International Conference on Mining, Mineral Processing and Metallurgical Engineering (ICMMME'2013) April 15-16, 2013 Johannesburg (South Africa)

Regeneration and Reuse of Clinoptilolite for

Recovery of Copper and Cobalt from Aqueous
Solutions
Elvis Fosso-Kankeu, Antoine-Floribert. Mulaba-Bafubiandi, Jim T. Modipe and Eunice S. Maroga

With large size of deposits around the world and wide

geographic distribution, clipnotilolite is considered as the
most abundant zeolite [7].
The remediation process may become more attractive if the
cost of the sorption agent is low. One way of ensuring
minimal cost of the sorbent is through its regeneration and
reuse, eliminating the need to use new sorbent for every
adsorption cycle and also ensuring the recovery of values.
Acidic and alkaline media have been used as eluents for the
regeneration of zeolites with different outcomes. Some
researchers have claimed that acidic eluents are responsible of
the degradation of zeolite and therefore reduction of their
adsorption capacity, while alkaline conditions were not
effective in most cases [8], [9]. Gorimbo [8] reported
dealumination and reduction of adsorption capacity of
clinoptilolite following exposure to high concentration of
acids, while exposure to base resulted to internal formation of
precipitates and clogging of the pores in the zeolite
framework.
Natural zeolites found in the environment often have
different structures [10] and therefore likely to exhibit
different adsorption capacity and robustness following reuse.
In this study clinoptilolite collected from the Vulture Greek of
Kwazulu Natal Province in South Africa was tested for its
potential of reuse during metal removal processes.

Abstract Ineffective recovery of metals from pregnant

solutions during hydrometallurgical processes mainly results in
residual value reporting to the liquid effluent. Previous studies have
shown that zeolite can be used for the recovery of base metals from
solution through ion-exchange process. The main objective of this
work was to investigate the potential regeneration of used
clinoptilolite in alkaline and acidic solutions. The batch adsorption
tests work was conducted at room temperature using 5g of zeolite for
the recovery of copper and cobalt present in aqueous solutions at
concentrations ranging from 10ppm to 50ppm. The maximum
adsorption rate achieved with non-regenerated zeolite was (50%),
adsorption capacity was increased to 90% after regeneration with
nitric and chloridric acid at 0.02 M. The poor performance of the noregenerated clinoptilolite would be due to the high poisoning level of
the zeolite whereas residual poisons have been removed through the
regeneration process. It is then concluded that regenerated zeolite
showed potential to be used as sorbent in the recovery of cobalt and
copper from their aqueous solutions.

KeywordsClinoptilolite, metal adsorption, regeneration, reuse

I. INTRODUCTION

HE potential of zeolite for removal of metals from

solutions has been extensively proven; naturally present in
the soil, it can also be synthesized for commercial and
research purposes. Widely available, zeolite could therefore
constitute a suitable adsorbing agent for bioremediation of
metal polluted effluents. High adsorption rate has been
achieved by several researchers [1], [2], [3] when using both
natural and synthetic zeolites for removal of metal from
solutions. Metal adsorption by zeolite mainly occurs through a
chemical mechanism or ion exchange process, and partly
through a physical mechanism dependent on the microporous
structure of the mineral [4], [5], [6]. Natural zeolite is often
preferred for metal bioremediation processes because of their
low cost and unique physical and chemical properties [5].

II. METHODOLOGY
A. Characterization of clinoptilolite
Preloaded and eluted clinoptilolite samples from previous
study (cobalt and copper adsorption) were grind in a mortar
and the mineralogical composition determined using the X-ray
fluorescence.
B. Determination of the poisoning level
To determine the level of poisoning with residual metals,
powder form of clinoptilolite was dissolved in aqua regia. The
mixture was then filtered and the concentration of copper and
cobalt in the filtrate was measured using atomic absorption
spectrophotometer (AAS).

Elvis Fosso-Kankeu is with the Mineral Processing and Technology

Research Centre of the University of Johannesburg, 37 Nind Street,
Doornfontein-Johannesburg-South Africa (Tel:+2711 559 6529; fax:+2711
559 6329; e-mail:elvisf@uj.ac.za).
Antoine-Floribert Mulaba- is with the Mineral Processing and Technology
Research Centre of the University of Johannesburg, 37 Nind Street,
Doornfontein-Johannesburg-South Africa (e-mail:amulaba@uj.ac.za).
Jim T Modipe and Eunice Maroga were with the Mineral Processing and
Technology Research Centre of the University of Johannesburg, 37 Nind
Street, Doornfontein-Johannesburg-South Africa.

