22 5 2012 5

Vol.22No.5 TheChineseJournalofNonferrousMetals May 2012

10040609(2012)05148809

1, 2111

(1. 4100832. 416000)

/

92.8% 0.045 mm 2.41.8 0.100mol/L
90min 30 (mL/g) 5:1 500r/min
87.7%

TF803.21 A

Oxidativeleachingoflowgradecopperorein
ammoniaammoniumsulfatesolutionwith ammoniumpersulfate
LIUZhixiong1, 2,YINZhoulan1,HUHuiping1, CHENQiyuan1

(1. Schoolof Chemistryand Chemical Engineering,CentralSouthUniversity,Changsha410083,China

2. CollegeofChemistryandChemicalEngineering,JishouUniversity,Jishou416000,China)

Abstract:Theoxidativeleachingoflowgradecopperorewasinvestigatedintheammoniaammoniumsulfatesolution
with ammonium persulfate. The effects of different parameters on the leaching of copper, including ammoniato
ammonium ion ratio, total ammonia concentration, concentrations of ammonia, ammonium sulfate and ammonium
persulfate, temperature, liquidtosolid ratio and stirring speed, were investigated. The result shows that the optimal
conditions for theleaching of lowgrade copper ore with a copper extraction87.7% arethe particlesizesof 92.8% of
samplefinerthan0.045mm,theconcentrationsofammonia,ammoniumsulfateandammoniumpersulfateare2.4,1.8
and0.100mol/L,respectively,leachingtime90min,temperature30,liquidtosolidratio(mL/g)5:1,stirringspeed
500r/min.
Key words: lowgradecopperoreoxidativeleachingammoniaammoniumsulfateammoniumpersulfate

[410]
70%~80%[1] [1114]

[12]

[23]

(2007CB13601)(10C1095)
2011060320111014
073188877364073188879616Email:yzllxh@gmail.com
225 1489

[5]
1
BINGL [15]
[16] 1.1

[17]

, 0.015~0.002
mm[20],

1
92.8% 0.045 mm
5
11510 t XRD 2 1
0.75% , 70% 2
30% (w(CaO+
MgO)40%) 1
[18]
70%() Table1 Distributionof samplegranularity
Granularity/ Distribution/ Granularity/ Distribution/
() mm % mm %

REED[19] +0.037 52.5 +0.0630.074 1.8

+0.0370.045 40.3 +0.0740.100 1.1

+0.0450.063 3.6 +0.100 0.7
S2 O82- + 2e 2SO2
- 0
4 E =+2.01V (1)

2
pH
Table2 Chemicalanalysisofsample(massfraction, %)
pH
CuO(Cu) CaO MgO SiO2

0.96(0.77) 29.00 12.92 25.90

Fe2O3 ZnO Al2O3 K2O Na2O

2.84 0.11 1.95 1.35 0.07

1 XRD
Fig.1 XRD patternofsample
1490 20125

40%() 0.77% EDS 1

XRD EDS1
XRD EDS1
EDS ( 4)
SEMEDS EDS
234
1.2

( 3)EDS2 3 1000mL
(CuSiO3)
EDS2 3

2 SEM EDS
Fig.2 SEMimages andEDSspectraof samples(white parts, containing copper minerals):(a),(b)Malachite and itsanalysis of
EDS1(c), (d)ChrysocollaanditsanalysisofEDS2(e), (f) BorniteanditanalysisofEDS3
225 1491
3 (4)~(7)
Table3 Chemicalphasecompositionofsample 2- - - 2- + -
2S2O8 + 2H2 O OH
SO4 +3SO4 + 4H + O2 (4)
Component w(Cu)/% Distribution/%
4 + OH
SO4- + OH- SO2
-
(5)
Freecopperoxide 0.383 49.74
Coppersilicates 0.220 28.57 OH+ O2- O2+OH (6)
Secondcoppersulfide 0.160 20.78
SO4- +O2- SO 2
-
4 + O2 (7)
Primarycoppersulfide 0.007 0.91
(4)~(7)
Total 0.770 100.00

2- - 2- +
1.3 2S2O8 + 2H2O OH
4SO4 + O2+4H (8)

(8) S2O82-
500 mL

2-
5 mL 2S2O8 + 4NH3+2H2O 4SO2
- +
4 + O2+4NH4 (9)
(10):
5 mL
2Cu5FeS4+ 18.5O2+36NH3+H2O+ 2(NH4)2SO4

10Cu(NH3)2
+ 2-
4 +2Fe(OH)3 + 10SO4 (10)
110 8 h
(9)(10)
:
2
2-
Cu5FeS4+ 18.5S2O8 + 55NH3+19H2O+(NH4)2SO4
5Cu(NH3)2
+ 2- +
4 +Fe(OH)3 + 42SO4 + 37NH4 (11)
2.1
(2)
2.2 /
(3)
6mol/L 4 h(mL/g)
Cu2(OH)2CO3+6NH4OH+2(NH4)2SO4 5:1 30 500r/min
2Cu(NH3 )2
+ 2- 2- +
4 + 2SO4 + CO3 + 2NH4 + 8H2O (2) /
3
CuSiO3H2O+2NH4OH+(NH4)2SO4
3/0.5~2.0
Cu(NH3)2
+ 2-
4 + SO4 + SiO2+4H2O (3)

