Minerals Engineering 19 (2006) 94–97

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Technical note

Research on the recycling of valuable metals

in spent Al2O3-based catalyst
Yun Chen *, Qiming Feng, Yanhai Shao, Guofan Zhang, Leming Ou, Yiping Lu
Department of Mineral Engineering, Central South University, Changsha, Hunan 410083, PR China

Received 5 May 2005; accepted 23 June 2005

Available online 10 August 2005

Abstract

A new technology was developed to recover multiple valuable elements in the spent Al2O3-based catalyst by X-ray phase analysis
and exploratory experiments. The experiment results showed: In the condition of roasting temperature of 750 °C and roasting time
of 30 min, mol ratio of Na2O: Al2O3 1.2, the leaching rate of alumina, vanadium and molybdenum in the spent catalyst is 97.2%,
95.8% and 98.9%, respectively. Vanadium and molybdenum in sodium aluminate solution can be recovered by barium hydroxide
and barium aluminate, the precipitation rate of vanadium and molybdenum is 94.8% and 92.6%. Al(OH)3 is prepared from sodium
aluminate solution with carbonation decomposition process, and the purity of Al2O3 is 99.9% after calcinations, the recovery of
alumina can reach 90.6% in the whole process. The Ni–Co concentrate was leached by sulfuric acid, a nickel recovery of 98.2%
and over 98.5% cobalt recovery was obtained respectively under the experimental condition of 30% (w/w) H2SO4, 80 °C, reaction
time 4 h, liquid:solid ratio (8:1) by weight, stirring rate of 800 rpm.
Ó 2005 Elsevier Ltd. All rights reserved.

Keywords: Recycling; Roasting; Leaching; Waste processing

1. Introduction ous wastes by the Environmental Protection Agency in

Spent catalysts contribute a significant amount of the
solid wastes generated in the petrochemical industry
(Anon, 2000). These spent catalysts have been discarded
for landfill in the past, but environmental pollution of
air, soil and ocean contaminated by these waste catalysts
has become a serious problem. Increasing environmen-
tal concerns and legislation regarding the disposal of
hazardous residues are forcing companies and countries
to process their own waste products and residues, Spent
hydroprocessing catalysts have been classified as hazard-
*
Corresponding author. Tel.: +86 731 8830227; fax: +86 731
8830913.
E-mail address: chenyunhn@hotmail.com (Y. Chen).
the USA (Rapaport, 2000). In short, the spent catalyst
wastes have become an environmental problem, and at
the same time, it has presented an opportunity for a
new business to rejuvenate, recycle and convert the spent
catalyst to an environmentally acceptable safe material
for recycle. Several alternative methods such as disposal
in landfills, reclamation of metals, regeneration/rejuve-
nation and reuse, and utilization as raw materials to
produce other useful products are available to the refin-
ers to deal with the spent catalyst problem (Chang, 1998;
Trimm, 2001; Marafi and Stanislaus, 2003).
During the past decade, considerable research was
devoted to the comprehensive utilization of spent
Al2O3-based catalyst. A survey of literature revealed
that the technology for recycling spent Al2O3-based cat-
alyst by roasting–extraction method (US Patent
5,431,892, 1995; US Patent 6,180,072, 2001; Yoo,

