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KINETIC STUDY ON THE LEACHING OF VANADIUM

FROM LD CONVERTER SLAG USING SULFURIC ACID
M Aarabi1, F Rashchi2, E Vahidi3 and N Mostoufi4
ABSTRACT
In order to reduce the environmental impact due to land disposal of LD (Linz-Donawitz) converter
slag from steelmaking plant and to valorise this waste material, an acid leaching study was
carried out to assess the effect of several parameters on the kinetics of vanadium dissolution. The
characterisation and morphology of the feed investigated using XRD, XRF. The factors influencing
leaching vanadium such as particle size, temperature, slurry density and the concentration of sulfuric
acid were investigated and optimised. The maximum vanadium recovery about 95 per cent achieved
at 70C, S/L: 1/15, acid concentration: 3M and for 150 minutes of leaching time. The dissolution
of vanadium in sulfuric acid shows that there are two stages in the kinetics of leaching. At the first
15 minutes, there is a sharp increase in the amount of vanadium extracted and at longer leaching
time, the extraction increase slightly. In the present work, the shrinking core model (SCM) was used
to describe the acid leaching of vanadium compounds. A summary of the controlling regimes in the
SCM are examined below for short time (less than 12 min.) and long time (more than 30 min.) stages.
So, it was found that the kinetics of leaching in both stages is controlled by solid product diffusion
regime.
Keywords: LD converter slag, vanadium, acid leaching, kinetics

INTRODUCTION
Recycling of waste material has become very important during the past decade due to the reinforcement
of environmental regulations which require minimising the waste disposal. Steelmaking operations
are specifically concerned by this problem because of the generation of a huge quantity of byproducts (Chaurand et al, 2006). Even if steelmaking slag is attractive as a building material in
civil engineering, its environmental impacts must be taken into account. Indeed steelmaking slag
contains trace amounts of potential toxic elements which can be released. This specially applies to
vanadium (V), which is among the most abundant heavy metals within the slag (Shen and Forssberg,
2003; Motz and Geisler, 2001).
The common grade of vanadium in processed ores is usually less than 2 per cent (Gupta and
Krishnamurthy; 1992). A common process for extracting vanadium from steelmaking refining
slag that had been proposed by many researchers is roasting, acid leaching and solvent extraction
(Navarro et al, 2006; Gupta and Krishnamurthy 1992).
Tsai and Tsai, (1998) investigated recovery of vanadium and nickel from oil-fried fly ash. Leaching
of the sample in sulfuric acid led to an extraction of 65 per cent vanadium and 60 per cent nickel.
However, in sodium hydroxide reported a higher vanadium concentrate of 80 per cent was obtained.
They also reported that extraction of nickel was negligible. In ammonia leaching, extraction of
vanadium decreased as compared to leaching in sulfuric acid and sodium hydroxide solutions.
Vitol, Seggiani and Falaschi (2001) investigated recovery of vanadium from heavy oil fly ash with
a high carbon content using three-step process consisting of a preliminary burning to reduce the
carbonaceous fraction, sulfuric acid leaching and oxidative precipitation of vanadium pentoxide.
Amer (2002) reported extraction of vanadium and nickel from boiler-ash. Atmosphere leaching of
boiler-ash in sulfuric acid led to a vanadium extraction of 85 per cent; however, under partial oxygen
1. School of Metallurgy and Materials Engineering, University of Tehran, Tehran, Iran. Email: [email protected]
2. Associate Professor, School of Metallurgy and Materials Engineering, University of Tehran, Tehran, Iran. Email: [email protected]
3. Iranian Standard and Quality Inspection Co, Tehran, Iran.
4. Professor, School of Chemical Engineering, University of Tehran, Tehran, Iran. Email: [email protected]

