Trans. Nonferrous Met. Soc.

China 27(2017) 2272−2281

Kinetics of zinc sulfide concentrate direct leaching in

pilot plant scale and development of semi-empirical model

Nima SADEGHI1, Javad MOGHADDAM2, Mehdi OJAGHI ILKHCHI1

1. Faculty of Materials Engineering, Sahand University of Technology, Tabriz, Iran;
2. Materials and Metallurgical Department, University of Zanjan, Zanjan, Iran
Received 11 August 2016; accepted 30 September 2017

Abstract: The direct leaching kinetics of an iron-poor zinc sulfide concentrate in the tubular reactor was examined. All tests were
carried out in the pilot plant. To allow the execution of hydrostatic pressure condition, the slurry with ferrous sulfate and sulfuric acid
solution was filled into a vertical tube (9 m in height) and air was blown from the bottom of the reactor. The effects of initial acid
concentration, temperature, particle size, initial zinc sulfate concentration, pulp density and the concentration of Fe on the leaching
kinetics were investigated. Results of the kinetic analysis indicate that direct leaching of zinc sulfide concentrate follows shrinking
core model (SCM). This process was controlled by a chemical reaction with the apparent activation energy of 49.7 kJ/mol.
Furthermore, a semi-empirical equation is obtained, showing that the order of the iron, sulfuric acid and zinc sulfate concentrations
and particle radius are 0.982, 0.189, −0.097 and −0.992, respectively. Analysis of the unreacted and reacted sulfide particles by
SEM−EDS shows that insensitive agitation in the reactor causes detachment of the sulfur layer from the particles surface in lower
than 60% Zn conversion and lixiviant in the face with sphalerite particles.
Key words: kinetics; direct leaching; sphalerite; shrinking core model (SCM); pilot plant

direct leaching of sphalerite.

1 Introduction MARKUS et al [6] have investigated particle size
variations during leaching process. The results confirmed
Leaching of sphalerite was, usually, carried out the formation of the product layer on the surface particles.
under pressure and oxygen plays a key role in zinc Moreover, other reports [1,8,12] confirmed shrinking
dissolution process [1,2]. Also, atmospheric leaching of core model (SCM) in atmospheric leaching that a sulfur
sphalerite has been studied by some researchers [3−8] layer is formed on solid particles. Three known control
and it has been shown that added ferric ions or other regimes in sulfide leaching kinetics are liquid film
oxidizing agents (in solution) usually oxidize sphalerite diffusion, solid product diffusion and chemical reaction
in atmospheric media. From these methods, an integrated controls. Several reports [8,13,14] have refused liquid
method has, also, been proposed where oxygen gas is film diffusion control, by determination of the processes
used to sphalerite leaching in the atmospheric media activation energy (Ea). Furthermore, due to intense
[9−11]. In this case, ferrous ionic species are oxidized by mixing in the reactor, sphalerite leaching may not be
oxygen blowing in the reactor. The generated ferric ions controlled by the liquid film diffusion.
are reduced to ferrous ion by sphalerite: On the other hand, a major feature of the kinetic
system is the chemical reaction step and reacting mass
Fe2(SO4)3(aq)+ ZnS(s)→ZnSO4(aq)+2FeSO4(aq)+S0(s)
transport coupled in series. In this case, the chemical
(1)
reaction occurs in an interface between the original solid
The ferrous ion (Fe2+) is re-oxidized in order to and the reaction product. If we assume that the zinc
continue the leaching. Therefore, concentration of ferric sulfide particles have a spherical geometry and the
ions, as an oxidant, could affect kinetic of zinc sulfide chemical reaction is the rate-controlling step, then it is
leaching. Oxygen blowing rate, particle size, temperature expression of the shrinking core model to describe the
and acid concentration are other effective factors in dissolution kinetics of the process as follows:

Corresponding author: Javad MOGHADDAM; Tel: +98-243-3054364; Fax: +98-243-2383400; E-mail: [email protected], [email protected]
DOI: 10.1016/S1003-6326(17)60253-X
 Nima SADEGHI, et al/Trans. Nonferrous Met. Soc. China 27(2017) 2272−2281 2273

