CATALYSIS, KINETICS AND REACTORS

Chinese Journal of Chemical Engineering, 18(5) 730 735 (2010)

Kinetics of Reductive Leaching of Low-grade Pyrolusite with

Molasses Alcohol Wastewater in H2SO4*
SU Haifeng (
)1, LIU Huaikun (
and
WEN Yanxuan (
)1,**
1
2

)1, WANG Fan (

)1, L Xiaoyan (

)2

School of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, China
Educational Administration Department, Guangxi University, Nanning 530004, China

Abstract The kinetics of reductive leaching of manganese from low grade pyrolusite in dilute sulfuric acid in the
presence of molasses alcohol wastewater was investigated. The shrinking core model was applied to quantify the
effects of reaction parameters on leaching rate. The leaching rate increases with reaction temperature, concentrations of H2SO4 and organic matter in molasses alcohol wastewater increase and ore particle size decreases. The
leaching process follows the kinetics of a shrinking core model and the apparent activation energy is 57.5 kJmol1.
The experimental results indicate a reaction order of 0.52 for H2SO4 concentration and 0.90 for chemical oxygen
demand (COD) of molasses alcohol wastewater. It is concluded that the reductive leaching of pyrolusite with molasses
alcohol wastewater is controlled by the diffusion through the ash/inert layer composed of the associated minerals.
Keywords pyrolusite, molasses alcohol wastewater, reductive leaching, kinetics

INTRODUCTION

With an ever increasing demand for manganese

and gradual depletion of high grade manganese ore,
many efforts have been made to recover manganese
from low-grade pyrolusite. Generally, pyrolusite can
be treated by roasting reduction-acid leaching [1] and
direct reductive leaching in H2SO4 or HCl solution.
The reductive agents in H2SO4 solution include H2O2
[2], H2C2O4 [1], FeSO4 [3] and SO2 [4 6], while the
reductive agents in HCl solution include alcoholic [6],
nickel matte [7], pyrite [8] and H2O2 [9].
Recently, carbohydrates from agriculture wastes
were treated as the potential reducing agents for the
leaching of manganese ore in mild acidic solution
[10 14]. Molasses alcohol wastewater (MSW), which
is generated from the fermentation of cane sugar molasses for production of alcohol [15], has a high reducing capacity in acidic medium for its content of
melanoidins, caramel and phenolics. In our previous
work, MSW was used as reducing agent to leach pyrolusite, and the optimum condition in dilute sulfuric
acid solution was reported [16]. In addition, color removal is a main problem in the treatment of such
wastewater [15]. As indicated in our research [17],
leaching is an effective method to remove the organics
in MSW by using pyrolusite and its slurry as reducing
agent and adsorbent.
Meanwhile, a comprehensible understanding of
the leaching kinetics is needed for an efficient design
of leaching manganese ore. Precious research [18] on
the leaching kinetics of MnO2 by SO2 showed that the
key step during the leaching process is chemical reaction and its apparent activation energy is 35.9 kJmol1.
Similarly, the leaching rate of MnO2 with Fe2+ in

H2SO4 solution is also controlled by chemical reaction

with the apparent activation energy of 28 kJmol 1 [19].
Momade and Momade [20] reported that the leaching
after 30 min in aqueous methanol-sulfuric acid system
can be described by the diffusion controlled shrinking
core model. According the investigation of Veglio et
al. [12], the leaching in lactose-sulphuric acid follows
a shrinking core model with variable activation energy.
Lasheen et al. [14] studied the leaching kinetics of
manganese oxide ore with molasses in nitric acid solution and found that the leaching is controlled by the
diffusion through the product layer composed of the
associated minerals and the apparent activation energy
is 27.5 kJmol1.
Most works [12, 14, 18 20] on the leaching kinetics of pyrolusite mainly focused on the reductive systems of small molecule. However, the reductive agents
in MSW are macromolecule with the molecular
weight of 2000 9000 [21]. To date, the leaching kinetics of pyrolusite by macromolecular reductive agents
has not been reported.
In this work, we investigated the kinetics of the
reductive leaching manganese from pyrolusite by the
macromolecular reductive agents of MSW and the main
system variables on the leaching rate. The kinetic model
and the apparent activation energy were determined.
2 MATERIALS AND METHODS
2.1 Materials
Manganese ore was obtained from Mugui Manganese Mine, Guangxi, China. The ore samples were
crushed to 0.147 mm (100 meshes). The chemical
composition of the manganese ore used are listed in

Received 2010-02-24, accepted 2010-05-02.

