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Minerals Engineering 45 (2013) 185–190

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Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

Copper leaching from chalcopyrite concentrate in Cu(II)/Fe(III) chloride system


Jianming Lu ⇑, David Dreisinger
Department of Materials Engineering, University of British Columbia, 309-6350 Stores Road, Vancouver, BC, Canada V6T 1Z4

a r t i c l e i n f o a b s t r a c t

Article history: This study was conducted to develop a novel process for copper recovery from chalcopyrite by chloride
Received 27 October 2012 leaching, simultaneous cuprous oxidation and cupric solvent extraction to transfer copper to a conven-
Accepted 8 March 2013 tional sulfate electrowinning circuit, and hematite precipitation to reject iron. Copper leaching from chal-
Available online 16 April 2013
copyrite concentrate in ferric and cupric chloride system was investigated using a two-stage
countercurrent leach circuit under a nitrogen atmosphere at 97 °C to minimize the concentrations of cup-
Keywords: ric and ferric ions in pregnant leach solution for subsequent copper solvent extraction while maintaining
Copper
a maximum copper extraction. A high calcium chloride concentration (110–165 g/L) was used to main-
Chloride leaching
Chalcopyrite
tain a high cuprous solubility and enhance copper leaching. With 3–4 h of leaching time for each stage,
the copper extraction reached 99% or higher while that of iron was around 90%. With decreasing concen-
trate particle size from p80 of 26 to 15 lm, the copper extraction increased by about 0.2% while the iron
extraction increased by about 2.0%. The concentration of Cu(II) + Fe(III) in the pregnant leach solution was
able to be reduced to 0.04 M. When the cupric concentration fell below the above limiting value, the ele-
mental sulfur present was reduced by cuprous ions to form copper sulfide, eventually stopping the leach-
ing of copper. Under this condition, only iron was leached. A very small amount of sulfur (1.2–1.4%) was
oxidized to sulfate, resulting in an increase from 3 to 9 g/L in HCl concentration. The extractions of trace
metals (Cr, Pb, Ni, Ag and Zn) were 96–100%.
Crown Copyright Ó 2013 Published by Elsevier Ltd. All rights reserved.

1. Introduction Only a very small amount of sulfide (typically less than 5%)
(Dutrizac, 1990, 1992) is oxidized to sulfate as a side reaction,
Ferric chloride and/or cupric chloride leaching processes have which may be expressed as:
been extensively studied to treat sulfide concentrates of copper,
lead and zinc (Peters, 1977; Dutrizac, 1990, 1992; O’Malley and
S0 þ 6Fe3þ þ 4H2 O ¼ 6Fe2þ þ SO2
4 þ 8H
þ
ð3Þ
Liddell, 1987). Chloride leaching has several advantages for hydro-
metallurgical processes, with respect to sulfate systems, in sup- S0 þ 6Cu2þ þ 4H2 O ¼ 6Cuþ þ SO2
4 þ 8H
þ
ð4Þ
porting high metal solubility, enhanced redox behavior, and The reduction of cupric ions by chalcopyrite (Reaction (2)) is
increased rates of leaching. In a chloride system, both cuprous also limited by the following thermodynamic equilibrium (McDon-
and cupric ions (Cu+ and Cu2+) are stabilized through complexation ald and Langer, 1983; McDonald et al., 1984):
with chloride ions. Another advantage is the minimization of sul-
fate formation and the formation of predominately elemental sul- 2Cuþ þ S0 () CuS þ Cu2þ k ¼ 3:5  1011 ð105  CÞ ð5Þ
fur that remains in the leach residue (Dutrizac, 1990). Pyrite is
The extent of the above reaction is dependent on temperature
generally not attacked during leaching (Demarthe and Georgeaux,
and the Cu+/Cu2+ ratio. The presence of chloride can significantly
1978).
reduce free Cu+ concentration through complexation. A higher
The following reactions are generally accepted as representing
chloride concentration results in a lower free Cu+ concentration,
the leaching of chalcopyrite using FeCl3 and CuCl2:
a higher Cu2+/Cu+ redox potential and therefore suppression of
CuFeS2 þ 4Fe3þ ¼ Cu2þ þ 5Fe2þ þ 2S0 ð1Þ Reaction (5). It is possible that the following reactions may also oc-
cur (Peters, 1977):
CuFeS2 þ 3Cu2þ ¼ 4Cuþ þ Fe2þ þ 2S0 ð2Þ Cu2þ þ CuFeS2 () Fe2þ þ 2CuS ð6Þ

2Cuþ þ CuFeS2 () Fe2þ þ CuS þ Cu2 S ð7Þ


⇑ Corresponding author. Tel.: +1 604 822 1357; fax: +1 604 822 3619.
E-mail address: Jianming.Lu@ubc.ca (J. Lu).

