Journal of Industrial and Engineering Chemistry 16 (2010) 251–255

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Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

Recovery of nickel from spent catalyst from palm oil hydrogenation process
using acidic solutions
Juferi Idris a, Mohibah Musa b, Chun-Yang Yin a,*, Ku Halim Ku Hamid a
a
Universiti Teknologi MARA Sarawak, Kampus Kota Samarahan, 94300 Kota Samarahan, Sarawak, Malaysia
b
Faculty of Chemical Engineering, Universiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia

A R T I C L E I N F O A B S T R A C T

Article history: In this study, recovery of nickel from spent catalyst from palm oil hydrogenation process is carried out
Received 26 May 2009 via extractive leaching process using sulfuric and hydrochloric acids. The effects of acid concentration,
Accepted 14 November 2009 solid-liquid ratio, temperature and digestion time on the recovery (acid dissolution) process are
investigated. It is found that sulfuric acid is the better leaching solution as compared to hydrochloric acid
Keywords: for recovery (dissolution) of nickel from the spent catalyst. Results from speciation modelling using
Spent catalyst VMINTEQ further imply that nickel can form sulfate complexes which are more stable than chloride
Nickel recovery
complexes at concentrations higher than 1 M. The optimum conditions for maximum recovery at 85% are
Hydrochloric acid
achieved at 67% sulfuric acid concentration, digestion time of 140 min, solid-to-liquid ratio of 1:14 and
Sulfuric acid
VMINTEQ reaction temperature of 80 8C. At solution temperatures higher than 80 8C, the percentage nickel
extraction is reduced. The optimization study presented here is useful for spent catalyst generators in the
palm oil industry intending to recover valuable metals which may assist in reducing palm oil processing
costs.
ß 2010 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

1. Introduction encouraged alternative to disposal due to its numerous advantages

The Malaysian palm oil industry has grown rapidly over the
years to become the world’s largest producer and exporter of palm
oil and its products with production in 2003 amounted to
approximately 49% of world palm oil output [1]. A main processing
step in production of palm oil is the hydrogenation process which
is utilized to modify the oil’s physical characteristics for specific
application and increase its stability towards oxidation and
decomposition [2]. A catalyst consisting predominantly of nickel
oxide is often used to facilitate the hydrogenation process. This
often presents a disposal problem in Malaysia as according to local
environmental legislations, spent catalyst is listed as a ‘‘scheduled’’
waste (hazardous waste) and must be treated by a licensed waste
treatment facility prior to proper landfill disposal [3]. It is therefore
desirable to recover and reuse the nickel from its spent form in
order to offset its cost. Spent catalyst recycling is a highly
* Corresponding author at: Faculty of Chemical Engineering, Universiti Teknologi
MARA, 40430 Shah Alam, Selangor, Malaysia. Tel.: +60 355436348;
fax: +60 355436300.
E-mail addresses: yinyang@salam.uitm.edu.my, yinyang@streamyx.com
(C.-Y. Yin).
in terms of economical and environmental factors.
There are numerous studies reporting on the extraction of
nickel from spent catalyst resulting from industrial processes using
mineral acids. Most of these studies reported on the optimum
conditions for maximum recovery of nickel. Ivascanu et al. [4]
reported 99% nickel sulfate recovery from spent catalyst via
dissolution of the catalyst in sulfuric acid solution (80%) for 50 min
at 70 8C. Loboiko et al. [5] reported that the recovery of nickel was
increased by extractive leaching at 60–70% nitric acid concentra-
tion at 120 8C for 2–3 h. In another study, Chandhary et al. [6]
reported a nickel extraction yield at about 18% from the low grade
spent catalyst from smelting industry by leaching with hydro-
chloric acid. Recently, Abdel-Aal and Rashad [7] investigated
leaching of spent nickel oxide catalyst from fertilizer and chemical
process using sulfuric acid. They found out that 94% nickel recovery
could be achieved at 50% sulfuric acid concentration, contact time
of 150 min and reaction temperature of 70 8C. In a recent article,
Marafi and Stanislaus [8] comprehensively reviewed the numerous
acid leaching studies that involved not just nickel-based catalyst,
but other metal-based catalysts as well. To date, there is no
identified study on acid leaching recovery of nickel from spent
catalyst used in palm oil hydrogenation process. As such, an
optimization study for such recovery process would be useful for
spent catalyst generators in the palm oil industry intending to

