
from Impala's stack gases is an
encouraging move in this direction.
The cost of producing sulphuric
acid from smelter gases depends on
the size of the plant and the type of
smelter, but it is likely to lie between
R20 per tonne for small plants and
R5 per tonne for very large plants.
In most instances, it is probable
that this byproduct acid will be sold
at a negligible profit, and, in an
assessment of pyrometallurgical
routes versus hydrometallurgical
routes, it seems sensible to neglect
any credit from the sale of the
sulphuric acid over and above the
production cost.
HYDROMET ALL URGICAL
PROCESSES FOR
COPPER
There are many excellent publi-
cations reviewing the hydrometal-
lllrgy of copper2, 3, 8, 9, and Subra-
manian and Jennings3 recently dis-
cussed, concisely and clearly, the
various alternatives that are being
investigated for the treatment of
chalcopyrite. Dasher2 recently critic-
ally assessed the ability of hydro-
metallurgy to compete with pyro-
metallurgy. In this paper, I wish to
discuss only those processes that
appear to be attracting major
attention or appear to be promising.
Some may regard the omission of
bacterial leaching as serious, but too
little is known about the engineering
of these processes on a large scale to
permit a critical assessment.
Discussion will be mainly limited
to the treatment of chalcopyrite
concentrates since chalcopyrite is
NOVEMBER1973 159
 COPPEA..lIN~ CONCEN TRATE

both the most-abundant

mineral and the most difficult to
copper J
NH3 PRES~URE LEACHING
leach. Any process that is to be AIR
successful must therefore be capable
of treating chalcopyrite. A good ,
deal has been written about hydro- LIS SEP.'l.HATI("~~t- NH3 D'ST~ON
metallurgical processes for the treat- J ~ 'r=- l
ment of oxide ores! , and these will
COt;CENTRt.TE
not be discussed here. After the RESIDUE AIR --J.GfDROLYSI;j
HEC'(CLED
various processes have been briefly 240'C. &00 psi
described, they will be compared --_J I

with respect to certain key factors, FLOTATION

namely, the degree of oxidation of
the sulphur (elemental sulphur or ---r-- J
hCRYLATE-
sulphate), the character of the iron
TAILING
product, and the ability to handle
mixed sulphides. The comparison
[LIS SEPA"~I:J
strictly applies only to chalcopyrite, RECOVERY]
PRECIOUS ME:TALS
and quite different conclusions can
be drawn if, for example, chalco-
cite is being considered.
Sherritt Gordon's Ammonia Pressure- ~
COP PER POWDER
~--
CO21100 PSi>
=:G
~ ZINC
---,
CARBONATE I
Leaching Process NH3 PR~(,IPITATIO~_J
Sherritt Gordon Mines were pio-
neers in hydrometallurgy, and much
of the credit for advancing the tech-
nology of pressure leaching must be
given to them. They use pressure-
leaching processes for treating nickel
concentrates, and they have licensed, .. SOLUTION
CAKE fOR ZINC
among others, Western Mining in
Australia and Impala Platinum to
RECOVERY
~::-J..~
use their technology. In laboratory H2S---L~S STR~::~
and pilot-plant tests on chalcopy-
ritell, a 95 per cent extraction of
copper has been achieved. Most of CRyST::'TlO~
the unleached copper can be floated
from the residue and recycled.
L
Their flowsheet for the treatment
AMMOI~IUM SULPHATE
of copper-zinc concentrates is shown
in Fig. 1. The basic equations for the Fig. I.-Flowsheet for ammonia pressure-leaching process (according to
Evans et a/11)
dissolution reactions are as follows:
2CuFeS2+8t02+12 NH3+2H20
that the ammonia will be regenerated veloped by Anaconda, is essentially
=2 Cu(NH3)4S04+2(NH4)2S04 using lime and the calcium sulphate a modification of the Sherritt Gordon
+Fe203' and will be disposed of. Process. It uses ammoniacal pro-
ZnS+2 2+4 NH3=Zn(NH3)4S04'
Sherritt Gordon Mines found that cessing but eliminates the use of
It will be noted that all the
pressures of at least 100 Ibfin2 or high pressures. In the leaching step,
sulphide sulphur is converted to
690 kPa (gauge) were necessary for oxygen, instead of air, is used
sulphate, and, where there is a
leaching. Copper was recovered as (tonnage oxygen makes this possible
market for ammonium sulphate, the
a metal by precipitation with hydro- in certain locations) with special
process has a definite attraction. In
gen at high pressures, and zinc was agitation techniques that result in
South Africa, where ammonia used
recovered by precipitation with car- good dispersion of the oxygen in
for fertilizer purposes is sold at a
bon dioxide at high pressures. All the slurry and with proper control
lower price than ammonia used for
these high-pressure operations result of the reaction by some undisclosed
industrial purposes, ammonia would
in an expensive plant requiring means. The availability of the liquid-
have to be purchased at the ferti-
careful maintenance and operation. liquid-extraction reagent LIX has
lizer price before the ammonium
For the reasons given above, these permitted the extraction of copper
sulphate could be sold competitively.
processes are unlikely to find much by liquid-liquid extraction and elec-
As it is unlikely that there will be a
application in copper processing. trowinning. Techniques are also now
large market for ammonium
sulphate, the process economics must The Arbiter Process! available for the recovery of zinc
normally be assessed on the basis The Arbiter Process (Fig. 2), de- and nickel without resort to the high

