Indian Journal of Chemical Technology

Vol. 12, July 2005, pp. 436-440

Removal and recovery of lead from aqueous solution using

supported liquid membrane
R Anupama & K Palanivelu*
Centre for Environmental Studies, Anna University, Chennai 600 025, India

Received 18 June 2004; revised received 10 March 2005; accepted 6 April 2005

A laboratory study was conducted to remove and recover lead from aqueous solution using supported liquid membrane
(SLM) process. Preliminary solvent extraction studies, on lead revealed the iodo system with tributyl phosphate (TBP) as
liquid membrane and sodium hydroxide as strippant to be an efficient one. Using synthetic lead(II) solution, the process
parameters like feed side pH, strippant concentration, KI concentration and stirring speed were optimized. The initial lead
concentration of 25 mg/L gave satisfactory result with complete removal and recovery in 4 h of operation with a
permeability coefficient of 1.146 × 10-5 m/s.

Keywords: Liquid membrane, recovery, lead, iodo system, tri butyl phosphate
IPC Code: B01D61/38

Rapid industrial growth has introduced a number of
pollutants in the environment. Among various
pollutants, heavy metals are of greater concern due to
their toxicity and non-biodegradability. Hence limits
have been prescribed on their concentration in potable
water and in effluent discharge. In order to meet the
prescribed standards, proper form of treatment is
necessary before disposal. The environment can be
kept clean not only by resorting to efficient removal
techniques, but also by recovering the heavy metals
and reusing them effectively1.
Lead is a well-known cumulative poison, found in
the environment mostly because of mining and
smelting, battery manufacturing and its use as
additive in fuel. Concern about the toxicity of lead has
brought about many substitutions in some appli-
cations such as plumbing, painting, etc 2.
Separation processes based on membrane
technology represent a sophisticated route for the
purpose of treating reasonable volumes of water as
they strongly limit the number of elementary steps
involved in the usual separation and recuperation
processes. Liquid membrane (LM) technology is a
subset of membrane science. Among LM’s,
Supported Liquid Membrane (SLM) is studied
________________
*For correspondence (E-mail: kpvelu@hotmail.com;
Fax: +91-44 -22354717)
extensively for its varied advantages like low
inventory of organic phase used, low energy
consumption, low capital and operating costs, good
selectivity and mass transfer in one step3.
Solvent extraction studies provide first hand
information for SLM studies. Extensive details on
solvent extraction with different carriers and solvents
are available in literature. Argekar and Shetty4 have
reported successful extraction of lead in the pH range
of 2.1-8.3 using cyanex-302 in toluene. The other
studies with extractants like n-octylaniline in toluene5,
zinc hexamethylene dithiocarbamate in dimethyl 4-
heptanone6 and tri iso octylamine in methyl
isobutylketone (MIBK)7 have been reported and all
these indicate that pH plays a major role in bringing
about the separation. Thus by tailoring the pH values
the desirable separation can be achieved.
Wei et al.8 have reported the extraction of lead
using room temperature ionic liquids as solvent which
replace chlorinated hydrocarbons like chloroform,
with dithizone as carrier. Another study by Yadav and
Khopkar9 reports application of TBP as carrier in
MIBK for the removal of lead. The authors have
identified that TBP alone cannot quantitatively extract
lead in the absence of a salting out agent.
Gyves & Miguel10 have studied the extraction of
lead and cadmium in two different systems namely
SLM and polymer inclusion membrane (PIM) using
 ANUPAMA & PALANIVELU: REMOVAL OF LEAD USING SUPPORTED LIQUID MEMBRANE
Kelex 100 as carrier and they have proposed a
chemical model for the transport. They have
identified that PIM systems show high fluxes and the
stability allows the membrane to be used repeatedly
