Hydrometallurgy 74 (2004) 189 – 194

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Kinetic study on the leaching of spent nickel oxide catalyst

with sulfuric acid
E.A. Abdel-Aal *, M.M. Rashad
Central Metallurgical Research and Development Institute, P.O. Box 87 Helwan, Cairo, Egypt
Received 14 July 2003; received in revised form 5 January 2004; accepted 23 March 2004

Abstract

The results of a leaching kinetics study of spent nickel oxide catalyst with sulfuric acid are presented. The effects of spent
catalyst particle size, sulfuric acid concentration, and reaction temperature on Ni extraction rate were determined. The results
obtained show that extraction of about 94% is achieved using
200 + 270 mesh spent catalyst particle size at a reaction
temperature of 85 jC for 150 min reaction time with 50% sulfuric acid concentration. The solid/liquid ratio was maintained
constant at 1:20 g/ml. The leaching kinetics indicate that chemical reaction at the surface of the particles is the rate-controlling
process during the reaction. The activation energy was determined as about 9.8 kcal/mol, which is characteristic for a surface-
controlled process.
D 2004 Elsevier B.V. All rights reserved.

Keywords: Spent catalyst; Nickel oxide; Nickel recovery; Leaching; Sulfuric acid

1. Introduction extraction of Ni. In industry, leaching of Ni is carried

The increasing demand for metals in the world has
required intensive studies for the extraction of metals
from low-grade ores and/or secondary resources.
Extraction of nickel can be performed from secondary
resources like spent catalysts, fly ash, and boiler ash.
There are many papers reporting on the extraction of
nickel from spent catalyst using different reagents.
However, the kinetics of leaching have not been
sufficiently studied. The applied conditions for kinetics
studies are different from those used for industrial
* Corresponding author. Particle Engineering Research Center,
Department of Materials Science and Engineering, University of
Florida, Gainesville, FL 32611-6400, USA. Fax: +1-352-846-1196.
E-mail address: eabde@yahoo.com (E.A. Abdel-Aal).
out at high solids content, high nickel sulfate product
concentration and stoichiometric amounts of sulfuric
acid using coarse spent catalyst.
Ivascanu and Roman (1975) studied extraction of
nickel from a spent nickel-catalyst-based-alumina
(NiO/Al2O3) in an ammonia plant by leaching with
sulfuric acid solution. Ninety-nine percent of the
nickel was recovered as nickel sulfate under the
following conditions: spent catalyst particle size:
0.09 mm; sulfuric acid concentration: 80%; reaction
time: 50 min; reaction temperature: 70 jC.
Loboiko et al. (1983) studied leaching of nickel
oxide with 60 –70% nitric acid concentration at 120 jC
for 2 –3 h. Chandhary et al. (1993) studied leaching of
the low-grade spent catalyst with hydrochloric acid.
They obtained low Ni extraction efficiency (only

0304-386X/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2004.03.005
190 E.A. Abdel-Aal, M.M. Rashad / Hydrometallurgy 74 (2004) 189–194
about 18%). Vicol et al. (1986) studied leaching of
spent catalyst with an aqueous solution of 15 –23%
ammonia at 60– 90 jC and at pH 7.5 –9. Floarea et al.
(1991) studied leaching of
600 Am spent catalyst
using ammonium carbonate at 80 jC.
Tsai and Tsai (1998) reported extraction of nickel
and vanadium from oil-fired fly ash from Taiwan.
They indicated that leaching of oil-fired fly ash in
0.5 N sulfuric acid led to an extraction of 65%
vanadium, 60% nickel, and 42% iron. Ni extraction
increased with an increase in the concentration of
sulfuric acid. When leached in 2 N sodium hydroxide
solution, the extraction of vanadium was 80%, and the
extraction of nickel was negligible. They also reported
that if oil-fired fly ash was leached in ammonia water,
the extraction of nickel increased with an increase in
the concentration of ammonia in water. When leached
with 4 N ammonia, the extraction of nickel was 60%,
the extraction of vanadium was less than that obtain-
able from leaching in sulfuric acid solution or in
sodium hydroxide solution. They proposed a flow-
sheet in which fly ash was first leached in an ammo-
niacal solution containing ammonium sulfate to
recover nickel. The leached residues were then taken
to recover vanadium.
Traditional methods of recovering nickel and va-
nadium from oil-fired fly ash were to burn and
concentrate the ashes to raise the grade of nickel
and vanadium then treat the concentrate together with
the oil slag in a process of sodium carbonate roast-
leaching (Tsukagoshi, 1986). Subsequently, ammoni-
um salts were added to the filtrate at pH 8– 9 to
precipitate and recover the ammonium metavanadate.
The leaching residues were used as source material for
extraction of nickel (Tsukagoshi, 1986). A process for
the recovery of nickel and vanadium in Japan is
reported in which water is used to dissolve the soluble
metal salts in fly ash (Committee of Nippon Industrial
Table 1
Chemical analysis of the studied spent catalyst fractions
Particle size of ore fractiona Ni% Al%
Mesh Am

