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A Process development studies by Dynatec for the pressure leaching of HBMS


copper sulphide concentrates

Article  in  CIM Bulletin · June 2000

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Process Development Studies by Dynatec for the Pressure Leaching of
HBMS Copper Sulphide Concentrates

J. Stiksma, Senior Research Metallurgist


M.J. Collins, Research Manager
P. Holloway, Research Metallurgist
I.M. Masters, Senior Consulting Scientist
Dynatec Corporation, Metallurgical Technologies Division
8301 – 113 Street
Fort Saskatchewan, Alberta, Canada T8L 4K7

G.J. Desroches, Superintendent of Metallurgical Services


Metallurgical Services, Hudson Bay Mining and Smelting Co. Ltd.
P.O. Box 1500
Flin Flon, Manitoba, Canada R8A 1N9

Writing Date: May 19, 1999

Page 1 of 16
_______________________________________________________________________

ABSTRACT

Preliminary process development studies have been conducted by Dynatec on a


hydrometallurgical process for treatment of Hudson Bay Mining & Smelting (HBMS)
copper concentrates, for possible replacement of the existing smelting operation at Flin
Flon, Manitoba, Canada. The studies consisted of the development of a conceptual
process flowsheet for the treatment of copper sulphide concentrates containing
significant levels of zinc and precious metals, and the generation of sufficient process
data from batch testwork for preliminary estimations of capital and operating costs for a
copper pressure leaching facility.

In the proposed process flowsheet, the copper and zinc are solubilized in the
pressure leach operation and the leach solution is processed in solvent extraction and
electrowinning operations to separate and recover copper as high purity copper cathode
product. To recover the zinc and to maintain an overall sulphate balance in the plant, a
bleed stream of solvent extraction raffinate solution is processed through acid
neutralization and iron-copper removal operations, producing a zinc sulphate solution
relatively low in copper and other impurities. The zinc sulphate solution, with a Zn:Cu
ratio of 100:1 or greater, may be treated with lime to precipitate basic zinc sulphate
(BZS), or added directly to an appropriate circuit in the existing HBMS Zinc Plant.
Laboratory batch testwork results indicate that improved copper and zinc recoveries, and
similar gold and silver recoveries, can be obtained in the proposed process flowsheet
compared to the existing smelter operations. The conceptual process flowsheet and the
key results from the laboratory batch testwork program are presented in this paper.

_______________________________________________________________________

Introduction

Hudson Bay Mining & Smelting (HBMS) and the Metallurgical Technologies
Division of Dynatec Corporation (formerly known as Sherritt International Consultants
Inc.) have a long association with each other in the development and commercial
application of the zinc pressure leach process at Flin Flon, Manitoba, Canada (Goodman
et al., 1999). The existing HBMS Zinc Refinery at Flin Flon, which was started up in
1993, utilizes the world’s first stand alone zinc pressure leach plant (Collins et al., 1994;
Ozberk et al., 1995; Collins et al., 1995).

HBMS operates a copper smelter complex in Flin Flon to produce anodes which
are shipped elsewhere for further processing. The feed to the copper smelter is a blend of
purchased concentrates and concentrates derived from HBMS mines. Although the
copper and precious metals recoveries in the existing copper smelter are better than 95%
for copper, gold and silver, the majority of the sulphur in the copper concentrate feed is

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emitted as sulphur dioxide to the atmosphere, and a large fraction of the zinc contained in
the copper concentrate feed is lost to the smelter slag.

HBMS is evaluating the possibility of replacing the existing copper smelter with a
hydrometallurgical process plant for the direct treatment of copper concentrates. The
preferred hydrometallurgical process would convert most of the sulphide sulphur in the
concentrate feed to elemental sulphur, which could be sold or stockpiled. In addition, the
hydrometallurgical process would potentially improve the recoveries of copper and the
precious metals, yield a high grade copper cathode product and allow the recovery of the
zinc via the existing HBMS Zinc Plant.