160 NOVEMBER 1973 JOURNAL OF THE SOUTH AFRICAN INSTITUTE OF MINING AND METALLURGY
 pressures used by Sherritt Gordon. It One further potential advantage of ion or electrowinning, is returned to
will be noted from Fig. 2 that, as the ammoniacal system is that the process for further leaching.
with high-pressure leaching, copper copper can exist in the cuprous form, The sulphuric acid shown in the
recovery is not complete and un- which makes the possibility of direct left-hand side of the first equation is
reacted copper has to be floated electrowinning of the copper from therefore recycle acid, and the
from the residue. the leach liquor rather attractive, process has a very low net acid
The Arbiter Process was de- since the power cost would probably consumption. In fact, it appears
veloped by Professor Arbiter of only be about 50 per cent of that that about 5 per cent of the sulphur
Anaconda, after a thorough review from cupric solutions and the cost will be converted to sulphuric acid,
of all the possible hydrometallurgical of liquid-liquid extraction would be thus providing the necessary make-
processes, as the process that re- eliminated. This, however, repre- up of acid12.
quired the least development and sents a major research project in These pressure-leaching processes
was most likely to produce the electrochemical engineering, and the have the advantage that iron is
cheapest copper for Anaconda. A purity of the copper might be lower precipitated as a ferric hydrous
large plant having a capacity of than that recovered from the strip oxide, which reports in the residue.
100 tonnes of copper per day is liquor of a liquid-liquid-extraction The quantity of iron remaining in
being erected in Arizona, and Ana- plant. solution is a function of the acidity
conda have claimed that the capital and of the time and temperature of
cost is only half that of a smelter. Sulphuric Acid Pressure-Leaching leaching, but, because the solution is
The process still suffers from the Processes recycled to the leach after the re-
major disadvantage that either am- moval of the copper, all the iron will
Complete oxidation of sulphide
monium sulphate must be sold or eventually report in the residue. It is
concentrates can be achieved in the
ammonia must be recovered by almost certain that the actual
relatively short time of 1 to 2 hours
neutralizing with lime. Where oxidation attack on the mineral is
if temperatures in the range of 140
precious metals are not of any by ferric iron, and a small quantity
to 200 C and high pressures of air
account, Arbiter suggests that the of dissolved iron is therefore neces-
or oxygen are used. However, the
lime should be added to the leach sary.
equipment is expensive, and the
because this eliminates one step in Owing to the relatively low level
costs of heating the slurry and com-
the liquid-solid separation and im- of iron in the leach liquor, direct
pressing the oxidant are considerable.
proves the filtration characteristics electrowinning of copper from the
Sulphate is formed under these
of the iron oxide in the leach residue. leach liquor can be considered, thus
conditions, and the costs of oxidant
Because very few metals form saving the costs of the liquid-liquid-
and lime are therefore the same as in
ammine complexes, all ammoniacal extraction plant.
the ammoniacal processes.
leaching processes have the ad-
vantage of being very selective. A lower-temperature process oper- The effect of various operating
This is particularly advantageous in ating below the melting point of parameters on the leaching process
avoiding the extraction of iron, sulphur in the temperature range have been studied extensively by
which is almost invariably present in 100 to 120 C is to be preferred, Vizsolyi et al.12, and Fig. 3 is a
all copper concentrates. since the engineering problems are flowsheet of the process suggested
Liquid-liquid extraction using not nearly so severe, and the costs by them. Under the optimum con-
LIX in ammoniacal systems has the of heating and compressing the ditions of a temperature of 115 C
advantage over acid systems that oxidant are also much less. A further and an oxygen partial pressure of
the solvent can take higher loadings major advantage is that, at these 200 to 500 Ibjin2 or 1380 to 3450 kPa
temperatures, elemental sulphur, (gauge) on a concentrate that had
of copper. A disadvantage, however,
is that LIX is less selective for rather than sulphate, is formed. This been ground to 99,5 per cent minus
copper over nickel and zinc than in means that a possible salable by- 325 mesh, the percentage copper
acid systems, but there are tech- product is produced instead of the extraction was only about 65 per
niques for overcoming this problem. sulphate, which requires lime for cent after 2t hours. After removal
Ammoniacal processes are ideal neutralization. In addition, the cost of the sulphur, the undissolved
when the gangue minerals are acid- of oxidizing the concentrate is only chalcopyrite was floated and re-
consuming (e.g., calcareous or dolo- about 30 per cent of that for the cycled for further leaching. Although
mitic). higher-temperature process where many of the hydrometallurgical pro-
The economics of the process are sulphate is produced. The difference cesses being considered appear to
clearly critically dependent on the is shown by the following two simple require flotation of the leach residue
availability of cheap oxygen, lime, equations: for the recovery of undissolved
and ammonia. The losses of am- mineral, such a low percentage
2 CuFeS2+2,5 O2 +2 H2SO4 dissolution as 65 per cent appears to
monia will probably be finally known
~2 CuS04+Fe203+4 S+2 H2O, be unacceptable, especially when it
only when a large-scale plant is in
and 2 CuFeS2+8,5 O2+2 H2O is considered that very intense
operation but should be less than in
~2 CuS04+Fe203+2 H2SO4' leaching conditions were used.
the Sherritt Gordon process. These
aspects will be discussed in greater The leach liquor, after removal of Vezina13 studied this problem in
detail later in the paper. the copper by liquid-liquid extract- greater depth on a chalcopyrite-

JOURNAL OF THE SOUTH AFRICAN INSTITUTE OF MINING AND METALLURGY NOVEMBER1973 161
 OXY9 en
Cu Concentrate
Ar(1monl a ~

EXTRACTION

STRIPPING

ELECTROWINNING
I _ Electrolyte
I \
5tron9

Direct discard of
--_::J
leached resldues and
9ypscm if Inlernallime Metallic
feed IS used. Discard of pyrite
and 9ypsum,if Copper
Applicable if concentrate
internal lime feed
feed contains ne91i9ible is used.
precious metal values.

Fig, 2-Slmpllfled flowsheet of the Arbiter Process (according to Prlcel)

CuFeS, CONC. (-30'/.Cu)

---F "

