23 12 2013 12

Vol.23 No.12 The Chinese Journal of Nonferrous Metals Dec. 2013

1004-0609(2013)12-3440-08

1 1 2

(1. 341000
2. 100160)

(44.284.28) kJ/mol




TF813TF111.31 A

Atmospheric direct leaching kinetics of

zinc sulfide concentrate in oxygen-rich sulfuric acid system
XU Zhi-feng1, ZHU Hui1, WANG Cheng-yan2

(1. School of Metallurgical and Chemical Engineering, Jiangxi University of Science and Technology,
Ganzhou 341000, China;
2. Institute of Metallurgy, Beijing General Research Institute of Mining and Metallurgy, Beijing 100160, China)

Abstract: The atmospheric direct leaching (ADL) kinetics of zinc sulfide concentrate in oxygen-rich sulfuric acid system
was studied by the integration of atmospheric leaching and pressure leaching. The results show that the extraction of zinc
is controlled by interface chemical reaction and the apparent activation energy of leaching reaction is calculated as
(44.284.28) kJ/mol. The leaching rate of zinc at the bottom of ADL tank is much higher than that at the top of ADL tank
and it is improved greatly with the increase of the slurry pressure at the bottom of ADL tank. The kinetic equation for zinc
leaching at the bottom of ADL tank was further established by quadratic regression on the basis of shrinking core model.
The influence of temperature on the extraction of zinc at the bottom of ADL tank is greater than that of slurry pressure.
Key words: zinc sulfide concentrate; sulfuric acid; atmospheric direct leaching; oxygen-rich; kinetics

(Roastleachelectrowinning
RLE) 85% SO2 RLE ZPL
[1]
RLE SO2 [35]
SO2 SO2 ZPL
[2]
RLE [67]
(Zinc pressure leachZPL) ZPL [89](Atmospheric direct

(50964004)([2010]209 )
2013-01-082013-10-12
010-88399551E-mail: wchy3207@sina.com
 23 12 3441

leachingADL)ADL (Shrinking core modelSCM)(

ADL 1)

[10]
(T=373 Kptotal=20 kPa)
1998 2004 (KokkolaFinland)
[1112]
(OddaNorway)
ADL 2008 [13] SCM
ZPL ADL

10~20 h 95%
ADL
1

1.1
74 m 86.88%
[14]
() 2 XRD (
ADL 1)

ADL

1 ZnS
Table 1 Kinetics parameters for atmospheric leaching of ZnS

Leaching system Model applied Activation energy/(kJmol1) Reference

HCl SCM with chemical reaction control 45.30 [15]

HCl+NaClO3 SCM with chemical reaction control 41.10 [16]

SCM with chemical reaction control 39.09 [17]

SCM with chemical reaction control 44.80 [18]
HCl+FeCl3
SCM with diffusion control 49.20 [19]
SCM 39.081.0 [14]

Crank-Ginstling and Brounschetein model 77.5102.5 [20]

FeCl3 SCM with mixed control
46.9 [21]
(diffusion and chemical reaction)

(33.04.0) for the fast Zn dissolution rate;

HClO4 Straight-line interpolation method [22]
(34.04.0) for the low Zn dissolution rate

SCM 41.072.0 [14]

SCM 46.0 [23]
H2SO4+
SCM with chemical reaction control 44.0 [24]
Fe2(SO4)3
First stage: SCM with chemical reaction control 27.5 [25]
Second stage: SCM with diffusion control 19.6

H2SO4+H2O2 SCM with chemical reaction control 50.0 [26]

T331 K: SCM with chemical reaction control
52.75
H2SO4+O2 T338 K: SCM with mixed control (diffusion and [27]
11.07
chemical reaction
3442 2013 12

2 AB
Table 2 Main chemical composition of zinc sulfide
concentrate (mass fraction, %) ()
Zn Fe Pb S Si Others 1.25 mol/L(mL/g)
30/1
46.83 7.62 2.41 28.08 1.96 13.10
373 K
A
348~368 K
() 0 MPa
1.0 L B
0.30.4 0.5 MPa
358~378
K B
1.0 L
500 r/min

500 r/min

1 XRD

Fig. 1 XRD spectrum of zinc sulfide concentrate

1.2 2

2.1
2
0 MPa( A )
( A )
348~368 K 3
( B )
3 60~360 min (xZn)

2 3
Fig. 2 Schematic diagram of atmospheric oxygen-rich direct Fig. 3 Atmospheric leaching results of zinc sulfide
leaching of zinc sulfide concentrate concentrate
 23 12 3443
368 3
K
360 min
13.60% ( 2 B )
348 K ( 2 A ) B
0.015 min1 0.033 min1
368 K
0.30.4 0.5 MPa
358~378 K 4 3
4 60~420 min Table 3 Leaching rate of zinc under different temperatures
420 min and slurry pressures
4 Leaching Slurry pressure/ Leaching rate,
temperature/K MPa k/min1

3 0 0.019
0.3 0.06
358
0.4 0.08
0.5 0.11
0 0.033
0.3 0.10
368
0.4 0.13
0.5 0.19
0.3 0.14
378 0.4 0.17
0.5 0.24

2.2
(ZnS)
(1)

ZnS(s)+H2SO4(aq)+1/2O2 ZnSO4(aq)+S0(s) +H2O(aq) (1)

(1)
SCM


k r c0
1 (1 x)1 / 3 t (2)
r0

x kr r0
c0
t


2 2 Ds c0
1 x (1 x) 2 / 3 t (3)
3 r02

Ds

4
Fig. 4 Effect of slurry pressure on zinc extraction at different (2)(3)
temperatures: (a) T=358 K; (b) T=368 K; (c) T=378 K ( 5)
3444 2013 12

5
Fig. 5 Plots of zinc leaching kinetics at different slurry pressures: (a) p=0 MPa; (b) p=0.3 MPa; (c) p=0.4 MPa; (d) p=0.5 MPa

k H3O+ Zn2+
ln k 1/T ( 6) 6 ln k 1/T
00.30.4 0.5
MPa 5 029.92 5 742.28
5 112.25 5 423.14
(Arrhenius)
41.847.742.5 45.1
kJ/mol 95%
(44.284.28) kJ/mol 40~300 kJ/mol

7 7 6 ln k1/T
Fig. 6 Plots of ln k1/T for zinc leaching at different slurry
pressures
 23 12 3445

7

Fig. 7 Backscattered electron image(a) and
elemental surface distribution((b)(e)) of
sphalerite in leaching residue

2.3 (5)
2.2
ln k 0 a ln T b ln p ln K E /( RT ) (6)

SCM ( 2 B ) y ln K E /( RT ) a0 ln k 0 x1 ln T
x2 ln p (6)
y a0 ax1 bx2 (7)
1 (1 x Zn )1/ 3 Kt (4)

K k 0T a p b exp[ E /( RT )] (5) 0.30.4
xZn (%)K k0 0.5 MPa (45.1 kJ/mol)
T (K)p (MPa) B
a b
E 4
(J/mol)t (min) F
3446 2013 12

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