30 2

CHINESE JOURNAL OF MATERIALS RESEARCH

2016 2

Vol. 30 No. 2
February 2 0 1 6

( 650093)
, ,
: CaCl2FeSO4
, ; FeSO4 0.15 SO2, FeO
FeO , 1373 K 30 min
0.40 Lmin-1CaCl2 0.20(CaCl2 ) FeSO4 0.15(FeSO4 ),
1.06% 0.11%,

, , ,
TF524

1005-3093(2016)02-0099-08

Removal of Copper from Copper-smelting Slags through

Chloridizing Roast
LI Lei**

ZHANG Renjie HU Jianhang

(State Key Laboratory of Complex Nonferrous Metal Resources Clean Utilization, Faculty of Metallurgical and
Energy Engineering, Kunming University of Science and Technology, Kunming 650093, China)
*Supported by National Natural Science Foundation of China No. 51204082.
Manuscript received January 19, 2015; in revised form June 29, 2015.
**To whom correspondence should be addressed, Tel: (0871)65178347, E-mail: tianxiametal1008@163.com

ABSTRACT The copper in copper-smelting slags can be removed effectively by means of chloridizing
roast process, which is beneficial to recover iron from the copper-smelting slags. Thermodynamic analysis was carried out to characterize the performance of copper and iron during the chloridizing roast process. It follows that in a certain range of processing parameters, the copper removal rate can be enhanced with the increasing ing temperature and time for the process, and the increasing amount of CaCl2
addition and FeSO4. When the addition amount of FeSO4 was higher than 0.15 (mass ratio of FeSO4 to
copper slags), SO2 was produced excessively and the (FeO) content in the reaction bed increased quickly. The generated FeO can be chlorinated easily, thereby caused an obvious increase of iron loss and decrease of the copper removal rates. The copper content in the slags decreased from 1.06% to 0.11% after a chloridizing roast treatment at 1373 K for 30 minutes, with an O2 flow velocity of 0.40 Lmin-1 and an
addition amount of CaCl2 of 0.20 (mass ratios of CaCl2 to copper slags) and FeSO4 of 0.15(mass ratios of
FeSO4 to copper slags).
KEY WORDS metallic materials, copper slags, chloridizing roast, copper removal

- [5]

(5 Kmin-1), 22%
85% [6]
,
[7],
(Fe2SiO4),
90% [8]

DOI: 10.11901/1005.3093.2015.035

[9], , [10]

, CuCo
Fe[1-4] , ,
35%, 29.1%
:

* 51204082
2015 1 19 ; 2015 6 29

100

30

2.1

[11],

CaCl2 ,

CaCl2 Cl2 Cl2

CaCl2 ,
2 (1)(2) 3 SO2 SO3
CaCl2 CaSO4( 2 (3)

(4)), CaCl2 CaO ,

,
1 1 ,

, 3 FeSO4
SO2 Fe2O3((5)), Fe2O3 (6)[13]

O ,

N2 , X
, 1
1 , Fe2SiO4

38.55%, FePb

CaCl2 FeSO4

Fe3O4, Cu2S CuS[12]

1.1

1.2

( 2),

1073-1873 K, 1 K
CaCl2, (CaCl2/
), FeSO4, (FeSO4/
) CaCl2 Fe-

1 X
Fig.1 XRD pattern of the copper slag cooled with the furnace in N2 atmosphere after melted

SO4

: CaCl2 FeSO4 ,
,
, 1 cm ,
O2(0.40 Lmin- 1),
,

1.3
(
ICP-1000),
, D/max3B X ()
, 21580 , 8min-1
HSC

2
Fig.2 Experimental device, 1-Furnace cover,2-MoSi2 heating staff, 3-Al2O3 furnace tube, 4-Thermocouple, 5Al2O3 gas piping, 6- Reactor, 7- Fire- resistant pad
block, 8- Control cabinet, 9- Flowmeter, 10- Relief
valve

1 (, %)
Table1 Chemical composition of the copper slag(%, mass fraction)
Components

Fe

CaO

SiO2

Al2O3

MgO

Cu

Pb

Zn

Others

Contents

38.55

2.77

34.08

3.90

1.14

1.06

0.52

2.07

1.84

14.07

101

:
2 CaCl2
Table 2 Reaction in the dissociation of CaCl2
rGm-T

Serial number

Reactions

(1)