- _l
[;299.S

250
GRINI)iHG

'~'-
-:j;~~~C:SH

,-3;zr~}11 COIK,
;]
~~~:~J~~:~~~

~
0,- "rl".",-.," LE~'
'JI
- r~H
PR""
" .;>30-:"';5
. "
,
'F, 2-3 Hrt:;.
2<)O"~-OO .
. 0, RP. !,ECYCLE
-)0 ,
r'.' (),.~~
,,
to,:,"?'MY, COIK,
"
?: so ~;~-~:F~ s ~pL Far
PHJI.O

~:-;~~;:;;';ATION
L~BO "F I 10 MIN.
'--

RETURN ACID

[
--- -J
FLI\~,H COOLING
STEMA
r--->

-
-100 91>1
20 ~pl Cu
H,SO.
5 ~pl fcr
212 of

L--;~;;~;;;-L" ,
-Le "~~~:'
--r'::'-1-

[~;~-~;)AHATlOr~
- LEACH
nfSIDUr:-
{~OT~TIOI~ --1.o.l~!:':1
l
--~-~ACHT~OL: N
-~:I~
J
-60 IIpl Cu - 5 9pl fe

Fe (OH.) GANGUE

-
I .
~,~~'-D_~
(I.
[
L'
S'
SE PM) AT
l'--
15--> !~I!"!f_~'
I ~~?iLu~.r
'~~'!:!~~QQ.f,.?
~~OD,UC! L--RECYCLE CON,C,

Fig, 3--Example of a pressure-leaching scheme for chalcopyrite (according to

Vlzsolyl et al. 11)

162 NOVEMBER 1973 JOURNAL OF THE SOUTH AFRICAN INSTITUTE OF MINING AND METALLURGY
pentlandite-pyrrhotite concentrate one step now appears to be a possi- Recla Mining Company19 recently
and showed that the degree of bility. It has been reported that conducted an extensive experimental
grinding is critical to the achieve- Lurgi are testing the process on a programme to develop the R-L-E
ment of high copper extractions. pilot-plant scale, and it must cer- process for use at its Lakeshore
On a product that was ground to tainly be regarded as one of the Mine. They operated a pilot plant
93 per cent minus 20 /Lm, the copper contenders for commercial appli- producing 1 ton of high-purity
extraction was 91 per cent after cation. cathode copper per day. This pro-
8 hours at an oxygen pressure of Other investigators have also cess has its major attraction when
80 Ibjin2 or 550 kPa (gauge). Analysis recognized the importance of acti- it is required to treat ores of mixed
of the residue showed that the vating chalcopyrite to make it oxides and sulphides, as at Lake.
extraction for particles less than easier to leach. Copper15, sulphur16, shore, and the flowsheet as de-
20 /Lm exceeded 95 per cent. nitric acid17, and hydrogen18 pre- veloped for Lakeshore is given in
The importance of grinding was treatments, among many others, Fig. 4. The sulphur eventually all
taken one step further by Gerlach have been tried. These are all de- reports as sulphuric acid, which can
et al.14. It was found that the sub- scribed and compared by Subra- be used in the leaching of the
jection of chalcopyrite to a milling manian and Jennings3. oxide. It would have been interest-
action involving a strong impact Roasting Processes ing if Recla had compared the eco-
(vibration mills are commercially Roasting processes are well- nomics of liquid-liquid extraction
available) resulted in copper ex- established and have been ex- with those of the sponge-iron pro-
tractions of 99 per cent in 1 hour at tensively described in the metal- cess in the production of copper from
an oxygen pressure of 2000 kPa and lurgical literature. The basic patent the oxide leaching circuit.
a temperature of 110 C. The degree using fluidized-bed reactors was Recla made extensive studies on
of grinding is not given. Gerlach issued in 1957, and successful com- the pilot plant to find the optimum
et al. attribute this surprising result mercial plants are operating in roasting temperature for copper re-
to the fact that impact milling not Zambia and Zaire. Over 300000 covery at a minimum production of
only comminutes the mineral sub- tonnes of copper per annum are dissolved iron. By operating in the
stances but also mechanically dis- produced by this process in Zaire temperature range 690 to 700 C,
turbs the lattice structure of the alone. they achieved copper dissolutions of
mineral so as to render it more Most processes involve a sul- 97 per cent and iron extractions of
susceptible to oxidizing chemical phation roast, followed by a water less than 5 per cent.
attack. This theory is supported by or dilute-acid leach of the copper
X-ray-diffraction studies and also with some dissolution of iron. Copper
Other organizations (e.g.,
by electrochemical studies, which CSIRO2O, V.S. Smelting & Refining
is recovered by electrowinning, and
showed that the redox potential for Company21, Dowa Mining22) have
the sulphate formed is removed by
activated chalcopyrite was only liming. (This process is often re- developed alternative methods for
320 mV, compared with 550 mV ferred to as the R-L-E process.)
the recovery of the copper from
for non-activated chalcopyrite. The temperature of roasting is
solution after roasting and leaching.
Most of these alternative processes
The approach being pursued by critical: it is essential to select a
Gerlach et al. clearly represents a temperature that is high enough to are designed for the treatment of
significant advance on the results of decompose Fe2(SO2)4 but is not high
mixed copper-zinc ores.
previous workers, mainly because enough to result in the formation Recently, the V.S. Bureau of
complete leaching of the copper in of insoluble copper ferrite. Mines23 proposed a sulphating roast
.Oxi~e ore E,..:~'.:le
with lime in the roast to overcome
. :'=e
one of the major disadvantages of
~""', t of
cR"JSE::;; the conventional R-L-E process,
I
:xi1~ :re c'.; ;('P c,.. namely the production of a roaster
"ater gas containing sulphur dioxide.
t * ~ .
Where there is no market for acid,
te31-:1'1e- ,B11e:::, <: '"~;':;.cr::;
L the sulphate may as well be con.
. I
C;n"~",n;.:e verted to gypsum in the roaster
11 rACia .--Air
rather than later by neutralization,
1- Gase,
t which is known to be a tricky oper-
S~LruP.IC ACD ?:J..NT
-I R:I,S':I;T:
1
cel:s:", ation. Roasting is done at about
Co;l -r--;:ater 600 DC,and, in work done at NIM
't' I
of...
on this process, extractions exceed-
I. S?JN.}E IP.~1f?LI.:r:: 1-p.eSio]ue-1 lEACHIN} 1,,;;;-',:ASC!IN}
I
ing 97 per cent have been achieved.
I :.,.eLe.',
Iron
C;l'on~e
Selr:'" The process appears to have a
SDen+~~
\ particular advantage for flotation
CEI.\E,;TA.TICN I~ S"d ELECTEIWI!C':2C
Solution I .o.lectrolyte I concentrates containing acid-con-
t
CellOcnt Copper C.thOdt CoDper
suming gangue. It has been shown24
that the quantity of lime required to
Fig. 4-Roast-leach-electrowlnnlng process as used by Hecla19 fix the sulphate can be decreased if

JOURNAL OF THE SOUTH AFRICAN INSTITUTE OF MINING AND METALLURGY NOVEMBER 1973 163
 the concentrate contains calcareous electrolytic dissolution cells (dia. The pilot-plant tests indicate that
material. phragm-fitted cells with a woven, about 50 per cent of the copper is
The major problem with roasting permeable synthetic material that dissolved in the ferric chloride
processes is the dissolution of iron. separates anode from cathode com. leaching step and another 30 per cent
If a strongly acid electrolyte is partments). Anodes are made of in the electrolytic cells, and 20 per
used for the dissolution of the titanium that is coated with con. cent is recycled by flotation. The
copper, iron dissolution may be ducting oxides, which permit high overall extraction exceeds 98 per
excessive, resulting in a neutrali- current densities (200 Ajft2) and cent.
zation problem and a less pure also give lower voltage drops. Copper
cathode. If water is used to dissolve Costs presented by Cymet for a