1226-086X/$ – see front matter ß 2010 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.jiec.2010.01.044
252 J. Idris et al. / Journal of Industrial and Engineering Chemistry 16 (2010) 251–255
recover valuable metals which may assist in reducing palm oil
processing costs.
The objective of this study was to determine the optimum
conditions for maximum recovery (or dissolution) of nickel from
spent catalyst from palm oil hydrogenation process. Among the
parameters studied were acid concentration, solid–liquid ratio,
temperature and digestion time. In addition, nickel recoverability
in sulfate or chloride forms was also analysed. To this end, nickel
speciation percentages in the presence of varying anionic
concentrations were determined using an established chemical
equilibrium model.
2. Experimental
2.1. Spent catalyst
Spent catalyst samples from oil palm hydrogenation process
used in this study were collected from a palm oil mill refinery
located in Selangor, Malaysia. The spent catalyst was crushed and
screened to particle sizes less than 500 mm. This particle size range
was selected based on a previous study conducted by Al-Mansi and
Andel-Nomen [9] where maximum recovery of nickel at about 99%
was obtained. X-ray diffractometry (XRD) analysis was conducted
on the spent catalyst to qualitatively determine its mineralogy and
crystalline phases by using Rigaku D/Max 2000 diffractometer
operated at 40 kV and 30 mA for the reflection angle (2u) in the
range 3–908.
2.2. Aqua regia digestion
Aqua regia digestion of the spent catalyst was conducted to
provide a benchmark to evaluate the efficiency of the acidic
leaching extraction. For this process, 10 g of spent catalyst was
added to concentrated mixture of HCl (15 mL) and HNO3 (6 mL) in
a flask and covered with glass. The solution was gently boiled using
a hot plate until 15 mL of extract remained in the flask. The
solution was allowed to cool for 15 min. Subsequently, 10 mL of
solution was transferred into a volumetric flask and topped up
with deionized water to 100 mL. The solution was analysed for
nickel via inductive coupled plasma-atomic emission spectropho-
tometer (ICP-AES).
2.3. Acidic leaching extraction
The acidic leaching extraction study was carried out in batch
processes. In each process, 10 g of spent catalyst was added to a
certain amount of sulfuric or hydrochloric acid having a specified
concentration. The effects of parameters such as solid-to-liquid
ratio, temperature and time of digestion were investigated.
Agitation of the extraction process was fixed at 300 rpm. The
reaction took place in a sealed Erlenmeyer flask and the resulting
reactant was filtered on sintered glass. After suitable dilutions, the
filtrate was analysed via ICP-AES to determine nickel concentra-
tion.
2.3.1. Effect of acid concentration
The concentrations of sulfuric or hydrochloric acid as leaching
solution were varied from 1 to 12 M with solid-to-liquid ratio fixed
at 1:12 at temperature 40 8C. Digestion time was fixed at an hour.
2.3.2. Effect of solid:liquid ratio
The solid-to-liquid ratios of sulfuric and hydrochloric acid as
leaching solution were varied from 1:2 to 1:18. The acid
concentration was fixed at the respective optimum nickel
extraction percentages as determined from Section 2.3.1. Agitation
of the solution was carried out for 1 h at 40 8C.
2.3.3. Effect of temperature of leaching solution
The temperatures of the leaching solution were varied from 40
to 120 8C. The acid concentration and solid-to-liquid ratio were
fixed at the respective optimum nickel extraction percentages as
determined from Sections 2.3.1 and 2.3.2, respectively. Mercury
thermometer was used to monitor the temperature of leaching
solution.
2.3.4. Effect of digestion time
The digestion time of the extraction process was varied from 20
to 200 min. The acid concentration, solid-to-liquid ratio and
temperature were fixed at the respective optimum nickel
extraction percentages as determined from Sections 2.3.1–2.3.3,
respectively. All experiments were carried out in triplicate to
ensure accuracy.
3. Results and discussion
3.1. Composition of spent catalyst
Proximate and ICP-AES analyses indicate that the spent catalyst
contains approximately 15 wt% nickel. Fig. 1 shows the XRD
patterns of the spent catalyst. The diffraction intensities as
reflected by corresponding counts per second (cps) were used as
qualitative indication of presence of a substance in the catalyst. It
should be noted that, in our study, the XRD indicates the types of
metal oxide but does not distinguish between the metal oxidation
state. It is evident that the predominant substance present in
the catalyst is nickel oxide while there is also presence of titanium,
magnesium, lithium and copper oxides. It is deemed that
titanium oxide acts as a carrier for nickel oxide in the palm oil
hydrogenation process. The combination of titanium- and nickel-
based oxides as catalyst was previously utilized by Uchiyama et al.
[10] in which the catalyst was prepared via coprecipitation of
nickel-containing catalyst with titanium and subsequently used in
the process route to produce higher alcohols such as ethanol and
propanol from synthesis gas. The well-defined XRD patterns with
prominent peaks indicate that the catalyst is primarily in
crystalline form with marginal presence of amorphous phase.
3.2. Speciation of nickel
In order to supplement understanding of this experimental
study, speciation diagrams for nickel as affected by changes in
Fig. 1. XRD patterns of spent catalyst.
 J. Idris et al. / Journal of Industrial and Engineering Chemistry 16 (2010) 251–255 253

