Journal of Alloys and Compounds 482 (2009) 328–334

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Journal of Alloys and Compounds

journal homepage: www.elsevier.com/locate/jallcom

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.

1. Introduction Large quantities of contaminated produced waters can have sig-

Since offshore oil and gas operations increase dramatically, the
potential environmental impacts associated with produced waters
have been ongoing concerned. To achieve a maximum oil and gas
recovery, additional water is usually injected into the reservoirs.
Both formation water (a natural water layer lying under the hydro-
carbons) and injected water are eventually produced along with
the hydrocarbons. The volumes and the difficulties of their treat-
ment tend to increase extensively as older as oil and gas wells.
The produced waters usually include dissolved salts, organic com-
pounds, oil, hydrocarbons, trace heavy and toxic metals, radioactive
elements, suspensions, nutrients and many other chemical sub-
stances that are used in technological waters during drilling [1,2].
As a result, heavy elements and compounds of arsenic, chromium,
mercury, lead, nickel, copper, cadmium, zinc, and others are found.
∗ Corresponding author. Tel.: +66 023264424; fax: +66 023264424.
E-mail address: kwanchal@kmitl.ac.th (A.W. Lothongkum).
nificant environmental impacts if they are not handled properly.
At the surface, the produced water is separated from the hydro-
carbons, treated to remove as much as oil as possible. Depending
on its quality, the produced water is subsequently either dis-
charged into the sea after cleaning up or injected back into the
disposal wells. Such cleaning under marine conditions is a com-
plicated technical task. Special separation units on the platforms
are used for the separation. In addition, some installations are
able to inject produced water into other suitable geological for-
mations. To date, a multidisciplinary research and technology have
been increasingly working out to reduce and control the environ-
mental effects of drilling waste discharges, particularly produced
water. The governments, the industry and environmental cam-
paigners have continued searching for ways to reduce the volume
of produced water, to re-inject it below the seabed, and to make it
clean to comply with the legislation discharge. Six water treatment
technologies, i.e., carbon adsorption, air stripping, filtration using
very fine membrane, UV light, chemical oxidation and biological
treatment, already proven onshore, were costed for offshore use.

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

Cf, in concentration of inlet feed (ppm)

Cf, out concentration of outlet feed (ppm)
Cs, out concentration of outlet stripping solution (ppm)
(NR4 )+ Cl− Aliquat 336