Various hydrometallurgical processes for the treatment of copper sulphide


concentrates have been proposed over the last four decades. The high temperature
pressure leach process (Stanczyk and Rampacek, 1963; King and Dreisinger, 1995;
Pieterse and Dreisinger, 1997) is run at temperatures of 200 to 220°C where complete
oxidation to sulphate sulphur occurs. Although single pass copper extractions are high,
the process would consume more oxygen due to oxidation of sulphides to sulphates,
thereby significantly increasing the requirement for neutralizing reagent (limestone/lime)
to remove sulphate from the system. The CESL copper process (Jones, 1998) has
undergone extensive laboratory, pilot plant, and process demonstration testwork and,
with the pressure leach operating at 150°C, converts a large fraction of the feed sulphide
sulphur to the elemental state. However, the process requires the use of high
concentrations of chloride ions in the pressure leach solution, and there may be concerns
on the compatibility of the process with the existing zinc refinery.

Recent copper process development activities by Dynatec have resulted in the


formulation of a new hydrometallurgical copper process for treatment of copper
concentrates (Collins and Kofluk, 1998; Buban and Collins, 1997; Collins et al., 1998;
Barta et al., 1999). The key feature of the new process is the use of an additive in
aqueous sulphate pressure leaching at moderate temperature. The additive allows the
reaction of chalcopyrite to continue in the presence of molten elemental sulphur, and the
relatively low temperature range promotes the formation of elemental sulphur instead of
complete oxidation to sulphate.

Dynatec’s process development work on additive enhanced pressure leaching of


chalcopyrite concentrates up to mid 1997 included batch pressure leach tests, locked
cycle pressure leach tests to evaluate recycle of unleached sulphides to the pressure
leach, and two continuous pressure leach campaigns. The results were very encouraging,
indicating overall copper extractions in excess of 98%, up to 70% conversion of sulphide
sulphur to elemental sulphur, and leach solutions amenable to copper recovery by solvent
extraction and electrowinning or possibly by direct electrowinning. In mid 1997, process
development was considered to be at a stage where specific potential applications could
be evaluated, such as at Flin Flon. Various flowsheet configurations were discussed with
HBMS personnel and were used as the basis for the subsequent process development
studies conducted by Dynatec for HBMS. The determination of potential gold and silver

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recoveries in the conceptual flowsheets were considered an important part of the study
since greater than 95% gold and silver recoveries are achieved in the existing HBMS
copper operations.

The preliminary studies (Phase 1) conducted by Dynatec in the fourth quarter of


1997 consisted of a small scope of batch laboratory testwork. These tests successfully
demonstrated the process concept. In the pressure leach greater than 95% first pass
copper extraction was achieved; about two-thirds of the sulphide sulphur was converted
to the elemental state and about one-quarter was oxidized to sulphate. Cyanide leach
amenability tests on the pressure leach residues and the oxidic solids fraction (pressure
leach residue flotation tailings) yielded up to 95% gold extraction and 99% silver
extraction. The pressure leach solution was amenable to copper recovery by solvent
extraction with a commercially proven extractant, Acorga M5640.

Recommendations for further work were outlined in the Phase 1 report to HBMS,
and formed the basis for defining the scope of the Phase 2 Process Development Studies.
The objectives of the Phase 2 studies were to develop a conceptual process flowsheet for
the treatment of copper sulphide concentrates at Flin Flon and to generate sufficient
process information from batch testwork for the preliminary estimation of capital and
operating costs for a copper pressure leaching facility. This paper describes the
conceptual flowsheet developed by Dynatec for HBMS and presents the key results from
the Phase 2 laboratory batch testwork program.

_______________________________________________________________________

Process Description

The process developed for treatment of HBMS copper concentrates is shown in


Figure 1. The copper concentrate and recycled sulphide cake solids are treated at
elevated temperature and pressure in an oxidative pressure leach to solubilize the copper.
The pressure leach discharge slurry is subjected to liquid-solid separation, and the
pregnant leach solution proceeds to the copper separation and recovery operations. The
leach residue proceeds to the sulphur recovery and the gold and silver recovery
operations.

