Food and Environment Safety - Journal of Faculty of Food Engineering, tefan cel MareUniversity - Suceava
Volume XI, Issue 3 – 2012

52

COPPER IONS CONCENTRATION USING ION EXCHANGE RESINS

*Petru BULAI1, Camelia POPA2

1 Faculty of Mechanical Engineering, Mechatronics and Management, tefan cel Mare University of Suceava,
Romania, bulaipetru@yahoo.com

2 Faculty of Food Engineering, tefan cel Mare University of Suceava, Romania,
camelia.popa@ fia.usv.ro
*Corresponding author

Received 2 September 2012, accepted 17 September 2012

Abstract: The paper present the recovery process of copper ions adsorbed onto Purolite S930
chelating resin. The recovery process was investigated using hydrochloric acid, sulfuric acid and
disodium salt of ethylenediaminetetraacetic acid solutions. Experiments were carrying out using
different resin dose in the range 1 - 25 g dried exhausted resin/L and varying the concentration of
regeneration solution in the range 0.1 - 2 eq./L for hydrochloric and sulfuric acid, and in the range
0.1 - 0.2 eq/L for disodium salt of ethylenediaminetetraacetic acid.

Keywords: recovery, concentration, ion exchange resins

1. Introduction

The heavy metals are non-biodegradable in
the nature, present bioaccumulation
tendency in environment and toxicity to
most  of  life  forms  [1,2].  When  they  are
found in water in soluble form, heavy
metal ions present a high mobility
increasing the risk of contamination of
large adjacent areas. Therefore the
presence of heavy metals in the
environment is still a major concern for
nature health. The most important source
of heavy metals for environmental is the
industrial wastewater [3]. To remove the
heavy metals from wastewater can be used
different treatment techniques such as
chemical precipitation, coagulation–
flocculation, flotation, membrane filtration
processes (ultrafiltration, nanofiltration
and reverse osmosis), electrochemical
treatment techniques (electro-dialysis,
membrane electrolysis, electroextraction
and electrochemical precipitation) and
sorption  treatment  techniques   (ion
exchange, adsorption and biosorption) [1,
3-7]. All these methods have been studied

extensively and can be successfully
applied in industry. Despite of these
possibilities, the industry still uses mainly
precipitation. By using precipitation
process  does  not  completely  eliminate  the
problem of heavy metals from wastewater.
The sludges that result in heavy metals
precipitation process need to be treated and
stored under special conditions. Recovery
of the precipitated metal ions is laborious
and expensive. Instead ion exchange
methods are ecological as purification
methods and may be used both for organic
and inorganic compounds [6].
Retention of metal ions from wastewater
by ion exchange resin process has a
number of advantages over other methods.
One of these advantage is the easiness in
recovery process. Recovery of metal ion
retained on resin can be concentrated and
recovered in the form of various salts
according to the substance used for
regeneration  of  resin:  acids  (HCl,  H2SO4,
HNO3), bases (NaOH) or salts (NaCl,
disodium salt of EDTA). Another

mailto:bulaipetru:@yahoo.com


Food and Environment Safety - Journal of Faculty of Food Engineering, tefan cel Mare University - Suceava
Volume XI, Issue 3 – 2012

53

advantage is the purity of the solution
obtained  from regeneration. This solution
may contains metal salt and acids, bases or
salts, depending on regeneration solution
used. These solutions can be reused  in
process, or used to obtain solid metal by
electrochemical methods or other products.

2. Materials and methods

The chelating resin used in the experiments
was S930 obtained from Purolite
International Limited (Hounslow, UK).
Table 1 presents the main physical and
chemical properties of the resin.

Table 1.
Proprieties of the chelating resin *

Polymer matrix
structure

Macroporous styrene
divinylbenzene

Functional groups Iminodiacetic acid
Ionic Form (as
shipped)

Na+

pH range (operating):
H+ form, Na+ form

2 - 6; 6 - 11

Maximum operating
temperature

70ºC

Particle size range + 1.0mm <10%, -0.3mm
<1%

Total exchange
capacity

 1.9 meq/mL

* Manufacturer supplied.