0892-6875/$ - see front matter Crown Copyright Ó 2013 Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.mineng.2013.03.007
186 J. Lu, D. Dreisinger / Minerals Engineering 45 (2013) 185–190

To suppress the above side reactions, a lower temperature Copper can be effectively leached from chalcopyrite and sec-
should be used. However, the reduction of cupric ions by chalcopy- ondary sulfide copper concentrates, and the copper extraction
rite (Reaction (2)) is slower at a lower temperature. can exceed 98% (Liddicoat and Dreisinger, 2007). However, in the
With respect to copper recovery and iron deportment, there are previous work, the pregnant leach solution contained an excess
four typical processes: Outokumpu HydroCopper, Intec, Sumitomo amount of cupric ions (0.5–1.3 M). This amount of copper has to
and Falconbridge copper chloride. In the HydroCopper process, be reduced using metallic copper from cupric to cuprous for sol-
copper concentrates are leached in strong sodium chloride solution vent extraction and purification stages. Therefore the reduction
using Cu(II) as an oxidant (Hyvarinen and Hamalainen, 2005). The of cupric to cuprous is costly (significant recycle of metallic copper
iron leached is oxidized to Fe(III) by oxygen and re-precipitated as to reduction step).
goethite/hematite. The pregnant leach solution is highly purified The objective of this study was to maximize copper extraction
using multi-steps. In the first step, the impurities (Fe, Ni, Zn, Co, while maximizing the reduction of cupric to cuprous, and further
Mg and Cu(II)) are first removed by raising the solution pH to 4– understand the copper leaching from chalcopyrite concentrate in
5 using CaCO3 and NaOH. In the second step, silver is removed as ferric–cupric chloride solutions under well-controlled conditions.
amalgam by cementation on copper. In the third step, the majority
of the remaining impurities (Zn, Pb, Ni, etc.) are removed by raising
pH to 6–7 using Na2CO3. In the last step, the impurities are re- 2. Experimental
moved to trace levels using a chelating resin. The above multi-step
purification contributes greatly to the process operating cost. Cu2O 2.1. Apparatus
is produced from the purified solution by addition of NaOH and
then reduced to metallic copper by H2. NaOH, H2 and Cl2 are gen- The schematic diagram of the two-stage countercurrent leach
erated by chlor-alkali electrolysis. Cl2 is used to oxidize Cu(I) and circuit is shown in Fig. 1. To prevent the oxidation of cuprous ions,
regenerate Cu(II) for leaching. all operations were conducted under a nitrogen atmosphere.
In the Intec copper process, copper concentrates are leached in a Chloride leaching was carried out in two 2-L water-jacketed
NaCl–NaBr solution at 80–85 °C during four-stage countercurrent glass reactors (12.5 cm ID  25 cm depth) with three built-in baf-

