Journal of Chemical Engineering of Japan, Vol. 37, No. 9, pp. 1129–1134, 2004 Research Paper
Copyright © 2004 The Society of Chemical Engineers, Japan 1129
Leaching of Nickel from a Hydrodesulphurization Spent Catalyst with
Ammonium Sulfate
Jae-Min YOO
1
, Jae-Chun LEE
2
, Byung-Su KIM
2
,
Hi Sun LEE
3
and Jin-Ki JEONG
2
1
Department of Metallurgical Engineering,
Chonbuk National University, Jeonju 561-756, Korea
2
Minerals and Materials Processing Division,
Korea Institute of Geoscience and Mineral Resources,
30 Gajeong-dong, Yuseong-gu, Daejeon 305-350, Korea
3
Research Division, Korea Environment Institute,
Eunpyung-gu, Seoul 122-040, Korea
Keywords: Recycling, Spent Catalysts, Leaching of Catalysts, Nickel Leaching
Leaching of nickel from a hydrodesulphurization spent catalyst generated from the sulfur removal
process of petroleum refineries was investigated using ammonium sulfate ((NH
4
)
2
SO
4
) solution. The spent
catalyst used in the study was composed of vanadium and nickel as sulfides, supported in an alumina
matrix. Experiments were carried out in a stirred batch reactor under the temperature range of
298–368 K and the (NH
4
)
2
SO
4
solution of 1.3–3.3 mol/dm
3
. As a result, about 94.0% of nickel was leached
from the 2.6 mol/dm
3
(NH
4
)
2
SO
4
solution in 90 min at the temperature of 368 K. A shrinking core model
was found to be useful in describing the rate of nickel leaching. The rate of nickel leaching is limited by
ash layer diffusion. The nickel leaching is of the first order with respect to the (NH
4
)
2
SO
4
concentration
and has an activation energy of 16.2 kJ/mol.
Introduction
Hydrodesulphurization catalysts have been usu-
ally used in the oil refining process to produce light
oil by removing sulfur from heavy oil. Most of the cata-
lysts are small spheres (diameter: 3 mm) composed of
nickel–molybdenum or cobalt–molybdenum, supported
on an aluminum inert substrate.
In general, hydrodesulphurization spent catalysts
can be regenerated two or three times, but eventually,
they become poisoned and must be discarded because
these catalysts lose activity or selectivity after being
used for a period of time. Large amounts of the spent
catalysts have thus been generated from oil refineries.
The spent catalysts contain significant amounts of valu-
able metals like nickel or cobalt, molybdenum, and va-
nadium as sulfides in an alumina matrix as well as some
organic contaminants. The vanadium and organic com-
pounds were deposited from the heavy oil in the sulfur
removal process. So, the disposal of the spent cata-
lysts is environmentally dangerous if improperly man-
aged (Habermehl, 1988; Berrebi et al., 1993).
A number of hydrometallurgical processes were
developed and commercialized to minimize the envi-
ronmental problems with recovering valuable metals
Received on December 12, 2003. Correspondence concerning
this article should be addressed to J.-C. Lee(E-mail address:
jclee@kigam.re.kr).
from hydrodesulphurization spent catalysts (Zhang et
al ., 1995). In general, the recovery of the valuable
metals from the spent catalysts has been carried out by
conventional methods (Toda and Matsuda, 1988; Toda,
1989): soda roasting, hot water leaching, and precipi-
tation as NH
4
VO
3
and CaMoO
4
by adding NH
4
Cl and
CaCl
2
, respectively. However, the recovery of nickel
using the conventional methods is very difficult be-
cause during roasting at the high temperature over
873 K with adding a soda salt like Na
2
CO
3
, Na
2
SO
4
or
NaOH the compound of NiAl
2
O
4
is formed, which is
insoluble in water (Toda and Matsuda, 1988; Toda,
1989). Thus, an autoclave process was additionally
used to recover nickel, by which the operating coast
would be expensive (Zhang et al., 1995). Moreover,
the price of nickel, which is second abundant element
in the spent catalysts, keeps increasing recently.
Therefore, it would be highly desirable to find an al-
ternative process for recovering nickel from
hydrodesulphurization spent catalysts.
Keeping this point in mind, the present research
is concerned with investigating the kinetics for nickel
leaching from a hydrodesulphurization spent catalyst
generated from an oil company in Korea using an am-
monium sulfate ((NH
4
)
2
SO
4
) solution. The effects of
stirring speed, (NH
4
)
2
SO
4
concentration, particle size,
and leaching temperature were investigated. It is
thus expected that this work will help to develop and