anionic concentrations are generated using VMINTEQ 2.61

Software [11]. VMINTEQ 2.61 is a chemical equilibrium model
for determination of metal speciation and solubility equilibria for
natural waters. A similar speciation technique was used by Barakat
et al. [12] to determine the various chloro-complexes of palladium
as a function of chloride ion concentration which indicated the
applicability of such technique within the area of metal recovery
from spent catalyst. Fig. 2 shows the speciation of nickel as a
function of free sulfate (from sulfuric acid) and chloride (from
hydrochloric acid) concentrations. The simulated nickel specia-
tions plotted are relative to the total nickel species in separate
acidic solutions. Nickel can form stable NiSO4, Ni(SO4)22, NiCl+
and NiCl2 complexes at concentrations higher than 1 M. It is
observed that in the case of low concentrations of sulfate (0.01–
1 M), NiSO4 complex can be formed at relatively high percentages
(30–95%) while for corresponding concentrations of chloride
(0.01–1 M), complexes can only be formed at very low percentages
(<10%). This observation has a significant implication on the nickel
recoverability in the form of either NiSO4 or NiCl2 and is further
discussed in following sections.

3.3. Effect of acid concentration

The percentage nickel recovery was determined via the

following equation [13].
 
M leach
Nickel recovery ð%Þ ¼  100% (1)
M digest Fig. 2. Speciation of nickel as a function of free (a) sulfate and; (b) chloride
concentrations.
where Mleach = amount of analyte from acid leaching extraction
technique (mg/kg), Mdigest = amount of analyte from aqua regia
extraction technique (mg/kg).
For this study, the following reactions with regards to NiO
occurred:

NiO þ H2 SO4 ! NiSO4 þ H2 OðsulfuricacidasleachingsolutionÞ

(2)

NiO þ 2HCl ! NiCl2 þ H2 OðhydrochloricacidasleachingsolutionÞ

(3)