leaching using Cu2+, O2 and BrCl2 as oxidants (Moyes et al., fles. The temperature was controlled at 97 ± 0.5 °C using two circu-
2000). Iron is leached and re-precipitated as goethite during the lating water baths. The reactors were sealed with a removable lid,
first three stage leaching. Copper is recovered by electrowinning which had several openings for the temperature probe, pH, and po-
from copper chloride/bromide solution in a diaphragm cell. The an- tential measurement, sampling, stirrer shaft, nitrogen gas and con-
ode product is the soluble salt NaBrCl2. Silver and mercury are re- nection to condensers. Agitation was provided by single 45°
moved as an amalgam by cementation on copper. The other pitched impellers with a diameter of 5.7 cm. The stirrers were sus-
impurities are removed by increasing pH. The operation cost is rel- pended around 1.5 cm from the bottom of the leach vessels. The
atively low. However, the copper extraction can be as low as 94%. rotational speed was controlled at 850 rpm.
Gold may be subject to sulfur encapsulation. Sulfur is rejected to A glass mini-thickener was used to separate solids and liquids
the leach residue, possibly causing an environmental issue on dis- for Stage 1 slurries. The pressure transfer of pregnant leach solu-
posal of leach residues. Even with a step for the removal of silver tion was used under a positive nitrogen pressure. A 1.5-L pressure
and mercury, the copper cathode may still be contaminated by sil- filter, lined with polyurethane, was used to filter solids for Stage 2
ver and mercury. The electrowinning process forms copper den- slurries.
drites which are difficult to strip and recover in the plating cell.
In the Sumitomo copper process, copper concentrates are lea-
ched in chloride solution using Cl2 as an oxidant (Asano et al., 2.2. Experimental procedures
2007). Cu(I) is extracted into the organic phase as H2CuCl3 from
the copper pregnant solution. Cu(I) is stripped from Cu(I)-loaded The continuous countercurrent leach tests began with 130–
organic phase to form a cuprous chloride solution. Copper metal 135 g of feed concentrate and 1 L of feed solution in each reactor
is produced in a diaphragm cell while Cl2 is produced at the anode (two reactors: one for Stage 1 and another for Stage 2). The leach-
for leaching. The Fe-containing raffinate is used to produce metallic ing conditions were identical for Both Stages 1 and 2 for the first
iron that is only saleable as scrap metal. The cost for production of cycle. At the end of the designated residence time countercurrent
metallic iron is high. transfer would occur with new feed chalcopyrite concentrate
In the Falconbridge copper chloride process, with respect to iron added to the reactor for Stage 1 and fresh feed solution was added
deportment (as hematite or goethite), two processes were pro- to the reactor for Stage 2. This leach/transfer was repeated for six
posed featuring chloride leaching of chalcopyrite combined with cycles to reach a steady state. The procedures are:
solvent extraction and conventional copper electrowinning from
sulfate media to recover a pure copper product (Liddicoat and Drei-
Leach solution
singer, 2007). The hematite process, in which no oxygen is intro-
duced to the leach, allows separate sulfur and iron residues to be
produced, thus making waste treatment and disposal easier. The Chalcopyrite Pregnant leachate
concentrate Fresh feed solution
hematite powder can be a saleable product such as pigment. The
goethite process is simpler in overall design, and air/oxygen is used
to precipitate iron as goethite for disposal with the leach residue.
The hematite process was further investigated in this study. In Pressure
the hematite process, the separate solvent extraction and hematite Slurry Solids Slurry
Leach Stage 2 Filtration
Leach Stage 1 Thickener
precipitation are expressed as the following reactions:

4CuCl þ 4HRðorgÞ þ O2 ¼ 2CuR2 ðorgÞ þ 2CuCl2 þ 2H2 O ð8Þ


Residue
6Fe2þ þ 1:5O2 ¼ Fe2 O3 þ 4Fe3þ ð9Þ Fig. 1. Schematic diagram for two-stage countercurrent leach circuit.
J. Lu, D. Dreisinger / Minerals Engineering 45 (2013) 185–190 187

