Waste Management 22 (2002) 85–90

www.elsevier.nl/locate/wasman

Recovery of nickel oxide from spent catalyst

N.M. Al-Mansi*, N.M. Abdel Monem
Chemical Engineering Department, Faculty of Engineering, Cairo University, Giza, Cairo, Egypt

Received 2 May 2000; received in revised form 10 January 2001; accepted 20 March 2001

Abstract
This study investigates the possibility of recovering nickel from the spent catalyst (NiO/Al2O3) resulting from the steam reform-
ing process to produce water gas (H2/H2O) in many industries. In the extraction process, nickel is recovered as sulfate using sulfuric
acid as a solvent. The considered parameters affecting nickel recovery were acid concentration, temperature and time of digestion
solid:liquid ratio, particle size and stirring rate. Nickel was to be directly recovered as a sulfate salt by direct crystallization method.
The conversion was 99% at 50% sulfuric acid concentration, solid: liquid ratio (1:12) by weight, particle size less than 500 micron
for more than 5 h and 800 rpm at 100
C. # 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Spent catalyst; Nickel oxide; Nickel recovery; Leaching

1. Introduction steps: feed preparation, reduction, smelting and casting.

For many years, nickel has been considered as the
most suitable metal in steam reforming of hydro-
carbons. Nickel is cheap, sufficiently active, and allows
suitable catalysts to be economically produced. Invas-
canu and Roman [1] studied the recovery of nickel from
a spent catalyst in an ammonia plant by leaching it in
sulfuric acid solution. Ninety-nine percent of the nickel
was recovered as nickel sulfate when the catalyst, having
a particle size of 0.09 mm, was dissolved in an 80%
sulfuric acid solution for 50 min in at 70
C. In another
study, Loboiko et al. [2] found that the recovery of
nickel is increased by dissolution with 60–70% nitric
acid concentration at 120
C for 2–3 h. By leaching the
spent catalyst with hydrochloric acid, Chandhary et al.
[3] found the recovery of nickel from a low grade spent
catalyst to be 17.7%. Vicol et al. [4] tried to recover
nickel by extraction of the spent catalyst with an aqu-
eous solution of 15–23% ammonia at 60–90oC and at
pH 7.5–9. Optimum leaching conditions of nickel from
Al2O3 support using (NH4)2CO3 were achieved by
Floarea et al. [5] for 600 mm particle size at 80
C. Fur-
ther, a high temperature metal recovery process was
developed by INMET CO to recycle nickel, chromium
and iron catalysts. This technology includes four basic
* Corresponding author.
0956-053X/02/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved.
PII: S0956-053X(01)00024-1
For the past 16 years, the INMET CO process has been
the only thermal recovery technology for metals [6]. The
acceptance of a waste to be processed depends on both
the total chemical analysis carrier out by INMET CO’s
laboratory and on the information supplied by the gen-
erator. The extraction of rare metals from the hydro-
desulfurization catalyst by leaching with sulfuric acid
yields an acidic solution rich in rare metals such as
molybdenum, vanadium, cobalt and nickel in addition
to aluminum [7]. Mixtures of LIX63 (5,8-diethyl-7
hydroxy-6-dodecanone oxime) and CYANEX272 (con-
taining bis (2,4,4-tri-methylpentyl) phosphinic acid as
the active components or PIA-8 (containing the active
component bis(2-ethylhexyl)phosphinic acid) were con-
sidered to be the most suitable for separating and reco-
vering cobalt and nickel from sulfuric acid solutions in
the presence of an appreciable amount of aluminum at a
low pH value. Although different acids have been pre-
viously used for leaching nickel from spent catalyst,
sulfuric acid has been selected as the cheapest and the
most effective. Also, applying sulfuric acid in the
extraction process allows aluminum to be readily
recovered as a sulfate salt by direct crystallization from
the raffinate. The aim of this work is to recover nickel
from the spent nickel catalyst based alumina (NiO/
Al2O3) used in the steam reforming industry. The spent
catalyst on being dumped would cause severe pollution
and thus using this method helps in preventing the
86 N.M. Al-Mansi, N.M. Abdel Monem / Waste Management 22 (2002) 85–90

accumulation of nickel which is considered a major
source of contamination. The study is mainly based on
leaching nickel oxide from the spent catalyst to produce
nickel sulfates and alumina, which is considered as an
inert. Different experiments were done to show the
effect of various factors affecting the optimum condi-
tions. The parameters considered were: acid concentra-
tion, time and temperature of digestion, solid:liquid
ratio, crushed spent catalyst, particle size and stirring
velocity.
The rate of the side reaction is very weak because
alpha alumina is completely inert towards acids [8]
because it was previously produced by calcination of
Al(OH)3 above 1000
C which gives it great stability
towards acids. Alpha alumina is used in the refractory
industry for making crucibles, bricks and spark plugs.
The cost of alpha alumina in Egypt is estimated to be
L.E. 6770 per ton according to the Academy of Scien-
tific Research and Technology.