Although each method presented technical problems, none of them

was insuperable. The combination of different technologies is found
to be possible to reduce and regulate the undesired components in
produced water to almost undetectable levels [1]. It is reported that
a chemical treatment process can be applied to remove arsenic and
mercury from the produced water prior to overboard discharge.
However, in certain fields of the Gulf of Thailand, the concentra-
tions of arsenic and mercury in the produced water are high. The
continuous on-line As and Hg monitors to determine the concen-
trations have been problematic and are needed to allow adjustment
of chemical treatment rates to achieve the desired metal discharge
concentrations [3].
Taking into account a promising metal separation and recovery
technique from aqueous solutions, supported liquid membranes
(SLMs), particularly hollow fiber supported liquid membrane
Fig. 1. Chemical structures of the extractants. (a) Cyanex® 923 where R/ is a mixture
(HFSLM) is of great interest due to the use of carrier for the transport
of C6 H13 and C8 H17 , (b) TBP, (c) Cyanex® 301, (d) TOA, and (e) Aliquat 336, (NR4 )+ Cl− .
mechanism resulting in highly selectivity and rapid transporta-
tion of the desired metal ions [4–11]. The simultaneous extraction
and stripping in a single unit operation of liquid membrane sys-
A number of researchers sought for the organic extractants to
tem is very remarkable. Especially, when applying it to remove and
remove arsenic ions, mostly they worked in a lab-scale using syn-
recovery of the precious metal from effluent wastewater allows its
thetic feeds. Cyanex® 923, Cyanex® 301, Cyanex® 925, mixture of
reuse. On the other hand, a good quality water will be obtained
Cyanex® 301 and Cyanex® 925, hydrophobic glycol and hydroxamic
and is able to reuse in the process. Recently, hollow fiber supported
acids were used to remove As(III) and As(V) from sulfuric acid solu-
liquid membrane is being looked into industrial applications, for
tion by liquid–liquid extraction. The acidic reagent, Cyanex® 301,
example, the treatment of wastewater, the recovery of metals from
could extract As(III) better than As(V). Cyanex® 925 and Cyanex®
dilute solutions, and for controlling certain problems in the oil well
923 were more suitable for As(V) extraction than As(III) [13,20–21].
control industry. HFSLM is known to be a separation process with
The mixture of Cyanex® 301 with Cyanex® 925 was good for both
low energy and extractant consumed and high efficiency. Another
As(V) and As(III) [20]. The extraction of both As(III) and As(V)
attractive point of the HFSLM is ease of scaling up. However, there
increased when the concentration of the sulfuric acid in the feed
are a few drawbacks such as a high hydrophobic membrane sol-
increased. The mixture of the organophosphorus extractants was
vent is required to maintain stability, and the hollow fiber must be
studied by Ballinas et al. [22]. The dibutyl butyl phosphonate (DBBP)
cleaned between uses otherwise there will be aqueous and con-
and di(2-ethylhexyl) phosphoric acid (D2EHPA) were used as a
taminant buildup [4].
mixture extractant to remove arsenic from sulfuric acid media in
In this current work a lab-scale microporous HFSLM is applied
a synthetic copper electrolyte solution. The DBBP–D2EHPA mix-
to control the concentration of arsenic ions in produced water com-
ture efficiently removed As(V) from copper electrolyte solutions
ing along with a gas separation plant from the Gulf of Thailand as a
with better yields than DBBP alone. Martinez Perez et al. [23] stud-
feed solution. The maximum permissible concentration of arsenic
ied a transfer of As(V) in sulfuric acid aqueous solution through
in natural water according to the Ministry of Industry, Thailand is
SLM with trioctylphosphine oxide (Cyanex® 921) in kerosene. The
not higher than 0.25 mg/L [12]. Several types of extractants were
highest As(V) transfer was observed by using 0.12 M Cyanex® 921.
used to find a suitable one. Their chemical structures are shown in
Our previous works reported the applications of HFSLM with syn-
Fig. 1. The concentration of the selected extractant in liquid mem-
thetic feed solutions: Prapasawat et al. [24] found that Cyanex®
brane, the concentration of the stripping solution and numbers of
923 diluted in toluene could extract both As(III) and As(V) ions
runs of the stripping solution through the HFSLM were studied.
from sulphate media but As(V) ions were more extracted. The result
agreed with the work of Wisniewski by liquid–liquid extraction
2. Theory [13]. Sangtumrong et al. [25] studied the separation of Hg(II) and
As(III) ions from chloride media by using a basic extractant of tri-