(1) 1 L of feed solution was added into each reactor. Once the (38–42 g/L) and ferric (72 to 82 g/L) chloride concentrations, and
temperature had reached a target value, the redox potential calcium chloride concentration (110–165 g/L). The typical results
was recorded, and then the concentrate was added into the are summarized in Table 2. With decreasing particle size from
reactors to start a test. 15 min prior to transferring Stage 1 P80 of 26 to 15 lm, the copper extraction increased only by 0.2%
slurry to the thickener, 10 mL of 1000 ppm SuperflocÒ while the iron extraction increased by 2.0% (Tests 1 and 2). The
A110 anionic flocculant was added to enable quick and com- extraction of copper increased with increasing total amount of
plete settling of solids. Cu(II) + Fe(III) added (precisely the total amount of Cu(II) + Fe(III)
(2) At the end of the leach residence time, all of Stage 1 slurry added per unit of chalcopyrite concentrate) since a higher concen-
was pumped to the thickener while all of Stage 2 slurry tration of Cu(II) + Fe(III) resulted in a higher reaction rate and then
was pumped to the pressure filter. The clarified pregnant a higher extraction of copper. However, in a two-stage countercur-
leach solution was first removed, and then the underflow rent leaching circuit, the decreases in the cupric concentration
(solids) was pressure-transferred to the reactor for Stage 2 from 41 to 37 g/L and ferric concentration from 82 to 75 g/L in feed
using nitrogen gas. After pressure filtration of Stage 2 slur- solution practically had no effect on copper and iron extractions
ries, the filtrate was sampled and pressure-transferred to (Tests 2 and 3). A high calcium chloride concentration (110–
the reactor for Stage 1 using nitrogen gas. When the leach 165 g/L) was used to maintain the cuprous solubility above 80 g/
solution temperature reached the target value, fresh chalco- L through complexation with chloride ions. Only 1.2–1.4% of sul-
pyrite was added to the reactor for Stage 1. The time for each fide was oxidized to sulfate for all tests based on the amount of sul-
transfer was generally about half hour. fate generated.
Since these test results were similar, only the results obtained
2.3. pH and redox potential measurements under the conditions of a retention time of 4 h per stage, and
130 g of concentrate for 1-L feed solution with 38 g/L Cu2+, 72 g/L
Due to the problems of quick probe fouling in hot concentrated Fe3+ and 165 g/L CaCl2 (Test 4) are discussed here.
chloride solutions, the pH was measured at room temperature in
the filtered samples. An epoxy body Ag/AgCl combination elec-
3.1. Potential, free acid and pH
trode with a flat bottom platinum sensor and free flow junction
was used to measure the solution redox potential in the reactors.
The solution redox potential vs. time is shown in Fig. 2. This po-
tential reflected the Cu2+/Cu+ and Fe3+/Fe2+ ratios. For Cycle 1, fresh
2.4. Preparation of feed concentrate and feed solution
chalcopyrite concentrate and feed solution (practically with no cu-
prous and ferrous ions) were used for both Stages 1 and 2. There-
The chalcopyrite concentrate from Antamina in northern Peru
fore the initial potential for Cycle 1 was much higher than those for
was ground to p80 (80% passing) of 26 and 15 lm. The particle size
Cycles 2–6 because a certain amount of cuprous and ferrous ions
was analyzed using a Malvern Mastersizer laser analyzer. The as-
were always present in the leach solution after Cycle 1. The initial
say of the concentrate sample is given in Table 1.
decrease in the potential for Cycle 1 was also faster due to higher
Feed solution was prepared using deionized water, technical
cupric and ferric concentrations and hence a higher reduction rate
grade ferric chloride, reagent grade calcium chloride, reagent grade
of ferric and cupric ions by chalcopyrite. After Cycle 1, the decrease
cupric chloride and reagent grade hydrochloric acid.
in the potential for Stage 1 was dependent on the concentrations of
ferric and cupric chlorides since the amounts of cupric and ferric
2.5. Chemical analysis
ions were limited compared to that of the chalcopyrite. For Stage
2 the change in the potential was dependent on the amount of
The slurry samples were taken and cooled down under the pro-
unleached chalcopyrite since the amount of chalcopyrite was lim-
tection of argon gas. After the solids settled and the solution sam-
ited compared to those of cupric and ferric ions.
ples were removed, the remaining solids were filtered and washed
The pH decreased from 0.6 to 1.0 in Cycle 1, and then fluctu-
with 5% HCl solution until the filtrate became colorless. Finally the
ated between 0.9 and 1.1. The decrease in the pH indicates that
solid was further washed with deionized water. The solid was
the proton (H+) concentration increased or the composition of the
dried in an oven at 40 °C for ICP and sulfur group analyses.
other species such as free Cl and iron/ copper chloride concentra-
The free acid titration was conducted with oxalate masking un-
tions changed since these species affect the activity coefficient of
der an inert environment. 2 M potassium oxalate was used to com-
H+. The free acid (HCl) concentrations for feed solution and preg-
plex metal ions that would normally contribute protons, via
nant leach solution of each cycle are shown in Fig. 3. The free acid
reaction with hydroxide ions in water. The titration end point
concentration increased from 3.0 to 6.9 g/L for the first cycle and
was determined using standard solutions with different concentra-
then fluctuated between 6 and 9 g/L. The acid was generated due
tions of iron and copper. The titration of reduced species was con-
ducted using standard acidic cerium (Ce4+) sulfate solution under
an inert environment. Table 2
Results of four leaching tests.