is recovered from the leach and
the copper, copper extraction may anolyte solutions in the cathode plant producing 80 000 tonnes of
be decreased, and, because of the compartment of the cell. The cath. wirebars per annum indicate that
low acid strength, electrowinning is odes are round copper rods uni- the operating and capital costs are
not so attractive although liquid- formly spaced and oriented parallel slightly less than those for a con-
liquid extraction now becomes pos- to the anodes in the opposite com- ventional smelter constructed in the
sible. The D.S. Bureau of Mines25 partment. Copper is precipitated as D.S.A. If credit is given for the
have recently shown that copper a powder and removed as a slurry. iron and sulphur, the Cymet Pro-
dissolution in the roasting process The copper powder goes to electro- cess is overwhelmingly cheaper (see
can be improved by the addition of refining.
Table I). A better estimate of the
Fe20a to the furnace charge, but According to Cymet, the equations
costs will be made when the large
the results need to be confirmed on a governing the processes in the cell
pilot-plant scale. are as follows: pilot plant has been operated.
The Cymet Process CuFeS2+3 HCI-3e4-CuCl+FeCI2 The Cymet Process is very in-
The Cymet Process is one of the +2 S+2 H+, genious in its use of electrical
many chloride processes being 3 CuCl+3 e4-3 Cu +3 Cl-, and energy. No figures for power con-
studied. One of the major attractions 3 H++3 CI-4-3 HCl. sumption are given by Cymet, but
of chloride processes is that the it is estimated that, allowing for
The solids from leaching are
leach can be operated at atmo- inefficiencies, the power consumption
autoclaved at about 135 C for 2
spheric pressure. It is reported that
hours to form globules of sulphur, of the two electrolysis steps is
Duval and Cominco are also de-
which, on being cooled, can be probably in the range of 3,3 to
veloping chloride-leaching processes,
screened off. The screen underflow is 4,5 kWh per kilogram of copper. In
but no details have been published.
subjected to flotation, the concen- addition, about 0,3 kWh per kilo-
In contrast, Cyprus Metallurgical
trate being recycled for leaching
Processes Corporation have pub- gram of copper is required for the
and the tailings being rejected.
lished the results of their research electrorefining of the copper. The
fairly extensively26. 27, and are pre- The spent copper catholyte is
power consumption for conventional
pared to discuss the possibility of further depleted of copper by ce-
electrowinning from sulphate media
licensing their technology. A pilot mentation with metallic iron. The
solution is further purified by zinc is about 2,2 kWh per kilogram of
plant treating 25 tonnes of concen-
cementation so that residual traces copper. The Oymet Process, in
trate per day is due to become
of copper and other impurities, such addition to winning copper, also
operational during 1973. The plant
cost is about R6 million. as lead, antimony, bismuth, and oxidizes the leach liquor and pro-
Fig. 5 presents the flowsheet de- arsenic, are removed. Zinc occurring duces metallic iron for the ad-
in the feed and added for purifi- ditionall,4 to 2,6 kWh per kilogram
veloped and the pilot plant tested
cation is removed by liquid-liquid of copper, which makes it very
for chalcopyrite. Reactivity is in-
extraction with a tertiary amine. attractive. In fact, if the iron can be
creased by an increase in the surface
area, and the flotation concentrate The purified ferrous chloride sold for the price suggested by
is ground to 95 per cent minus 200 solution is sent to electrolytic iron Cymet, the cost of iron recovery will
mesh. Leaching with ferric chloride cells, which plate massive high-
be less than half the sales value.
anolyte solution from the iron purity iron on iron starter sheets,
The production of this salable iron
electrolytic cells produces the follow- and ferric chloride is regenerated
at the anodes. Because of the byproduct appears to be the major
ing reaction:
imbalance between cathode and advantage of the Cymet Process.
6 FeCla+2 CUFeS24-2 Qual
anode efficiencies, and the use of There are other chloride and sulphate
+8 FeC12+4 S.
The countercurrent leaching, iron to cement the copper, an ad- processes that produce elemental
which takes place at about 75 to ditional amount of iron must be re- sulphur, so that the Cymet Process's
80 C, employs cyclones between moved from the circuit. This is production of elemental sulphur
leaching stages to provide maximum done by hydrolysis. The reactions gives it no particular advantage.
efficiency. This results in a negli- occurring at the iron cells are as
gible concentration of ferric chloride follows: Cymet have taken advantage of
in the leached slurry, which goes to 3 FeC12+6 E4-3 FeO+6 Cl-, and the fact that, in chloride media,
the anode compartment of the 6 FeC12-6 e+6 CI-4-6 FeCla. copper can exist in the cuprous

164 NOVEMBER 1973 JOURNAL OF THE SOUTH AFRICAN INSTITUTE OF MINING AND METALLURGY
 TABLE I costs are low and the byproduct
COMPARISON OF COPPER PRODUCTION COSTS, CONVENTIONAL SMELTER VERSUS CYMET
PROCESS (U.S. CENTS PER POUND OF RECOVERED COPPER) iron can be sold.
Conventional Cymet
Process +
Ferric Chloride Leahing and Liquid-
pyrosmelter + liquid Extraction
electrorefining electrorefining
Direct operating costs 10,103 9,568
Administrative and indirect
""""""""""""costs. ............. 0,781 1,019 During the past two years, NIM28
has investigated, on a pilot-plant
Total direct and indirect costs. ............... 10,884 10,587 scale, a ferric chloride leaching pro-
Fixed costs (depreciation) 2,733 2,022
"""""""""" cess involving copper recovery by
Totaloperatingcosts ,.... 13,617 12,609 liquid-liquid extraction with LIX-
Credits.
Gold, silver, lead, and z.inc ,............. 0,790 0,790 64N and electrowinning of the
Sulphur and iron ,.... 0,535 4,361 copper from the sulphate strip
liquor. Because of pressure of work'
Totalcredits 1,325 5,151
"""""""""""""" the research is not complete, but
Conversion cost per Ib of recovered copper. . . . . . 12,292 7,458 certain basic features of the process
Conversion cost per Ib of total contained copper. . 12,939 7,590
Capital costs 1,0 compared with 0,83 have been proven. A flowsheet of one
. Credits were """"""""""""""""
estimated on the following values: version of the process is Rhown in
gold at $42,00 per oz tr., silver at $1,45 per oz tr., lead at $0,06 per Ib, zinc at $0,085 Fig. 6.
per Ib, iron (electrolytic) at $0,05 per Ib, sulphur equivalent at $10,00 per long ton, Laboratory and pilot-plant ex-
and power cost at $0,0105 kWh.
perience has shown that, for copper
form, and the power consumption all the leaching in the primary extractions to exceed 90 per cent, it
for winning it is therefore only ferric-leaching step, thus simplifying is necessary for the concentrate to
about half of that in sulphate media. the cell operations. be ground to 95 per cent minus
A disadvantage is that, because it is The Cymet Process certainly 400 mesh, thus confirming the ex-
necessary to operate the cells at merits consideration where power perience of other investigators in