for at least 20 cycles without any appreciable loss of
permeability. Canet and Seta11 have studied the
transport of lead using lasolocid as carrier in
n-nitrophenyloctyl ether with polypropylene as
support. Selective separation of lead was observed by
tailoring the pH value. Lamb and Nazarenko12 have
reported that PIMs are easy to prepare in laboratory
and high permeabilities are observed with them. In
this system lead was extracted as iodo, thiocyanate
complexes with high efficiency.
In the present study transport of lead across a SLM
comprising of TBP and KI as reagents was inves-
tigated. The effects of various operational parameters
were optimized systematically. The permeability
coefficient and diffusion coefficient were estimated.
Experimental Procedure
Materials and methods
Hexane, MIBK, toluene, methylene dichloride and
tri butyl phosphate were used as solvents. Lead nitrate
was used to prepare standard lead solution. Sodium
hydroxide, sodium carbonate and ammonia buffer
(pH 10) were used as strippants. All chemicals were
of analytical grade procured from SRL, India and
were used as such without any further purification.
10% hydrochloric acid and 1 M sodium hydroxide
were used for adjusting pH to desired value. All
reagents were prepared using distilled water.
The instruments used for the study were pH meter
(Li 120, Elico make), magnetic stirrer (1 mL, Remi
make), spectrophotometer (20 Genesys, Spectronic
Instruments limited) and flame atomic absorption
spectrophotometer (aa/ae spectrophotometer 495,
Instrumentation lab).
For the selection of suitable carrier/solvent and
strippant for SLM studies, the following solvent
extraction procedure was adopted,
Twenty five mL of lead(II) solution and KI
solution were added and lead was extracted as iodo
complex with 10 mL of organic phase (solvent) by
shaking in a separatory funnel for 10 min. Then the
system was allowed to stand till the layers separated.
The aqueous phase was then analyzed for remaining
lead to evaluate the extraction efficiency. In order to
recover lead from organic layer back to aqueous
phase, 10 mL of strippant was added to the organic
437
phase, again shaken well for 10 min and allowed to
separate. The amount of lead present was estimated in
the aqueous phase to evaluate percentage recovery.
The lead present in the feed and receiving phase were
analysed using PAR13 method or atomic absorption
spectrophotometer (AAS).
The SLM laboratory experiments were conducted
with 140 mL each of feed and strip solution. All
experiments were conducted with 25 mg/L of initial
lead concentration except for those, which were
conducted to observe the effect of initial concen-
tration. The membrane soaked in selected diluent/
extractant overnight was used after draining the
excess adhering liquid. The feed and strip solutions
were thoroughly mixed with the help of magnetic
stirrer. The samples from each side were periodically
taken and analyzed for lead content by either PAR13
method or AAS. The experimental set-up consisted of
two cylindrical cells one for feed solution and another
for strippant. Poly tetrafluoroethylene (Teflon)
membrane of 10-micron thickness was used as
support and the membrane was placed in between the
cells. The effective membrane area was 1.59×10-3 m2.
The schematic diagram of the reactor is shown in
Fig. 1.
Results and Discussion
Solvent extraction studies
Solvent extraction studies provide the preliminary
data for the liquid membrane systems. All
experiments were carried out with lead(II) solution
containing 25 mg/L of lead. It is well known that lead
reacts with KI in acidic medium to form golden
yellow spangles. The selection of suitable extracting
solvent was then made by conducting a series of
experiments with various solvents. The extraction
efficiencies obtained with various solvents are as
follows: MIBK=95, toluene=16, hexane=14,
methylene dichloride=76 and TBP=100%. From the
Fig. 1⎯Schematic diagram of SLM reactor.
438 INDIAN J. CHEM. TECHNOL., JULY 2005