3. Results and discussion Test No. 1 2 3 4


Feed CuFeS2 concentrate mass (g) 135 135 135 130
Leaching was conducted under different sets of conditions Concentrate particle size (P80) (lm) 26 15 15 26
(retention time (3–4 h), particle sizes (p80 of 15 and 26 lm), cupric Cu2+ as CuCl2 in feed solution (g L1) 42 41 37 38
Fe3+ as FeCl3 in feed solution (g L1) 81 82 75 72
CaCl2 in feed solution (g L1) 110 110 125 165
HCl in feed solution (g L1) 3.2 3.3 3.3 3.0
Retention time (h) 3 3 3 4
Table 1
Assay of Antamina chalcopyrite. Cu extraction (%) 98.9 99.1 99.2 99.0
Fe extraction (%) 88.9 90.9 91.0 89.0
0 2
Cu (%) Fe (%) STotal (%) SðSO2 S (%) S (%)
4 Þ (%) Average oxidation of S to SO2
4 (%)
1.26 1.22 1.34 1.37
29.4 28.6 31.8 0.68 <0.01 31.2 
Cu and Fe extractions were those in the last cycle.
188 J. Lu, D. Dreisinger / Minerals Engineering 45 (2013) 185–190

800 Stages 1 and 2 in Cycle 1 because the identical conditions were


used at Stages 1 and 2. The leach solution composition for Stage
Stage 1 Stage 2 1 was the same for Stage 2 for Cycle 1. The extractions of copper
Potential vs. AgCl/Ag / mV

700
and iron for Stage 1were calculated based on the changes in the
600 concentrations of copper and iron in the solution while those for
Stage 2 were based on the residue analysis.
500
The extractions of copper and iron vs. time are shown in Fig. 4.
The final (Stage 2) extractions of copper and iron fluctuated slightly
(95.4–99.1% for copper and 88.3–92.1% for iron) while Stage 1
400
extractions fluctuated significantly (5.5–88.3% for copper and
9.6–80.1% for iron). The extractions of copper and iron at Stage 1
300
Cycle 1 Cycle 2 Cycle 3 Cycle 4 Cycle 5 Cycle 6 were related to the concentrations of ferric and cupric ions in the
leach solution from Stage 2 in the previous cycle. In Cycle 1, the
200 chalcopyrite concentrate (Feed 1) was contacted with fresh feed
0 4 8 12 16 20 24
solution and therefore Reactions (1) and (2) were fast, resulting
Time / Hour
in higher extractions of copper and iron in Stage 1.
Fig. 2. Solution redox potential vs. time. At Stage 2 (Cycle 2), the residue from Stage 1 (Cycle 1) was con-
tacted with fresh feed solution. Since the chalcopyrite content of
the residue was low, only a small amount of cupric and ferric ions
to Reactions (3) and (4). The amount of sulfate generated during were consumed and so the concentrations of cupric and ferric ions
leaching was calculated based on the analysis of sulfate in feed were maintained at a high level in Cycle 2. This resulted in higher
solution, chalcopyrite concentrate, residue, leach solution and final extractions of copper and iron for Feed 1 at Stage 2 (Cycle 2).
wash solution. In the presence of 110–165 g/L CaCl2, nearly all At Stage 1 (Cycle 2), the fresh chalcopyrite concentrate (Feed 2)
the sulfate was precipitated as gypsum. The concentration of sul- was contacted with the leach solution (filtrate) from Stage 2 (Cycle
fate was below 0.2 g/L. Based on the amount of sulfate generated, 1). The ferric and cupric concentrations were low in this Stage 2
the average HCl concentration was calculated according to Reac- leach solution. Therefore the extractions of copper and iron were
tions (3) and (4) and is shown in Fig. 3. The HCl concentration of low (5.5% and 9.6% respectively) due to the slow reaction. The cop-
pregnant leachate from Stage 1 was close to the average HCl con- per extraction was lower than that of iron mainly due to the side
centration calculated in Cycles 4–6 while it was about 1.5 g/L lower reactions (Reactions (5)–(7)).
than the average HCl concentration calculated in Cycles 1–3 At Stage 2 (Cycle 3), the residue from Stage 1 (Cycle 2) was con-
mainly due to the following reactions: tacted with fresh feed solution and the final copper extraction for
Feed 2 was slightly lower than that for Feed 1. Since the residue
Cuþ þ 1=4O2 þ Hþ ¼ Cu2þ þ 1=2H2 O ð10Þ contained a larger amount of chalcopyrite and most of the cupric
and ferric ions were consumed in this stage, ferric and cupric con-
Fe2þ þ 1=4O2 þ Hþ ¼ Fe3þ þ 1=2H2 O ð11Þ centrations were not maintained at high levels, resulting in a
slower reaction and therefore a lower extraction of copper. At
The oxidation of cuprous or ferrous ions occurred during leach- Stage 1 (Cycle 3), the fresh chalcopyrite concentrate (Feed 3) was
ing and solid/liquid separation since the equipment was not per- contacted with the leach solution from Stage 2 (Cycle 2). Since
fectly sealed against oxygen. The oxidation of cuprous or ferrous the ferric and cupric concentrations were high in this leach solu-
also occurred during the free acid titration if a titration flask was tion, the extractions of copper and iron at Stage 1 were higher
not well sealed against oxygen, resulting in a lower analyzed value. (63.4% and 61.7% for copper and iron, respectively). These extrac-
tion values were still smaller than those for Feed 1, since Feed 1
3.2. Copper and iron extractions was contacted with fresh feed solution in which the ferric and cup-
ric concentrations were the highest.
To start a test, fresh feed solution and fresh chalcopyrite con- In Cycle 4 (Stage 2), the residue from Stage 1 (Cycle 3) was con-
centrate were added to the reactors for Stages 1 and 2. Therefore tacted with fresh feed solution at Stage 2 (Cycle 4). Since over 60%
the extractions of copper and iron were 88.1% and 80.3% for both of iron and copper were leached at Stage 1 (Cycle 3), higher ferric