PARK [5] REILLY SCOTT[21] pH

[22]
FURMAN ()

4 EDS
Table4 EDS elements analysisofsample
Massfraction/%
SampleNo.
Cu Fe S O Si Ca Mg C Cl
EDS1 60.89 1.95 26.00 3.89 1.08 6.18
EDS2 45.13 1.60 30.92 21.43 0.71 0.21
EDS3 60.13 10.11 22.08 1.22 1.40 2.94 1.22
Malachite 57.21 36.02 5.4
Chrysocolla (CuSiO3) 45.53 34.40 20.06
Bornite 63.32 11.16 23.92
1492 20125

4
3 / Fig. 4 Effect of total ammonia concentration on copper
extraction
Fig. 3 Effect of ammonia/ammonium ion mole ratio on
2.3
copperextraction atdifferentoxidants
30
90min(mL/g)
5:1
2.4
1.8 0.050
/5:7 ,
mol/L

55
75.9%85.5%85.9% 86.5%
400r/min

/ 5:7
400r/min
9%(11)

3
500 r/min

/ 5:7

0.05mol/L(mL/g) 5:1
500r/min 30/
5:7
( 4) 4

60 min
5
90 min 5 Fig.5 Effectofstirringspeedoncopperextraction
6 7 mol/L 85.5%86.5%
86.6% 2.4
90 min 6 mol/L 0.05 mol/L(mL/g)5:1
2.4 1.8mol/L 500 r/min 30
6
225 1493
86.5%86.7% 86.8%


1.8 3.0mol/L
0.3% 0.05mol/L
1.8mol/L
1.8
mol/L

2.4 1.8mol/L

2.5
2.4 1.8 mol/L
(mL/g) 5:1 500 r/min 30

7

6
Fig. 6 Effectsof concentrationsof ammoniaandammonium
sulfate on copper extraction: (a) Ammonia concentration
(b) Ammoniumsulfate concentration

1.8mol/L 7
6(a) 6(a) Fig. 7 Effect of ammonium persulfate concentration on
copperextraction

2.0mol/L 7
2.4 3.0
mol/L 90 min 86.5%
86.7%
2.4mol/L
2.4mol/L
6(b) 6(b) 0.100
mol/L
0.100 0.200
mol/L 90 min 87.7%
1.8mol/L 87.8% 0.100
1.82.4 3.0 mol/L 90 min mol/L
1494 20125

2.6
2.41.8
0.100 mol/L 500 r/min 30

88
60 min

(mL/g) 5:1

(mL/g) 5:1

9
Fig.9 Effectoftemperatureoncopperextraction

92.8% 0.045 mm
2.41.8 0.100mol/L
90min 30 5:1
500 r/min 87.7%

2.8
EDS SEMEDS
5 10
( 2)
8

Fig.8 Effectofliquidtosolidratiooncopperextraction
EDS2(2(d))EDS4
( 10(b) 5)) 10(a)
2.7

2.41.8 0.100 ,
mol/L 5:1 500 r/min EDS3
9 ( 2(f)) EDS5( 10(d))
9
50 10(c)
40 min 86.7% 90 min ,
3040 50 87.7%87.8%
87.8%
6
30

5 EDS
Table5 EDS elementanalysisofleachingresidue
Massfraction/%
SampleNo.
Cu Fe S O Si Ca Mg C Al
EDS4 32.08 1.37 0.54 23.43 14.51 4.96 2.82 17.96 0.59
EDS5 2.63 49.80 8.07 7.48 3.86 8.07 1.57 0.67
225 1495

10 SEM EDS
Fig.10 SEMimagesandEDSspectraofleachingresidue(whiteparts,containingcopperminerals):(a),(b)Leachingresidueof
chrysocollaanditsanalysisofEDS4(c), (d) LeachingresidueofborniteanditsanalysisofEDS5

6 SEMEDS
Table 6 Chemical phase composition of copper in samples
beforeandafterleaching
Beforeleaching Afterleaching 2) 92.8%
Component w(Cu)/ Distribution/ w(Cu)/ Distribution/ 0.045 mm
% % % % 2.41.8 0.100mol/L 90 min
Freecopper 30 (mL/g) 5:1 500
0.383 49.74 0 0
oxide
r/min 87.7%
Copper 3)
0.220 28.57 0.101 93.52
silicates

Primary
0.007 0.91 0.003 2.78
coppersulfide
Secondcopper REFERENCES
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