Int. J. Miner. Process.

77 (2005) 231 – 235

www.elsevier.com/locate/ijminpro

Kinetics of nickel leaching from spent catalyst in

sulphuric acid solution
Wyadysyawa Mulak *, Beata Miazga, Anna Szymczycha
Institute of Inorganic Chemistry and Metallurgy of Rare Elements, Wrocy aw University of Technology,
Wybrzeże Wyspiańskiego 27, 50-350 Wrocy aw, Poland
Received 20 December 2004; received in revised form 22 June 2005; accepted 29 June 2005
Available online 1 August 2005

Abstract

The kinetics of spent nickel oxide catalyst (NiO/Al2O3) leaching in sulphuric acid solutions was investigated. The effects of
sulphuric acid concentration, temperature, stirring speed, and particle size on the rate of nickel leaching were studied. In
addition, the reaction residues at various levels of nickel extraction were examined by SEM, X-ray diffraction, electron
microprobe, and chemical analysis. The results of the kinetic analysis of the leaching data for various experimental conditions
indicated that the reaction is controlled by diffusion through the catalyst network with the activation energy of 16.6 F 0.9 kJ/
mol. A linear relationship between the rate constant and the inverse square of the initial particle diameter is also characteristic
for a diffusion-controlled process.
D 2005 Elsevier B.V. All rights reserved.

Keywords: Spent catalyst; Nickel; Leaching; Sulphuric acid

1. Introduction hardening process (Ni, Mo/Al2O3, Nio/Al2O3, Raney

Recently, relatively great attention has been paid to
the research connected with the recovery of nickel from
secondary resources.
Recycling of spent catalysts became an unavoidable
task not only for lowering the catalyst cost but also for
reducing the catalyst waste to prevent the environmen-
tal pollution. Nickel is widely used as a catalyst in
several technological processes: in hydrogenation,
hydrodesulphurisation, hydrorefining including fat
* Corresponding author. Tel./fax: +48 71 32843 30.
E-mail address: wladyslawa.mulak@pwr.wroc.pl (W. Mulak).
0301-7516/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.minpro.2005.06.005
nickel alloy); in refinery hydrocracking (NiS, WS3/
SiO2Al2O3); in methanation of carbon oxide from
hydrogen and ammonia synthesis gas (NiO/Al2O3, Ni
SiO2) (Thomas, 1970).
Typically, nickel spent catalysts contain metallic
nickel and nickel oxide, although nickel sulphides
may occasionally occur as well as admixtures of
coke, hydrocarbons or fat.
Ivascan and Roman (1975) published their studies
on the recovery of nickel from a spent catalyst ammo-
nia plant by leaching in sulphuric acid. The nickel was
recovered as NiSO4 with 99% yield. Al-Mansi and
Abdel Monem (2002) studied the sulphuric acid
232 W. Mulak et al. / Int. J. Miner. Process. 77 (2005) 231–235
Table 1
Chemical analysis of spent catalyst
Element Ni Al Ca Mg C H
Weight percentage %; 13.5 40.2 0.33 0.05 1.08
(the oxygen content
is not included)
leaching process for the recovery of nickel as a sul-
phate from a spent catalyst in the steam reforming
industry. It was also shown that high recovery of 99%
nickel as nickel sulphate was achieved.
Chaudhary et al. (1993) reported hydrochloric acid
leaching process for the recovery of nickel as nickel
oxide from a spent catalyst containing 17.7% Ni.
They found that maximum of nickel extraction 73%
could be achieved by carrying out the leaching pro-
cess with 28.8% HCl at 80 8C. In an attempt to
improve the nickel extraction the application of chlor-
ine gas was investigated but no appreciable improve-
ment was observed. Several other methods have been
also reported for the leaching of nickel from a spent
refinery catalysts (Furimsky, 1996).
In this paper the effects of sulphuric acid concen-
tration, temperature, stirring speed, and particle size
on the leaching rate of nickel from a spent catalyst
have been examined.
2. Experimental
2.1. Materials
Spent nickel oxide catalyst used in this study was
obtained from Fertilizers Research Institute in Pulawy,
Poland. The spent catalyst was in the form of granules
with a diameter of 3.0–8.0 mm. The chemical analysis
of the spent catalyst is shown in Table 1. The exis-
tence of nickel oxide in the spent catalyst was con-
firmed by X-ray diffraction and a comparative
infrared spectra methods.
2.2. Equipment and procedures
All the experiments were performed with grains of
the size 4.0–5.0 mm, except those relating to the effect
of particles size on the reaction kinetics. In each
experiment a flask containing 200 ml of sulphuric
acid solution was submerged in a tank, the tempera-
ture of which was kept constant to within 0.1 8C.
When the required temperature was reached, a 0.25
g of the spent catalyst was added and the stirring was
0.31 started. A mechanical glass agitator of L shape with
25 mm impeller was applied. Its tip speed converted
from 600 rpm equals 0.785 m/s. The leaching was
carried out for 60 min during which five 1 ml samples
of the solution were taken for determination of the
nickel concentration by atomic absorption method.
The aluminium concentration in the final solution
was determined complexometrically.
3. Results and discussion
3.1. Effect of stirring speed
The effect of stirring speed on the nickel extrac-
tion from a spent catalyst was investigated in a
solution of 2.0M H2SO4 at 50 8C in the range of
300 to 1200 min
1.
The results presented in Fig. 1 show that the
leaching rate of nickel is independent of the stirring
speed. This indicates that the diffusion of the reac-
tants from the solution towards the surface of the
particle, and the products away from the surface of
the particle were fast, and hence did not control the
leaching rate within the range of stirring speeds
tested. All subsequent experiments were carried out
at a stirring speed of 600 min
1 to assure invariance
of this parameter.
0.8
0.7
Fraction of nickel extracted (α)
0.6
0.5
0.4
300 rpm
0.3 600 rpm
900 rpm
0.2 1200 rpm
0.1
0.0
0 10 20 30 40 50 60
Time, min
Fig. 1. Effect of stirring speed in 2.0M. H2SO4 at 50 8C.
 W. Mulak et al. / Int. J. Miner. Process. 77 (2005) 231–235 233