10 100 98.9 99.1 97.1 99.0


95.3
92.1
90 88.1
90.3 91.1
88.2 89.0
-1

80
HCl concentration / g L

80.3
8
Extraction / %

70 64.5

63.0 62.1
60
6 61.6
50
Stage 1 40
4 Stage 2
Average calculated 30
21.5
20 17.4
2 13.2 16.9
10 Feed 2 9.6 Feed 4
Cycle 6 Feed 1 5.6 Feed 3 Feed 5 Feed 6
Cycle 1 Cycle 2 Cycle 3 Cycle 4 Cycle 5
0
0 0 Cycle 1 4 Cycle 2 8 Cycle 3 12 Cycle 4 16 Cycle 5 20 Cycle 6 24
0 4 8 12 16 20 24
Time / Hour
Time / Hour
Fig. 4. Copper and iron extractions of six chalcopyrite concentration feeds vs. time
Fig. 3. HCl concentration of leach solution for each cycle. (solid markers for Cu and open markers for Fe).
J. Lu, D. Dreisinger / Minerals Engineering 45 (2013) 185–190 189

and cupric concentrations were maintained in Stage 2 (Cycle 4), 3.5


resulting in a higher extraction of copper for Feed 3. Similar anal-
ysis can be applied to Feeds 4–6. 3.0
The concentrations of copper and iron in the leach solution for

Concentration / M
2.5
each cycle are shown in Fig. 5. According to Reactions (1) and (2),
the maximum concentrations of copper and iron in pregnant leach 2.0
solution from Stage 1 are (1 + 1/3)[Cu]Feed + 1/3[Fe]Feed and (1 + 1/ Stage 1 Total [Cu + Fe]
3)[Fe]Feed + 1/3[Cu]Feed respectively. Since some of cupric and ferric 1.5 Stage 1 [Cu(I) + Fe(II)]
ions were consumed due to the oxidation of sulfur to sulfate (Reac- Stage 1 [Cu(II) + Fe(III)]
tions (3) and (4)), and cupric and ferric ions cannot be completely 1.0
reduced by chalcopyrite (discussed in Section 3.4), the maximum
0.5
reachable concentrations of copper and iron were lower than those Cycle 1 Cycle 2 Cycle 3 Cycle 4 Cycle 5 Cycle 6
given above. At Stage 1, the amount of chalcopyrite in fresh chalco- 0.0
pyrite concentrate was much larger than that stoichiometrically 0 4 8 12 16 20 24
required to reduce cupric and ferric ion in the leach solution from Time / Hour
Stage 2 since some of cupric and ferric ions was consumed at Stage
2. Although the copper and iron concentrate in the leach solution Fig. 6. Concentrations of total copper and iron, Cu(I) + Fe(II) and Cu(II) + Fe(III) at
Stage 1 for each cycle.
from Stage 2 varied for each cycle, the leaching of copper and iron
reached or almost reached its limit for all cycles in 4 h (discussed in
Section 3.4). The concentrations of copper and iron in the leach 3.5
solution from Stage 1 were close to their maximum values and Stage 2 Total [Cu + Fe]
Stage 2 [Cu(I) + Fe(II)]
hence fluctuated slightly. At Stage 2, the amount of chalcopyrite 3.0 Stage 2 [Cu(II) + Fe(III)]
in the residue from Stage 1 was generally much smaller than that