C. Regeneration technique
Regeneration of poisoned clipnoptilolite was done using
either alkaline or acidic solution. Alkaline solution was
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International Conference on Mining, Mineral Processing and Metallurgical Engineering (ICMMME'2013) April 15-16, 2013 Johannesburg (South Africa)

prepared by dissolving potassium chloride in distilled water to

obtain a concentration of 0.02M. The loaded clinoptilolite was
immersed in the solution for one hour, then dried at 50C for
24 h in an oven prior to use for adsorption experiments.
Concentrated solution of chloridric and nitric acids were
dissolved in distilled water to prepare solution solutions of
0.02 M. They were then used to regenerate loaded
clinoptilolite for one or eight hours. Clinoptilolite was then
dried as above before used for adsorption of metals.

reducing the cation exchange capacity of the zeolites.

B. Level of clinoptilolite poisoning
Dissolution of the clinoptilolite in the aqua regia allowed to
determine the level of poisoning. It was observed that a
maximum of 3.2 mg/g and 1.9 mg/g of residual copper and
cobalt respectively were still occupying the binding sites on
the clinoptilolite. The clinoptilolite was then regenerated into
alkaline or acidic solution to free the binding sites.
C. Study of alkaline regeneration
Clinoptilolite regenerated with alkaline solution was a
relative poor sorbent as it was reused for adsorption of cobalt
and copper. As shown in Figure 1 below, the maximum
adsorption capacities were 0.12 mg/g and 0.1 mg/g for cobalt
and copper respectively, and no metal removal was achieved
in diluted solutions (initial concentrations 10 and 20 mg/L).

D.Adsorption of metals
Batch adsorption experiments were conducted at room
temperature using 5 g of clinoptilolite in 50 ml solutions of
10, 20, 30 and 50 mg/L initial concentrations of either cobalt
or copper ions. Solutions of metal ions were loaded into
columns in glass containing 5 g of regenerated clinoptilolite
and the exposure was allowed for a period of one hour, then
the effluent was collected for measurement of residual metal
ions using AAS.
III.

RESULTS AND DISCUSSION

A. Mineralogical composition
The mineralogical composition (Table 1) indicates that
clinoptilolite studied has relatively high silica level. The Si/Al
ratio was 5.91, while the (Na + K)/Ca ratio was 3.62. For
typical theoretical exchange capacity, Si/Al ratio of natural
clinoptilolite can generally range from 4 to 5.5 [10], implying
that the clinoptilolite used in this had the capacity to exchange
ions. Moreover, the clinoptilolite studied contains relatively
high silica level and could be classified as high silica member,
a group reported to be also rich in sodium, potassium and
magnesium [10].

Fig.1 Removal of cobalt and copper by clinoptilolite regenerated in

alkaline solution (KCl, 0.02M)

D. Study of acidic regeneration

Regeneration with nitric acid After regeneration with nitric
acid, clinoptilolite showed good adsorption capacity as it
removed almost all the metal ions from the solution (Figure
2). There was no significant change of the adsorption capacity
over time, however it increased with the initial concentration
of metal, a phenomenon explained by the mass transfer. The
regenerated clinoptilolite showed similar affinity for both
cobalt and copper. The optimum time of adsorption was then
one hour at which the maximum adsorption capacities were
0.47 mg/g and 0.48 mg/g for cobalt and copper respectively.

TABLE I
X-RAY FLUORESCENCE RESULTS

No

Compound

% weight

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16

Na2 O
MgO
Al2 O3
SiO2
P2 O5
SO3
Cl
K2 O
CaO
TiO2
MnO
Fe 2 O3
Co2 O3
NiO
CuO
ZnO

1.0469
0.8082
13.0621
77.1781
0.0104
0.2917
0.2819
4.1793
1.4442
0.1465
0.0202
1.2662
0.0263
0.0046
0.0232
0.0062

X Ray Fluorescence results also revealed that the

clinoptilolite used in this study contained Cu, Zn, Ni, Co, Fe
and Mn in the form of oxides. These ions might be held on the
active available sites for adsorption, during the adsorption of
targeted metals they may act as competitive ions, hence

Fig. 2 Removal of cobalt and copper by clinoptilolite regenerated in

nitric acid (0.02M)

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International Conference on Mining, Mineral Processing and Metallurgical Engineering (ICMMME'2013) April 15-16, 2013 Johannesburg (South Africa)

Regeneration with hydrochloric acid Despite some few

disparities, the general pattern of metal adsorption by
clinoptilolite regenerated with hydrochloric acid (Figure 3)
was similar to the clinoptilolite regenerated with nitric acid.
The maximum adsorption capacities at the optimum time were
0.42 mg/g and 0.43 mg/g for cobalt and copper respectively.

regenerated clinoptilolite, hence the need of regeneration. On

the other hand it can be seen that potassium chloride was not a
good medium for regeneration; Figure 4 shows that the
performance of clinoptilolite was even reduced (comparing
with non-regenerated clinoptilolite) when exposed to
potassium chloride. Using different chemicals (1M NaCl,
KCl, CaCl and HCl) to regenerate clinoptilolite and adsorp
cadmium, Gedik and Imamoglu [9] found that KCl and HCl
had a poor performance. On the contrary, Vasylechko et al.
[12] observed favourable cadmium removal after pretreatment
with HCl.
IV.