The first pass extraction of copper in the pressure leach step is controlled in the
80 to 90% range, to minimize the autoclave retention time. At the moderate leach
temperature, the sulphide sulphur in the feed is predominantly converted to the elemental
state instead of to the fully oxidized sulphate state. The leach residue is then subjected to
sulphur flotation, producing a sulphur-sulphide concentrate and an oxidic tailings.

The sulphur concentrate proceeds to a sulphur melt and filtration operation. The
elemental sulphur filtrate is solidified and stockpiled or sold, depending on market
conditions. The sulphide filter cake is recycled to the pressure leach to recover the

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remaining leachable copper, and to return to the process the precious metals not reporting
with the flotation tailings.

The oxidic tailings, preferably containing a minimal amount of the copper and
most of the precious metals, proceed to a gold and silver recovery operation. A silver
enhancement treatment (SET), which involves the reaction of sulphate species (e.g.,
jarosite or basic iron sulphate) with lime at elevated temperature, ahead of the cyanide
leach, may improve silver extraction. The gold and silver are recovered from the cyanide
leach solution using the conventional carbon-in-pulp (CIP) process. The loaded carbon
removed from the lead CIP tank is first acid washed to remove lime scale and residual
oxide fines, and then the gold and silver are stripped from the carbon in cyanide solution
at elevated temperature and pressure. Silver and gold may be recovered from the strip
solution either by cementation with zinc powder, or by electroplating onto steel wool
cathodes in an electrowinning cell. The resulting gold and silver precipitate or cathodes
would be melted, fluxed to remove base metals as slag, and cast as bars of Doré metal
(>95% Au and Ag) for refining to bullion elsewhere.

The solution produced in the additive enhanced pressure leach of copper


concentrate, typically containing about 40 g/L Cu, 5 g/L Fe and 20 g/L H2SO4, can be
treated in solvent extraction (SX) to separate the copper without prior solution
neutralization or purification. Copper in the pregnant SX solution is recovered as
cathodes by copper electrowinning (EW). Spent electrolyte from electrowinning is
recycled to SX to act as strip liquor.

A large portion of the SX raffinate is recycled to the pressure leach step. A bleed
stream of the SX raffinate, containing about 6 g/L Cu and 80 g/L H2SO4, is treated in
acid neutralization, iron-copper removal and zinc recovery operations to maintain an
overall sulphate balance and to remove sufficient zinc to maintain an acceptable zinc
concentration in the copper pressure leach circuit. The raffinate bleed stream is treated
with limestone or lime to neutralize the acid. The precipitated gypsum residue is
separated and sent to a tailings pond. Part or all of the neutralized solution, depending on
the overall sulphate balance, is treated with lime to about pH 5.5, under oxidizing
conditions and at 85°C, to precipitate iron and copper. The iron and copper residue,
along with the small amount of co-precipitated zinc and gypsum, is separated from
solution and returned to the copper pressure leach circuit for redissolution of the metal
values. Finally, the low copper and iron containing solution, with zinc concentrations in
the range of 15 to 45 g/L, is treated with lime to precipitate and recover basic zinc
sulphate, which may be processed in the HBMS Zinc Plant. Alternatively, the zinc
containing solution following iron and copper removal is directed to the existing zinc
hydroxide precipitation circuit in the HBMS Zinc Plant.

Page 5 of 16
_______________________________________________________________________

Feed Materials

A blend of approximately 50 kg of copper concentrate was prepared from


materials which were received from HBMS by Dynatec on September 25, 1998, and
served as the feed solids for the batch testwork program. Key chemical analyses of the
copper concentrate blend are provided in Table I.

Table I − Copper Concentrate Blend Chemical Analysis

Analysis (wt%, or g/t for Au and Ag)


Cu Fe Zn S Al Ca Mg Si Au Ag
27.8 26.2 4.48 33.1 0.25 0.38 0.10 1.70 13.7 186

The mineralogical composition of the blend, calculated directly from the


chemical analysis, was: 64% chalcopyrite, 10% bornite, 12% pyrite, 7% sphalerite, 0.3%
galena, 3% quartz, and the remainder as other gangue minerals.