such high current densities and in
Copper concentrates
the presence of such high concen-
trations of iron, copper powder is
produced, which requires further
the electrorefining. It is known that,
although the power consumption for
the electrorefining of copper is much
lower than for the electrowinning, Electro-dissolution Copper product
---
the capital costs of the plants, if
working capital for copper is in-
cluded, are not very different. It
would therefore be a great ad- Sulphur agglomeration Sulphur
vantage if high-purity copper could
be produced direct, but the chances
of doing this appear to be small. Recycle
Flotation concentrates
The major disadvantage of the
process concerns the technological
problems involved in the operation Tailings
of the slurry electrolytic cell. This (Solutionl
slurry operation appears to be un-
necessary because, at first sight, the
anode reaction in this cell is merely Cu and Pb cementation .. r Cu cement
1 Pb cement
the oxidation of ferrous to ferric ion
and/or cuprous to cupric ion. The
chalcopyrite is then oxidized in situ. ZnIOH},
Zn solvent extraction { FelOHIJ
It is claimed that the advantage of
this 'electro-oxidation' step is that
lower leaching temperatures can be
used and less sulphate is formed Iron electrolysis 1ran cathodes
than in conventional ferric chloride
leaching. Experience with direct
ferric chloride leaching28 does not
Iron hydrolysis Iron oxides
confirm this, especially if the ob-
jective is to achieve a primary dis-
solution of only 80 per cent as in (Solution)

the Cymet Process. I wonder whether

Cymet should not consider doing Fig. 5-Flowsheet for the Cymet Process 26' .7

JOURNAL OF THE SOUTH AFRICAN INSTITUTE OF MINING AND METALLURGY NOVEMBER 1973 165
 Flotation concentrate

Fine grinding

Air or
oxygen
Oxidation

Solvent extractior.

A'~+ Ag
Cu electrowinning

Copper cathodes

Final copper remo.'al

Iron removal
Return of HCt or FeCI, solution

Fe,O, or Fe

Fig. 6-NIM ferric chloride leaching circuit

the leaching of chalcopyrite.
Copper extractions have been
found to be variable, depending on
such factors as age of the con-
centrate, whether it was stored wet
or dry, whether it had been pre-
leached with hydrochloric acid for
the removal of zinc, etc. Leaching
at 95 C for about 8 hours gave
copper extractions of 95 to 97 per
cent. Leaching vessels lined with
hard rubber were used, and these
appeared to stand up to the leaching
conditions without deterioration.
Contrary to statements by other
researchers, the amount of sulphur
going to sulphate did not exceed
5 per cent of the total sulphur.
Copper was extracted from the
leach liquors with LIX-64N, the
loaded solvent was suitably scrubbed
to reduce the iron and chloride
levels, and the copper was finally
stripped with spent electrolyte from
the electrowinning plant. The copper
cathodes produced were of a high
quality. Because the loading of using air at about 45 Ibjin2 or 300
copper in LIX from chloride media kPa (gauge), has no moving parts,
is lower than that from sulphate and is of cheap and simple con-
media owing to the complexing struction. Good rates of oxidation
effect of the chloride ions, it is are achieved at 95 to 100 C. Oxi-
necessary to operate with moderately dation of the leach slurry has also
high levels of copper in the raffinate. been successfully attempted.
This means, then, that copper must Initial plans for the removal of
be removed from the bleed stream dissolved iron from the circuit re-
before the iron is recovered. If the volved round the use of a pyro-
bleed stream is first oxidized to hydrolysis technique (well proven
convert ferrous chloride to ferric for pickle liquors, e.g., the Aman
chloride, the excess hydrochloric Process), in which iron chlorides
acid generated in the liquid-liquid- are converted to iron oxides by
extraction process is consumed and water vapour at high temperatures.
most of the remaining copper can be This serves to regenerate the
extracted in a secondary liquid- chlorides as hydrochloric acid for
liquid-extraction circuit. Various recycle to the oxidation step of the
techniques such as iron and zinc process. The iron oxide might be a
cementation can be used to remove salable byproduct. However, de-
the last traces of copper. tailed studies have indicated that,
A special foam aeration column except when very cheap fuel is
has been developed and tested on available, the cost of fuel is rather
a pilot-plant scale to oxidize ferrous high. Capital costs represent a fairly
chloride to ferric chloride. This significant proportion of the total
device gives good oxygen efficiency, plant cost.

166 NOVEMBER 1973 JOURNAL OF THE SOUTH AFRICAN INSTITUTE OF MINING AND METALLURGY
 Tests are being done on an al-
teI'Ilative route involving the preci-
pitation of FeO. OH by oxidation
of the feITous chloride liquor at
about 100 DC using the oxidizeI'
previously mentioned. A filterable
precipitate has been produced, but
so far it has not been possible to
reduce the chloride content of the
precipitate to a level acceptable for
discharging. This process would
otherwise be much cheaper.
The remaining alteI'Ilative is to
make electrolytic iron and oxidize
ferrous to ferric chloride as is done
in the Cymet Process. If the iron can
be sold for a reasonable price, this is
most likely to be the best route to
follow.
A detailed comparison of the
Cymet Process with the NIM feITic
chloride process has not been under-
taken, but it is believed that the
NIM process could well be cheaper,
especially as the Cymet Process in-
volves the extra step of electro-
refining the copper powder. Further
pilot-plant testwork is required be-
fore the process can be regarded as
proven on this scale of operations.
Haver and Wong29 of the V.S.
Bureau of Mines also studied a feITic-
leaching process but suggested the
production of cement copper, which,
in my opinion, is a retrograde step.
DEVELOPMENT IN THE
FIELD OF COPPER
RECOVERY FROM
SOLUTION
The use of LIX liquid-liquid-ex-
traction reagents combined with
copper electrowinning in sulphate
media is now an industrially proven
process4, 5. Extremely pure copper
cathodes can be produced from these
processes, the only problem element
being lead, which originates from
the lead-antimony anodes used. A
lead content of less than 10 p.p.m.
is highly desirable, and hence a
great deal of attention has recently
been devoted to finding a means of
reducing the lead value, which in
some plants has been as high as
100 p.p.m. It has been found that
the addition of very small quantities
of cobalt greatly assists in de-
creasing the lead content.
De Nora of Italy and I.C.I. in
Britain both have substantial re-
search programmes aimed at pro-
JOURNAL OF THE SOUTH AFRICAN INSTITUTE
ducing titanium anodes coated with the cost of the electrowinning plant.
precious metal that have a long life Research to decrease the cost of the
in copper sulphate electrowinning liquid-liquid-extraction plant and its
circuits. According to present indi- solvent inventory is therefore urgent.
cations, the life of these anodes is not ly required.
long enough to justify their very An alteI'Ilative solvent, KELEX,
high capital cost, but they do permit is selective for copper and under