* Supported by the National Natural Science Foundation of China (20866001) and the Natural Science Foundation of Guangxi
Province (0832035).
** To whom correspondence should be addressed. E-mail: wenyanxuan@vip.163.com

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Chin. J. Chem. Eng., Vol. 18, No. 5, October 2010

Tables 1 and 2. MSW (Nanning Sugarcane Refinery,

Guangxi, China), containing 7.3% organic compounds,
2.9% reducing sugars, CODCr 1.3 105 mgL1 and
BOD5 7.0 104 mgL1, was used in this work. All
other chemicals were of analytical grade and used
without further purification.
Table 1 Chemical composition of the pyrolusite sample
Component

Mass content/%

Mn

22.25

MnO2

31.78

Fe

12.35

SiO2

24.17

Al2O3

11.36

CaO

0.12

MnO

0.12

0.005

0.078

particle size of manganese ore were selected as 80 C,

1.0 molL1, 37.7 gL1 and 0.0676 mm, respectively.
At the end of leaching experiment, the slurry was filtered and the filtrate was analyzed for leached manganese concentration. All the experiments were repeated twice, and their relative deviation is always
below 1.0 %.
3 RESULTS AND DISCUSSION
3.1 Chemical reaction
The reduction and dissolution mechanism of pyrolusite in H2SO4 solution with MSW still remains
unclear. The chemical reactions taking place during
dissolution of the manganese dioxide in the presence
of sucrose [6] or glucose [13] can be described by the
following reactions:
24MnO 2 C12 H 22 O11 24H 2SO 4
24MnSO4 12CO 2
12MnO2

Table 2 Manganese content of different

particle size of pyrolusite
Particle size d0/mm

Manganese mass content/%

0.134

25.72

0.078

24.10

0.068

9.94

0.046

19.00

2.2 Leaching procedure

To investigate the effects of reaction parameters,
including stirring speed, particle size, acid concentration, MSW concentration and leaching temperature,
the comparative leaching experiments were carried out.
The leaching experiments were carried out in a 1000
ml three-neck flask immersed in thermostat water bath
with mechanical stirring. In a typical experiment, 5.0
g of ore was added to 500 ml sulfuric acid-MSW solution under stirring (700 rmin1), and leaching started
after manganese ore was added to the solution. After
reaction, the slurry was filtered and the residue was
washed with distilled water. The filtrate was then diluted in HNO3 solution (pH 2) for analysis. The Mn
concentration during the leaching process was measured by an inductively coupled plasma spectrophotometer (ICP, Optima 5300 DV, Perkin Elmer). The
leaching efficiency was calculated by referring the
amount of leached metal in the liquor to its original
input quantity. Organic MSW concentration (the mass
of the all organic compounds in the dilute sulfate acid
solution) is expressed by the COD values. The ratio of
liquor to solid was kept as 100 1. The changes of
H2SO4 concentration and COD can be neglected during each leaching test. Unless otherwise specified, the
values of temperature, H2SO4 concentration, COD and

35H 2 O

(1)

C6 H12 O6 12H2SO4

12MnSO4

6CO2

18H 2 O

(2)

In this study, XRD was used to identify the mineralogical composition of ore samples before and after
leaching treatment. The corresponding XRD patterns
are shown in Fig. 1. The raw ore comprises of pyrolusite (MnO2), hematite (Fe2O3), silicon oxide (SiO2)
and kaolinite (Al2Si2O5(OH)4), while the leach residues are mainly silicon oxide, kaolinite and some
hematite. These results suggested that no insoluble
product forms during the leaching processes. So the
reaction between pyrolusite and MSW in H2SO4 solution can be written as follows:
(C - H x O y ) m 2mMnO2 2mH 2SO4
2mMnSO4

mCO2

zH 2 O

(3)

Figure 1 XRD pattern of pyrolusite and its residue after

leaching
1 pyrolusite;2 residue; MnO2; SiO2; Al2Si2O5(OH)4;
Fe2O3

3.2 Effect of parameters

Figure 2 shows the effect of stirring speed in the
range of 100 1100 rmin1 on the reductive leaching

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Chin. J. Chem. Eng., Vol. 18, No. 5, October 2010