Most of the laboratory testwork was conducted on the copper concentrate blend
after regrinding.

_______________________________________________________________________

Process Chemistry

Chalcopyrite reacts in sulphuric acid or ferric sulphate solution at relatively low


temperature, between about 25 and 150°C, according to the following reactions.

CuFeS2 + O2 + 2 H2SO4 → CuSO4 + FeSO4 + 2 S° + 2 H2O . . . . . . . . . . . . (1)

CuFeS2 + 4 O2 → CuSO4 + FeSO4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (2)

2 FeSO4 + 0.5 O2 + H2SO4 → Fe2(SO4)3 + H2O . . . . . . . . . . . . . . . . . . . . . . . . (3)

CuFeS2 + 2 Fe2(SO4)3 → CuSO4 + 5 FeSO4 + 2 S° . . . . . . . . . . . . . . . . . . . . . . (4)

3 Fe2(SO4)3 + 14 H2O → 2 H3OFe3(SO4)2(OH)6 + 5 H2SO4 . . . . . . . . . . . . . . . . . (5)

Fe2(SO4)3 + 3 H2O → Fe2O3 + 3 H2SO4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (6)

Ferrous sulphate can be oxidized to ferric sulphate in the same reaction vessel in
the presence of a suitable oxidant such as oxygen. Iron precipitates as a combination of
hydrated iron oxides and sulphate bearing solids such as basic iron sulphate. Hematite is

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preferentially formed in copper sulphate solution at the higher temperatures in this range
and under lower acid conditions.

The overall reaction of chalcopyrite, with the formation of elemental sulphur and
hematite, is as follows.

2 CuFeS2 + 2.5 O2 + 2 H2SO4 → 2 CuSO4 + Fe2O3 + 4 S° + 2 H2O . . . . . . . (7)

Other minerals in the copper concentrate such as bornite (Cu5FeS4), pyrite (FeS2)
and sphalerite (ZnS) react in sulphuric acid solution by the following reactions.

Cu5FeS4 + 6 H2SO4 + 3 O2 → 5 CuSO4 + FeSO4 + 4 S° + 6 H2O . . . . . . . . . (8)

FeS2 + H2O + 3.5 O2 → FeSO4 + H2SO4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (9)

ZnS + H2SO4 + 0.5 O2 → ZnSO4 + S° + H2O . . . . . . . . . . . . . . . . . . . . . . . . (10)

One advantage of the reactions at moderate temperatures, compared with a high


temperature sulphuric acid leach process, is that sulphur is oxidized primarily to the
elemental form, rather than to sulphate. Consequently, the oxygen and neutralization
requirements are substantially reduced in the process flowsheet proposed for HBMS,
compared to a higher temperature, total sulphur oxidation process.

The mineralogical composition of the copper concentrate, however, has an effect


on the conversion of sulphide sulphur to elemental sulphur. Typically, sphalerite and
bornite would give high yields of elemental sulphur, while pyrite would be oxidized to
sulphate.

_______________________________________________________________________

Laboratory Testwork

The testwork conducted on the HBMS copper concentrate blend consisted of


small scale pressure leach rate tests, material balance pressure leach tests, residue
flotation tests, sulphur melting tests, locked cycle testing of the leaching, flotation and
sulphur melting steps, gold and silver extraction tests, copper solvent extraction tests, and
raffinate bleed neutralization and zinc recovery tests.

Small Scale Pressure Leach Rate Tests

Small scale batch pressure leach rate tests were conducted to evaluate the effects
of various leach parameters (such as additive dosage, feed particle size, initial acid and
zinc concentrations, and retention time) on pressure leach performance.

