Environmental Poilu tion 48 (1987) 213-222

Sorption Studies of Heavy Metal Ions on a Novel

Chelating Resin and its Application in the Stripping of
Mercury (II)

L u c y J o s e p h & V. N. S i v a s a n k a r a Pillai

Department of Applied Chemistry,

Cochin University of Science and Technology,Cochin 682022, India

(Received 29 January 1987; accepted 15 June, 1987)

ABSTRACT

A chelating resin containing a stable thiol group was synthesised, using

polystyrene as the starting material. The resin is stable towards conc. HCI,
O'IM H N O 3 and O'lM NaOH. The resin shows affinity towards Ag +, Hg 2+ ,
Bi 3 +, Pb 2 +, Cu 2 +, Z n 2 + and C d 2 +. Extraction o f these metal ions as a
function o f pH, kinetics of exchange and breakthrough capacities is
evaluated. The selectivity o f the resin for the metal ions is in the order
Ag + > Hg 2+ > Cu 2+ > Pb z+ > Cd 2+ > Zn z +. The equifibrium constants
for exchange and kinetics o f exchange are favourable .for the recovery of
mercury from lean sources. Application of the resin in the stripping of mercury
f r o m chlor-alkali plant affluent, and in the enrichment o f mercury from sea-
water, have been investigated. Mercury sorbed resin can be regenerated using
5% thiourea in O'IM HCl.

INTRODUCTION

A large number of chelating resins have been synthesised and investigated

by different workers for the separation, removal, and recovery of metal ions,
either for pollution control or for raw material recovery. Since polystyrene is
readily available and is sufficiently durable, it has been extensively used as a
matrix in the synthesis of chelating resins. The efficiency of a chelating resin
is attributed to factors like fast sorption kinetics, stability of the matrix,
resistance to hydrolysis, high selectivity and reversible complexation. The
213
Environ. Pollut. 0269-7491/87/$03'50 © Elsevier Applied SciencePublishers Ltd, England,
1987. Printed in Great Britain
214 Luo' Joseph, V. N. Sivasankara Pillai

sulphur-containing ligands are found to be more selective towards heavy

metal ions than their nitrogen and oxygen analogues (Beamish, 1967;
Moyers & Fritz, 1976) and thus have attracted attention because of their
increased application in effluent treatment and analytical chemistry.
Although a number of investigations have been done on these materials
(Parrish, 1956; Egawa et al., 1979; Slovak et al., 1979, Slovak & Docekel,
1980), only very few have found industrial acceptance. Chelating ion
exchangers bearing thiol, dithiocarbamate and benzyl thiouronium salts
have been used for the separation and enrichment of Ag(I), Hg(II), Cd(II),
Pb(II), Cu(II), etc. (Koster & Schmuckler, 1967; Moyers & Fritz, 1976;
Muzarelli & Tanfani, 1982; Nakayama et al., 1982; Sugii et al., 1984). Of
these resins studied, benzyl thiouronium salt has proved to be the most
useful (Koster & Schmuckler, 1967).
The increasing concern about pollution of the aquatic environment by
mercury has led to the development of new processes for the removal of
mercury at the ngml 1 level. One of the major consumers of mercury is the
chlor-alkali industry, where most of the mercury used ends up in the effluent.
The current practice followed in industry is to fix the mercury as HgS, which,
in turn, settles as a solid waste, leading to secondary pollution. An ion-
exchange process, if used, has two advantages--low secondary pollution
and a possibility of recycling of the mercury (Forstner & Wittmann, 1981).
However, the resin must be capable of competing with C1- ions present in
high concentration in the brine effluent. The process developed by Akzo-
Zoat Chemie of the Netherlands based on a thiol-containing exchanger is
among the most successful and commercially exploited (Dejong & Rekers,
1974). The ion-exchanger developed by them removed mercury down to
about 2 ng ml
This work deals with the sorption characteristics of various metal ions on
a novel chelating resin (ST-3), prepared in our laboratory. Application of the
resin in the removal of mercury from chlor-alkali plant effluent, as well as
enrichment from sea-water, is also presented here.