Figure 2 Manganese extraction vs. time at various stirring

speeds
100 rmin1; 200 rmin1; 500 rmin1; 700 rmin1;
1100 rmin1

of pyrolusite. The conversion of manganese first increased when stirring speed increased from 100 to 700
rmin1 due to enhanced diffusion of liquid reactants.
However, a slight decrease in the conversion of manganese was detected when stirring speed was increased
from 700 to 1000 rmin1, because violent agitation
may cause some pyrolusite particles adhered onto the
inner wall of three-neck flask and worse contact between particles and liquid reactants, which reduce the
leaching efficiency. The most leaching rate is achieved
at 700 rmin1 stirring speed, which was used in the
subsequent experiments.
The effects of initial particle size of manganese
ore, H2SO4 concentration, COD and leaching temperature on the leaching of ore are illustrated in Fig. 3,
respectively. The results show the conversion of manganese increases gradually with the increase of H2SO4
concentration, MSW concentration and leaching temperature and with the decrease of the average sizes
of particle.
3.3

Kinetic analysis

Kinetic modeling yields comprehensive information regarding leaching mechanisms. In fact, reactions
involved in this process are heterogeneous in nature
involving mass transport of reactant and product ions.
In acidic leaching, the heterogeneous non-catalytic
reaction for most manganese ore might be kinetically
interpreted by using the shrinking core model (SCM)
[18 20].
In the SCM model, the solid reactant is considered as non-porous particle and is initially surrounded
by a fluid film through which mass transfer occurs
between the solid particle and the bulk of the fluid. As
the reaction proceeding, an ash/inert layer forms
around the unreacted core. Detailed derivation of the
shrinking core model can be found in Refs. [22 24].
The dissolution of pyrolusite can be expressed as
follows:
A (fluid) bB (solid)
fluid products
(4)
The rate-limiting step, which decides the form of
the rate equation, may be one of the following three

(a) Influence of particle size of manganese ore

d0/mm: 0.0134; 0.078; 0.068; 0.046

(b) Influence of sulfuric acid concentrations

cH/molL 1: 0.4; 0.6; 0.8; 1.0; 1.2

(c) Influence of molasses alcohol wastewater concentration

cW/gL 1: 10.0; 20.0; 30.0; 37.7; 50.0

(d) Influence of leaching temperature

T/K: 313; 323; 333; 343; 353; 363
Figure 3 Manganese extraction vs. time at different conditions

steps: (1) diffusion through the liquid film surrounding a solid particle, (2) diffusion through the ash/inert
solid layer and (3) chemical reaction on the surface of
the unreacted core. The simplified equations of the
shrinking core model when liquid film diffusion,
ash/inert solid layer diffusion or the surface chemical

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Chin. J. Chem. Eng., Vol. 18, No. 5, October 2010

reactions is the slowest step can be expressed as follows, respectively [22]:

x
1

2
x
3
1

3kG M S
cA0 t
a S r0
1 x

1 x

1
3

2
3

kf t

(5)

2M S DAeff cA0
a

2
S r0

M S kc
cA0 t
a S r0

kr t

kd t

(6)
(7)

where kf, kd and kr are calculated from Eqs. (5), (6)

and (7), respectively.
To obtain the leaching kinetic equation, the experimental data in Fig. 3 were transformed and fitted
to Eqs. (5), (6) and (7), respectively. As shown in Fig. 4,
Eq. (6) fitted the data best for the range of experiments
and the correlation coefficients (R2) were greater than
0.98. It is suggested that the reductive leaching of pyrolusite was controlled by the diffusion through the
ash/inert solid layer. Hence, the insoluble oxide minerals (hematite, quartz, kaolinite, etc.) associated with
pyrolusite may act as the ash/inert layer [2, 14].
Leaching kinetic constant varies with the inverse
square of initial particle size for diffusion-controlled
reactions in Eq. (6), or the inverse of the size or the
surface chemical reaction in Eq. (7). Fig. 5 shows the
quantitative relationship between the apparent rate
constant (kd) and particle size ( r0 2 ), indicating the
linear relationship between kd and r0 2 with R2 of 0.96.
It is affirmed that the leaching of pyrolusite with
MSW is controlled by the diffusion of reactant
through a solid product layer.
The apparent activation energy was determined
based on the Arrhenius equation:
ln kd

ln A

Ea 1
R T

(8)