Page 7 of 16
Generally, the HBMS concentrate blend responded to the leach parameter
variations as expected based on previous process development testwork. However, new
responses were observed in the tests with variable zinc concentrations in the head
solution (0 to about 50 g/L Zn). With increased zinc concentration the copper and zinc
extraction rates were slightly lowered. Also, and more significantly, as the zinc level
increased, the terminal acidity and iron concentration decreased. Analysis of the leach
residues indicated that the amount of sulphate in the solids increased with increasing zinc
in the head solution, although the total oxidation of sulphide sulphur to sulphate sulphur
remained relatively constant at about 30% over the range of zinc levels tested.

Material Balance Pressure Leach Tests

Larger scale batch pressure leach tests in the material balance mode (i.e. without
any intermediate sampling) were conducted to confirm selected pressure leach conditions
from the small scale tests and to generate solids and solution for downstream testwork.
The feed solution was synthetic SX raffinate, containing 40 g/L Zn. The molar ratio of
free sulphuric acid plus equivalent acid as iron sulphates in the raffinate, to copper plus
zinc in the feed solids, was 0.9:1.

The material balance tests, simulating a single pass of leaching in the proposed
partial leach-sulphide recycle flowsheet, confirmed the rate test results, giving 85%
copper extraction, 99% zinc extraction, 3% iron extraction, 28% sulphide sulphur
oxidation to sulphate, and 60% sulphide sulphur conversion to elemental sulphur in the
final solids. The final solution composition was about (g/L): 39 Cu, 0.6 Fe2+, 3.3 FeT,
18 H2SO4, and 43 Zn, which is suitable as feed to the subsequent solvent extraction
operation.

Residue Flotation Tests

Leach residue solids produced in the material balance tests were subjected to
rougher-scavenger and cleaner flotation tests. Good recoveries of copper and sulphur
and good rejection of silica and iron were achieved. Approximately 95% of the copper
and 76% of the sulphur were recovered to the rougher-scavenger concentrate, producing
tailings containing 0.46% Cu. With the recycle of the sulphide cake to the pressure
leach, this corresponds to less than 1% of the copper in the copper concentrate feed to the
process reporting to the tailings.

Gold in the pressure leach residue was split between the concentrate and tailings
fractions, with the larger part reporting to the cleaner concentrate. A significant portion
of the gold in the feed, therefore, will be recycled back to the pressure leach with the
sulphide cake. The silver reported predominantly to the flotation tailings, presumably
with the jarositic and/or oxidic components.

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Locked Cycle Testing

Nine cycles of locked cycle testwork, consisting of pressure leaching, residue


screening and flotation, sulphur melting and hot filtration, sulphide cake grinding, and
recycle of the ground sulphide cake to the leach step, were performed using the HBMS
concentrate blend as the feed. The purpose of locked cycle testing was to evaluate the
effect of sulphide cake recycle on overall copper extraction, sulphur deportment, and
precious metals deportment. A block flow diagram of the locked cycle test is shown in
Figure 2. In the batch test, the pressure leach residue was screened prior to flotation. In
commercial operation, it is expected that the pressure leach residue would be subjected to
flotation directly.

The selected conditions for the locked cycle test were based on the previous batch
test results and preliminary mass balances done on the proposed copper plant flowsheet.
A summary of copper, iron and zinc deportment in the locked cycle test is given in
Table II.

Table II − Deportment of Copper, Iron and Zinc in Locked Cycle Test Output Solids

Analysis, % Amount, % *
Cu Fe Zn Cu Fe Zn
Flotation Tailings
Cycle 1 ** 1.08 36.9 0.89 0.44 14.5 2.16
Cycles 2 to 9 0.33 39.6 0.05 0.74 86.4 0.73
Cycle 9 Sulphide Cake 9.59 22.5 0.04 1.20 2.74 0.03
Cycle 9 Flotation Recycle *** 0.60 34.9 0.03 0.12 6.91 0.03
* weight percentage of metals in feed solids
** contained abnormally high copper and zinc levels
*** cleaner tails plus scavenger con

The median analysis of copper in the flotation tailings was 0.34%; this
corresponds to less than 1% of the copper in the copper concentrate reporting to the
flotation tailings, corresponding to an overall recovery of copper to solution of greater
than 99%. The zinc concentration in the flotation tailings was typically less than 0.10%,
corresponding to an overall recovery of zinc to solution of about 99% as well.