1  (1  X )1/3  kr t , atmospheric leaching process. Moreover, studies about

direct leaching of sphalerite [18,19] were carried out at
bkc CAn bench scale, while the effect of various factors on direct
kr  (2)
 (ZnS)r0 leaching kinetics should be surveyed at the larger scale.
The aim of this work is to investigate effects of
When the diffusion of lixiviant (such as Fe3+)
kinetic characteristics (such as kinetic control regime,
through the elemental sulfur layer is the rate-controlling
activation energy of the dissolution and reaction order of
step, the following expression can be described as kinetic
different parameters) on direct leaching of zinc sulfide
model:
concentrate. All tests were performed in tubular reactor
1  3(1  X )2/3  2(1  X )  kd t , and pilot scale and then the collected data were analyzed
6bDCA by SCM. Influences of the particle size, acid
kd  (3) concentration, zinc sulfate concentration, temperature,
 (ZnS)r02
and solid to liquid (S/L) ratio were also studied on
where X is the fraction reacted and kr and kd are the sphalerite direct saturation kinetics. The activation
apparent rate constants for chemical reaction control and energy of the dissolution process was evaluated and
product diffusion in the product, respectively. Also, kc is semi-empirical rate equation was presented based on the
the chemical reaction rate constant, CA is the experimental and calculated results.
concentration of the lixiviant in the solution, b is
stoichiometric coefficient of the reactant in the leaching 2 Experimental
reaction, r0 is the initial radius of the solid particle, n is
the order of reaction with respect to CA and D is the The zinc concentrate enriched through the flotation
diffusion coefficient in the product layer. If the chemical of Angouran mine sulfide ore in the Aria flotation plant
reaction on the surface or diffusion through the product (Zanjan, Iran) was used in this work. First, sulfide
layer controls the leaching rate, there must be a linear concentrate was ground in rod mill and then it was
relation among the left side of Eq. (2) or Eq. (3) and sieved to obtain the particle size distribution. Mean
time. particle size and chemical compositions of the
Results of the investigation on determination of concentrate were determined by LPSA (laser particle size
kinetic mechanism of sphalerite leaching were totally analyzer) and atomic absorption spectroscopy,
different. DUTRIZAC [14] and PECINA et al [8] respectively. The crystalline ferrous sulfate and sulfuric
indicated that the kinetics of sphalerite dissolution in acid of industrial grade were used to make up all needed
ferric sulfate media is controlled by a chemical reaction solutions. Analytical grade chemicals were used for
on the surface of the particles. Also, XIE et al [1] solution analysis. Results of sulfide concentrate analysis
mentioned that the interface chemical reaction is the can be seen in Table 1. The low content of iron is
controlling step in the pressure leaching. remarkable, which can influence zinc dissolution rate.
On the other hand, some authors [7,15] have The contents of the metallic ions (Zn, Fe) in the
reported that the kinetics could be controlled by a sample solutions obtained from the leaching experiments
non-reaction mechanism. An investigation [16] reported were analyzed by atomic absorption spectroscopy
that both phenomenon of diffusion in product layer and (Varian, AA240). The ferrous and ferric ion
the reaction between the particle surface and the product concentrations were analyzed by titration of cerium (IV)
layer play a key role in controlling reaction rate. sulfate with Phenanthroline indicator and EDTA with the
Generally, the kinetic model of zinc sulfide leaching is salicylic acid indicator, respectively. The sulfuric acid
affected by different factors, such as agitation rate, and concentration was determined by titration of sodium
minerals composition in ore [17]. hydroxide and Methyl yellow indicator.
Even though all these studies provide valuable Leaching experiments were carried out in a tube
background on sphalerite dissolution kinetics, their reactor equipped with a thermometer, air inlet at bottom
results do not cover the dissolution kinetics during direct of tube, indirect steam coil, pump and a prime tank for

