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Treatment of arsenic ions from produced water through hollow fiber supported
liquid membrane
Ura Pancharoen a , Woradej Poonkum a , Anchaleeporn Waritswat Lothongkum b,∗
a
Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, Patumwun, Bangkok 10330, Thailand
b
Department of Chemical Engineering, Faculty of Engineering, King Mongkut’s Institute of Technology Ladkrabang, Chalongkrung Rd., Bangkok 10520, Thailand
a r t i c l e i n f o a b s t r a c t
Article history: Treatment of arsenic ions from produced water coming along with a gas separation plant in the Gulf
Received 11 December 2008 of Thailand by hollow fiber supported liquid membrane (HFSLM) was studied. Cyanex® 923 (a mix-
Received in revised form 29 March 2009 ture of phosphine oxide), tri-n-butylphosphate (TBP), bis(2, 4, 4-trimethylpentyl) dithiophosphinic acid
Accepted 2 April 2009
(Cyanex® 301), tri-n-octylamine (TOA) and methyltrioctylammonium chloride (Aliquat 336) were used
Available online 10 April 2009
as the extractants. The stripping solution was sodium hydroxide. The concentration of the extractant in
liquid membrane and concentration of sodium hydroxide were examined. In addition, the influence of
Keywords:
various numbers of runs of the stripping solution through the HFSLM on the concentration of arsenic ions
Arsenic
Produced water
in the outlet stripping solution was observed. Of all the extractants used, 35% (v/v) Aliquat 336 attained
Hollow fiber high percentages of extraction and recovery of arsenic ions because it reacted with both undissociated
Supported liquid membrane arsenic (H3 AsO3 ) and dissociated arsenics (H2 AsO4 − and HAsO4 2− ). Cyanex® 923, TBP and TOA had low
Amine extractability since Cyanex® 923 and TBP reacted only with undissociated forms while TOA reacted only
with dissociated forms. In case of Cyanex® 301, although it offered a relatively high percentage of extrac-
tion but very poor recovery due to this extractant formed very strong complex species with arsenic ions,
which slowed down and made the stripping difficult. It was found that the percentage of arsenic recovery
increased with the concentration of sodium hydroxide and was almost constant after 0.5 M due to the
limitation of mass transfer area of the hollow fibers. After 3-cycle separation, the extraction and recovery
of arsenic ions from produced water were 91% and 72%, respectively. Accordingly, the concentration of
arsenic ions of 0.1201 ppm in produced water was observed, which was in accordance with the legislation
discharge of industrial effluent in Thailand. More arsenic ions were recovered by increasing the numbers
of runs of the recycling stripping solution through the HFSLM.
© 2009 Elsevier B.V. All rights reserved.
0925-8388/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jallcom.2009.04.006
U. Pancharoen et al. / Journal of Alloys and Compounds 482 (2009) 328–334 329
Nomenclature
Fig. 3. As(V) species, H3 AsO4 , H2 AsO4 − , HAsO4 2− and AsO4 3− , at different pH [29]. Fig. 5. Schematic representation of HAsO4 2− coupled transport with Aliquat 336.
U. Pancharoen et al. / Journal of Alloys and Compounds 482 (2009) 328–334 331
HAsO4 2− + 2(NR4 )+ X− (NR4 )2 (HAsO4 ) + 2X− (2) In this work, the percentages of extraction and recovery are
determined as follows:
H3 AsO3 + (NR4 )+ CI− NR4 CI(H3 AsO3 ) (3)
Cf,in − Cf,out
%extraction = × 100 (9)
(NR4 )(H2 AsO4 ) + NaOH NR4 OH + NaH2 AsO4 (4) Cf,in
(NR4 )2 (HAsO4 ) + 2 NaOH 2NR4 OH + Na2 HAsO4 (5) Cs,out
%recovery = × 100 (10)
+
NR4 CI(H3 AsO3 ) + NaOH NaAsO3 + (NR4 ) CI− + H2 O (6) Cf,in
For Cyanex® 301, the schematic of AsO+ coupled transport is where Cf, in concentration of inlet feed (ppm); Cf, out concentration of
shown in Fig. 6 and the extraction and stripping reactions are in the outlet feed (ppm); Cs, out concentration of outlet stripping solution
following equations: (ppm).