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pressure of 20 bars a vanadium recovery of 95 per cent was achieved. Luo et al, (2003) studied
recovery of tungsten and vanadium from a tungsten alloy scrap by dissolving in with an alkali solution
containing magnesium chloride (MgCl2) and ammonia. Then, a small amount of acetic acid was
used to dissolve vanadium from the residue selectively. Haoran et al (2008) studied extraction of
vanadium oxide (V2O5) from Xichuan clay vanadium minerals using an acid leaching method. They
also investigated effect of oxidant additives as well as sodium chlorate (NaClO3) and manganese
dioxide (MnO2), the reductant additives such as ferrous sulfate (FeSO4), elemental sulfur (S) and
pyrites (FeS2) on the recovery ratio of V2O5. The extraction efficiencies of V2O5 were determined to
be 81.1 per cent and 79.4 per cent in the presence of NaClO3 and MnO2, respectively. However, the
extraction efficiency of V2O5 remained almost unchanged when reductant additives were used.
In the roasting process, the vanadium compounds in the sample turned into leachable compounds
of vanadium (V) in acid solution, such as V2O5, in acid solution. Thus, vanadium compounds present
in the roasted sample reacted with sulfuric acid according to the following reaction (Haoran et al,
2008):
V2 O5 + H2 SO4

(VO
VO2 )2 SO4

H2 O

(1)

Navarro et al, (2007) studied extraction of vanadium from oil fly ash by sulfuric acid, sodium
hydroxide and sodium carbonate leaching. Vanadium extraction by sulfuric acid and sodium
hydroxide resulted in a recovery of about 98 per cent and by sodium carbonate the recovery about
80 per cent was achieved. Minting Li, Papangelakis and Perederiy (2009) reported extraction of
vanadium from black shale using acid pressure leaching. They showed that the leaching efficiency of
vanadium in two-step process could reach above 90 per cent.
There are many papers reporting the extraction of vanadium from its secondary sources such as
fly ashes, spent catalyst, oil-fried fly ash and alloyed scrap using different operations. There are few
researches done on the extraction of vanadium from LD converter slag.
In the present study effect of particle size, acid concentration, reaction temperature and solid: liquid
ratio (S/L) on the extraction of vanadium from LD converter slag using sulfuric acid as leaching
agent have been investigated. However, kinetics of vanadium leaching form secondary materials has
not been sufficiently studied yet. The kinetics of the leaching process was also studied. Shrinking
core model (SCM) (levenspiel, 1999) was used and the best fitted equation to the experimental data
was determined. Then, according to the best fitted equation, activation energy of the process was
determined.

MATERIALS AND METHODS

Sample characterisation
The LD converter slag was collected from disposal sites of waste materials of Esfahan steel Company,
in Iran. After crushing and grinding, the sample was divided into three size fractions, <0.850 mm,
0.850 - 1.135 mm and 2.350 - 3.360 mm. Mineralogical and chemical analyse of the sample were
done using X-ray diffraction (XRD, Philips model, Netherlands) and X-ray fluorescence (XRF,
S4explorer model, Germany). The XRD pattern of the sample and the major chemical composition
of the minerals present in the sample are shown in Figure 1. The XRD result revealed that the major
phases in the slag are Portlandite (Ca(OH)2), calcium iron oxide (CaFeO2), calcium silicate (Ca3SiO5)
and sodium vanadium oxide (NaV6O15). Table 1 presents the major chemical composition of the slag
which contains 1.2 per cent Vanadium totally.

Procedure
Alkaline roasting
Alkaline roasting was used to change vanadium to a soluble form. The roasting stage was conducted
by placing the sample mixed with sodium carbonate in a muffle furnace for a certain temperature
and time. The roasting condition was 1000C, 2h time and 20 per cent sodium carbonate.

Acid leaching
For the leaching and kinetic experiments, sulfuric acid was obtained from Merck Company, with a
purity of 9598 per cent. The roasted sample was leached in sulfuric acid at certain temperature,
S/L ratio and time. The leaching experiments were performed at atmospheric pressure in a Pyrex
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TABLE 1
Major elements of the sample wt%.
Wt%

compound

4.15

L.O.I

0.42

0.37

Na20

1.83

MgO

2.36

Al2O3

12.14

SiO2

1.91

P2O5

o.77

SO3

0.08

K 2O

50.82

CaO

1.12

TiO2

1.97

V2O5

4.52

MnO

5.03

FeO

12.24

Fe2O3

reactor equipped with a reflux condenser. The reaction mixture was agitated with a magnetic stirrer
and heated on a hot plate indirectly, through a water bath. For each leaching test, the sample and
the solution of predetermined concentration were charged into the reactor and the mixture was well
mixed at 600 rpm.
After a specific leaching time a Buckner funnel equipped with a glass filter was used for the filtration
step. The slurry was filtered and the filtrate was analysed by ferrous ammonium sulfate titration
(Vogel, 1989) method to determine the amount of vanadium pentoxide in the leaching solution.
In order to check the titration results, atomic adsorption spectroscopy (AAS) was applied to some
samples and the difference between the two methods was below 3 per cent.