The median analysis for the pressure leach product solution from the locked cycle
test is given in Table III. The copper pickup in solution was about 34 g/L and the zinc
pickup was about 5 g/L. The concentration of iron in the product liquor was 2.5 g/L,
which was similar to that of the raffinate used as the lixiviant in pressure leaching. The
net extraction of iron to solution was limited to about 1%. The concentration of free
sulphuric acid in the product liquor, at 16 g/L, was relatively low, making this solution
readily treatable in solvent extraction.

Page 9 of 16
Table III − Pressure Leach Solution Analysis

Median Analysis, g/L


2+
Ca Cu Fe Fe Mg Mn Si S (calc) Zn H2SO4
0.45 38.6 0.47 2.49 0.98 0.79 0.54 47.5 42.4 15.9

A summary of sulphur deportment in the locked cycle test is given in Table IV.

Table IV − Deportment of Sulphur in Locked Cycle Test Output Solids

Analysis, % Amount, % *
S° S(SO4) STotal S° S(SO4) STotal
Flotation Tailings 6.5 6.7 13.7 14 15 29
S° Filtrate 100 - 100 44 - 44
Sulphide Cake 38.9 1.0 49.9 4.4 0.1 5.6
Flotation Recycle ** 13.3 5.5 19.8 2.2 1.0 3.3
Total - - - 65 16 82
* weight percentage of sulphide sulphur in feed solids
** cleaner tails plus scavenger con

The conversions of sulphide sulphur to elemental sulphur and sulphate sulphur in


the solids were about 65 and 16%, respectively, and about 18% of the sulphur reported to
the solution as sulphate. These values were in good agreement with the sulphur
deportment observed in the large scale material balance tests, after scaling to account for
100% reaction of sulphide sulphur, compared with about 85% reaction in the single pass
material balance tests. About 68% of the elemental sulphur produced in the locked cycle
test was recovered as an elemental sulphur filtrate during hot filtration of the cleaner
concentrate. About 22% reported to the tailings and the remaining 10% was contained in
the solids recycle streams from Cycle 9.

The elemental sulphur filtrate contained 4 g/t As, 3 g/t Hg, 10 g/t Se and 2 g/t Te.
The low levels of selenium and tellurium were surprising in light of the relatively high
concentrations of these elements in the feed copper concentrate blend. The impurity
levels in the elemental sulphur produced in the test program were compared with typical
smelter acid and battery grade acid impurity levels, and indicated that, for the elements
analyzed, the sulphur produced in the locked cycle test may be saleable for making
battery grade acid.

About one third of the gold in the copper concentrate feed to all nine cycles in the
locked cycle test reported to the flotation tailings. The amount of gold in the tailings
increased slowly through the locked cycle test, ranging from 4.8 to 7.3 g/t over nine
cycles. As expected, gold also built up in the sulphide cake as the test progressed, up to
79 g/t in Cycle 9. The deportment of gold was not at equilibrium after nine cycles of

Page 10 of 16
locked cycle testing, but the test confirmed that a significant amount of gold will recycle
with the sulphide cake to the pressure leach.

About 95% of the silver in the copper concentrate feed to all nine cycles in the
locked cycle test reported to the flotation tailings, and about 3% reported to the Cycle 9
sulphide cake. The remaining silver was accounted for in the final Cycle 9 flotation
recycle solids and in the intermediate sulphide cake solids that were sampled for
analyses. The silver analysis in the tailings ranged between 219 and 299 g/t with a
median analysis of 245 g/t.

Gold and Silver Extraction Tests

Selected pressure leach residue and flotation tailings solids were subjected to
cyanidation either directly or after a lime boil pretreatment step to liberate silver from
jarosite or basic iron sulphate components. The lime boil step has also been referred
to as silver enhancement treatment (SET) (Berezowsky et al., 1990).