0892-6875/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2005.06.008
 Y. Chen et al. / Minerals Engineering 19 (2006) 94–97
1998; Al-Mansi and Abdel, 2002; Chmielewski et al.,
1997). In the present research, the main process of
recovering metals from spent catalyst are roasting and
solvent extraction (Inoue et al., 1995; Edward, 1996;
Luo et al., 2003). Most of the valuable elements in the
catalyst had been recovered, but as the main body of
the catalyst, carrier Al2O3 failed to have a good recov-
ery, and this also leads to another new pollution. There-
fore, the aim of this paper was to recover valuable
metals in spent Al2O3-based catalyst.
2. Materials and methods
2.1. Materials
Spent catalyst (Ni 4.77%, Co 0.35%, Mo 0.48%, V
0.55%, Al2O3 70.95%) was obtained from the atmo-
spheric residue hydrodesulfurization unit of China Na-
tional Petroleum Company, the particle size is between
0.06 and 0.1 mm. Fig. 1 is the X-ray diffraction result
of spent catalyst.
2.2. Method
Mixing the catalyst and alkali in a certain proportion
and then put the mixture in a furnace, roasting it and
then dissolve it in water, this leads to the formation of
sodium aluminate solution, filter the solution. The Ni–
Co concentrate after filtering is leached with the sulfuric
acid; the impurity of V and Mo in sodium aluminate
solution is recovered by barium hydroxide and barium
aluminate, and then Al(OH)3 is prepared from sodium
aluminate solution with carbonation decomposition
process, high quality Al2O3 is prepared by calcinations
Fig. 1. The X-ray diffraction result of spent catalyst.
95
of Al(OH)3 at high temperature. Fig. 2 is the recovering
flowsheet of spent catalyst.
3. Results and discussion
3.1. Roasting
Mixing spent catalyst with alkali and roasting
it at high temperature, vanadium, molybdenum and
nickel turn into the oxide at first, and then these metal
oxides react with alkali. In this process, sodium hydr-
oxide was chosen to react with spent catalyst at high
temperature because the main form of alumina in
catalyst is alpha-Al2O3 (Fig. 1). Under the condition
of roasting at 750 °C for 30 min, mol ratio of Na2O:
Al2O3 = 1.2, the leaching rate of alumina, vanadium
and molybdenum in the spent catalyst is 97.2%, 95.8%
and 98.9%, respectively, nickel and cobalt in Ni–Co
concentrate are enriched (Ni 30.15%, Co 2.21%, Mo
0.07%, V 0.08%, Al2O3 10.37%). The dissolving of
alumina disintegrates aluminates formed by alumi-
num and other valuable metals, and this is very
significant for the next recovering of other valuable
elements.
3.2. Recovering of V and Mo
After roasting with alkali at high temperature, vana-
dium and molybdenum are dissolved in sodium alumi-
nate solution in the dissolving process. In order to get
high quality product of alumina, the impurity of V
and Mo in sodium aluminate solution must be removed.
Considering the low solubility of BaMoO4 and
Ba3(VO4)2 in water (Xia and Fuenzalida, 2003; Oka
et al., 1995). In this process, barium hydroxide and bar-
ium aluminate were added to recover V and Mo, respec-
tively. With barium hydroxide, under the condition of
40 °C, reaction time 15 min, stoichiometric quantity of
Ba(OH)2 (according to the chemical reaction), the pre-
cipitation rate of V is 94.8%; In the precipitation of
molybdenum, 92.6% of Mo was precipitated under the
condition of reaction time 40 min, 80 °C and the stoichi-
ometric quantity of BaAl2O4 (according to the chemical
reaction). Barium hydroxide and barium aluminate had
no side effect on the decomposition of sodium aluminate
solution.
3.3. Production of alumina
After the recovery of V and Mo by precipitation, the
sodium aluminate solution was purified, the carbonation
decomposition process was applied to the production of
Al(OH)3, and then Al(OH)3 was calcinated at 1200 °C to
produce alumina. The recovery of alumina can reach
90.6% in the whole process, and the purity of alumina
96 Y. Chen et al. / Minerals Engineering 19 (2006) 94–97
Mixing (catalyst &alkali)
roasting
dissolving
Solid/liquid separation
Ba(OH)2
Liquid
Solid/liquid separation
BaAl2O4
liquid
Solid/liquid separation
CO2
Sodium aluminate solution
Al(OH)3
Al2O3
Fig. 2. Recovering flowsheet of spent catalyst.
is 99.9%, this quality is higher than the first class prod-
uct of China
s national standard (Al2O3 is no less than
98.6%).
3.4. Acid leaching of Ni–Co concentrate
The Ni–Co concentrate is a kind of metallurgical raw
materials with high content of nickel and cobalt (Ni:
30.15%, Co: 2.21%). In each leaching experiment, 10 g
Ni–Co concentrate was added to a certain amount of
sulfuric acid having a specified concentration. Tempera-
ture, reaction time, liquid:solid ratio (L/S), stirring rate
were adjusted. The reaction took place in a sealed con-
tainer and the resulting slurry was filtered on sintered
glass. The content of nickel and cobalt was determined
by Atomic Absorption Spectroscopy.
According to the results of exploratory experiments,
the suitable leaching condition was 30% (w/w) H2SO4,
L/S = 8, reaction time 4 h, 800 rpm, under this operat-
ing condition the leaching rate of nickel and cobalt
can reach 98.2% and 98.5%, respectively.
Ni-Co Acid
concentrate leaching
Ba3(VO4)2
BaMoO4
4. Conclusions
The catalyst wastes have rapidly been increasing
worldwide. Recovering of valuable elements of spent
catalyst became an unavoidable task not only for lower-
ing the catalyst cost but also for reducing the catalyst
waste to prevent the environmental pollution. Based
on results obtained from the current work, the following
conclusions are made:
(1) By this novel process, the purity of alumina is
99.9% produced with carbonation decomposition
process, the recovery of alumina can reach 90.6%
in the whole process.
(2) Under the suitable condition, with barium hydrox-
ide and barium aluminate, the precipitation rate of
vanadium and molybdenum is 94.8% and 92.6%,
the precipitate can be sold as chemical product
or further deep-processed.
(3) The Ni–Co concentrate was leached by sulfuric
acid, a nickel recovery of 98.2% and over 98.5%
 Y. Chen et al. / Minerals Engineering 19 (2006) 94–97
cobalt recovery was obtained respectively under
the experimental condition of 30% (w/w) H2SO4,
80 °C, L/S = 8, reaction time 4 h, stirring rate of
800 rpm.
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