RESULT AND DISCUSSION

Effect of reaction temperature
Figure 2 illustrates the effect of reaction temperature on vanadium extraction at different reaction
time for LD converter slag and in the range of 25-70C. This obtained optimum condition is of below

FIG 1 - XRD pattern of the LD converter slag.

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FIG 2 - Effect of temperature on vanadium recovery as a function of time (particle size 0.850 mm, 3M H2SO4 and S/ L of 1:15).

0.850 mm particle size and sulfuric acid concentration of 3 M, S/L ratio of 1:15 (g/ ml). As shown in
this figure, there is a two stage leaching process for the vanadium extraction. At the first 15 minutes
there is a sharp increase in the amount of vanadium extracted and at longer leaching time, the rate
of vanadium extraction slightly decreased.

KINETICS
In the present work, the shrinking core model (SCM) was used to describe the acid leaching of
vanadium compounds (Abdel-Aal and Rashad, 2004; Espiari, Rashchi and Sadrnezhad, 2006).
Figure 2 shows that there are two stages in the kinetics of leaching (Momade and Momade, 1999).
The first stage occurs at the beginning of the leaching process (0-12 minutes) and the second stage
occurs after 30 minutes. The rate of leaching at the two stages is considerably different suggesting
a different controlling step in each stage. Moreover, when any of the equations related to different
controlling regimes (described below) was examined with the experimental data for the whole
leaching period, a change in the trend before and after 30 minutes was observed, indicating that the
whole leaching period is not governed by a single mechanism. As a result, in the following discussion,
the controlling regimes in the SCM (Levenspiel, 1999) were examined for short time (less than 12
min.) and long time (more than 30 min.) stages, separately.

Liquid film diffusion control

The fraction of reacted vanadium at any time t in the film diffusion control mechanism can be
predicted by (Levenspiel, 1999):
2

t
= 1 (1 x ) 3

R02

2bDC

(2)

(3)

Using the data shown in Figure 2, the right hand side of Equation 2 is plotted vs. time for the short
time leaching process in Figure 3 (a). It can be seen that the experimental data do not fit the model
satisfactorily; suggesting that the short time leaching process is not controlled by the liquid film
diffusion.
Equation 2 cannot be applied to the long time process since the boundary condition for this section
is different from that of short time. In fact, applying Equation 2 to the long term data would results
in lines which do not cross the origin as imposed by this equation; indicating that initial condition
should be changed for the long time process. Thus, the mechanism of leaching process has been
changed in the long time process, ie, the integration limits of the corresponding differential mass
balance equation has been changed accordingly. Based on Figure 2, it can be considered that the long
time mechanism starts from t = 30 min. (rather than t = 0 in the short time section, Equation 2). At
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(a)

(b)
FIG 3 - (a) Right hand side of equation (2) vs. time, (b). Right hand side of equation (4) vs. time.

this time, the recovery (or conversion) is not zero and its value from Figure 2 should be considered
as the initial condition (rather than 0 in the short time section), when integrating the mass balance
differential equation. In the case of liquid film diffusion control, the alternative equation is derived
as follows:
t t1

1 x
=1

1 x1

(4)

In the present work, t1 = 30 min. and x1 should be read from Figure 2.

Using the data shown in Figure 2, the right hand side of Equation 4 is plotted vs. time in Figure 3b
for the long time leaching (30 to 150 minutes). As can be seen, there is a good agreement between the
proposed kinetic model and the experimental data at low temperature while the deviation between
the model and the data is evident at high temperature. Therefore, it can be concluded that the kinetics
of leaching of vanadium ore is controlled by diffusion through the liquid film in the long time, ie,
after 30 minutes from the start of the leaching process, at low temperature.