Only high acid concentrations are used in the study (1 M)

since it is shown in Fig. 2 that nickel complexes can only be formed
at substantial percentages within this acid concentration range.
Fig. 3 shows the effect of acid concentration on nickel extraction.
With regards to sulfuric acid extraction, nickel extraction increases
from 35% at 1 M to an optimum extraction of 63% at 11 M while for
hydrochloric acid extraction, the optimum extraction is approxi- Fig. 3. Effect of acid concentration on nickel extraction.
mately 49% at 6 M. Generally, an increase in sulfuric acid
concentration results in increased nickel extraction whereas for
hydrochloric acid, minor fluctuations in nickel extraction due to 3.4. Effect of solid-to-liquid ratio
changes in acid concentration are observed. In fact, it can be said
that the percentage of nickel extracted from spent catalyst in Fig. 4 shows the effect of solid-to-liquid ratio on nickel
hydrochloric acid remains comparatively consistent (40%) even extraction. In this case, the concentrations of sulfuric and
with increases in acid concentration. This result was also observed hydrochloric acids were fixed at 11 and 6 M respectively since
by Chandhary et al. [6] in which they reported that the effect of these values were determined to optimum values for nickel
hydrochloric acid strength on nickel extraction was insignificant. extraction. It is evident that there are optimum solid-to-liquid
In essence, sulfuric acid provides better nickel dissolution (nickel ratios at 1:14 for extraction of 63.60% (sulfuric acid) and 1:12 for
recovery) as compared to hydrochloric acid. This can be attributed extraction of 55.78% (hydrochloric acid).
to the presence of twice the amount of H+ ions for sulfuric acid as
compared to hydrochloric acid which enables greater ion exchange 3.5. Effect of temperature
capabilities with nickel ions. This observation is also consistent
with a relatively similar study conducted by Valverde Jr. et al. [14] Fig. 5 shows the effect of temperature of leaching solution on
in which they showed that sulfuric acid was a better leachant than nickel extraction. Similarly, the curves are clearly bell-shaped
hydrochloric acid in relation to the higher amount of insoluble indicating optimum temperatures of leaching solution at a range
nickel-based matter found in the latter. from 60 to 80 8C for both sulfuric and hydrochloric acids. At
254 J. Idris et al. / Journal of Industrial and Engineering Chemistry 16 (2010) 251–255

Fig. 4. Effect of solid-to-liquid ratio on nickel extraction. Fig. 6. Effect of time of digestion on nickel extraction.

further increases in time of digestion result in fluctuation of

percentage nickel extraction. This instance is observed at 140 min
for sulfuric acid and 100 min for hydrochloric acid which
coincidentally, represents the time of digestion for optimum
nickel extraction.

3.7. Comparison with other studies

Table 1 shows the comparison of optimum conditions for

Fig. 5. Effect of temperature of leaching solution on nickel extraction.
temperatures higher than 80 8C, the percentage nickel extraction
reduces. This observation was also reported by Al-Mansi and
Andel-Nomen [9] in which they explained that it was due to
evaporation of water from leaching solution thereby increased the
concentration of solution. They further elucidated that the high
solution temperature facilitated reaction between nickel atoms
and sulfuric/hydrochloric acid resulting in formation of nickel
oxide layers which surrounded the nickel atoms and decreased the
amount of nickel recovered.
3.6. Effect of time of digestion
Fig. 6 shows the effect of time of digestion on nickel extraction.
For both types of acid, the increase of time of digestion increases
the percentage nickel extraction until it reaches an instance where
maximum recovery of nickel from spent catalyst with other
pertinent studies. The maximum nickel recovery of 85% can be
considered as high even though Al-Mansi and Andel-Nomen [9]
as well as Abdel-Aal and Rashad [7] obtained higher recovery
percentages. Nonetheless, it should be noted that the spent
catalysts in other studies were NiO/Al2O3-based which is a rather
established nickel-based catalyst. Our study, on the other hand,
detected presence of titanium oxide which may have compli-
cated the extraction process. It is noted that maximum recovery
of nickel in these studies is only achieved via usage of sulfuric
acid as leachant and not hydrochloric acid, further reinforcing
the argument that sulfuric acid provides better nickel dissolu-
tion.
3.8. Reutilization of nickel salts
In order to fully recover nickel sulfate salt from the solution,
the solution can be subjected to the established evaporation/
crystallization process to produce the salt in crystalline form. For
recovery of nickel sulfate salt, evaporation of some of the water
from the solution is carried out so that the solubility limit of nickel
sulfate in the remaining acid-enriched liquor is exceeded [15].