The  conversion  of  the  sodium  form  of  the
resin into hydrogen form was done with
10% HCl solution, followed by washing
with  distilled  water  until  the  pH  of  the
effluent  dropped  to  neutrality.  Then,  the
resin has been dried at 60 ºC using an
oven.
Exhausted resin was obtained using 50.0
ml of Cu2+ with initial concentration C0 =
300 mg Cu2+/l that were added to
Erlenmeyer flask already containing 0.05 g
of dry resin in H form. The initial pHi = 5
of  the  solution  was  adjusted  by  using
diluted  solutions  of  H2SO4. The flasks
where mechanically shacked at several
fixed temperatures and at the rate of 120
cycles min 1 using Orbital Shaking

Incubator GFL 3031.  After equilibrium
(24 hours), the resin and solution were
separated by filtration and the copper
content of the solution was measured. The
resin  was  washed  with  distilled  water  and
then dried using an oven. Further the resin
was used in the regeneration and
desorption experience
Concentration  of  Cu  (II)  in  solution  was
determined by spectrophotometric method
with rubeanic acid ( =395 nm, linear range
1-4 mg Cu /L) using a Hach DR/2000
spectrophotometer.
Concentration ratio was calculated using
Equation 1.

o
r

d

C
C

C
(1)

where,
rC  - is concentration ratio,

0C - is copper concentration in solution
used in the resin exhausted process (eq./L)
and

dC  - is copper concentration in
regeneration solution after resin
regeneration process.
Recovery  percent  meaning  the  percent  of
copper recovery in the regeneration
solution from the copper retained onto ion
exchange resin was calculated using
Equation 2.

*
*100

*p d

a q
R

C V
(2)

where,
pR  - is recovery percent in %,

a  - the resin dose, g/L,
q -  amount  of  Cu  (II)  retained  on  resin,
mg/g,

dC  - is copper concentration in
regeneration solution after resin
regeneration process, and
V  - the volume of regeneration solution.



Food and Environment Safety - Journal of Faculty of Food Engineering, tefan cel Mare University - Suceava
Volume XI, Issue 3 – 2012

54

3. Results and discussion
3.1.	Desorption	using	hydrochloric	acid		

To study the resin regeneration process  a
range of resin dose from 1 to 25 g dried
exhausted resin/L. In the regeneration
experiments the concentration
hydrochloric acid solutions were varying
in the range 0.1 - 2 eq./L. Figure 1 present
Copper concentration ratio using
hydrochloric acid solution for
regeneration. Using a concentration
regeneration  solution  of  1eq  HCl/L
Concentration ratio increase from 0.54 for
o resin dose of 1 g dried exhausted resin/L
to 12.21 for a resin dose of 25 dried
exhausted resin/L. Using a concentration
of 2eq. HCl/L the concentration ratio
increase from 0.54 for o resin dose of 1 g
dried exhausted resin/L to 13.40 for a resin
dose of 25 dried exhausted resin/L.

Figure 1. Copper concentration ratio varying
dried exhausted resin dose

Figure 2. Copper recovery percent using a
regeneration solution of 2eq HCl/L and varying

dried exhausted resin dose

Figure 2 illustrate the influence of  dried
exhausted resin dose onto copper recovery
percent using a regeneration solution of
2eq  HCl/L.  Using  the  same  volume  of
regeneration  solution  and  the  same
concentration of hydrochloric acid the
percent of recovered copper decrease
100% for a dry exhausted resin above 5
g/L.

3.2.	Desorption	using	sulfuric	acid		
In the regeneration experiments using
sulfuric acid  the concentration of
regeneration solution was varying in the
range 0.1 to 2 eq H2SO4/L and the dry
exhausted resin was varying in the range  1
to 25 g/L. Figure 3 present the influence of
dry exhausted resin dose onto  copper
concentration ratio using sulfuric acid
solution for regeneration.