3.2. Effect of sulphuric acid concentration 0.8

Fraction of nickel extracted (α)

0.7
The influence of H2SO4 concentration on the
0.6
leaching of nickel and aluminium from a spent cata-
lyst was determined by varying the initial concentra- 0.5
tion of H2SO4 from 1.0 to 5.0 M. The experimental 0.4 30oC
results in Fig. 2 show that extraction of nickel and 40oC
0.3
aluminium from a spent catalyst was not affected by 50oC
H2SO4 concentration for the above leaching condi- 0.2 60oC
tions. To exclude the lixivant composition changes a 70oC
0.1
high excess of the acid (H2SO4/Ni molar ratio c 340
0.0
was applied). 0 10 20 30 40 50 60

3.3. Effect of temperature
The leaching was carried out in the temperature
range 30–70 8C with 2.0 M sulphuric acid solution at
constant stirring speed of 600 min
1. The leaching
results for the temperature effects on nickel extraction
from a spent catalyst are presented in Fig. 3. These
results show that temperature only mildly affected the
nickel leaching.
The experimental data have been analysed in terms
of several models connecting the fraction reacted (a)
with time (t) (Wadsworth, 1979). The diffusion model
(Ginstling and Brounshtein, 1950) for the relationship
a (t) has been applied:
1
2=3a
ð1
aÞ2=3 ¼ kt

1
where k (min ) = const / d o2
is the rate constant and d o
denotes the initial particle diameter.
Time, min
Fig. 3. Effect of temperature on the fraction of nickel extracted in
2.0 M. H2SO4.
The plot of the data from Fig. 3 for temperature
range 30–70 8C drawn according to Eq. (1) is depicted
in Fig. 4. The apparent rate constant, k, obtained from
the slopes of the straight lines in Fig. 4 was used to
determine the activation energy of 16.6 F 0.9 kJ/mol
with the correlation coefficient R 2 = 0.995, as is shown
on Arrhenius plot in Fig. 5. The magnitude of the
activation energy may support the theory that the
leaching of nickel from a spent catalyst is controlled
by a solid state diffusion process. This activation
energy is close to the values of the activation energy
ð1Þ of 13.4 kJ/mol calculated for the diffusion controlled
reactions of low-grade zinc silicate ore with sulphuric
acid (Abdel-Aal, 2000) and 18.4 kJ/mol calculated for

70 Ni 0.12 R2=0.991
Al 30oC
60 R2=0.998
0.10 40oC
Ni, Al extraction (%)

50 50oC
1- 2/3 α - (1- α )2/3

R2=0.999
0.08 60oC
40
70oC R2=0.995
30 0.06
R2=0.978
20
0.04
10
0.02
0
1 2 3 4 5
0.00
Concentration H2SO4, M 0 10 20 30 40 50 60 70 80

Time , mi n
Fig. 2. Effect of H2SO4 concentration on nickel and aluminium
extraction at 50 8C. Fig. 4. A plot of the data in Fig. 3 according to Eq. (1).
234 W. Mulak et al. / Int. J. Miner. Process. 77 (2005) 231–235