EXPERIMENTAL

Materials and methods

The resin was prepared by a novel easy route which gave very high yield
(Lucy & Sivasankara Pillai, 1986). Granular particles of 2 0 0 4 0 0 mesh size
were used in the batch technique, while particles of 100-200 mesh size were
used in the column technique. A glass column, 10cm long, 0-5cm id, was
 Chelating resin for mercury (II) sorption 215

employed for breakthrough and elution studies. Stock solutions of metal

ions were prepared from analytical grade reagents, pH was adjusted using
NaOH/acetate buffer/HC1. Metal ion concentrations were determined by
UV-VIS spectrophotometry or by atomic absorption spectrophotometry,
and for mercury analysis cold vapour atomic absorption spectrophotometry
was employed.

Samples

Synthetic sea-water was prepared by the procedure given elsewhere (Muroi

e t al., 1985), while sea-water was collected from Cochin off-shore at ca. 1 m
depth. Effluent samples containing mercury were collected from the plants
of Travancore Cochin Chemicals Ltd., Udyogamandal, Cochin.

Characterisation of the resin

The resin was characterised by ir spectroscopy and by elemental analysis.

Sulphur content determined by the oxygen flask method is 8"3%, which
corresponds to 2-75mmol - l g - 1 of resin. Stability of the resin to
concentrated HC1, 0"IM HNO3 and 0.1M NaOH was checked by soaking in
the media for 24 h. The soaked resin was filtered through a sintered glass
crucible, washed with distilled water, dried i n - v a c u o on a boiling water-bath
for 1 h, as done in the preparation of the resin, and reweighed. The resin
samples showed no significant loss in weight.
Metal uptake capacities of the resin, as a function of pH and kinetics of
sorption, were studied by the batch technique. A 0"log sample of the resin
was added to 20ml of buffered metal ion solutions of concentration
400/~g ml 1. After shaking for 8 h, an aliquot of the solution was withdrawn
using a filter-stick with sintered glass disc and the residual concentration of
metal ion was determined.
In the column technique, a glass column (10cm × 0"5cm) was slurry
packed with the resin to a height of 10 cm (0"9 g resin). Breakthrough studies
using Hg(II), Cu(II), Pb(II) and Cd(II) were done by passing 100/~gml- 1
solutions at a flow rate of 0-5 ml min-1. Fractions were collected and the
concentration in each fraction was determined. Recovery studies were
carried out for Hg(II) from synthetic sea-water spiked with 100/~gml-1 of
mercury, as well as from real sea-water.
Selectivity of the resin for Hg(II) was studied using a solution containing
10/tgml-1 each of mercury(ll), copper(II), lead(II) and cadmium(II)ions.
The mixture was run through the resin bed and the effect of added ions on
the sorption of mercury was noted from the breakthrough curve.
216 Lucy Joseph, V. N. Sivasankara Pillai

Pre-treatment of chlor-alkali plant efliuent

The cell house effluent from a chlor-alkali plant is alkaline (pH 11) and rich
in chloride ions. Mercury is present as fine droplets, which are difficult to
precipitate. Chlorine was added to the effluent until saturated, and left
overnight. It was then acidified with HC1 and excess chlorine removed by
aeration (3 h), or by filtering through a specially developed activated carbon.
The granular activated carbon was sieved and particles of 40-100 mesh
size were packed in a column of dimensions 20 × 2.7cm. The effluent
containing chlorine was allowed to percolate through the carbon bed held
on a filter disc and was then fed into the resin column.

RESULTS A N D DISCUSSION

The resin shows excellent stability towards concentrated HC1, 0"IM H N O 3

and 0"IM NaOH and it is resistant to air-oxidation.