values it is evident, that, TBP in presence of KI acts

as a very good solvent.
Since the extraction takes place at acidic medium
the stripping of lead can be brought back in alkaline
medium. Hence, the selection of suitable strippant
was attempted with alkalies like 1 M NaOH, 1 M
Na2CO3 and ammonia buffer of pH 10. The percen-
tage recoveries obtained for each system are as
follows: NaOH=85, Na2CO3=23 and ammonia
buffer= 30%. Hence, it is quite obvious that sodium
hydroxide acts as a good strippant.
Thus, the suitable extractant and strippant for
lead(II) system were identified as TBP and sodium
hydroxide, respectively. This system was then applied
to SLM to evaluate the transport. Fig. 2⎯Effect of feed side pH on removal efficiencies
(Conditions: KI concentration=0.045 M, stirring speed=600 rpm,
Effect of operational parameters in SLM strippant concentration=1 M NaOH, initial lead concentration=25
mg/L).
Effect of feed side pH
The solvent extraction studies revealed that the
system is efficient in acidic medium. Hence the effect
of pH, on removal efficiency was studied in the pH
range 1-4. The results are depicted in Fig. 2. The
results revealed that the system is effective at pH
value of 2.0. Hence, feed side pH of 2.0 was
maintained for further studies.

Effect of KI concentration
In the system under study, lead(II) is extracted as
iodo complex with the addition of KI. Hence, it
becomes necessary to optimize the concentration of
KI. The effect of KI was studied in the range of
0.013-0.045 M. The experimental results showed that
the removal and recovery efficiency were 99% for KI
concentration of 0.045 M; this is in accordance with
that reported by Dagnall et al.13. Hence KI
concentration of 0.045 M was selected for further
studies.
Effect of strippant concentration
The effect of strippant (NaOH) concentration was
studied in the range 0.1-1.0 M. The results obtained
are shown in Fig. 3. From the figure it is clear that
maximum recovery is obtained with 1 M NaOH
concentration. Hence, the strippant concentration is
recommended as 1 M for stripping of lead.
Effect of stirring speed
In order to study the need for stirring, an
experiment was conducted in static mode i.e. without
stirring. The reactor was filled with feed and strip
solution and left overnight and the samples were
Fig. 3⎯Effect of strippant concentration. (Condition: Initial lead
concentration =25 mg/L, KI concentration =0.045 M, stirring
speed=600 rpm, feed side pH=2).
analyzed for lead concentration. After 20 h the
removal and recovery efficiencies were 58.7 and
45.7%, respectively. Hence it is clear that stirring is
necessary to achieve good results in a shorter time.
There is always a increase in the shear force across
the membrane as the stirring speed increases. The
stirring speed was varied in the range 200-600 rpm.
From the results obtained it is inferred that speed of
600 rpm is desirable one as it gives maximum
removal and recovery efficiencies of 99% each after 4
h of operation.
Effect of initial lead concentration
The effect was studied in the range of 10-50 mg/L.
The effect on initial concentration revealed that
 ANUPAMA & PALANIVELU: REMOVAL OF LEAD USING SUPPORTED LIQUID MEMBRANE 439

