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INDIAN NUCLEAR SOCIETY

13th Annual Conference – INSAC 2002


October 9-11, 2002, Mumbai.

Acrylic acid grafting on polypropylene membrane


by γ-rays and its application in rare earth
extraction

Jatinder Singh Gill and Harvinderpal Singh

Rare Earths Development Section


Bhabha Atomic Research Centre, Trombay
Mumbai - 400 085.

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Acrylic acid grafting on polypropylene membrane by γ-rays and its
application in rare earth extraction

Jatinder Singh Gill and Harvinderpal Singh


Rare Earths Development Section
Bhabha Atomic Research Centre, Trombay
Mumbai - 400 085.

E-mail: jsgill@apsara.barc.ernet.in

Summary: Thin polypropylene (PP) membrane (Celgard 2500) was grafted with
acrylic acid using γ-rays irradiation obtaining grafting yield of about 32%. A transport
study of Praseodymium (Pr) on this grafted ion-exchange membrane showed good
permeability. But this transport was found to taper off near 50% of extraction. The
grafted PP membrane was used in conjunction with ungrafted PP membrane loaded
with di-2 ethyl hexyl phosphoric acid (D2EHPA) in supported liquid membrane
(SLM) mode. Total extraction of Pr was found to be feasible, besides providing
stability to the SLM against solvent loss.

Introduction:
In hydrometallurgical processing and effluent treatment, the separation of
valuable and/or toxic metals from dilute and impure technological solutions and waste
waters is a frequent requirement. Commercial scale rare earth production is carried
out via liquid-liquid extraction process, using extractants like D2EHPA, TBP etc. The
recovery and separation of lanthanides by solvent extraction require a large number of
stages for the preparation high purity products. Recently the use of SLM for
lanthanides has become of interest as an energy saving method(1-6). In SLM, a
desired extractant dissolved in suitable solvent like kerosene is loaded in the pores of
the membrane. This loaded membrane is used to extract and separate metal of interest.
In comparison with traditional solvent extraction technique, SLM offers a number of
potential advantages such as low solvent inventory, high diffusion rate, low operating
cost and energy, no need of phase separation and no solvent attrainment in aqueous
feed or strip solution etc. The major reason SLM has not been implemented into large
scale industrial separation processes is due to its short life time caused by loss of
membrane liquid loaded into its pores.
We have grafted polypropylene membranes (Celgard 2500) with acrylic acid
using γ-rays so as to obtain cation exchange membranes. Such cation membranes find
applications in fuel cells, electrodialysis, chlor-alkali cell etc. (7-9). We have used this
grafted cation exchange membranes in Pr extraction with a view to avoid solvent loss
of SLM.

Experimental:
(a) Membrane: polypropylene membranes Celgard 2500, pore size 0.075µm, porosity
45% and thickness 25µm obtained from m/s Hoechst Japan.
(b) Grafting: 45 mm dia disks were cut from the PP membrane sheet. Grafting was
carried out by keeping the membrane in a glass bottle containing aqueous solution
of acrylic acid and irradiating in a 60
Co γ-rays chamber (Dose rate 8 KGy/h) at
RTDS. Ferrous ammonium sulphate was used as inhibitor to check the
homopolymerisation of acrylic acid. A total dose of 16kGy was imparted to get
32% of grafting of acrylic acid on PP membrane. The membrane was washed
repeatedly with acetone till constant weight. The hydrophobic PP membrane
became hydrophilic on acrylic acid grafting. The degree of grafting was
determined by following equation:
% Grafting = 100(W1 - W0)/W0
where W1 and W0 are the weights of grafted and ungrafted membrane disks.
(c) Rare earth transport: The Praseodymium transport studies were carried out using
two compartments perspex transport cell (Fig. 1). One compartment of the cell
contained 28 ml of feed solution of Pr (0.6 g/L) at pH of 3 and the other
compartment was filled with 28 ml of 1M HCl as strip solution. These two
compartments were separated by the membrane. In this process metal ions are
extracted by the membrane and transported to the strip compartment of the
transport cell. The Pr transport studies were made in two ways. In the first case
only grafted PP cation exchange membrane was used. In the second case 1M
D2EHPA in kerosene was loaded into the pores of the ungrafted PP membrane
(SLM mode), surrounded on both sides by two grafted PP membranes (Fig. 2) so
as to protect the SLM against solvent loss. The grafted membranes were pre
treated in 1M HCl overnight before use. Feed and strip solutions were stirred with
magnetic pellets at 400 rpm. Samples from feed and strip compartments were
drawn at regular intervals and analysed for their Pr contents by visible
spectrophotometry employing ArsenazoIII as complexing agent.

Results and discussions:


In the first case when grafted PP membrane was used in the Pr transport, it
was observed that the Pr concentration decreased with time in the feed compartment.
It reduced to 50% in 5 hours (Fig. 3). But it did not reduce further significantly even
after 24 hours indicating limitation of this grafted membrane used alone. However
when these grafted membranes were used in second case by sandwiching the SLM,
50% transport was found to be achieved in 5 hours (Fig. 4). This was improved to
86% in 24hours of run. Many more runs were made after removing the feed solution
and replacing with fresh 0.6g/L Pr solution each time and similar activity was
exhibited by the composite membrane system.

Acknowledgement: We are very thankful to Dr. S. Sabharwal, Shri S.P. Ramnani


and Dr. Y.K. Bhardwaj of RTDS for using their 60Co source and helpful discussions.

References:

1) G. Schulz, Desalination 68(1988) 191-202.


2) J.S. Gill, U.R. Marwah, B.M. Misra, J.Memb.Sci. 76(1993)157-163.
3) J.S. Gill, U.R. Marwah, B.M. Misra, Sep.Sci.&Technol. 29(1994) 193-203
4) B. M. Misra and J.S. Gill, Supported Liquid Membranes in Metal Separations
with Liquid Membranes,ACS Symposium Series 642, Chapter XXV; Eds.
R.A. Bartsch and J.D. Way; Americal Chemical Society, Washington, U.S.A.,
1996.
5) J.S. Gill and H. Singh, Indian J. Chem. Tech., 7(2000), 38-42.
6) J.S. Gill, H. Singh and C.K. Gupta, Hydrometallurgy 55(2000) 113-116.
7) H. Kawate, K. Tsuzura and H. Shimizu, Ion exchange membranes in Ion
Exchangers, ed. K. Dorfner, W. deGruyter, New York, 1991.
8) B. Gupta et.al., J.Polym.Sci. A:Polym.Chem. 34(1996)1873-1880.
9) J. St-Pierre, D.P. Wilkinson, AIChE J. 47(2001) 1482-1486.
Supported liquid membrane(SLM)
SLM

IEM
Feed Strip

Magnetic pellets

Fig. 1 : Transport Cell Fig. 2 : SLM sandwiched by 2 IEMs

1 .0

0 .9

0 .8
C/Co

0 .7

0 .6

0 .5

0 .4
0 5 10 15 20 25

T im e (h )

Fig. 3 : Pr transport through grafted PP ion exchange membrane (IEM)

1 .0

0 .8

0 .6
C/Co

0 .4

0 .2

0 .0
0 5 10 15 20 25

T im e (h )

Fig. 4 : Pr transport through sandwiched SLM