Reaction control
The fraction of reacted vanadium at any time t in the reaction control mechanism can be predicted
by (Levenspiel, 1999):
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1
t
= 1 (1 x ) 3

(5)

R0

(6)

bk
ks c

Using the data shown in Figure 2, the right hand side of Equation 5 is plotted vs. time for the
short time leaching process in Figure 4a. It can be seen that the experimental data do not fit the
model satisfactorily; suggesting that the short time leaching process is not controlled by the chemical
reaction.
Similar to the discussion in the previous section, Equation 5 cannot be applied to the long time
process since the boundary condition for this section is different from that of the short time. In fact,
the integration limits of the corresponding differential mass balance equation should be changed
accordingly. In the case of chemical reaction control, the alternative equation is derived as follows:
t t1

1 x
=1

1 x1

(7)

Using the data shown in Figure 2 and considering t1 = 30 min., the right hand side of Equation 7
is plotted vs. time in Figure 4b for the long time leaching (30 to 150 minutes). As can be seen in this

(a)

(b)
FIG 4 - (a). Right hand side of equation (5) vs. time, (b). Right hand side of equation (7) vs. time.

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figure, there is a good agreement between the proposed kinetic model and the experimental data at
low temperature, while the deviation between the model and the data is evident at high temperature.
Although it was suggested above (in Figure 3b) that the mechanism of leaching at long time and
low temperature might be controlled by diffusion through the liquid film, Figure 4b indicates that
chemical reaction can be equivalently taken as the controlling mechanism. Since liquid film diffusion
control mechanism is usually observed when using very fine particles, where the liquid film is thick
compared to the size of the particle, it can be concluded that in the present case, the rate is controlled
by the chemical reaction.

Solid product diffusion control

When diffusion thorough the product layer is the rate controlling step, the fraction of reacted
vanadium at any time t can be predicted by (Levenspiel, 1999):
2
t
= 1 3(1 x ) 3 + 2(1 x )

(8)

R2
6bDc

(9)

Again, based on the experimental data of Figure 2, the right-hand side of Equation 8 vs. time is
shown in Figure 5a for the short time leaching process. This figure demonstrates that the plots are

(a)

(b)
FIG 5 - (a). Right hand side of equation (8) vs. time, (b) Right hand side of equation (10) vs. time.

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linear against time which indicates that the rate of leaching in the short time process is controlled by
diffusion through the product layer.
To test the validity of diffusion thorough the product layer mechanism in the long time process,
the corresponding differential mass balance equation should be integrated using new boundary
conditions (x1 at t1). Accordingly, the kinetic equation of chemical reaction control becomes as follows:
t t1

1 x
= 1 3

1 x1

1 x
+ 2

1 x1

(10)

Using the data shown in Figure 2 and taking t1 = 30 min., the right hand side of Equation 10 is
plotted vs. time in Figure 5b for the long time leaching (30 to 150 minutes). As can be seen in this
figure, there is a good agreement between the proposed kinetic model and the experimental data at
high temperature while the deviation between the model and the data is evident at low temperature.
Therefore, it can be concluded that the kinetics of leaching of vanadium ore is controlled by diffusion
through solid product layer in long time, ie, after 30 minutes from the start of the leaching process,
at high temperature.

CONCLUSIONS
Based on the results obtained from the current work, the following conclusions are made:
A maximum vanadium recovery of 95 per cent was obtained by leaching with 3M sulfuric acid for
150 minutes at 70 0C with 1:15 solid: liquid ratio agitated at 600 rpm.
According to kinetics, two leaching stages are proposed. At stage one (the first 15 minutes) a sharp
increase in the amount of vanadium extracted was observed (fast leaching rate) and at stage two
(more than 30 minutes) a slower leaching rate was encountered.
The SCM equation was improved to be applied to long time leaching, for which the existing equation
do not cross the origin since the concentration of vanadium is not zero at the onset of this period.
The rate of leaching of vanadium is controlled by chemical reaction at low temperatures; whereas,
it is controlled by diffusion through the solid product at high temperatures.

ACKNOWLEDGEMENTS
The authors wish to thank to Esfahan steel Company of Iran for free sample of LD converter. Also,
the help of Dr. Amir Azaad-Mehr for vanadium titration procedure is highly appreciated.

NOMENCLATURE
b stoichiometric coefficient
c
concentration of sulfuric acid (kg/m3)
D
diffusion coefficient of sulfuric acid (m2/s)
ks
rate constant (s-1)
R0
initial radius of particle (m)
R
vanadium extracted divided by vanadium in the un-leached sample
t
time of reaction (sec.)
t1
start of long time period (sec.)
x
fraction of reacted vanadium
x1
fraction of reacted vanadium at time t1

time for dissolution (sec.)

density of vanadium ore (kg/m3)

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