Concentration / M
stoichiometrically required to reduce ferric and cupric ions in feed 2.5
solution. The chalcopyrite in the residue from Stage 1 was com-
2.0
pletely or nearly completely leached at Stage 2. The concentrations
of copper and iron in the leach solution from Stage 2 were depen- 1.5
dent on the amount of chalcopyrite in the residue from Stage 1. As
the amount of chalcopyrite in the residue from Stage 1 varied sig- 1.0
nificantly, the concentrations of copper and iron in the leach solu-
0.5
tion from Stage 2 fluctuated greatly. The fluctuation in copper and
Cycle 1 Cycle 2 Cycle 3 Cycle 4 Cycle 5 Cycle 6
iron concentrations decreased with increasing number of cycles as 0.0
the leaching circuit reached its steady state. 0 4 8 12 16 20 24
Time / Hour

Fig. 7. Concentrations of total copper and iron, Cu(I) + Fe(II) and Cu(II) + Fe(III) at
3.3. Cupric/cuprous and ferric/ferrous concentrations Stage 2 for each cycle.

The concentrations of total Cu and Fe, Cu(I) + Fe(II) and Cu(II) + -


Fe(III) are given in Figs. 6 and 7 for Stages 1 and 2 respectively. For decreased with increasing number of cycle as the leaching circuit
Stage 1, the concentrations of total Cu and Fe and Cu(I) + Fe(II) in- reached its steady state.
creased from 1.9 to 2.9 M and from 0 to 2.8 M respectively and
then fluctuated slightly for each cycle. The concentration of
Cu(II) + Fe(III) decreased from the feed concentration (1.9 M) to 3.4. Oxidation of chalcopyrite by Cu(II) and Fe(III) with extended time
0.17 M for the first cycle and then fluctuated around 0.10 M. For
Stage 2, the concentrations of total Cu and Fe, Cu(I) + Fe(II) and When the ratio of [Cu(II) + Fe(III)] to [Cu(I) + Fe(II) is not very
Cu(II) + Fe(III) fluctuated greatly since the contents of copper and low, the reduction of Cu(II) and Fe(III) by chalcopyrite can be ex-
iron in the residue from Stage 1 fluctuated. The fluctuation pressed by Reactions (1) and (2). When Cu(II) and Fe(III) are reduced
to some extent, the side reactions such as Reaction (5) should be
considered. The question is how much of Cu(II) can be reduced by
120 chalcopyrite with extended retention time. Therefore an experi-
ment was conducted to investigate the behavior of reduction of
100 Cu(II) and Fe(III) by chalcopyrite. 1 L of fresh feed solution was con-
Concentration / g L -1

tacted with 135 g of chalcopyrite for 3 h (Phase 1). The slurry was
80 pressure-filtered and the leach solution was further contacted with
135 g of fresh chalcopyrite concentrate for 27 h (Phase 2). The po-
60 tential vs. time is shown in Fig. 8. In Phase 1, the potential decreased
quickly in the first hour and decreased slowly since both the amount
40 of chalcopyrite and concentrations of Cu(II) and Fe(III) were de-
Stage 1 Cu Stage 2 Cu
creased significantly. In Phase 2, the potential decreased relatively
Stage 1 Fe Stage 2 Fe
20 fast in the first 8 h and then very slowly since the reduction of Cu(II)
Cycle 1 Cycle 2 Cycle 3 Cycle 4 Cycle 5 Cycle 6
or Fe(III) was slow due to their low concentrations. The concentra-
tions of total Cu, total Fe, total Cu + Fe, Cu(I) + Fe(III) and Cu(II) + -
0
0 4 8 12 16 20 24 Fe(III) vs. retention time for Phase 2 are shown in Fig. 9. In the
Time / Hour first hour leaching, the copper and iron concentrations increased
from 1.20 to 1.26 M and from 2.06 to 2.13 M respectively and then
Fig. 5. Concentrations of copper and iron in the leach solution for each cycle. they virtually stabilized. After 4 h, the copper concentration de-
190 J. Lu, D. Dreisinger / Minerals Engineering 45 (2013) 185–190