High gold and silver extractions (from 95 to 98%) were obtained in the cyanide
leach tests conducted on the flotation tailings obtained from the locked cycle leach test
residues, at cyanide additions of about 10 kg NaCN per tonne of tailings, or 7 kg NaCN
per tonne of copper concentrate feed to the process, even without a prior SET step.
Based on these test results alone, the SET step appears not to be required to obtain high
silver extraction. This would simplify the precious metals recovery operations and
significantly reduce the reagent requirements. However, cyanide leach tests conducted
on residues produced in the larger scale material balance pressure leach tests showed that
a SET step was required to obtain high silver extractions. It is expected that the
requirement for a SET step will be better defined in future process development testwork
on residues produced in a continuous miniplant pressure leach operation.

Copper Recovery Tests

Extraction and strip isotherms were generated in two series of batch shakeout
solvent extraction tests using an organic phase consisting of 32 vol% Acorga M5640
organic extractant in Shellsol 2046 diluent. The isotherms were subsequently used to
predict the copper and acid profiles in a solvent extraction circuit containing three
extraction stages and two strip stages. About 84% copper extraction was predicted, to
produce a raffinate containing 6.4 g/L Cu and 69 g/L H2SO4. In the strip section, spent
electrolyte would be used to strip about 69% of the copper to produce a pregnant
electrolyte containing 40 g/L Cu and 165 g/L H2SO4. A loaded organic phase containing
13.9 g/L Cu would be expected, while the stripped organic would be expected to have a
residual copper content of 4.3 g/L.

Page 11 of 16
Raffinate Bleed Neutralization and Zinc Recovery Tests

Neutralization tests were conducted to define the proposed bleed neutralization


flowsheet, which consisted of acid neutralization, iron/copper removal and basic zinc
sulphate precipitation steps. Batch neutralization tests were conducted on the
representative raffinate which was generated from pressure leach solution. These tests
were performed to confirm the feasibility of the proposed process steps and to evaluate
minor element deportment through the bleed neutralization flowsheet.

In the acid neutralization test, a final solution with 0.3 g/L H2SO4 was achieved
with very small losses of copper and zinc to the acid neutralization solids (about 0.9% of
the copper and about 0.3% of the zinc contained in the raffinate). At the relatively low
final acid level, about 75% of the iron was precipitated and reported to the gypsum. At a
higher final acid level, less iron would be precipitated in the acid neutralization step and
thus more iron would be removed in the subsequent iron-copper removal step. Because
of the relatively low amount of ferrous iron in the final solution from the acid
neutralization test, the iron/copper removal step was quite fast. The concentrations of
copper and iron in solution were reduced to each less than 0.1 g/L. About 12% of the
zinc in the raffinate bleed was coprecipitated with the iron-copper removal solids. The
zinc in the iron/copper removal solids would be recycled to the process and, thus, would
eventually report to the basic zinc sulphate cake. In the basic zinc sulphate precipitation
test, zinc in solution was lowered to 0.01 g/L, and copper and iron were lowered to <0.5
and <1 mg/L, respectively. The zinc to copper ratio in the basic zinc sulphate cake was
196:1.

Two tests were conducted to determine if the iron-copper removal solids from
raffinate bleed neutralization could be recycled to the process to recover the copper and
zinc values. The conditions and solutions used in the two tests were chosen to simulate
the addition of the iron-copper removal solids to the acid neutralization step in raffinate
bleed neutralization, and to the pressure leach conditioning tank. In both tests, the
copper, iron and zinc values were readily dissolved leaving final residue solids
containing relatively pure gypsum with minimal metal content. In the two cases that
were simulated, the dissolved iron, after building up to a certain equilibrium level in
solution, would eventually report to the pressure leach. Iron deportment in the pressure
leach is dictated by the leach conditions (e.g. temperature, acidity), with the majority of
the iron reporting to the leach residue and eventually to the oxidic tailings stream.

The basic zinc sulphate (BZS) cake would be added to an appropriate circuit in
the existing HBMS Zinc Plant, taking into account the contained impurities, most of
which were at relatively low levels in the BZS cake produced in the test program. The
BZS cake contained only 0.11% Cu, corresponding to a Zn:Cu ratio of about 200:1, and
thus should be readily treated in the zinc plant, from a copper content perspective (i.e.,
without significantly affecting the consumption of zinc dust in the zinc plant purification
circuit).