Table 1 Chemical composition of different fractions of complex concentrate

Mean diameter/μm w(Zn)/% w(Fe)/% w(Pb)/% w(Cd)/% w(Cu)/10−6 w(Ni)/10−6 w(Mn)/10−6
52 50.8 2.6 3.6 1.65 910 463 174
65 46.5 2.1 3.3 1.6 827 433 170
85 50.6 2.4 3.1 2.1 870 450 172
115 46.7 2.5 3.46 2.1 911 715 200
2274 Nima SADEGHI, et al/Trans. Nonferrous Met. Soc. China 27(2017) 2272−2281
making solution. It should be noted that for ideal product [4,8], controls the entire process. However, some
agitation, slurry was circulated from bottom to top of the investigations [7,25] confirmed both equations. When
tube. Volume of the reactor, slurry height, rate of the chemical reaction is first-order with respect to
circulation of pulp and rate of air blowing were 0.44 m3, lixiviant (such as Fe3+) concentration, linear regression
9 m, 80 L/min and 180 L/min, respectively. First, the analysis is used for evaluation of each model (Eqs. (2)
solution was prepared in the prime tank with acidity, and (3)). The closer the correlation coefficient (R2) to 1,
determined iron concentration and desired temperature. the better the regression line will be, which fits the data
After preparing slurry in the main tank, the slurry was in this way.
pumped into the tubular reactor and the first sample was The correlation coefficients for 0.2 and 0.4 mol/L
taken at that time. Fe were calculated from above equations in Fig. 2.
Findings of the study revealed that the values for
3 Results and discussion correlation coefficient (R2) of chemical reaction control
are closer to 1 than diffusion control regime. This result
3.1 Direct leaching curve trends is in balance with findings observed in DUTRIZAC’s
Figure 1 presents zinc extraction for 0.2 mol/L Fe, study where they determined that sphalerite leaching by
52 μm mean diameters of particles and 30 g/L solid to ferric sulfate is controlled by chemical reaction.
liquid ratio at 0.25 and 0.5 mol/L H2SO4. There is a
linear relationship between zinc extraction and time in
initial period, but when zinc extraction is increased by
more than 65%, the dissolution rate is reduced in both
curves, obviously. BUBAN et al [20] observed similar
results in direct leaching experiments, which were
carried out in the sulfate solution. SOUZA et al [7] and
WEISENER et al [21] attributed the decrease in zinc
dissolution rate to the formation of an elemental sulfur
layer. However, a different approach was used by
DUTRIZAC and MACDONALD [22] and XU et al [23],
and they reported that the produced quantity of elemental
sulfur is too low so that the diffusion resistance is small.
So, a comprehensive study should be carried out in direct
leaching sphalerite to understand kinetics of the zinc
dissolution and other product formation.

Fig. 2 Comparison of shrinkage core model for chemical

reaction control (a) and diffusion control (b)

Fig. 1 Zn extraction rates for 0.2 mol/L Fe, 52 m mean size of 3.2.1 Influence of initial iron concentration
particles Direct leaching reaction involves ferric ions (Eq. (1))
directly, which is regenerated by ferrous ions and oxygen
3.2 Kinetics model gas reaction, and it would be expected that the ferric
Two kinetic regimes were studied in leaching sulfate concentration would be an important parameter in
process. Equations (2) and (3) can be used to describe the the process. According to the Fe3+ analysis, in constant
leaching of zinc when only one step, chemical sulfuric acid concentration, there is a direct relationship
reaction [12,14,22,24] or diffusion through the reaction between Fe3+ and total iron concentration in the solution.
 Nima SADEGHI, et al/Trans. Nonferrous Met. Soc. China 27(2017) 2272−2281 2275
Hence, the study of the iron concentration effect can be sulfate sources in these studies. In the previous
useful on the zinc sulfide dissolution rate. studies [7,14], the ferric sulfate was added to the solution
For the reactions at 87 C, 0.15 g/L sulfuric acid and at the beginning of the reaction and Fe3+ concentration
30 g/L solid to liquid ratio, apparent rate constants (kr) was decreased by ZnS oxidation, while the ferric ions are
were deduced from the slopes of the individual regenerated dynamically by Fe2+ oxidation in the tubular
1−(1−X)1/3 versus time straight lines, and these rate reactor.
constants are displayed as a function of the iron 3.2.2 Influence of H2SO4 concentration
concentration in Fig. 3. The plot from both ln kr and The effect of H2SO4 concentration on the
ln[Fe] values was used to determine the order of a dissolution rate of 55 g/L of sphalerite was surveyed at
reaction with respect to the Fe concentration. As it is 87 °C in 0.2 mol/L Fe solution. The apparent rate
seen in Fig. 4, the order of the iron concentration is 0.982, constants (kr) were calculated from the straight line
being close to 1 and similar to those values available for slopes of 1−(1−X) 1/3 versus time curves (Fig. 5(a)). The
the oxidative leaching [26,27]. apparent rate constant is the function of H2SO4
concentration of the solution. As acid concentration
increases, the zinc sulfide leaching rate increases,
accordingly, from about kr=0.0078 at 0.05 mol/L H2SO4
to kr=0.0120 at 0.5 mol/L H2SO4. Moreover, the reaction
order with respect to H2SO4 concentration was calculated
by slope line of ln kr versus ln[H2SO4] (Fig. 5(b)). As can
be seen, the reaction order of H2SO4 is 0.189.