CaCl2+1/2O2(g)=CaO+Cl2(g)

(2)

CaCl2+SiO2+1/2O2(g)=CaSiO3+Cl2(g)

(3)

CaCl2+SO2(g)+O2(g)=CaSO4+Cl2(g)

(4)

CaCl2+2SO3(g)=CaSO4+SO2(g)+Cl2(g)

CaCl2 , FeSO4

rGm=137.16-0.02T
rGm=46.79-0.02T

rGm= -352.36-0.24T
rGm= -157.93-0.06T

Cu2SCuS FeS,
, 4 5 5 ,

FeSO 4 = 1/2Fe 2 O 3 + SO 2 (g) + 1/4O 2 (g)

SO 2 (g) + 1/2O 2 (g) = SO 3(g)

(5)

(12)-(15),

(6)

: FeSCuSCu2S
4 5 , ,

2.2

Cl2

, 3 ,

, , Fe2O3Fe3O4

FeS Fe2O3Fe3O4,

, FeOCu2O CuO

, Cu2S Cu2O CuO,

, ,

, FeO
Fe2O3
Fe3O4

4 rGm-T

Fig.4 rGm- T relation graph of the oxides chlorination

by Cl2

3 CaCl2 rGm-T
Fig.3 rGm-T relation graph of CaCl2 dissociation

Table 3 Reactions during the roasting process between the copper, iron oxides and Cl2
Serial number
(7)

(8)

(9)

(10)
(11)

Reactions

T/K

CuO+Cl2(g)=CuCl2+1/2O2(g)

473~1073

CuO+Cl2(g)=CuCl2(g)+1/2O2(g)

1073~1873

FeO+Cl2(g)=FeCl2+1/2O2(g)

473~1273

1/3Fe2O3+Cl2(g)=2/3FeCl3(g)+1/2O2(g)

1273~1873

1/3Fe2O3+Cl2(g)=2/3FeCl3+1/2O2(g)

473 ~873

FeO+Cl2(g)=FeCl2(g)+1/2O2(g)

873~1873

2/9Fe3O4+Cl2(g)=2/3FeCl3+4/9O2(g)

473~873

2/9Fe3O4+Cl2(g)=2/3FeCl3(g)+4/9O2(g)

873~1873

Cu2O+Cl2(g)=2CuCl+1/2O2(g)

473~1873

102

30

4
Table 4 Reactions during the roasting process between the main sulfides and Cl2
Reactions

T/K

1/2Cu2S+Cl2(g)=CuCl2+1/4S2(g)

473~1073

1/2Cu2S+Cl2(g)=CuCl2(g)+1/4S2(g)

1073~1873

CuS+Cl2(g)=CuCl2+1/2S2(g)

473~1073

CuS+Cl2(g)=CuCl2(g)+1/2S2(g)

1073~1873

FeS+Cl2(g)=FeCl2+1/2S2(g)

473 ~1273

FeS+Cl2(g)=FeCl2(g)+1/2S2(g)

1273~1873

2/3FeS+Cl2(g)=2/3FeCl3+1/3S2(g)

473~873

2/3FeS+Cl2(g)=2/3FeCl3(g)+1/3S2(g)

873~1873

Serial number
(12)

(13)

(14)

5 rG -T

Fig.5 rGm-T relation graph of the sulfides chlorination

by Cl2
5
Table 5 Polymerization of the chlorides during the copper
slag chlorination roasting
Reactions

T/K

2FeCl3=Fe2Cl6(g)

473~973

2FeCl3(g)=Fe2Cl6(g)

973~1873

2CuCl2=Cu2Cl4(g)

473~1073

2CuCl2(g)=Cu2Cl4(g)

1073~1873

Serial number

(17)

,
[14],

5, rGm-T
6 6 ,

3
3.1 CaCl2
0.40 Lmin FeSO4 0.15
-1

6 rGm-T

Fig.6 rGm-T relation graph of the polymerization of the

chlorides

2.3

(16)

(15)