The plot of lnkd versus 1/T data for the six temperatures is linear (Fig. 6). The apparent activation energy
(Ea) was, hence, determined to be 57.5 kJmol1,
which is about twice of that reported by Lasheen et al.
[14]. The reason may be that the diffusion of the macromolecular reductive agents in MSW is slower than
that of small molecular reductive agents in molasses.
To decide the apparent reaction order with respect to reagent concentration, the kd values for each
H2SO4 concentration and COD were determined from
Figs. 3 (b) and 3 (c);and the plots of lnkd versus lncH
or lncW were obtained. As shown in Fig. 7, the order
of reaction was found be 0.52 with respect to H2SO4
concentration and 0.90 with respect to COD. It seems
that the leaching rate of manganese depends more on
the concentration of reductive organics.
According Eq. (6), the apparent rate constant kd
can be expressed as follows:
kd

k0
exp
r02

57500 0.52 0.90

cH cW
RT

(9)

(a) Influence of particle size of manganese ore

d0/mm: 0.0134; 0.078; 0.068; 0.046

(b) Influence of sulfuric acid concentrations

cH/molL1: 0.4; 0.6; 0.8; 1.0; 1.2

(c) Influence of COD of waste water

cW/gL1: 10.0; 20.0; 30.0; 37.7; 50.0

T/K:

(d) Influence of leaching temperature

313; 323; 333; 343; 353; 363
2

Figure 4

Plot of 1

2
x (1 x ) 3 vs. time at different
3

conditions

and k0 119.09 mm2(molL1)0.52(gL1 )0.90s1 as

calculated from the provided data in Fig. 4.

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Chin. J. Chem. Eng., Vol. 18, No. 5, October 2010

Figure 5 Relationship between rate constant and average

initial particle diameter

Figure 6 Arrhenius plot of reaction rate against reciprocal

temperature

Figure 8 Mn extraction (x) of calculation and experiments

was investigated. The main parameters influencing

leaching rate, such as leaching H2SO4 concentration,
molasses alcohol wastewater concentration, particle
size and stirring speed, were studied. The results reveal that the leaching rate increases gradually with the
increase of H2SO4 concentration, COD of molasses
alcohol wastewater and leaching temperature and with
the decrease of the size of particles.
The kinetic analysis shows that the leaching
process is controlled by diffusion through the insoluble layer of the associated minerals. The leaching
process follows the kinetic model:
1

2
x
3

1 x

2
3

119.09
exp
r02

57500 0.52 0.90

cH cW t
RT

with apparent activation energy of 57.5 kJmol1. The

experimental results also show a reaction order of 0.52
with respect to H2SO4 concentration and a reaction
order of 0.90 with respect to molasses alcohol wastewater. The effects of particle size and rate constant further
confirm the mechanism of the leaching kinetic model.
NOMENCLATURE
Figure 7 Determination of reaction order for pyrolusite
dissolution with respect to H2SO4 and COD of molasses
alcohol wastewater
COD; H2SO4 concentrations

By the above analysis, the kinetic model of pyrolusite leaching by MSW is:

2
x
3

2
3

57500 0.52 0.90

cH cW t
RT
(10)
To determine the adaptability of Eq. (10), the x
values calculated by Eq. (10) were compared with that
obtained from the experiments. The calculated conversions in Fig. 8 agree well with the experimental
data with the average relative error of 0.00107.
1

1 x

119.09
exp
r02

CONCLUSIONS

The reductive leaching kinetics of pyrolusite with

molasses alcohol wastewater in dilute H2SO4 solution

A
b
cA0
cH
cW
DAeff
Ea
kc
kd
kf
kG
kr
k0
MS
R
r0
T
t
x
s

constant of the Arrhenius equation

stoichiometric coefficient
concentration of component A in bulk phase, molL1 or gL1
H2SO4 concentration, molL1
COD of molasses alcohol wastewater, gL1
effective diffusion coefficient of component A in the ash/inert
solid layer, ms2
apparent activation energy, kJmol1
chemical kinetic constant, ms 1
apparent rate constant when ash/inert solid layer diffusion controls, min1
apparent rate constant when liquid film diffusion controls, min1
mass transfer coefficient of component A in the liquid film, ms 1
apparent rate constant when chemical reaction controls, min1
kinetic constant, mm2(molL1)0.52(gL1)0.90s1
molecular weight of MnO2
gas constant, 8.314 Jmol1 1
initial radius of pyrolusite, mm
reaction temperature, K
reaction time, min
fraction of reacted pyrolusite
pyrolusite density, kgm3

Chin. J. Chem. Eng., Vol. 18, No. 5, October 2010

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