Fig. 3 Kinetic plot of surface chemical reaction for dissolution

of zinc sulfide concentrate in different concentrations of ferrous
sulfate (0.15 mol/L H2SO4, 30 g/L solid to liquid ratio, 87 C
and 0.27 mol/L ZnSO4 initial concentration)

Fig. 4 ln kr vs ln[Fe] plot

On the other hand, the reaction order determined by Fig. 5 Kinetic plot of surface chemical reaction for dissolution
AYDOGAN [28], DUTRIZAC [14], DUTRIZAC and of zinc sulfide concentrate at different concentrations of H2SO4
MACDONALD [22] and SOUZA et al [7] is (0.027 mol/L ZnSO4 initial concentration, 0.4 mol/L Fe, 87 C
approximately 0.50. The main reason for such and 55 g/L solid to liquid ratio) (a) and ln kr vs ln[H2SO4]
disagreement may be due to the difference in the ferric plot (b)
2276 Nima SADEGHI, et al/Trans. Nonferrous Met. Soc. China 27(2017) 2272−2281
CRUNDWELL [12] and SOUZA et al [7] have lines. The reaction rate dependence on the temperature
reported conflicting results for the reaction order with follows the Arrhenius equation [31].
respect to sulfuric acid concentration. They mentioned
that the reaction order was around 1, while
DUTRIZAC [14] reported that the reaction rate increases
gradually for more than 0.1 mol/L sulfuric acid
concentrations. These observations were attributed to
direct acid attack reaction increasing in zinc sulfide
leaching process. However, LAMPINEN et al [19]
reported that the sulfuric acid concentration has no
significant influence on the reaction rate of the direct
leaching of zinc, but they did not present any reaction
order for H2SO4 concentration.
In addition to the acid attack reaction, the sulfuric
acid has a desirable effect on Fe2+ oxidation reaction
rate [29] that can increase zinc dissolution rate,
consequently. Thus, the sulfuric acid concentration
would rather increase zinc leaching and Fe2+ oxidation
rates in the tubular reactor, simultaneously.
3.2.3 Influence of mean particle size
Different sizes of sphalerite were leached at 87 °C
in 0.4 mol/L FeSO4−0.25 mol/L H2SO4 to assess the
effect of grinding on the dissolution rate of zinc, and the
leaching kinetic curves under chemical control regime
are presented in Fig. 6(a). The kinetic constant (kr)
changes from 0.02412 to 0.1090 when the mean size of
the particle increases from 52 to 115 m. It is clear that
the rate increases, significantly, as the particle size of
sphalerite decreases. A decrease in particle size causes an
increase in the solid’s total surface area. Also, the size of
particles with lower iron content could have a greater
Fig. 6 Kinetic plot of surface chemical reaction for dissolution
impact on dissolution rate due to lower reactivity of
of zinc sulfide concentrate with different mean particle sizes
sphalerite [7,30]. de LOS SANTOS et al [30] have
(0.25 mol/L H2SO4, 0.027 mol/L ZnSO4 initial concentration,
reported that the presence of a catalytic surface of pyrite
0.4 mol/L Fe, 87 C and 30 g/L solid to liquid ratio) (a) and
with sphalerite favors the electronic transfer of sphalerite
ln kr vs ln[H2SO4] plot (b)
to pyrite in the ferric sulfate solution. So, the catalytic
and galvanic effects of pyrite decrease particle size
effects in the zinc extraction of sphalerite.
lnkr versus lnr0 plot is presented in Fig. 6(b). As it
can be seen, the slope of the straight line in the plot
shows that the order of reaction with respect to the initial
radius of the particle is close to −1. This value confirmed
surface reaction control in SCM that kr varies with the
inverse of the initial particle radius (kr∝1/r0). The result
is in agreement with the results obtained by
DUTRIZAC [14] and XIE et al [1] .
3.2.4 Influence of temperature
Figure 7 illustrates the 1−(1−X)1/3 versus time
curves for the dissolution of zinc when Angouran zinc
sulfide concentrate (65 m) was leached at various
temperatures (70, 80, 87 and 95 C) in 0.4 mol/L Fig. 7 Kinetic plot of surface chemical reaction for dissolution
FeSO4−0.15 mol/L H2SO4 solutions. The dissolution of zinc sulfide concentrate at different temperatures
curves are essentially linear at 70−95 °C and the rate (0.25 mol/L H2SO4, 0.027 mol/L ZnSO4 initial concentration,
constants (kr) were calculated from slopes of the straight 0.4 mol/L Fe and 30 g/L solid to liquid ratio)
 Nima SADEGHI, et al/Trans. Nonferrous Met. Soc. China 27(2017) 2272−2281 2277
By plotting the natural logarithm of the rate affects the fluid flow through solid particles and mass
constant (ln k) against the reciprocal of the reaction transfer of lixiviant around the particle is decreased,
temperature (1/T), the Arrhenius plot is shown in Fig. 8. accordingly [32].
The slope of this plot (−E/R) is −5.978 and the apparent
activation energy for sphalerite direct leaching is
obtained as 49.70 kJ/mol by multiplying gas constant.
Similar results were reported by other authors [1,22,25],
who calculated in SCM with chemical control regime.