maximum extraction efficiency of 100 % was attained

for an initial concentration of 25 mg/L after 4 h of
operation. As the concentration increases more time is
required to attain good efficiencies. The concentration
profile for initial concentration of 25 mg/L is shown
in Fig. 4.
Transport studies
In the extraction process using solid supported
liquid membranes the solute diffuses through the
aqueous feed boundary layer and reacts, at the liquid
interface, with the extractant which is placed in the
pores of the support. Then the complex species
diffuses through the membrane to the stripping phase
because its concentration gradient is favourable.
Fig. 4⎯Concentration profiles at initial concentrations of 25
Therefore to study the transport of Pb(II), it is mg/L (Conditions: Strippant concentration=1 M NaOH, KI
necessary to consider diffusion of solute through the concentration=0.045 M, Stirring speed=600 rpm, feed side
aqueous feed boundary layer, reversible chemical pH=2.0).
reaction at the interface, diffusion of metal complex
species and chemical reaction at the strip interface14.
Reaction at feed side
The addition of KI results in the formation of PbI2.
Thus Pb(II) present in the feed side is extracted as
iodo complex. The same can be represented by the
following equation
Pb (NO3)2+ KI PbI2 + 2KNO3 … (1)
This lead iodide reacts with TBP, the carrier at the
feed-membrane interface to form lead TBP complex
PbI2 + TBP PbI2.TBP … (2)
Apart from the extraction equilibrium at the
interface represented by Eq. 2 there exists another
Fig. 5⎯Kinetic study of lead removal.
equilibrium in the feed solution
Pb2+ + 2I- PbI2 … (3) Permeability can be calculated using the following
relation15
Reaction at strip side
At near neutral condition lead exists as lead ln (Cs/Co)=-P(A/V) t … (5)
hydroxide, but in extremely alkaline condition as in
strip side lead remains as soluble lead plumbate. This where, P is the permeability coefficient (m/s); Cs is
can be represented by the following Eq. the solute concentration at time (mg/L); Co is the
initial solute concentration (mg/L); V is the volume of
PbI2.TBP + 4NaOH Na2PbO2 + 2NaI + TBP feed solution (m3) and A is the membrane area (m2).
+ 2H2O … (4) The permeability coefficient is thus estimated by
Estimation of permeability plotting ln (Cs/Co) versus time and this is graphically
The mass transfer of the metal crossing the shown in Fig. 5. The diffusion coefficient is calcu-
membrane is described considering only diffusional lated from permeability value using thickness (l=10
parameters. The interfacial flux due to the chemical micron) across the membrane. The details of the
reaction has been neglected, as the chemical reactions permeability values for Pb(II) at optimum conditions
seem to take place instantaneously relative to the are summarized in Table 1. The permeability at 50
diffusion processes14. mg/L is lower than 25 mg/L. This may be due to
440 INDIAN J. CHEM. TECHNOL., JULY 2005
Table 1⎯Summary of lead transport permeate values
S. No Initial lead concentration Permeability
(mg/L) (m/s)
1 25 1.146×10-5
2 50 1.579×10-7
lower effective area for the transport (or) due to
maximization as a result of saturation of the
membrane pores with the metal carrier species and
build-up of the carrier layer on the membrane
interface, enhancing the retention of the separating
constituent on the entry side and thus causing the
permeability to be lower16. Moreover D values
reported for known supported liquid membrane
ranges from 10-10 to 10-11 m2/s. The D value obtained
for present system is 1.1×10-10 m2/s.
Conclusion
From the results of the study, it can be concluded
that the supported liquid membrane consisting of
TBP-iodo system with NaOH as strippant is an
effective system for the treatment of lead bearing
effluents. It can be inferred, that the permeability
value is higher for low lead concentration and it
decreases with increase in lead concentration. Thus,
the system identified works effectively for low
concentrations of lead.
References
1 Winston W S, Wang B, Neumuller T E & Roller T,
Environmental Progress, 20 (2001) 117.
2 Barbara E, Stephen H & Gail S, Ulmann Encyclopedia of
Industrial Chemistry (Cambridge), 1990.
3 Mohapatra P K & Manchanda V K, Indian J Chem, 42 A
(2003) 2925.
4 Argekar A P & Shetty A K, Talanta, 45 (1998) 909.
5 Shilimkar T N & Anuse M A, Sep Purif Technol, 26
(2002)185.
6 Dapaah A R K, Takano N & Ayama A, Anal Chim Acta, 386
(1999) 281.
7 Delves, Shepherd, Vinter, Analyst, 96 (1971) 262.
8 Wei G T, Yang Z & Chao J C, Anal Chim Acta, 488 (2003)
183.
9 Yadav A A & Khopkar S M, Talanta, 18 (1971) 121.
10 Gyves J & Miguel E R, Ind Eng Chem Res, 38 (1999) 2182.
11 Canet L & Seta P, Pure Appl Chem, 73 (2001) 2039.
12 Lamb J D & Nazarenko A Y, J Membrane Sci, 134 (1997)
255.
13 Dagnall R M, West T S & Young P, Talanta, 12 (1965) 583.
14 Sastre A, Modi A, Cortina J L & Miralles N, J Membrane
Sci, 139 (1998) 57.
15 Yang X J, Fane A G & Soldenhoff K, Ind Eng Chem Res, 42
(2003) 392.
16 Alguacil F J, Caravaca C & Isabel M, J Chem Technol
Biotechnol, 78 (2003) 1048.