CONCLUSION

Zeolite has been an attractive adsorbent over the years

because it is environmentally friendly and cheap. One critical
aspect for the application of adsorption is therefore the
availability and cost of adsorbents. Regeneration of adsorbent
with suitable medium is then imperative. It has been
demonstrated in this study that regeneration of natural
clinoptilolite originating from the Vulture Greek of Kwazulu
Natal Province in South Africa, is effective when using nitric
acid (0.02 M) for one hour. The possible use of this
clinoptilolite for more than one adsorption cycle will make it
an adequate sorbent for treatment of mine effluents.

Fig. 3 Removal of cobalt and copper by clinoptilolite regenerated in

chloridric acid (0.02M)

Mineral acids are suitable eluents because of their relative

small molecular size and their ability to competitively remove
residual metals from the binding sites of clinoptilolite through
an ion exchange process [11]. In this case proton released in
solution by nitric and chloridric acids exchange with bound
metals, and the dissolution effect under low pH promotes
liberation of micropores. Relatively weak binding of proton is
an advantage for effective adsorption of metals in the next
cycle as they will be easily displaced.

REFERENCES
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[10] E. Erdem, N. Karapinar, R. Donat, The removal of heavy metal cations
by natural zeolites, Journal of Colloid and Interface Science, Vol. 280
No. 2, 2004, pp. 309-314.
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E. Relevance of clinoptilolite regeneration

To minimise the cost of the adsorption process it is
important to use over several cycles an adsorbent with an
undiminished capacity and make possible the recovery of
valuable metals that can be commercialized. All this is
possible by regenerating the biosorbent with a suitable
medium. As shown in Figure 4, nitric acid was the better
medium for the regeneration of clinoptilolite.

Fig. 4 Comparison of the effect of regenerants on clinoptilolite

adsorption performance

A comparative observation show that clinoptilolite

regenerated by nitric acid perform twice better than the non152

International Conference on Mining, Mineral Processing and Metallurgical Engineering (ICMMME'2013) April 15-16, 2013 Johannesburg (South Africa)

Born in Cameroon, the author obtained the certificate for completion of high
school in Bafoussam-Cameroon and then completed a BSc in Bioichemistry at
the University of Dschang in Cameroon. He then traveled to South Africa
where he continued his studies and completed a B-Tech and M-Tech in
Biotechnology; after a year in the consulting sector, he went back in academia
to complete a D-Tech in Extraction Metallurgy focusing on Bioprocessing.
He worked for two years in the marketing sector for a company based in
Camerron, after his B-Tech he was concurrently appointed as a part-time
research associate for six years and also worked as a part-time lecturer for five
years. He is currently a Postdoctoral fellow at the University of JohannesburgSouth Africa and lectures on a part-time basis. He has published a couple of
articles in accredited journals including: The health implication of
relationships between bacterial endotoxin, cyanobacteria, coliforms and water
stored in domestic containers of rural households in South Africa. Journal of
Water and Health, Vol 8 (4), 2010, pp 601-610; A comprehensive study of
physical and physiological parameters that affect biosorption of metal
pollutants from aqueous solutions. Journal of Physics and Chemistry of the
Earth, Vol 35, 2010, pp 672-678 and Prediction of metal-adsorption
behaviour in the remediation of water contamination using indigenous
microorganisms. Journal of Environmental Management, 92 (10), pp 27862793. Examples of book chapters published include: Metal derived complexes
for improved fight against bacteria. In: Mishra A.K., Tiwari A. and Mishra
S.B. (Eds). Smart Biomolecules in Medicine. VBRI Press, India. ISBN 97881-920068-01, 2010, pp. 199-226 and High-technology therapy using
biomolecules or synthetic compounds for HIV inhibition. In: Mishra A.K
(Eds). Nanomedecine for Drug Delivery and Therapeutics. Wiley, Scrivener
Publisher. ISBN: 978-1-1184-1409-5. 2013, pp 3-38. His main research focus
has been on the monitoring of water quality and bioremediation of polluted
water.
Dr Elvis Fosso-Kankeu has been a recipient of several merit awards, the
more recent is the best paper award received at the International Mine Water
Conference in Bunbury-Australia, October 2012.

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