Figure 3. Copper concentration ratio using a
regeneration solution of H2SO4 and varying

dried exhausted resin dose

Using a concentration of 2eq. HCl/L the
concentration ratio increase from 0.53 for
o resin dose of 1 g dried exhausted resin/L
to 12.67 for a resin dose of 25 dried
exhausted resin/L. The concentration ratios
obtained using hydrochloric acid solution
for regeneration were higher up to 6
percents  by values obtained using sulfuric
acid solution with the same concentration
for regeneration. Figure 2 illustrate the
influence  of   dried  exhausted  resin  dose



Food and Environment Safety - Journal of Faculty of Food Engineering, tefan cel Mare University - Suceava
Volume XI, Issue 3 – 2012

55

onto copper recovery percent using a
regeneration solution of 2eq H2SO4/L.

Figure 4. Copper recovery percent using a
regeneration solution of 2eq H2SO4/L and

varying  dried exhausted resin dose

Using the same volume of  regeneration
solution  and the same concentration of
sulfuric acid, 2eq./L, the percent of
recovered copper decrease for a dry
exhausted resin above 3 g/L.

3.2.	Desorption	using	disodium	EDTA		
In the regeneration experiments using
disodium EDTA, the concentration of
regeneration solution was varying in the
range 0.1 to 0.2 meq.disodium EDTA/L
and the dry exhausted resin was varying in
the range  12.5 to 37.5 g/L (Figure 5).

Figure 5. Copper concentration ratio using a
regeneration solution of disodium EDTA and

varying  dried exhausted resin dose

Using a concentration of 0.2 meq.
disodium EDTA/L the concentration ratio
increase from 2.15 for o resin dose of 12.5

g dried exhausted resin/L to 9.11 for a
resin dose of 25 dried exhausted resin/L.

4. Conclusion

The highest rate of regeneration, 13,40,
was obtained using hydrochloric acid
solution  of 2eq/L and a high dose of  dried
exhausted resin. Good rates of regeneration
was also obtained using sulfuric acid
solution  of 2eq/L or 0.2meq disodium salt
of ethylenediaminetetraacetic acid/L and a
high dose of  dried exhausted resin.

5. References

[1]. KURNIAWAN T. A., CHANA G.Y.S., LOA W.,
BABEL S., Physico–chemical treatment
techniques for wastewater laden with heavy
metals, Chemical Engineering Journal, 118, 83–
98, (2006).

[2]. BULAI P., BALAN C., BILBA D.,
MACOVEANU M., Study of the Copper (II)
removal from aqueous solutions by chelating
resin Purolite S930, Environmental Engineering
and Management Journal, 8, 213-218, (2009).

[3]. POLAT H., ERDOGAN D., Heavy metal
removal from waste waters by ion flotation,
Journal of Hazardous Material., 148, 267–273,
(2007).

[4]. SMARA A., DELIMI R., POINSIGNON C.,
SANDEAUX J., Electroextraction of heavy
metals from diluted solutions by a process
combining ion-exchange resins and membranes,
Separation and Purification Technology, 44,
271–277, (2005).

[5]. Bernat  X.,  Fortuny  A.,  Stüber  F.,  Bengoa  C.,
Fabregat A., Font J.,  Recovery of iron (III) from
aqueous streams by ultrafiltration, Desalination,
221, 413–418, (2008).

[6]. POPA C., BULAI P., MACOVEANU M., The
study of iron(II) removal from 34% calcium
chloride solutions by chelating resin Purolite
S930, Environmental Engineering and
Management Journal, 9, 651-658, (2010).

[7]. JUANG R.S., SHIAU R.C., Metal removal from
aqueous solutions using chitosan-enhanced
membrane filtration, Journal of Membrane
Science, 165, 159–167, (2000).