the use of higher current densities certain circumstances promises to be
than do conventional anodes, and preferable to LIX, but it does not yet
the voltage drop is slightly less. It is have the advantage of having been
possible that further development used on a large plant. Many com-
will result in their application to mercial firms are actively developing
copper processing. new solvents for copper.
Recent work by many workers3O-33 One of the major disadvantages of
has demonstrated that it is possible liquid-liquid extraction is that the
to operate copper-electrowinning leach liquors must be clarified after
plants at much higher current densi- liquid-solid separation so that the
ties (600 Afm2) than previously losses of solvent are minimized. With
practised (250 Afm2). This can be the recent successful development of
done by periodical interruption of a continuous ion-exchange tech-
the cUITent32 or by specially designed nique34, new horizons open up, and
ail' nozzles33 to improve the circu- it is possible to consider the possi-
lation of the liquor, especially near bility of ion-exchange processes for
the cathode surface. Others3O have the recovery of copper from a
improved the liquor circulation by dilute-leach sIUITY. This would re-
various means. duce the costs of liquid-solid sepa-
The production of a purer electro- ration and also eliminate the need
lyte when LIX is used makes it for clarification. The major area of
possible to operate at higher CUITent application for ion-exchange pro-
densities than when the liquor is cesses would doubtless be the leach-
impure. It may be possible in certain ing of oxide or carbonate ores, wherb
Instances to justify the cost of the costs of liquid-solid separation
iiquid-liquid extraction by the lower are very high and a dilute copper
cost of the electrowinning plant. The solution is produced. The ion-ex-
results of a cost-optimization study31 change step could then be used as a
indicate that the optimum CUITent concentrating step, followed by a
density, considering the operating liquid-liquid-extraction step if neces-
and the capital costs, is in the region sary. For these objectives to be
of 600 Afm2, which appears to be realized, new and improved resins
within the bounds of practical appli- having properties similar to or better
cation in the near future. The than those of LIX or KELEX must
problem of how to control the mist be developed.
arising from cells operating at these
high current densities still requires COMPARISON OF
to be solved. It is worth thinking PROCESSES
about the possibility of ducting the The only fully realistic and con-
oxygen away for use in the leaching vincing basis for a comparison
step and thus also overcoming the of processes is, of course,
mist problem. operating and capital cost. How-
The capital cost of a typical ever, when so many processes are
circuit for liquid-liquid extraction available and such a variety of
and electrowinning is proportioned feed materials can be considered, it
approximately as follows: liquid- seems to be important at least to
liquid-extraction plant 20 per cent, make a rough comparison of the
solvent 20 per cent, and electro- various major features of the pro-
winning plant 60 per cent. Operating cesses available. A change in the
at high current densities will mean 'ground rules' (e.g., CQst of power or
that the cost of the electrowinning lime) can alter a comparison ap-
plant will be reduced by about one- preciably.
third, and the cost of the liquid- In Table n, eight different pro-
liquid-extraction plant and its cesses have been compared, and
solvent will then be about equal to some of the features of the pro-
OF MINING AND METALLURGY NOVEMBER1973 167
 ....- cesses will now be discussed in mote
M' ";,.; ..;
'" ,.;
'"
....
~-g ~ .....
'"11
,.;
'" ~ ..; 1111 11 11
detail. The numbers used in the
u;: 11 11 11 11 ...: :-'"
""" :1~:1
+11+ discussion refer to the numbers given
,5
rJ
"l :1 "'. :1 :1 ++"
;;;::'8 :::1:: in the Table for the different pro.
~c +
oZ .
+ + + +
,.; ++" +++ B
,.; 0'" 0'" ",.... cesses.
u" '"+ + + + + """"
OO~ '" c
~"
'" ,.;
'"
....
1"':-
"". 0'" 35 ~
"':-"':-0

35S ~
~
Iron Removal, and Oxidation State of
'" 0
the Sulphur Produced
<:
is
i:i; .",~ ,,><: '"
.=:~ .", .;;
~ These two features together, more
00
~
c > ~" 0.<:
" o.~
"a1!, 80. c",
-ge" ..co "-::: than any other feature, probably
H~ " "0.
,,~
"0
.=:~ .=:~ a"~
';;; .~c lE'" ~
:!!'5 8 ~ o.rJ 8.?i 8.?i .?i~ ~ :a""2c
",0 '8~~ c distinguish the various processes
"',!:! ~ ea lEt: lEt: .~.", -;:
._~ c 0> ~.", !I
0 lE"'> ,~
_I~~ c;j<;l .-
~o. "
.-
~o.
" "c
~" ~..c
""
~
0. "c~
>,,0. is] ~ ~ from one another, and also have the
~ greatest impact on the operating
~ a0
:a cl costs. Those processes that form
~, ~,
0
..c ~. ~.
"0
....
,9
sulphur (nos. 3, 4, 7, and 8) have
g ~ ".-.
,,~ ~
tl
0.., ~~ ~co" rJ
i"s co~ ~
only about 30 per cent of the
"c" rJ .g rJ

"c .", .", c" ~ co

"c
~.~ ]o.~gJ, ]gJ, :c :c :2<5 gJ,] :c :c "
o.~ 0. 0. ..e",
0.. ~o.
,,- 0. 0. -s
" :8 oxidation requirement of those pro-
~"0.~ ~g -" ii1g ~ ~ -s::Z:
~....
,,0
gii1 ~ ~ B e cesses that make sulphate (nos. 1,
"'~ .",~
.-~~ .-~~
,"u" ,"u"
.",
j
~
.",
~
j"
;:1"
o~
~.",
~~
".-
u,"
.",
j
~
.",
~
j"
g~
]-g 3 "1! 2,5, and 6). The processes in the first
~~ 0 "
-S
....
group have the additional advantage
-- 1!~ ii 0
:::- .-. .... that the sulphur byproduct has a
s~
0 .
~ ] potential sales value either do-
8g~ ~ "" .::e 'S
c
;:1
"" ""
;:1 ;:1 ,,~ '~
~
..e mestically or on the export market.
1:'cb
"0,, '~
~ ~ ~ ~ E-S 8
.... .... .... '0 The processes in the second group
'ar~,
p,j:o. 0'0
~c ~g
0 0
c ~ ~
0
c H] -S"co
~ have the disadvantage that the
,0::8
0' -..e" J '0"
~.Q ~
+'~
0'0
.9
~;;;
:;"15 '"
'"
~ ~
~.9
1i6E
-jj,g
~
'"
gb
"
"0
.~
~
"
oB
~
:a
'S:
<:
sulphate must be neutralized with
" """ "" '" '" I~'" 0 lime to form calcium sulphate, which
""" """ '" '" Eo; & ~
~ i ,g~ '0 must then be dumped.
"Qj' !:. ~ co
"c"
"Qj' In some processes (nos. 1, 2, 3,
z co
"Qj' "Qj' co~~~ ~]
0
en ~ co
"" "Qj' ~ ~" l
co
,,~
co
,,~ :;:,uuu
~""" "
_oS
,,>
rJ
~
co
"
~ and 4), the Iron is advantageously
~ :::'" tf", :;:'" ~'"
p,u u "
CO"
~u "CO" co00co ~'S +" 0
H -<i "a~ ~uco gJ,u
~co
~u ~............
,,~~~
p,--- ~g
,,0 :.= ~ "~
precipitated during the leach. In
H
~ '5er 00 ~<2
""co
oCO I
~~ "2
p,....co
~-'~ others (nos. 5 and 6), the iron is
a> 0 $Oi;~ 1i6<2 0 ~<2
"";":: "";"::
M'o "i<
"
;Co ~ ~~ :::~~ ::::.~~ 1'!-'~ 1'!~~ ~~~.:q~ .~ " rendered insoluble in the roasting
aj en c ~~""o ~ ~ ~",'" ~c",o ~
o ~ ~ o 1! ~
0 -S
~ "
E-<
~
0
.9
;;;
.",
.;;;
.5-.11'"
:: g ;;,;-;::;~ 1~~
-""" .- 11 :: 11
.c" go'~
11
g i~." .5",11
-'"
~ :<;-11 ~ all - - .c g .g
11
.5",11
-'" <;I
~~~~~
._~~~II
:<;-11
-. ~
c
c
orB i" - -g step. The two chloride processes
(nos. 7 and 8) are unique in that iron
0
~ O'~ :<;-
-0.21 ~o.@ s~.~ SO.21 ~ ~o .!! c8," ~ 1!
il<
0 ~..;IE ': ~iS ~ ~~
"0" ...e. "".
",,"
;;;
~iS
.,," ;;;~~r
e . .~1! . ~
~8~
;;;
.~1!
~ ~ ~~ .9
!:. e.,; c
'" ~ i1:~'~ is dissolved, and they thus require
~~o Of-<O 0~0 O~o <f-<O <f-<O Z <f-< 0 .~ ~ is '0 1!.5 an extra step for its removal. How-
------- ~
"":.= .;;..: 1:'.Ia;;: ever, there is a possibility that a
1:'. !I 0

