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 extensively for its varied advantages like low
pollutants in the environment. Among various inventory of organic phase used, low energy
pollutants, heavy metals are of greater concern due to consumption, low capital and operating costs, good
their toxicity and non-biodegradability. Hence limits selectivity and mass transfer in one step3.
have been prescribed on their concentration in potable Solvent extraction studies provide first hand
water and in effluent discharge. In order to meet the information for SLM studies. Extensive details on
prescribed standards, proper form of treatment is solvent extraction with different carriers and solvents
necessary before disposal. The environment can be are available in literature. Argekar and Shetty4 have
kept clean not only by resorting to efficient removal reported successful extraction of lead in the pH range
techniques, but also by recovering the heavy metals of 2.1-8.3 using cyanex-302 in toluene. The other
and reusing them effectively1. studies with extractants like n-octylaniline in toluene5,
Lead is a well-known cumulative poison, found in zinc hexamethylene dithiocarbamate in dimethyl 4-
the environment mostly because of mining and heptanone6 and tri iso octylamine in methyl
smelting, battery manufacturing and its use as isobutylketone (MIBK)7 have been reported and all
additive in fuel. Concern about the toxicity of lead has these indicate that pH plays a major role in bringing
brought about many substitutions in some appli- about the separation. Thus by tailoring the pH values
cations such as plumbing, painting, etc 2. the desirable separation can be achieved.
Separation processes based on membrane Wei et al.8 have reported the extraction of lead
technology represent a sophisticated route for the using room temperature ionic liquids as solvent which
purpose of treating reasonable volumes of water as replace chlorinated hydrocarbons like chloroform,
they strongly limit the number of elementary steps with dithizone as carrier. Another study by Yadav and
involved in the usual separation and recuperation Khopkar9 reports application of TBP as carrier in
processes. Liquid membrane (LM) technology is a MIBK for the removal of lead. The authors have
subset of membrane science. Among LM’s, identified that TBP alone cannot quantitatively extract
Supported Liquid Membrane (SLM) is studied lead in the absence of a salting out agent.
________________ Gyves & Miguel10 have studied the extraction of
*For correspondence (E-mail: kpvelu@hotmail.com; lead and cadmium in two different systems namely
Fax: +91-44 -22354717) SLM and polymer inclusion membrane (PIM) using
 ANUPAMA & PALANIVELU: REMOVAL OF LEAD USING SUPPORTED LIQUID MEMBRANE 437

Kelex 100 as carrier and they have proposed a phase, again shaken well for 10 min and allowed to
chemical model for the transport. They have separate. The amount of lead present was estimated in
identified that PIM systems show high fluxes and the the aqueous phase to evaluate percentage recovery.
stability allows the membrane to be used repeatedly The lead present in the feed and receiving phase were
for at least 20 cycles without any appreciable loss of analysed using PAR13 method or atomic absorption
permeability. Canet and Seta11 have studied the spectrophotometer (AAS).
transport of lead using lasolocid as carrier in The SLM laboratory experiments were conducted
n-nitrophenyloctyl ether with polypropylene as with 140 mL each of feed and strip solution. All
support. Selective separation of lead was observed by experiments were conducted with 25 mg/L of initial
tailoring the pH value. Lamb and Nazarenko12 have lead concentration except for those, which were
reported that PIMs are easy to prepare in laboratory conducted to observe the effect of initial concen-
and high permeabilities are observed with them. In tration. The membrane soaked in selected diluent/
this system lead was extracted as iodo, thiocyanate extractant overnight was used after draining the
complexes with high efficiency. excess adhering liquid. The feed and strip solutions
In the present study transport of lead across a SLM were thoroughly mixed with the help of magnetic
comprising of TBP and KI as reagents was inves- stirrer. The samples from each side were periodically
tigated. The effects of various operational parameters taken and analyzed for lead content by either PAR13
were optimized systematically. The permeability method or AAS. The experimental set-up consisted of
coefficient and diffusion coefficient were estimated. two cylindrical cells one for feed solution and another
for strippant. Poly tetrafluoroethylene (Teflon)
Experimental Procedure membrane of 10-micron thickness was used as
Materials and methods support and the membrane was placed in between the
Hexane, MIBK, toluene, methylene dichloride and cells. The effective membrane area was 1.59×10-3 m2.
tri butyl phosphate were used as solvents. Lead nitrate The schematic diagram of the reactor is shown in
was used to prepare standard lead solution. Sodium Fig. 1.
hydroxide, sodium carbonate and ammonia buffer
(pH 10) were used as strippants. All chemicals were Results and Discussion
of analytical grade procured from SRL, India and
Solvent extraction studies
were used as such without any further purification.