800 4. Conclusions

700
Potential vs. Ag/AgCl/ mV

The copper extraction was able to exceed 99.0% using two-stage


600 countercurrent leach circuit with 3–4 h of retention time for each
stage while the iron extraction was maintained at 90%. Some iron
500 was not extracted since pyrite is not readily attacked in chloride
400
leaching. Only 1.2–1.4% of sulfur was oxidized to sulfate, resulting
in an increase from 3 to 9 g/L in HCl concentration. The concentra-
Phase 1
300 tion of Cu(II) + Fe(III) in the pregnant leach solution was
Phase 2 0.04–0.21 M, which depended on the concentrations of the
200
Cu(II) + Fe(III) in feed solution, retention time and the mass of feed
100 chalcopyrite concentrate for each cycle. The copper extraction only
increased by 0.2% with decreasing particle size from p80 of 26 to
0 15 lm with the iron extraction increased by about 2.0%. Cupric
-5 0 5 10 15 20 25 30
ions cannot be fully reduced by chalcopyrite. When cupric concen-
Time / Hour tration was below a limit (around 0.04 M), elemental sulfur was be
reduced by cuprous ions and only iron was leached. The extrac-
Fig. 8. Redox potential vs. retention time.
tions of trace metals (Cr, Pb, Ni, Ag and Zn) were in the range of
94–100%.
4.0 A 3–4 h retention time for each cycle is recommended to reach a
high copper extraction. The temperature for Stage 1 should be con-
3.5 trolled between 90 and 97 °C to get a reasonably high reaction rate
3.0
and also reduce the side reaction (the reduction of elemental sulfur
Concentration / M

by cuprous ions) while the temperature for Stage 2 can be con-


2.5 trolled over 97 °C since the cupric and ferric concentrations were
high and the side reaction is negligible. The CaCl2 concentration
2.0
should be 110–165 g/L to maintain a high solubility of cuprous
1.5 chloride (over 80 g/L Cu+).
1.0
Total Cu Total Fe Acknowledgement
Total [Cu+Fe] [Cu(I)+Fe(II)]
0.5 [Cu(II) + Fe(III)]
The authors would like to thank Falconbridge Limited (now
0.0
0 4 8 12 16 20 24 XSTRATA) for funding this Project and allowing for publication.
Time / Hour
References
Fig. 9. Concentrations of total Cu, total Fe, total Cu + Fe, Cu(I) + Fe(II) and
Cu(II) + Fe(III) vs. retention time. Asano, S., Imamura, M., Takeda, K., Ando, K., Nagase, N., 2007. Chloride processing of
chalcopyrite copper concentrate, copper 2007 short course.
Demarthe, J.M., Georgeaux, A., 1978. Hydrometallurgical treatment of complex
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Table 3 and Metallurgy, London, pp. 113–120.
Contents in the head, concentrations in pregnant and extractions of trace metals. Dutrizac, J.E., 1990. Elemental sulfur formation during the ferric chloride leaching of
chalcopyrite. Hydrometallurgy 23, 153–167.
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Hyvarinen, O., Hamalainen, M., 2005. HydroCopper™ – a new technology producing
Concentration (mg/L) 68 533 36 20 2000
copper directly from concentrate. Hydrometallurgy 77, 61–65.
Extraction (%) 97 100 98 96 99
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compounds for simple copper ore concentrations. Metallurgical Transactions B
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with cupric chloride leaching of chalcopyrite concentrate. Hydrometallurgy 13,
ing Phase 2. The concentrations of total copper and iron and Cu(I) + - 125–135.
Fe(II) almost stabilized after 1 h. The concentration of Cu(II) + Fe(III) Moyes, J., Houllis, F., Bhappu, R.R., 2000. The Intec copper process demonstration
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0.04 M. This indicates that the reduction of Cu(II) + Fe(III) by chalco-
72.
pyrite reached a limit. O’Malley, M.L., Liddell, K.C., 1987. Leaching of CuFeS2 by aqueous FeCl3, HCl and
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3.5. Extractions of trace metals
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The concentrations of main trace metals in the pregnant solu- 36.
tion and their extractions in Cycle 6 are given in Table 3. The
extractions of these metals were over 96%.

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