Page 12 of 16
_______________________________________________________________________

Conclusions

A hydrometallurgical process for the treatment of HBMS copper concentrates


was evaluated in a batch test program. The test data were used to develop a conceptual
process flowsheet and to prepare preliminary process design criteria for a conceptual
engineering study, in which preliminary estimations of capital and operating costs for a
copper pressure leaching facility were determined.

The batch test results indicate that the proposed process flowsheet, based on the
direct hydrometallurgical treatment of HBMS copper sulphide concentrates, should give
improved copper and zinc recoveries (98% each) compared to those obtained in the
existing copper smelter operations (better than 95% for Cu and 10% for Zn). The
recoveries of gold and silver should remain at levels similar to those achieved in the
existing smelting operations (better than 95%).

_______________________________________________________________________

Acknowledgements

The authors thank the management of Hudson Bay Mining and Smelting Co.,
Limited, and the management of Dynatec Corporation for permission to publish this
paper.

_______________________________________________________________________

References

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’99, sponsored by TMS of AIME, Phoenix, Arizona, USA, 10-13 October 1999.
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1990. Silver and Gold Recovery From Zinc Pressure Leach Residue. Lead~Zinc
’90, T.S. Mackey and R.D. Prengaman, Eds., The Minerals, Metals and Materials
Society of AIME, Warrendale, PA, USA, 1990, 135-150.
BUBAN, K. and COLLINS, M.J., 1997. Acid Pressure Leaching of Chalcopyrite by
Dynatec. Paper presented at Randol at Vancouver ’97, 3rd Annual Copper Hydromet
Roundtable, Vancouver, BC, Canada, 2-5 November 1997.
COLLINS, M.J., McCONAGHY, E.J., STAUFFER, R.F., DESROCHES, G.J. and
KRYSA, B.D., 1994. Starting Up the Sherritt Zinc Pressure Leach Process at
Hudson Bay. Journal of Metals, Vol. 46, No. 4, April 1994, 51-58.
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1995. Deportment of Selected Minor Elements at the HBMS Zinc Pressure Leach
Plant. CIM Bulletin, Vol. 88, No. 986, January 1995, 62-67.

Page 13 of 16
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Extraction of Copper from Sulphidic Concentrates. United States Patent, No.
5,730,776, 24 March 1998.
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Page 14 of 16
Copper Concentrate

Additive Water Air Water

Grinding Flotation Tailings L


S
Water Concentrate

Pressure L Lime
Leach S
Oxygen Lime Boil
Limestone (SET)

Acid S Melting and


Neutralization L Sulphide Filtration Lime NaCN
Water Raff- Scrub Cake
inate Water Cyanide
S SX Elemental Sulphur Leach
L Load/Scrub
Lime Gypsum Organic
Residue L Carbon-in-Pulp
Fe/Cu SX S (CIP)
Removal Strip Loaded Stripped
Oxidant Carbon Carbon
Solution to Iron Au/Ag
S Electrowinning Effluent Residue Recovery
L Treatment
Lime
Au/Ag
BZS Copper Doré
Precipitation Cathode

L Solution to
S Effluent Treatment
or to Pressure Leach

Basic Zinc Sulphate


to Zinc Plant

Figure 1 − Dynatec’s Copper Pressure Leach Process Flowsheet Proposed for HBMS

Page 15 of 16
Copper
Concentrate Synthetic
Raffinate
Pressure
Leach

-63 µm solids
Screening Rougher-Scavenger Scavenger Tailings
Flotation to PM Recovery
Scavenger
+63 µm solids Concentrate
Rougher Concentrate
Sulphide Cleaner
Grinding Cake Melting and Tailings Cleaner
Filtration Flotation

Cleaner Concentrate
Elemental
Sulphur

Figure 2 − Locked Cycle Test Block Flow Diagram

Page 16 of 16

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