2. Theoretical background
The reaction of nickel oxide with sulfuric acid is a
heterogeneous reaction. In a heterogeneous reaction
system the overall rate expression becomes complicated
because of the interaction between physical and chemi-
cal processes. The reactants in one phase have to be
converted to another phase in which the reaction takes
place. The mechanism of the uncatalyzed heterogeneous
reaction may take place as follows. Initially, the reac-
tants diffuse from the bulk of the first phase to the
interface between the phases. If an additional layer of
solid product and inert material is present at the inter-
face the reactants would have to overcome the resis-
tance of this layer before reaching the surface of the
second phase. Then, diffusion of reactants from the
interface to the bulk of the second phase takes place.
Further, chemical reactions between the reactants in
phase one and those in phase two occur. Finally, the
products diffuse within the second phase and/or out of
phase two into the bulk of phase one.
The reactions involve: (1) Main reaction:
NiO þ H2 SO4 ! NiSO4 þ H2 O
3. Materials
The specifications of the sample collected from Abu-
Quir Fertilizer Company [9] are shown in Table 1.The
price of the spent catalyst was determined according to
the amount of nickel. However, its price (in our case) is
around one $ per kg.
Sulfuric acid of commercial grade was chosen as a
solvent for treating metal oxides to convert them into
metal sulfates. Using sulfuric acid has the following
advantages:
1. nickel sulfate is commercially the most important
nickel compound due to its various uses especially
in electroplating;
2. sulfuric acid is a cheap solvent compared to other
acids. The price of the commercial acid (98% by
weight) is L.E. 600 per ton from Abuzabal
Company.
Fig. 1 shows the sequence of the applied process.
Table 1
Specifications of the sample collected from Abu-Quir Fertilizer Com-
pany

Company Abu-Quir
Where NiO is the limiting reactant. The nickel sulfate
Process used in Primary steam Secondary steam Methanator
crystals are used in electroplating and in the ceramic reformer reformer
industries. According to Sedasa Misr Company for
Chemicals, nickel sulfate has a cost of L.E. 8000 per Volume m3/unit 30 35 28
Bulk density kg/l 1.1 1.1 1.1
ton.
Crushing strength kgf 18.1 24.8
(2) Side reaction: Nickel oxide% 7.12 12.59 18.6
Alumina% 92.88 87.41 81.4
Alpha-Al2 O3 þ 3H2 SO4 ! Al2 ðSO4 Þ3 þ3H2 O

Fig. 1. Flow diagram of the process.

 N.M. Al-Mansi, N.M. Abdel Monem / Waste Management 22 (2002) 85–90 87

Fig. 2. Effect of particle size on percentage conversion.

Table 2 5.2. Effect of sulfuric acid concentration

Factors affecting nickel recovery

Acid concentration (10–98%) by weight Fig. 3 illustrates the effect of varying sulfuric acid
Digestion temperature (20–120)
C concentration from 10 to 90% by weight. The percen-
Digestion time (15–60) min tage recovery of nickel increased with increasing sulfuric
Solid:liquid (1/12–3/4) by weight acid concentration up to a certain range and then
Particle size (as received–less than 500 micron)
decreased with further increase in concentration. A
Stirring velocity (50–1400) rpm
maximum of 99% conversion took place at 50% acid
concentration. This indicates that the rate of dissolution
of low acid concentration was small, then increased,
4. Experimental procedure reaching a maximum value at 50% acid concentration;
the rate of dissolution then started to decline by
Spent catalyst was crushed and screened to attain the increasing the acid concentration.
required particle size. In each experiment, 1 g of spent
catalyst was added to a certain amount of sulfuric acid 5.3. Effect of solid:liquid ratio
having a specified concentration. Temperature, reaction
time, solid:liquid ratio, particle size, and stirring velocity Experiments were carried out using different waste
were adjusted. The reaction took place in a sealed con- solid:sulfuric acid ratios with 50% acid concentration
tainer and the resulting slurry was filtered on sintered and particle size < 500 micron. It was found that using
glass. Atomic Absorption Spectroscopy was used to the stoichiometric amounts of solid:liquid gives a low
determine the nickel content in the filtrate after a sui- conversion (26.3%) while increasing the acid amount
table dilution. Table 2 shows the different factors improves the conversion reaching 98% at a solid:liquid
affecting nickel recovery. ratio (1:12) as shown in Fig. 4. As the amount of acid
increases, the conversion increases, but the further
separation of sulfates from the excess acid is difficult
5. Results and discussion and is achieved by many ways.