80 + 170
177 + 88 11.9 42.9

170+ 200
88 + 74 11.9 42.8

200 + 270
74 + 53 12.1 42.6
a
ASTM standard.
News, 1974). After solid and liquid were separated,
the double salt of nickel could be obtained from the
filtrate by crystallization. Addition of oxidants to the
residual liquid of the nickel would yield the precipi-
tation of vanadium pentoxide. Parton et al. (1993)
used the method of leaching in sulfuric acid and
selective precipitation to recover nickel, vanadium,
iron, magnesium hydroxide, and carbon material in fly
ash. Amer (2002) optimized the conditions of extrac-
tion of nickel and vanadium by hydrometallurgical
processing of Egyptian boiler ash using aqueous
sulfuric acid under atmospheric and oxygen pressure
to produce leach liquor of sulfates of both nickel and
vanadium free from iron. Al-Mansi and Abdel
Monem (2002) investigated the possibility of extrac-
tion of nickel from Egyptian spent catalyst. The
optimum conditions for 99% nickel extraction were
50% sulfuric acid concentration, solid/liquid ratio of
1:12, less than 500 micron particle size for contact
time higher than 5 h and 800 rev/min stirring rate at
100 jC reaction temperature.
This study investigates the kinetics of leaching
nickel from spent catalyst (NiO/Al2O3) with sulfuric
acid. The process conditions studied include particle
size of spent catalyst, sulfuric acid concentration,
temperature, and time.
2. Experimental
2.1. Materials and apparatus
Spent nickel oxide catalyst used in this study was
kindly provided by El-Nasr Fertilizers and Chemicals
Company in Talkha (Egypt). The spent catalyst was
ground and sieved. The elemental compositions of the
different size fractions are given in Table 1. Commer-
cial sulfuric acid from Abu-Zabaal Fertilizers and
Na% Mg% Ca% Co% Cd% Cu%
1.1 0.75 0.28 0.013 0.0061 0.0051
1.2 0.72 0.29 0.011 0.0058 0.0048
1.0 0.77 0.27 0.010 0.0051 0.0046
 E.A. Abdel-Aal, M.M. Rashad / Hydrometallurgy 74 (2004) 189–194
Chemicals Company was also used in this study. It
had a concentration of 98% H2SO4 and a density of
1.84 g/mL. The reaction between spent catalyst and
sulfuric acid was performed in a 500-mL round-
bottom flask placed in a thermostatically controlled
water bath.
2.2. Procedure
Twenty grams of spent catalyst was added at one
time to the agitated sulfuric acid solution (400 mL) of
the required concentration at the required temperature.
The reaction mixture was agitated at a rate of 500 rev/
min. At selected time intervals, 2-mL solution sam-
ples were taken using a syringe filter of 1 Am pore size
and the solids corresponding to that volume were
discarded. Consequently, the solid/liquid ratio was
maintained constant at 1: 20 g/mL. The cumulative
volume removed by sampling was not significant
compared to the original solution (about 6%). The
samples were chemically analyzed for determination of
nickel content using atomic absorption spectroscopy
(AAS). After that, the percentage extraction of nickel
was calculated.
3. Results and discussion
3.1. Effect of particle size
The effect of particle size on leaching of spent
nickel oxide catalyst was studied using different size
fractions (
80 + 170 mesh,
170 + 200 mesh and