7 CaCl2
Fig.7 Effects of CaCl2 addition amounts on the slag copper contents after treatment

1273 K 30 min , CaCl2

0.100.150.200.25 0.30,

7 , 30 min, CaCl2
0.10 0.20, , CaCl2
,

103

(5)(6)), (3)(4), Cl2

0.30

, ,

-1

CaCl2 0.20 0.40 Lmin

, 0.29% 0.12%( 10), FeSO4

CaCl2 ,

0.15 0.30 0.12%

0.57%, FeSO4

8 , CaCl2

SO2 , CaO SiO2 , SO2

, ,

FeSO4 Fe2O3 Fe3O4

Fe2SiO4Fe3O4

, (18)(19) 6(FeO)

Fe2O3 Fe3O4( 9),

Cl2 ,

[16, 17]

, CaCl2 0.20

, FeSO4 0.15
FeSO4

CaO + Fe 2 O 3 + SO 2 (g) = 2FeO + CaSO 4

3SiO 2 + CaO + Fe3O 4 + SO 2 (g) =

3.2 FeSO4
0.40 Lmin CaCl2 0.20
-1

3FeOSiO 2 + CaSO 4

1273 K 30 min , FeSO4

(18)
(19)

0.100.150.200.25 0.30,

11 , FeSO4

Fe FeSO4 0.10

0.20, Cl2

FeSO4 0.15, SO2SO3

FeSO4 (

( 11), Fe 34.93% 36.68%

FeSO4 0.20 , SO2
(FeO),

FeO

FeSO4 ( 11),

36.68% 35.76% (FeSO4

0.30)

, FeSO4 0.15

3.3

SO4 0.15 30 min ,

1173 K1273 K1373 K 1473 K,

8 CaCl2
Fig.8 Effects of CaCl2 addition amounts on the slag iron
contents after treatment

0.40 Lmin-1CaCl2 0.20Fe-

, FeSO4 Fe Fe

9 X
Fig.9 XRD pattern of the copper slag after treatment by
chlorination roasting

10 FeSO4
Fig.10 Effects of FeSO4 addition amounts on the slag copper contents after treatment

104

30

6 1073-1473 K (18)(19)
Table 6 Gibbs free energy and equilibrium constants of reaction (18) and (19) at 1073-1473 K

T/K

Reactions

1073

1173

1273

1373

1473

DG /(KJmol )

-13.89

-10.44

-7.07

-3.76

-0.55

Equilibrium constants/k18

673.21

88.24

16.33

3.94

1.22

DGQ/(KJmol-1)

-13.70

-9.30

-4.97

-0.76

3.36

Equilibrium constants/k19

615.68

53.93

7.22

1.31

0.34

(18)

(19)

-1

CaCl 2 (s) + 1/2O 2 (g) + Al 2 O 3(s) + 2SiO 2 (s) =

CaOAl 2 O 32SiO 2 (s) + Cl 2 (g)

(20)

1373 K ,

12 , 1173 K

1373 K, 0.35% 0.11%

, ( 14),

1473 K,

0.12%, CaO

( 15),

Al2O32SiO2 , CaCl2

, Cl2

, (20) 7

, 30 min

, ( 13)
, 1373 K

: 1373 K,

30 min, CaCl2 0.20, FeSO4

0.15 1.06%

0.11%, 37.58%, ,

0.40 Lmin-1

7 1173-1473 K (20)

Table 7 Gibbs free energy and equilibrium constants of reaction (20) at 1073-1473 K

T/K

1073

1173

1273

1373

1473

DG /KJ/mol

-4.48

-4.99

-5.45

-5.88

-6.30

8.23

8.56

8.62

8.61

8.61

11 FeSO4
Fig.11 Effects of FeSO4 addition amounts on the slag iron
contents after treatment

Equilibrium
constants/k29

12
Fig.12 Effects of roasting temperature on the slag copper
contents after treatment

13
Fig.13 Effects of roasting temperature on the slag iron
contents after treatment

105

FeSO4 Fe2O3 Fe3O4

FeO FeSiO3, Cl2

, ;
4. 0.40 Lmin-1 1373 K

0.15 , 1.06%

0.11%, 37.58%,

14
Fig.14 Effects of residence time on the slag copper contents after treatment

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