10% hydrochloric acid and 1 M sodium hydroxide Solvent extraction studies provide the preliminary
were used for adjusting pH to desired value. All data for the liquid membrane systems. All
reagents were prepared using distilled water. experiments were carried out with lead(II) solution
The instruments used for the study were pH meter containing 25 mg/L of lead. It is well known that lead
(Li 120, Elico make), magnetic stirrer (1 mL, Remi reacts with KI in acidic medium to form golden
make), spectrophotometer (20 Genesys, Spectronic yellow spangles. The selection of suitable extracting
Instruments limited) and flame atomic absorption solvent was then made by conducting a series of
spectrophotometer (aa/ae spectrophotometer 495, experiments with various solvents. The extraction
Instrumentation lab). efficiencies obtained with various solvents are as
For the selection of suitable carrier/solvent and follows: MIBK=95, toluene=16, hexane=14,
strippant for SLM studies, the following solvent methylene dichloride=76 and TBP=100%. From the
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 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 Fig. 3⎯Effect of strippant concentration. (Condition: Initial lead
concentration of 0.045 M; this is in accordance with concentration =25 mg/L, KI concentration =0.045 M, stirring
that reported by Dagnall et al.13. Hence KI speed=600 rpm, feed side pH=2).
concentration of 0.045 M was selected for further
studies. analyzed for lead concentration. After 20 h the
removal and recovery efficiencies were 58.7 and
Effect of strippant concentration 45.7%, respectively. Hence it is clear that stirring is
The effect of strippant (NaOH) concentration was necessary to achieve good results in a shorter time.
studied in the range 0.1-1.0 M. The results obtained There is always a increase in the shear force across
are shown in Fig. 3. From the figure it is clear that the membrane as the stirring speed increases. The
maximum recovery is obtained with 1 M NaOH stirring speed was varied in the range 200-600 rpm.
concentration. Hence, the strippant concentration is From the results obtained it is inferred that speed of
recommended as 1 M for stripping of lead. 600 rpm is desirable one as it gives maximum
removal and recovery efficiencies of 99% each after 4
Effect of stirring speed
h of operation.
In order to study the need for stirring, an
experiment was conducted in static mode i.e. without Effect of initial lead concentration
stirring. The reactor was filled with feed and strip The effect was studied in the range of 10-50 mg/L.
solution and left overnight and the samples were 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 the system identified works effectively for low
S. No Initial lead concentration Permeability
concentrations of lead.
(mg/L) (m/s)
References
1 25 1.146×10-5 1 Winston W S, Wang B, Neumuller T E & Roller T,
2 50 1.579×10-7 Environmental Progress, 20 (2001) 117.
2 Barbara E, Stephen H & Gail S, Ulmann Encyclopedia of
Industrial Chemistry (Cambridge), 1990.
lower effective area for the transport (or) due to 3 Mohapatra P K & Manchanda V K, Indian J Chem, 42 A
maximization as a result of saturation of the (2003) 2925.
membrane pores with the metal carrier species and 4 Argekar A P & Shetty A K, Talanta, 45 (1998) 909.
build-up of the carrier layer on the membrane 5 Shilimkar T N & Anuse M A, Sep Purif Technol, 26
interface, enhancing the retention of the separating (2002)185.
6 Dapaah A R K, Takano N & Ayama A, Anal Chim Acta, 386
constituent on the entry side and thus causing the (1999) 281.
permeability to be lower16. Moreover D values 7 Delves, Shepherd, Vinter, Analyst, 96 (1971) 262.
reported for known supported liquid membrane 8 Wei G T, Yang Z & Chao J C, Anal Chim Acta, 488 (2003)
ranges from 10-10 to 10-11 m2/s. The D value obtained 183.
9 Yadav A A & Khopkar S M, Talanta, 18 (1971) 121.
for present system is 1.1×10-10 m2/s. 10 Gyves J & Miguel E R, Ind Eng Chem Res, 38 (1999) 2182.
11 Canet L & Seta P, Pure Appl Chem, 73 (2001) 2039.
Conclusion 12 Lamb J D & Nazarenko A Y, J Membrane Sci, 134 (1997)
From the results of the study, it can be concluded 255.
that the supported liquid membrane consisting of 13 Dagnall R M, West T S & Young P, Talanta, 12 (1965) 583.
TBP-iodo system with NaOH as strippant is an 14 Sastre A, Modi A, Cortina J L & Miralles N, J Membrane
Sci, 139 (1998) 57.
effective system for the treatment of lead bearing 15 Yang X J, Fane A G & Soldenhoff K, Ind Eng Chem Res, 42
effluents. It can be inferred, that the permeability (2003) 392.
value is higher for low lead concentration and it 16 Alguacil F J, Caravaca C & Isabel M, J Chem Technol
decreases with increase in lead concentration. Thus, Biotechnol, 78 (2003) 1048.