200 + 270 mesh). Within the series of tests, the
Fig. 1. Relation between Ni extraction and time using different spent
catalyst particle sizes (at 75 jC, 30% H2SO4).
191
Fig. 2. Relation between Ni extraction and time using various
sulfuric acid concentrations (
200 + 270 mesh particles at 75 jC).
initial sulfuric acid concentration and leaching tem-
perature were kept constant at 30% and 75 jC,
respectively. The solid/liquid ratio was 1: 20 g/mL.
The results are given in Fig. 1. These results show that
particle size has a significant effect on the dissolution
of nickel oxide. After 3 min leaching time, 2.5 –3.2%
Ni was extracted, depending on the spent catalyst
particle size. In addition, the results show that about
71% of the Ni present in the fine fraction (
200 +
270 mesh) of the spent catalyst was extracted after
150 min.
3.2. Effect of sulfuric acid concentration
A plot of Ni extraction against time is presented in
Fig. 2 for fine spent catalyst of
200 + 270 mesh
particle size and sulfuric acid concentration in the
range of 5 – 50% at a constant temperature of 75 jC.
The solid/liquid ratio was kept constant at 1: 20 g/mL.
The sulfuric acid concentration also has a pronounced
effect on the dissolution of NiO. About 86% of the
Ni present in fine fraction of the spent catalyst was
extracted using 50% sulfuric acid solution after
150 min.
3.3. Effect of reaction temperature
The effect of reaction temperature on Ni extraction
at different reaction times is plotted in Fig. 3 for spent
catalyst of
200 + 270 mesh particle size and sulfu-
ric acid concentration of 50% at temperatures in the
range of 35 – 85 jC. The solid/liquid ratio was kept
constant at 1: 20 g/mL. The obtained results show that
the studied reaction temperatures have a noticeable
192 E.A. Abdel-Aal, M.M. Rashad / Hydrometallurgy 74 (2004) 189–194
Fig. 3. Relation between Ni extraction and time at various reaction
temperatures (
200 + 270 mesh particles in 50% H2SO4).
effect on dissolution of NiO. About 94% of the Ni
present in fine fraction of the spent catalyst is
extracted after 150 min at a reaction temperature of
85 jC.
3.4. Kinetic aspects
Nickel oxide present in the spent catalyst reacts
with sulfuric acid according to the following reaction
equation (Al-Mansi and Abdel Monem, 2002):
NiO þ H2 SO4 ! NiSO4 þ H2 O
The matrix (a-alumina) is not reacted with sulfuric
acid (Treybal, 1980). The reaction of nickel oxide can
proceed in a topochemical manner, in which the inner
core of the unreacted particle decreases with time. It is
clear in Fig. 1 that the rate of reaction decreases with
time. This is due to the decrease of the reactant surface
Fig. 4. Plots of 1
(1
x)1/3 versus time at various reaction
temperatures (
200 + 270 mesh particles in 50% H2SO4).
Fig. 5. Plots of 1
2/3x
(1
x)2/3 versus time at various reaction
temperatures (
200 + 270 mesh particles in 50% H2SO4).
area. The rate of reaction is given for models based on
control by (a) chemical reaction at the particle surface;
(b) diffusion through the product layer; and (c) a
combination of both.
(a) Rate control by chemical reaction at the particle
surface (Habashi, 1969 and Levenspiel, 1972):
Kc t ¼ 1
ð1
xÞ1=3 ð2Þ
ð1Þ
where Kc = reaction rate constant (min
1); t = time in
minutes; x = fraction reacted of NiO.
x ¼ %Ni extraction=100 ð3Þ
Based on the experimental data in Fig. 3, a plot of
the right-hand side of Eq. (2) versus time is given in
Fig. 4. During the whole reaction time, the data in this
figure are linear, which indicates that the rate of
reaction is controlled by chemical reaction at the
surface of nickel oxide particles. The results correlated
Fig. 6. Arrhenius plot for the leaching of spent nickel oxide catalyst.
 E.A. Abdel-Aal, M.M. Rashad / Hydrometallurgy 74 (2004) 189–194
by this model yield straight lines and nearly zero point
intercepts were obtained. In the case of straight lines,
the slope equals the rate constant Kc:
Kc ¼ MbKcc C=qr min
1 ð4Þ
where Kcc = chemical rate constant (cm min
1); b =
stoichiometric coefficient (dimensionless); M = mole-
cular weight of NiO (the major dissolved compound
in spent catalyst); C = concentration of sulfuric acid
(mol/m 3 ); r = radius of unreacted particle (m);
q = density of spent catalyst (kg/m3), (pycnometer
method = 4380 kg/m3).
(b) Rate control by diffusion through the product
layer (Habashi, 1969; Levenspiel, 1972).
When diffusion through the product layer is rate-
controlling, the kinetics may be correlated graphically
using the Valensi equation:
Kp t ¼ 1
2=3x
ð1
xÞ2=3 ð5Þ
where Kp =rate constant (cm min
1).
Again, based on the experimental data in Fig. 3, a
plot of the right-hand side of Eq. (5) against time is
given in Fig. 5. The data cannot be correlated by this
model as neither straight lines nor zero point inter-
cepts were obtained.
(c) Calculation of the activation energy.
The activation energy of a diffusion-controlled
process is characterized as being 1 to 3 kcal/mol
(Habashi, 1969), 2 to 5 kcal/mol (Anand and Das,
1988) or 3 to 6 kcal/mol (Romankiw and De Bruyn,
1963). In addition, the activation energy for a chem-
ically controlled process is usually greater than 10
kcal/mol (Habashi, 1969) or more specifically falls
between 10 to 20 kcal/mol (Anand and Das, 1988). To
calculate the activation energy, the values of ln Kc
were plotted against 1/T in Fig. 6. The activation
energy of the overall reaction is calculated as about
9.8 kcal/mol (41.1 kJ/mol). This activation energy is
near the values of activation energy of 45.9 kJ/mol
calculated for sodium hydroxide leaching of a gibb-
sitic bauxite (Abdel-Aal, submmitted for publication),
48.15 kJ/mol calculated for oxidative ammonia leach-
ing of sphalerite (Ghosh et al., in press), and 34 kJ/mol
calculated for oxidative sodium hydroxide leaching of
mechanically activated low-grade wolframite concen-
trate (Amer, 2000).
193
4. Conclusions
Leaching of spent nickel oxide catalyst with sul-
furic acid was studied. Extraction efficiency of about
94% of the NiO present in the spent catalyst was
achieved under the following conditions: particle size

200 + 270 mesh, temperature 85 jC, reaction time
150 min, sulfuric acid concentration 50% and solid/
liquid ratio 1:20 g/ml. The kinetic study indicates that
the leaching of NiO is a surface chemically controlled
process. The activation energy was calculated as about
9.8 kcal/mol (41.1 kJ/mol) which is consistent with
values of activation energies reported for surface-
controlled reactions.
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