5.1. Effect of particle size 5.4. Effect of temperature

The influence of spent catalyst particle size was stud-
ied using the particle size range (as received, >2000, 850
< 2000, < 500 micron). Fig. 2 represents the effect of the
particle size of the spent catalyst on the percentage
conversion at different sulfuric acid concentrations (10,
20, 35, and 50% by weight), at room temperature with-
out mixing. The data show that as the particle size
decreases to < 500 micron, a maximum conversion was
obtained at 50% acid concentration.
The effect of temperature on the system was studied
by performing experiments at 20, 40, 60, 80, 100 and
120
C. Fig. 5 reveals that the conversion was influenced
by the temperature of the reaction. The recovery
increases as temperature increases reaching 99% con-
version at reaction temperatures of 80–100
C, with acid
concentration of 50%. At higher temperatures, the recov-
ery decreases because water evaporates and the solution
becomes concentrated. This may be due to the fact that
88 N.M. Al-Mansi, N.M. Abdel Monem / Waste Management 22 (2002) 85–90

Fig. 3. Effect of sulfuric acid concentration on percentage conversion.

Fig. 4. Effect of solid:liquid ratio.

Fig. 5. Effect of temperature on percentage conversion.

 N.M. Al-Mansi, N.M. Abdel Monem / Waste Management 22 (2002) 85–90 89

Fig. 6. Effect of time of digestion on percentage conversion.

Fig. 7. Effect of stirring velocity on percentage conversion.

Table 3
Cost aspects based one ton of spent catalyst charge

Cost of raw materials (L.E.) Price of products (L.E.)

Average cost of spent catalyst according to nickel content=L.E. 308.8 Price of nickel sulfate crystals (assuming 100% conversion)=L.E. 3526
Cost of sulfuric acid consumed=L.E. 92.32 Price of alpha alumna produced=L.E. 591

the reaction between nickel atoms and sulfuric acid
form a layer of nickel oxide which surrounds the nickel
atoms and decreases the amount of nickel recovered.
Nickel sulfate solution is heated and the nickel sulfate
salt is crystallized as separate single nickel salt crystals
(NiSO4.7H2O).
5.5. Effect of time of digestion
Fig. 6 illustrates the significant effect of time on the
recovery of nickel. Prolonging the contact time is
accompanied by a noticeable increase in the metal
removal which means that nickel recovery is a rate process
depending on the time of the reaction. For more than
5 h, 99% conversion was achieved.
5.6. Effect of stirring velocity
A series of experiments were undertaken to study the
influence of agitation on conversion. Different stirring
rates ranging between 50 and 1400 rpm have been
applied. The experimental results shown in Fig. 7 indi-
cate that the rate of reaction is controlled by the degree
of agitation and the conversion increases with increas-
ing the stirring velocity. The optimum stirring rate
which gives the maximum percentage removal is
90 N.M. Al-Mansi, N.M. Abdel Monem / Waste Management 22 (2002) 85–90
obtained at 800 rpm. Increasing stirring above that rate
has no effect on conversion.
6. Cost aspects
The cost items based on a ton of spent catalyst charge
can be calculated as shown in Table 3 Douglas [10]:
Cost of products/Cost of raw materials =L.E. 10.26,
which indicates that the process is profitable, where
$=3.9 L.E.(Egyptian pound).
Actually, there are several methods to remove excess
sulfuric acid from nickel sulfate solution:
1. sulfuric acid can be separated by using membranes
[8];
2. adding calcium hydroxide which reacts with sulfu-
ric acid to form a white precipitate of calcium sul-
fate at room temperature;
3. adding barium hydroxide solid in stoichiometric
amounts to the excess acid react to form barium
sulfat; and
4. nickel sulfate solution is evaporated and nickel
is crystallized as single nickel salt crystals
(NiSO4.7H2O).
7. Conclusions
It is possible to utilize spent catalyst (NiO/Al2O3)
obtained from the steam reforming plants to produce
nickel sulfates by using sulfuric acid. According to
environmental considerations it is very useful to reuse
the solid waste to produce a salable product such as
nickel sulfates which can be used in electroplating.
Moreover, the efficient separation of nickel from spent
catalyst create a possibility for reusing the alumina
support in the catalyst and thus the solid waste spent
catalyst is completely utilized. The operating conditions
required to reach 99% conversion were 50% acid con-
centration, solid: liquid ratio (1:12), less than 500
micron particle size for a contact time higher than 5 h
and 800 rpm stirring rate a temperature of 100
C.
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