Fig. 9 Kinetic plot of surface chemical reaction for dissolution

of zinc sulfide concentrate in different ZnSO4 initial
concentrations (0.4 mol/L Fe, 0.25 mol/L H2SO4, 30 g/L solid
to liquid ratio, 87 C and 52 m mean particle size)

Fig. 8 Arrhenius plot of reaction rate against reciprocal

temperature

3.2.5 Influence of ZnSO4 initial concentration and pulp

density
In any commercial leaching process, the
electrowinning output could be restored to the leaching
reactors, which may lead to higher initial concentration
of zinc in the solution. Increasing ZnSO4 initial
concentration in the solution could affect Fe2+
re-oxidation and zinc dissolution, simultaneously [14,19].
Accordingly, a series of tests were done at 87 °C where
sphalerite was leached using 0.4 mol/L FeSO4−
0.15 mol/L H2SO4 solutions, to which different initial Fig. 10 Kinetic plot of surface chemical reaction for dissolution
concentrations of ZnSO4 were added. As can be seen in of zinc sulfide concentrate in different solid to liquid ratios
Fig. 9, the kinetic constant (kr) was calculated from (0.4 mol/L Fe, 0.25 mol/L H2SO4, 87 C and 52 m mean
straight line slope of 1−(1−X)1/3 versus time which was particle size)
achieved at 0.02403, 0.01902, 0.01650 for 0.027, 0.5 and
1 mol/L initial zinc concentration, respectively. It is clear The reaction orders related to zinc concentration
that ZnSO4 species has a damaging effect on the and solid to liquid ratio are determined in Figs. 11(a) and
dissolution rate of direct leaching and this should be (b), respectively. In Fig. 11(a), the order of the initial
considered in the design of industrial processes. zinc sulfate concentration is 0.097 that shows increase
Also, to survey the effect of the pulp density on the in the initial concentration of zinc sulfate changes the
rate of sphalerite dissolution, rate constants were apparent rate constant, slightly. The order of pulp density
calculated from kinetic curves and the calculated rate is calculated to be 0.886, which implies significant
constants are displayed in Fig. 10. Various masses (30, impact of the factor on dissolution rate.
55 and 80 g/L) of the sphalerite were leached at 87 °C in 3.2.6 Mathematical modeling of sphalerite direct
0.4 mol/L FeSO4−0.15 mol/L H2SO4 solution. The leaching
kinetic constant (kr) was reduced by increasing solid to The apparent rate constant (kr) for the surface
liquid ratio, significantly. Based on Eq. (1), change in chemical reaction was calculated from slopes of the
pulp density changes reactant (Fe3+ and ZnS) ratio which straight lines in the previous sections. The slope of the
influences reaction rate. Also, increasing pulp density line in each plot presents the calculated order of
2278 Nima SADEGHI, et al/Trans. Nonferrous Met. Soc. China 27(2017) 2272−2281
dissolution rate with respect to the related parameter for seen in Fig. 12, a good coincidence was achieved
a chemical reaction controlled process. Accordingly, the between the calculated and the experimental values.