Si: Si:
c;;;
"
sos.
.-s 'o:;;8,5~
0 ~o.~;;:'E
~: 8<:" 0"
" salable byproduct can be recovered,
which would mean that these pro-
Q 1!& ~s-s.g
C"
tl
0.",
c 1!
'u" ~" 'u ~
~ <'u
5~ :::: ~~~ls
cesses have the edge over those In
~o
"" "" "..!!i! <;I".", .g::Z:<;I oB~ ~OB~ g~ which iron is not recovered.
~ .",
"" .",
""
c';;; .",
c';;; .",
c';;; .00>
.5:EE .:~:g-; * 0.0. a ~~ The cost comparison In Table 11
~ ~o;~=~
,5'~ .- ~ .- ~ <;I
.- ~ 's. 's. 0> ..: 0.':
~'5 ~'5 0'5 ~'5 0."~'u 0 ~'u 5 """
~~~ E~
" -'~~"" '" serves to bring out the above points
." i-H 8 uoBoB-S.2
':
~..!!
"" ~..!!
"" i~ ~..!!
"" i1:0.~
" I
i1: 35S ~'2 ",.Ia.Ia;;;" more clearly. The following com.
~2 ~ ~-S-S ments can be made.
;;;" .!,8 8 ~ ~
:;0
cl ,5~ ...:--g-g (1) At the price of oxygen and power
]<5 8~ ,.;~~~~
:!:~~~~ assumed, the Arbiter Process has
~tl
.0'"
::z: 15:~
~" little advantage in the operating
..e"
,,~
0.""
-0 . <5 en ~o~
<5 ~ "0
~~~ ::;~.~.88
+1!1!1111
0. o. <5. ",u'"" ",u" g"'"
-i:; ~" -"'0.0. cost of the leaching step over the
'" ",0 ",0 ~13 ~13 .1a,1a '"
~ '"
~ ~~ ~~ ~~~ conventional Sherritt Gordon
~'1J ~'1J ",c ",c ."
::z:u ::z:u "",<;I 5 a '"
"",<;I "":; c 0';
"'.;;; '" '" ';'0 ~uu.,,'"
~';;: ::oOoO~~ process. Its advantages lie In
Z~
~o Z~
~o N~ NI" ~ ~~ J~ '"
/\ '"
/\ 0",;~~~11
---- 'B~~oB1111~~ much simpler equipment and a
<;I e~8c88;:j;:j lower ammonia loss, together
<;("~~p,p",,,
..e c ~~-S]iSiS-S-S with the introduction of the
""
'S
0 "" ~ ".-
0
~;;; b ,,~o~~~..~
e ..!! ~
.9 15:.is ~ oB. li qui d -li qui d -extraction/ electro-
e <;I ii1 ~.~ tl
~
~ ~ ~'g ~
11
80.
8 ~~ 8 -'" winning step.
11 <
": 'S
0.
.",1:.= ~
I~ 1!1!.91! ~~
0
.g'5 0 :gG ~
~
~:;i!J' f-<f-;If-< UU (2) Both ammonia leaching pro.
~
iS~ e '~9' ~ 11 ',:.",.~
c
~
11
e ,,0 ..e o"~c
0'- cesses are considerably more ex-
eJ-
~~
.'C: "
"
'3
,g'g ~
I
0
~ -"
":'= 8
.~.,;
~ 35 S s pensive than the other processes.
.!i ..e..e ~
.E:;;'e: 0>
a
~~"
..e~
:E
~~ .9<".- "5
;:j
t;'S'U
In large measure this is due to
",co ~ "'- ~~E ~
'"" u'" i1:g-ij
the cost of liming, thus demon.
I
~ [- ['"
strating that these processes have
I '" I ['" I'" I I'"
168 NOVEMBER 1973 JOURNAL OF THE SOUTH AFRICAN INSTITUTE OF MINING AND METALLURGY
 their major advantage where
(NH4)2S04 can be sold.
(3) The other processes do not differ
very much in cost, and the choice
of process must probably be made
on the basis of other factors, in-
cluding capital costs, costs of
chemicals, etc.
(4) The sulphuric acid pressure-
leaching processes and the chloride
processes have the advantage of
producing elemental sulphur,
which, if sold at RIO per tonne,
would provide a credit for these
processes of 1 cent per kilogram
of copper.
(5) The Cymet Process has the ad-
ditional advantage that the iron
can be sold. Its value is un-
certain but would probably be in
the range of R15 to R50 per
tonne, depending on its purity
and end use. This would provide
an additional credit of 1,5 to
5 cents per kilogram of copper,
which tends to make the Cymet
Process very attractive if both
iron and sulphur can be sold.
(6) The ferric chloride process using
electrolytic recovery of iron (no.
8) is also very attractive if both
iron and sulphur can be sold.
Its capital cost is likely to be
less than that of the Cymet
Process.
Copper Recovery from Solution
At least six of the processes listed
(all except nos. 1 and 7) have a
conventional copper-electrowinning
plant. The cost of these plants
represents anything from 20 to 40
per cent of the total capital cost and,
therefore, although the cost will
vary slightly for the different pro-
cesses because of different electro-
lyte conditions, in principle all these
processes have a common capital and
operating cost. The possible ad-
vantages of a very pure electrolyte
have already been discussed.
As already indicated, the capital
cost of an electro-refining plant
when the copper inventory is in-
cluded is not much less than the
cost of an electrowinning plant, so
that this is a cost common to the
Cymet Process and the other pro-
cesses. The power consumption for
electro-refining is, of course, only
about 15 per cent of that for electro-
winning (about 1,3 cents per kilo-
gram of copper at a power cost of
0,6 cents per unit). The cost in the
Sherritt Gordon process of precipi-
tating copper powder by the use of
hydrogen is not known, but, at the
price of hydrogen in South Africa, it
is unlikely to be much less (if any)
than the cost of electrowinning. The
copper powder produced is a
speciality sales product. The fact
that Anaconda have chosen liquid-
liquid extraction and electrowinning,
rather than hydrogen precipitation,
suggests that, even in the D.S.A.,
cathodes are preferable and cheaper.
The purity of copper produced by
hydrometallurgical processes using
liquid-liquid extraction (nos. 2 and
7, and possibly 4, 5, and 6 if desired)
is superior to that from pyrometal-
lurgical processes and from other
hydrometallurgical processes not em-
ploying liquid-liquid extraction, and
under difficult marketing conditions
is likely to be a selling advantage.
The cost of solvent make-up is
estimated to lie in the range 0,3 to
0,5 cent per kilogram of copper.
Cost of Chemicals
The cost of the lixiviant for the
four sulphate-based processes (nos.
3 to 6) can be regarded as negligible.
The price of ammonia in South
Africa is very high compared with
its price in other industrialized
countries, although it is predicted
that, with the increasing shortage of
oil and natural gas and hence the
rising prices, ammonia produced
from cheap South African coal will
eventually be among the cheapest
in the world. No realistic figures are
available for the consumption
ammonia in the two processes con-
sidered, but it is believed that it
should be possible to limit the losses
so that the make-up cost will be
in the range 1,0 to 2,0 cents per
kilogram of copper. The Arbiter
Process will probably be lower in
cost than the Sherritt Gordon pro-
cess. As mentioned previously,
(NH4)2S04 is to be sold as a fertilizer,
ammonia will have to be purchased
at the fertilizer producer's price.
No realistic figures for chloride loss
are available, but it is expected that
the make-up cost would be less than
that for the ammoniacal processes
(say 0,5 to 1,0 cent per kilogram of
copper), because chlorides are vola-
tile like ammonia, and the basic
raw-material price (hydrochloric
acid) is somewhat lower. Much of
the ammonia could be lost with the
CaSO4, but no CaSO4 is produced in
the chloride processes.
Type of Concentrate
Where a concentrate contains
acid-consuming gangue (e.g., of a
calcareous nature), only the am-
moniacal and the lime-roast-Ieach
processes are applicable. The lime-
roast-leach process (no. 6) seems to
be particularly suitable for this
purpose, because the presence of
calcareous material reduces the oper-
ating cost.
The ability of the various pro-
cesses to treat mixed concentrateE
(e.g., copper-zinc, copper-zinc-Iead,
and copper-nickel-cobalt) is of im-
portance because this is a field in
which hydrometallurgical processef
have a possible major advantagE,
over pyrometallurgical processes. It
is believed that adequate processing
knowledge is available to solve these
separation problems for ammoniacal,
sulphate, and chloride processes.
Separations can probably be more
effectively achieved in ammoniacal
and chloride systems, but every case
has to be looked at separately. More
research is certainly needed to pro-
vide improved and cheaper sepa-
ration processes.
From a survey of the experience
of various investigators in the leach-
ing of chalcopyrite, it appears that
the reactivity of chalcopyrite varies
considerably, and much more at-
tention should be given to an under-
standing of the reasons for this
of difference. One investigator even
found that, by dissolving the flo-
tation chemicals from a concentrate
in an organic solvent, the copper
dissolution increased from 90 to
95 per cent.
Recovery of Precious Metals
Sulphide ores always contain some
if precious metals. The degree to
which precious metals will dissolve
in the leaching step will depend
very much on how they are present
in the concentrate, e.g., they can be
alloyed with base metals. However,
it is fairly certain that, the more
intense the leaching conditions and
the finer the grind, the greater will
be the tendency for the preciom
metals to dissolve if the leaching
conditions permit this. Palladium,