Arsenic is a metalloid element which naturally occurs in various n-octylamine (TOA) dissolved in toluene. The Hg(II) ions could be
geological formations. It is also found in shale rock and in sulfide extracted because they formed anion complex of HgCl4 2− but As(III)
minerals such as pyrite. The widespread occurrence of arsenic com- ions could not because they were in a neutral form of H3 AsO3 .
pounds is hazardous due to its carcinogenic effect. The toxicity of The studies on lanthanum, neodymium, palladium, and a mixture
arsenic depends on its oxidation state. Chronic exposure to arsenic of copper, chromium and zinc were also carried out by HFSLM
even at a very low concentration increases the risk for develop- [17,26–27]. In addition, industrial applications of the HFSLM by
ing various forms of cancers, such as bladder, lung, liver, kidney our group were reported [11,28]. The HFSLM system consists of
and skin cancer. Additionally, it may cause chromosomal abnor- three solution phases. The first phase is aqueous feed solution
malities, breakdown of nasal tissue, diabetes and increased systolic which initially contains metal ions. The second phase is the liquid
blood pressure [18,19]. membrane extractant phase which consists of an organic solution
330 U. Pancharoen et al. / Journal of Alloys and Compounds 482 (2009) 328–334
Fig. 2. As(III) species, H3 AsO3 and H2 AsO3 − , at different pH [29].
or organic carrier embedding in a polymeric-hydrophobic micro-
porous hollow fiber through capillary forces. The third phase is
aqueous stripping solution which initially contains no metal ions
and finally attains the desired extracted metal ions. Transportations
of metal ions are due to the driving force between the two opposite
sides of the aqueous phases [5].
In fact, arsenic in produced water comes from groundwater and
the components of a common drilling fluid additives. In groundwa-
ter arsenic presents in As(III) and As(V) depending on the pH value
as shown in Figs. 2 and 3. The As(III) occurs as H3 AsO3 and H2 AsO3 −
complexes, and the As(V) occurs as H3 AsO4 , H2 AsO4 − , HAsO4 2− and
AsO4 3− . At the pH of most groundwaters, about 6.7–8.8 in shad-
ing area, the amount of As(III) in terms of H3 AsO3 is more than
H2 AsO3 − . In the case of As(V), the H2 AsO4 − and HAsO4 2− complexes
are much greater than H3 AsO4 and AsO4 3− [29].
The produced water from offshore gas plant is generally more
acidic than that from offshore oilfield [30]. However, the pH of the
produced water from gas separation plant used as a feed solution
of HFSLM in this current work is closed to neutral (about 6–6.5).
According to Wilson et al. [29], it inferred that As(III) in this pro-
duced water presented in neutral form or undissociated arsenic
of H3 AsO3 , and As(V) presented in dissociated arsenics or anion
complexes of H2 AsO4 − and HAsO4 2− . It is important to take into
consideration that some research groups recommended neutral
extractants to extract arsenic in neutral forms [13,20-25,31]. In this
regard, the neutral extractants (Cyanex® 923 and TBP) were used
in this work. However, because arsenic ions might exist in anion
complexes, the basic extractants (TOA and Aliquat 336) were also
used. The acidic extractant (Cyanex® 301) was selected because of
its very high efficiency in arsenic extraction as well [20,21].
Fig. 3. As(V) species, H3 AsO4 , H2 AsO4 − , HAsO4 2− and AsO4 3− , at different pH [29].
Fig. 4. Schematic representation of H2 AsO4 − coupled transport with Aliquat 336.
The undissociated and dissociated arsenic forms were reacted
with the extractant to become the arsenic complex ions. The trans-
port mechanisms were shown using Aliquat 336 and Cyanex® 301
for the explanations. As noted, Aliquat 336 can react with both dis-
sociated forms (H2 AsO4 − and HAsO4 2− ) and undissociated form
(H3 AsO3 ) of the arsenic ions while Cyanex® 301, an acidic solution,
H3 AsO3 species are in the form of AsO+ [20,21]. The examples of
transport mechanisms of the dissociated arsenic forms with Aliquat
336 as the extractant through the liquid membrane are schemat-
ically illustrated in Figs. 4 and 5. The process is driven by the
concentration gradient of the OH− . The hydroxide ion is counter-
transported with arsenic ion. The extraction reactions of dissociated
arsenic forms are shown in Eqs. (1) and (2). X− is denoted as Cl− in
feed and membrane phases for the first cycle, and OH− (a counter
ion in the stripping phase) will take the place of Cl− for the fol-
lowing cycles [32]. The stripping reactions or recovery reactions by
sodium hydroxide solution are shown in Eqs. (4) and (6). In case of
the undissociated arsenic form, the extraction equation is expressed
in Eq. (3) and recovery reactions are in Eqs. (4) and (6).
H2 AsO4 − + (NR4 )+ X−  (NR4 )(H2 AsO4 ) + X− (1)
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).