orders of the reaction related to iron concentration,
sulfuric acid concentration, zinc sulfate concentration
and initial radius of the particle are 0.982, 0.189, 0.097
and 0.992, respectively. Also, the apparent activation
energy is obtained to be 49.70 kJ/mol. Hence, a
mathematical model for direct leaching of zinc sulfide
concentrate is as follows:
1  (1  X )1/3  k0 [Fe]0.982 [H 2SO4 ]0.189 

 49.7 
[ZnSO 4 ]0.097 [r0 ]0.992 exp   (7)
 RT 
According to the value of activation energy and the
inverse relationship between kr and initial particle radius,
chemical reaction was stabilized as control regime.
Fig. 12 Comparison of experimental and calculated data of
Furthermore, plotting the rate constant (kr) values versus
sphalerite concentrate dissolution in direct leaching of zinc
the right side expressions of Eq. (7) gives a k0 value of
sulfide concentrate
29.131, 17.016, 12.204 for 30, 55 and 80 g/L of solid to
liquid ratio, respectively.
3.3 Morphology of leaching residues
The morphology of the leaching residual was
examined at different time intervals of the process by
SEM−EDS (Fig. 13). The particle’s precipitation after
10%, 35% and 60% Zn conversion is presented in
Fig. 13.
As can be seen in Fig. 13(a), the particle surface is
approximately clear; however, the sulfur is dispersed on
the particle. The sulfur particle is dispersed on the
sphalerite surfaces in Fig. 13(b). In Fig. 13(c), the sulfur
layer covers parts of the particles but the leach liquor is
faced with the sphalerite particles. The morphology of
the leach residue implies that major amount (higher than
60%) of zinc sulfide is dissolved in the solution without
sulfur interference, whereas some studies [7,21] reported
that sulfur covers particle surface after 35%−40% zinc
extraction. The Fe3+ concentration analyses show that
only 10% of iron concentration is oxidized to Fe3+ and
the ferric ions attacks to the mineral surface, slowly. A
thin sulfur layer is formed on the surface by the reaction
of Fe3+ attacks. It seems that extreme turbulence in the
present reactor causes the break-down of the thin sulfur
layer on sphalerite surface and dispersion in the system.
SANTOS et al [33] considered that leaching
residues showed no change in the sphalerite composition
after the leaching by the electron microprobe analysis. In
this regard, the elemental analysis result of this
micrograph is presented in Table 2. According to Table 2,
the content of sulfur increased on residue surface, while
Fig. 11 ln kr vs ln[ZnSO4] plot (a) and ln kr vs ln[S/L] plot (b) the zinc content was decreased in the zinc dissolution
reaction progress. Furthermore, the XRD pattern of
To test the accordance between the experimental leaching residue is demonstrated in Fig. 14. The sulfur
values and the calculated values from the empirical peaks are observed in the pattern, obviously, which
equation, a plot of these values was drawn. As can be confirms that the sulfide layer is formed on the surface.
 Nima SADEGHI, et al/Trans. Nonferrous Met. Soc. China 27(2017) 2272−2281 2279