Metal uptake as a function of pH

Metal-thiol complexation releases protons according to the reaction:

nRSH + M"+ ~.-~-(RS),M + n H +
and thus is pH dependent. The uptake of various metal ions (Ag +, Hg 2+,
Cu 2+, Pb 2+, Cd 2+, Z n 2+) w a s investigated over the pH range 0-7. It was
found that metal ion sorption increases with pH and is highest above pH 5

100

BO
Z
o
7- 60

~0

20

I
0 I 2 3 4 5 6 7 8
pH
Fig. 1. Effect o f p H on the uptake of metal ions by ST-3 resin: initial concentration of metal
ions, 400 mg litre- 1; shaking time, 8 h; ST-3 resin, 200~300 mesh size; (A) Hg 2 + ; (©) Cu 2 ÷ ;
([]) Pb2+; (A) Zn2+; ( 0 ) Ag+; (m) Cd 2+
 Chelating resin for mercury (II) sorption 217

1600'
1400

1000

600

o 200 7
k,-

6C

40

20:

0
0 1 2 3 4 5 6 7
p8
Fig. 2. Effect of pH on K D (K o = (Cs/Cm)x (V/M)): Initial metal concentrations,
400mglitre -~ shaking time, 8h; ST-3 resin, 200-300 mesh size; (A) HgZ+; (1-1) PbZ+;
(C)) Cu2+; (m) Cd 2+.

except for Ag + and Hg 2+ (Fig. 1). Sorption of Ag + and Hg 2+ is almost

complete in the pH range 1-6. The high K D value observed for Hg 2 + (Fig. 2)
indicates that the structural features are favourable for chelate formation
with mercury(II). The apparent loss in capacity, observed in the case of
certain metal ions, may be due to the formation of a hydroxide complex.
There is a wide difference between the half sorption pH of different cations,
justifying the usefulness of the resin in the selective separation and recovery
of metal ions.

Kinetics of sorption of metal ions

The kinetic curves for the uptake of Hg 2+, Cu 2+, Bi 2+, and Pb 2+ (Fig. 3)
show that the half-times of sorption (t½) are less than 15 min at the optimum
pH, which ensures its use in a dynamic process of metal ion extraction.

Removal of mercury from sea-water

To find out whether the resin is suitable for the collection of mercury from
estuarine and sea-water, the influence of foreign ions was also examined.
Breakthrough studies carried out using 100 #g m l - 1 solution of mercury(II)
218 Lucy Joseph, V. N. Sivasankara Pillai

1°°t

t
"iI
"" 2

I I I I I 1
0 10 20 30 40 50 60
TIME (MINUI"ES)

Fig. 3. Kinetics of sorption of metal ions on ST-3 resin: Initial concentration of metal
ions, 400mg litre 1; volume, 20ml; weight of resin, 0.1g; pH, Hg2+ -2, Cu 2+ -4,
Bi3+ --0"IM HCI, P B 2+ -4; (O) Hg2+; (A) Cu2+; (O) Bi3+; (A) Pb 2+.
and sea-water spiked with 100/tg m l - ~ of mercury(II) gave superimposable
curves (Fig. 4), illustrating its effectiveness in the removal of mercury(II)
from sea-water. The uptake of mercury(II) from a chloride rich medium
indicates the following equilibria to be operative (Dejong & Rekers, 1974):
HgC12 ~,-~--HgC13+ CI-~,-~-HgC1 z + 2C1-
,-~-Hg+C1 + 3C1- ~,-~--Hg2+ + 4 C 1 -
2RSH + Hg 2 ÷ ,~- RSHgSR + 2H +
RSH + Hg+CI~,-~-RSHgCI + H ÷
In all these cases, the equilibrium is in favour of H g - - S bond formation.
Thus the resin can compete successfully with stable H g C I ] - complex, even
in saturated brine.
Selectivity of the resin for mercury(I1) was studied using a solution
containing 10/~gml 1 each of Hg(II), Cu(II), Pb(II) and Cd(II) ions. The
breakthrough curve (Fig. 5) obtained using this solution indicates that the
addition of Cu 2+, Pb 2+ and Cd z+ has little effect on the sorption
mercury(II). The concentration of the three metals in the effluent equals that
in the feed long before mercury finally breaks-through. This may be due to
the following competitive reaction:

2 R S - - H + M 2 +. ' R S - - M SR~--- RS--Hg S R + M 2+

These findings indicate that the ST-3 resin can be applied effectively for
the collection of mercury(II) from estuarine and sea-water containing Cu 2 +,
Pb 1+ and C d 2 + ions.
 Chelating resin for mercury (II) sorption 219

E
::T,5o

~. . J 40
LI.
i,i

,., 30
_z
d 20
Z
8

n.,
w
¢~ . ~ j i
30 60 90 120 150 180
VOLUME OF EFFLUENT (BED VOLUMES)

Fig. 4. Break-through curve of Hg2+: Column, 0.5cm id and 10cm length; ST-3 resin,
100-200 mesh size; flow rate, 18 bed volumesh-1 bed volume, 1.6cc; (A) 100mglitre
standard solution at pH 5-5; (O) sea-water spiked with 100mg litre-~ Hg 2+ at pH 5-5.

15L Cu
Pb

N
~10

Hg
Z

'/ I
0 50 1O0 150 200 250 300
VOLUME OF EFFLUENT (BED VOLUMES)

Fig. 5. Replacement of Cd 2+, Pb 2+ and Cu 2 + ions by Hg 2+ ions: Concentration of feed,

10mglitre each of Cd 2+, Pb 2+, Cu 2+ and Hg 2+.
220 Lucy Joseph, V. N. Sivasankara Pillai

TABLE 1
Concentration of Mercury in the Chlor-alkali Plant Effluent after Different
Treatments

Nature of sample Concentration of mercury(H)

(#g ml- 1)

1. Oxidised effluent* 2"75

2. Dechlorinated effluent I** 2"75
3. Dechlorinated effluent II*** 0"02
4. Effluent from ST-3 resin column 0"005

* Chlor-alkali plant effluent oxidised using chlorine.

** Excess chlorine removed by aeration in acid medium.
*** Excess chlorine removed by passing through charcoal filter.

Removal of mercury(II) from chlor-alkali plant effluent

Mercury was oxidised using chlorine at pH 11 and excess chlorine was

removed after adjusting the pH to 3. In a continuously operated stream,
aeration can effect the removal of C12 (Dejong & Rekers, 1974). The use of
activated carbon necessitates periodic regeneration of carbon. However,
carbon has an added advantage in that it removes a good proportion of
mercury also, as is seen from Table 1. The resin removed mercury from the

E
o'~
::3.

_J 90
b-
b.
LU
,,,
"1"
70

/
Z
d 50
Z
3
~30
2:)

~A
:E10
1 I I I I I I I I I
10 30 50 70 90 110
VOLUMEOF EFF'LUENT (BED VOLUMES)
Fig. 6. Break-through curve of chlor-alkali plant effluent: pH 3: mercury concentration in
feed, 2.75 mg litre 1; flow rate, 15 bed volumes h-~; one bed volume--1'6 cc.
 Chelating resinfor mercury (H) sorption 221

treated effluent to a residual level of 5 ng m l - 1. The breakthrough curve of

mercury(II) in the chlor-alkali effluent is shown in Fig. 6. The concentration
o f mercury(II) in the column effluent was below 5 n g m 1 - 1 up to the
breakthrough point. At a flow rate of 0-4mlmin -1, the sorption of
mercury(II) was efficient (60 bed volumes of effluent was collected before
breakthrough point). The resin can be regenerated using 5% thiourea in 0" 1M
HC1.
The results presented here indicate the viability of ST-3 resin for the
treatment ofchlor-alkali effluent which necessitates the removal of mercury
to less than 5 ng m i -
ST-3 resin has similar sorption characteristics to the Imac T M R resin of
Dejong & Rekers (1974). It has, however, an advantage in being prepared by
a simple three-step procedure, and a higher stability due to the thiol group
being protected from oxidation (by mild oxidants) by an additional
functional group.

ACKNOWLEDGEMENT

LJ is thankful to CSIR, Government of India, for financial assistance. The

authors thank TCC Ltd, Udyogamandal, for getting some analyses done.

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