Table 1
Comparison of optimum conditions for maximum recovery of nickel from spent catalyst with other studies.

Researchers Type of spent catalyst Acid concentration Solid-to-liquid ratio Temperature Time of Recovery
(8C) digestion (h) (%)

Abdel-Aal and Rashad [6] Spent catalyst (NiO/Al2O3) 50% sulfuric acid 1:20 85 2.5 94
from fertilizer process.
Al-Mansi and Andel-Nomen [8] Spent catalyst (NiO/Al2O3) 50% sulfuric acid 1:12 100 >5 99
from steam reforming process.
Mulak et al. [17] Spent catalyst (NiO/Al2O3) 18% sulfuric acid 1:800 70 1 77
from fertilizer process.
Sahu et al. [18] Spent catalyst (NiO/Al2O3/Fe2O3) 8% sulfuric acid Pulp density = 10% 90 2 98
from urea production unit. (100 g/L)
This study Spent catalyst (NiO/TiO) from 67% sulfuric acid 1:14 80 2.33 85
hydrogenation process.
 J. Idris et al. / Journal of Industrial and Engineering Chemistry 16 (2010) 251–255
Crystallisation of nickel sulfate occurs according to the following
reaction:
Ni2þ ðaqÞ þ SO4 2 ðaqÞ þ 6H2 ONiSO4 6H2 OðsÞ
Nyirenda and Phiri [15] demonstrated that this evaporation/
crystallization process is a very effective process in recovering
nickel sulfate salt from a solution. In this process, the concentrated
solution was heated to approximately 400 8C prior to overnight
cooling to allow formation of the nickel sulfate crystals. As such,
the authors surmise that this process can be considered as an
option to recover crude nickel sulfate salt from the sulfuric acid-
extracted nickel solution. However, this option should be exercised
with proper discretion since it may only be feasible if impurities
are present in low amounts which require a preceding purification
step.
With regards to hydrochloric acid extraction, the majority of
metals can exist as soluble anionic chloride complexes in
concentrated hydrochloric acid [5,16]. Therefore, this factor may
contribute to the difficulty of using the evaporation/crystallization
process to fully recover nickel salt from the leaching solution. In
addition, VMINTEQ simulation shown in Fig. 2 clearly indicates the
difficulty of formation of nickel chloride complexes compared to
nickel sulfate. An alternative method of using hydrogen chloride
gas to saturate the solution at 21 8C in order to yield precipitated
nickel chloride was described by Chandhary et al. [6] to be an
alternative nickel salt recovery method. However, practitioners of
this saturation technique should be well aware of the complica-
tions that may arise due to accidental release of hydrogen chloride
gas since it is well known that it has adverse health effect on
human beings.
4. Conclusions
Sulfuric acid was the better leaching solution compared to
hydrochloric acid for recovery (dissolution) of nickel from the spent
catalyst. VMINTEQ modelling showed that nickel could form stable
NiSO4, Ni(SO4)22, NiCl+ and NiCl2 complexes at concentrations
higher than 1 M. The maximum nickel recovery (dissolution) was
255
85% by using aqua regia digestion as the recovery benchmark. The
optimum conditions for maximum recovery were achieved at 67%
sulfuric acid concentration, digestion time of 140 min, solid-to-
(4) liquid ratio of 1:14 and reaction temperature of 60 8C. At solution
temperatures higher than 80 8C, the percentage nickel extraction
was reduced. It was deemed that recoverability of nickel sulfate salt
was a more feasible option compared to nickel chloride salt. The
nickel sulfate salt could be recovered by utilizing an evaporation/
crystallization process while for hydrochloric acid extraction, nickel
chloride salt could be recovered using HCl gas precipitation method.
Acknowledgement
The authors gratefully acknowledge the Faculty of Chemical
Engineering, Universiti Teknologi MARA, Malaysia for providing
the necessary facilities and equipment.
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