The feed solution is produced water from a gas separation plant in the Gulf
of Thailand, the pH of about 6–6.5. The compositions of feed solution which was
measured by the inductively coupled plasma spectroscopy (ICP) are shown in
where R is a part of Cyanex® 301, Table 1. The extractants are Cyanex® 923, tri-n-butylphosphate (TBP), bis(2, 4, 4-
Fig. 7 shows flow pattern of the hollow fiber module, it consists trimethylpentyl) dithiophosphinic acid (Cyanex® 301), tri-n-octylamine (TOA) and
methyltrioctylammonium chloride (Aliquat 336). The diluent was kerosene, JPI
of a liquid membrane and two aqueous sides of feed and strip-
grade without further purification, supplied by PTT Public Co. Ltd. The stripping
ping solutions which flow counter-currently. The liquid membrane solution is sodium hydroxide, analytical grade, from Merck Ltd.
which separates the feed and stripping solutions is trapped in the
hydrophobic microporous hollow fiber module. 3.2. Apparatus
Celgard® x-30 240 microporous polypropylene hollow fibers were woven into
fabric and wrapped around a central tube feeder that supplied the shell side fluid.
The woven polypropylene fabrics allowed more uniform fiber spacing, which in turn
led to higher mass transfer coefficient than individual fibers and they served as a
support for the liquid membrane. The characteristics of the hollow fiber module are
shown in Table 2.
3.3. Procedures
Liquid membranes are various organic solutions of Cyanex® 923, TBP, Cyanex®
301, TOA and Aliquat 336 dissolved in kerosene. Feeding solution is produced water
from a gas separation plant and filtered by a filter paper (Whatman No. 42) via a vac-
uum pump. The stripping solution is sodium hydroxide solution. Firstly, the organic
solution was circulated in the shell and tube side of the hollow fiber module for
30–40 min to assure the liquid membrane was trapped in the porous hollow fibers.
The experiment was started by flowing the feed solution into the module. Simul-
taneously, the stripping solution was pumped into the shell side counter-currently.
The one-through-mode operation (Fig. 8) was used. The operating time for 1 run
was 50 min. Sample of about 10 cm3 was taken at the end of each experiment from
the feed and recovery reservoirs. The concentration of arsenic ions was determined
by the Inductively Coupled Plasma Spectroscopy. In case the study of numbers of
runs of the stripping solution, the outlet stripping was recycled through the HFSLM.
Table 1
Fig. 6. Schematic representation of AsO+ coupled transport with Cyanex 301. Compositions of the produced water.
As 1.2842
Fe 0.8642
Mg 21.364
Ca 94.364
Na 621.364
Table 2
Properties of the hollow fiber module.
Property Description
Material Polypropylene
Fiber inside diameter 240 m
Fiber outside diameter 300 m
Pore size 0.05 m
Number of fiber 240
Porosity 30%
Contact area 1.4 m2
Area per unit volume 29.3 cm2 /cm3
Module diameter 6.3 cm
Fig. 7. Flow pattern of hollow fiber supported liquid membrane [4]. Module length 20.3 cm
332 U. Pancharoen et al. / Journal of Alloys and Compounds 482 (2009) 328–334
Fig. 10. Plot of the percentages of the extraction and recovery of arsenic ions from
produced water against the concentration of Aliquat 336 in liquid membrane at 1 M
NaOH. The flow rates of feed and stripping solutions were100 ml/min.
5. Conclusions
The hollow fiber liquid membrane using 0.75 M (35%, v/v) Ali-
quat 336 as the extractant and 0.5 M NaOH as the stripping solution
successfully reduced the concentration of arsenic ions in produced
water from the gas separation plant in the Gulf of Thailand to
comply with the permissible limit of the Ministry of Industry
(∠0.250 ppm). Similar to the filtration, the HFSLM system required
some pre-treatment of produced water. The Aliquat 336, a quater-
Fig. 12. Plot of the percentages of the extraction and recovery of arsenic ions from
nary amine, showed higher extractability and recovery of arsenic
produced water against the number of runs through HFSLM at Aliquat 336 35% (v/v) ions than TOA, a tertiary amine, because it reacted with both dis-
and 0.5 M NaOH. The flow rates of feed and stripping solutions were 100 ml/min. sociated and undissociated forms of the arsenic ions. Although
Cyanex® 301 showed relatively high percentage of extraction, it
achieved very low percentage of recovery as this type of extrac-
tant formed very strong complexes with arsenic ions, which slowed
down and made the stripping difficult. The percentage of the recov-
ery of arsenic ions increased with the concentration of sodium
hydroxide up to 0.5 M. And by recycling of the stripping solu-
tion through the HFSLM up to 9th run, more arsenic ions were
recovered.
Acknowledgments