Fig. 14 XRD pattern of leaching residue

The direct leaching process has been designed in

more than one stage to overcome sulfide barrier layer, as
a possible problem [10,34,35]. The sulfur is removed
from residue and the sulfur-free residue is recycled back
into the leaching process. Present processes could reduce
sulfide barrier layer and increase leaching rate in the first
stage. So, the mass of residue for subsequent operations
is reduced, obviously.

4 Conclusions

The kinetics of direct leaching of zinc sulfide

concentrate was investigated in the tubular reactor (9 m
in height) and pilot scale. Results of the present study
reveals that the values of correlation coefficient (R2) for
chemical reaction control process are closer to 1 than
those for diffusion control. The dissolution rate increases
when the iron concentration, in proportion to the amount
of re-oxidized ferrous concentration, is increased and
kinetic constant and iron concentration have a linear
relationship with each other. As presented by chemical
reaction control regime in SCM, the reaction rate is
inversely proportional to the particle size. Also, the rate
is increased with increasing temperature and the apparent
activation energy is 49 kJ/mol. The high value
Fig. 13 SEM photographs of zinc concentrate and leach (>40 kJ/mol) of the apparent activation energy and the
residues: (a) Residue after 10% zinc extraction; (b) Residue inverse relationship between the kinetic apparent rate
after 35% zinc extraction; (c) Residue after 60% zinc extraction constant (kr) and particle size stabilize the chemical
reaction as control step of leaching. SEM–EDX analyses
Table 2 EDS analysis result of residue
on residue confirm the shrinking core model, so that
Zinc extraction w/% elemental sulfur covers some parts of particle surface.
rate/% Zn S Si Fe O Cd
10 48 25.2 5.3 4.12 10.38 2.7 Acknowledgments
35 37.8 32.2 8.4 5.2 15.2 1.4 The authors gratefully acknowledge the Zanjan Zinc
60 33.6 38.2 5.67 4.51 15.7 −
Khalessazan Industries Company (ZZKICO) for the
financial and technical support of this work.
2280 Nima SADEGHI, et al/Trans. Nonferrous Met. Soc. China 27(2017) 2272−2281
[18] HAAKANA T, LAHTINEN M, TAKALA H, RUONALA M,
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硫化锌精矿直接浸出动力学及其半经验模型
Nima SADEGHI1, Javad MOGHADDAM2, Mehdi OJAGHI ILKHCHI1

1. Faculty of Materials Engineering, Sahand University of Technology, Tabriz, Iran;

2. Materials and Metallurgical Department, University of Zanjan, Zanjan, Iran

摘 要：在中试规模管式反应器中直接浸出贫铁硫化锌精矿，研究其浸出动力学。为满足静压浸出条件，将含硫
酸亚铁和硫酸的矿浆注入到垂直放置的直径 8 m 的管式反应器中，空气从反应器的底部吹入。考察了初始硫酸浓
度、反应温度、矿粒直径、初始硫酸锌浓度、矿浆浓度和铁含量对反应动力学的影响。结果表明，硫化锌精矿的
直接浸出遵循收缩核模型，过程受化学反应控制，其表观活化能为 49.7 kJ/mol。采用半经验模型描述该过程，得
到铁含量、硫酸浓度、硫化锌精矿浓度和矿粒直径的反应级数分别为 0.982、0.189、−0.097 和−0.992。采用 SEM−EDS
对硫化锌精矿浸出反应前后的矿粒进行分析，发现当锌的浸出率低于 60%时，由于反应器搅拌的问题，颗粒表面
硫产物层脱落，会影响浸出溶液与颗粒表面的接触。
关键词：动力学；直接浸出；闪锌矿；收缩核模型；中试
(Edited by Bing YANG)