-6.2 0.7

Fraction of nickel extracted (α)

0.6
-6.4
Ea= 16.6 +/- 0.9 kJ/mol 0.5
ln k, min-1

-6.6 0.4

0.3
-6.8 4.0-5.0 mm
0.2 5.0-6.3 mm
6.3-8.0 mm
-7.0
0.1

-7.2 0.0
2.9 3.0 3.1 3.2 3.3 0 10 20 30 40 50 60

Time, min
1000 / T, K-1
Fig. 7. Effect of particle size on the fraction of nickel extracted in
Fig. 5. Arrhenius plot for leaching of nickel in 2.0 M. H2SO4.
2.0 M. H2SO4 at 50 8C.

vanadium leaching from spent sulphuric acid catalysts

of the particle shows two phases. Electron microprobe
by H2SO4 solution (Lozano and Juan, 2001).
analysis of the particle cross-section indicated by a
cross in Fig. 6 shows high content of aluminium
3.4. Characterization of reaction products
(47.6%) but very small amount of nickel (2.0%).
Unreacted core of a particle (marked by a circle in
Residues from several leaching experiments at var-
Fig. 6) shows higher content of nickel (14.0%) and
ious levels of nickel extraction were examined using a
39.6% of aluminium. The aluminium-rich layer sur-
scanning electron microscope (SEM), X-ray diffrac-
rounds the unreacted part of the particle and grows
tion (XRD), microprobe and chemical analysis. The
inward as particle reacts. The reacted particle retains
most interesting microscopic evidence found in this
the same geometrical shape and dimension of the
study is provided in the cross-section shown in Fig. 6.
particle before leaching even when nickel is almost
Reacted particle (a = 0.69) were mounted in a low
completely extracted. The X-ray diffraction patterns
viscosity embedding media and then polished to
of this reaction residue (4 h leaching, 60 8C, a = 0.99)
reveal the product layer which rims the unreacted
confirmed that it is composed mainly of a-Al2O3
core of a particle. As seen in Fig. 6 the cross-section
which is the catalyst network. This confirmed that
the reaction rate of nickel leaching from a spent

0.08
R2=0.999
4.0-5.0 mm
5.0-6.3 mm R2=0.996
1-2/3 α - (1-α)2/3

0.06 6.3-8.0 mm
R2=0.998

0.04

0.02

0.00
0 10 20 30 40 50 60 70 80
Fig. 6. SEM micrograph of the particle cross-section of spent catalyst Time, min
after 1 h leaching in 2.0M H2SO4 at 50 8C, a = 0.69, + and 8 = two
different phases subjected to the electron microprobe analysis. Fig. 8. A plot of the data presented in Fig. 7 according to Eq. (1).
 W. Mulak et al. / Int. J. Miner. Process. 77 (2005) 231–235
1.4
R2=0.999
1.2
k*10-3, min-1
1.0
0.8
0.02 0.03 0.04
1/do2, mm-2
Fig. 9. A plot of the rate constant versus square of the initial particle
diameter of a spent catalyst.
catalyst is controlled by diffusion through this porous
solid state layer.
3.5. Effect of particle size
The experiments were carried out with the three
particle sizes (4.0–5.0, 5.0–6.3, 6.3–8.0 mm) in 2.0 M
H2SO4 solution at 50 8C. The results are shown in Fig.
7. The data from Fig. 7 were analysed according to
Eq. (1), the plot of these data is demonstrated in Fig.
8. The calculated apparent rate constants are plotted
vs. the inverse square of the initial particle diameter d o
(Fig. 9). The linear relationship between the rate con-
stant and the inverse square of d o indicates that the
product layer diffusion is, indeed, the rate limiting
step of the leaching process. The d o was estimated
as the arithmetic average for the 4.0–5.0 mm grain
fraction after the sieve separation.
4. Conclusions
From the results of these studies the following
conclusions can be drawn:
(1) The leaching rate of nickel from a spent catalyst
in sulphuric acid is independent of the stirring
235
speed, which indicates that the reaction is not
controlled by the diffusion in the liquid phase.
(2) The change in the concentration of sulphuric
acid within the range 1.0–5.0 M has no signifi-
cant effect on the nickel leaching.
(3) The leaching rate at temperatures between 30–
70 8C is controlled by the diffusion through the
catalyst network with an activation energy of
16.6 F 0.9 kJ/mol.
(4) A linear relationship between the rate constant
and the inverse square of the initial particle
0.05
diameter was established.
Acknowledgements
The authors wish to thank the Polish Committee
for Scientific Research for financial support (grant No
4T09B 13725).
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