JOURNAL OF THE SOUTH AFRICAN INSTITUTE OF MINING AND METALLURGY NOVEMBER 1973 169
 platinum, and silver, for example,
are all soluble in ammoniacal
solutions, and under pressure-leach-
ing conditions appreciable quantities
of palladium, especially, have been
found to dissolve. Palladium and
silver are soluble in sulphate media,
but there is no reported instance of
any investigator having detected the
dissolution of these metals in
sulphate-leaching tests. All the
precious metals are soluble in
chloride media, and experience here
seems to vary. Work done at NIM
on a local chalcopyrite and copper-
nickel matte showed negligible dis-
solution of precious metals. However,
Cymet report recoveries of silver
and gold into the copper of 96 per
cent and 60 per cent respectively27.
How this took place is difficult to
understand.
Various workers have investigated
the recovery of gold and silver from
leach residues using the cyanidation
process, and good success has been
achieved. Thiourea processes might
also be considered under certain
circumstances.
CONCLUSION
This review has demonstrated
that, within a few years, a variety
of hydrometallurgical processes will
be available that are likely to be
competitive with pyrometallurgical
processes when there is no sale for
sulphuric acid from the smelter.
The selection of the right process will
depend on the character of the feed
material, the location and size of
the plants, and the byproducts that
can be recovered and sold. In
general, it appears that processes
producing sulphur have an ad-
vantage over processes producing
sulphate as a reaction product.
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170 NOV(:"'!;I~R 19~ JOURNAL OF THE SOUTH AFRICAN INSTITUTJ;: OF MIN'N~ AND "'~TAI-I-~~~Y