AsO+ + XR  RAsO + H+ (7) 3. Experimental

RAsO + NaOH  NaR + HAsO2 (8)
3.1. Chemicals

where R is a part of Cyanex® 301,
Fig. 7 shows flow pattern of the hollow fiber module, it consists
of a liquid membrane and two aqueous sides of feed and strip-
ping solutions which flow counter-currently. The liquid membrane
which separates the feed and stripping solutions is trapped in the
hydrophobic microporous hollow fiber module.
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
Table 1. The extractants are Cyanex® 923, tri-n-butylphosphate (TBP), bis(2, 4, 4-
trimethylpentyl) dithiophosphinic acid (Cyanex® 301), tri-n-octylamine (TOA) and
methyltrioctylammonium chloride (Aliquat 336). The diluent was kerosene, JPI
grade without further purification, supplied by PTT Public Co. Ltd. The stripping
solution is sodium hydroxide, analytical grade, from Merck Ltd.
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.

Composition mg/dm3 (ppm)

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. 8. Counter-current flow diagram of one-through-mode HFSLM operation. (1)
Inlet feed solution reservoir; (2) gear pumps; (3) inlet pressure gauges; (4) outlet
pressure gauges; (5) flow meters; (6) outlet stripping solution reservoir; (7) hollow
fiber module; (8) inlet stripping solution reservoir; (9) outlet feed solution reservoir.
4. Results and discussion
4.1. Influences of the extractants
It is known that types and concentrations of the extractants
play a significant role in the separation. For HFSLM system acidic,
neutral and basic extractants have a specific mechanism with
anionic/cationic metal ions. Fig. 9 is a comparative plot of the
maximum percentages of the extraction and recovery of arsenic
ions from produced water against different extractants. From the
results Cyanex® 923 and TBP offered poor separation performance
although the neutral extractants were recommended for the extrac-
tion and recovery of arsenic ions [13,20–25,31]. This results agrees
that a neutral extractant reacts with only undissociated form
(H3 AsO3 ) [31] because at the pH of produced water about 6–6.5,
arsenic ions exist as H3 AsO3 , H2 AsO4 − and HAsO4 2− , as described
[29]. However, the previous works using Cyanex® 923 [13,24] found
that by adding a few H2 SO4 as a modifier in synthetic feed solutions,
it enhanced both the extraction and recovery of arsenic ions. There-
fore, Cyanex® 923 might perform well with acidic feed solution. In
case of strong acidic extractant, Cyanex® 301, showed a relatively
high percentage of extraction but very poor recovery due to this
type of extractant formed a very strong complex with arsenic ions
(see Eqs. (7) and (8)), which slowed down and made the stripping
difficult [8]. High percentage of extraction by Cyanex® 301 can be
explained from the fact that in a strong acidic solution, arsenic ions
Fig. 9. Plot of the maximum comparative percentages of extraction and recovery
of arsenic ions from produced water against different extractants at 1 M NaOH:
Cyanex® 923 (33%, v/v), TBP (2.2%, v/v), Cyanex® 301 (2%, v/v), TOA (20%, v/v) and Ali-
quat 336 (35%, v/v). The flow rates of feed and stripping solutions were 100 ml/min.
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.
(III) are in the form of AsO+ that can react with the acidic extractant
[20,21].
Among all the extractants used, Aliquat 336 attained high
percentages of extraction and recovery of arsenic ions at the con-
centration of 35% (v/v) (0.75 M) because it could react with both
dissociated forms (H2 AsO4 − and HAsO4 2− ) and undissociated form
(H3 AsO3 ) of the arsenic ions, while TOA reacted with only the disso-
ciated arsenic ions. This is because Aliquat 336 (a quaternary amine)
is more basicity than TOA (a tertiary amine) [33]. The concentra-
tion of Aliquat 336, the selected extractant, was varied from 5% to
50% (v/v). As can be seen from Fig. 10, both the percentages of the
extraction and recovery of arsenic ions increased abruptly with the
extractant concentration. The maximum values of the extraction
and recovery were achieved at about 35% (v/v) (0.75 M) Aliquat
336 then decreased. This fact can be explained by Le Chatelier’s
principles that the increase of the extractant concentration in liq-
uid membrane results in higher fluxes but apparently above 0.75 M
the flux decreases because the increased film viscosity becomes
dominant and obstructs mass transfer. This result appears to be in
agreement with the study on recovery of nickel ions by supported
liquid membrane extraction [8].
4.2. Influence of sodium hydroxide concentration
The influence of sodium hydroxide concentration as the strip-
ping solution is shown in Fig. 11. From Le Chatelier’s principles, as
the concentration of sodium hydroxide increases, the concentration
gradients of the hydronium ions between the feed and stripping
solutions increase. Therefore, arsenic ions were extracted into the
liquid membrane and recovered into the stripping solution. The
percentage of the recovery of arsenic ions increased with the con-
Fig. 11. Plot of the percentages of the extraction and recovery of arsenic ions from
produced water against the concentration of sodium hydroxide concentration at
Aliquat 336 35% (v/v). The flow rates of feed and stripping solutions were 100 ml/min.
 U. Pancharoen et al. / Journal of Alloys and Compounds 482 (2009) 328–334
centration of sodium hydroxide and almost constant after 0.5 M due
to the limitation of mass transfer area of the hollow fibers [26].
4.3. Influence of the numbers of runs through the hollow fiber
module
Fig. 12 shows the influence of the numbers of runs of feed and
stripping solutions through the hollow fiber module. The percent-
ages of extraction and recovery for arsenic ions increased when a
number of runs increased. At the third run (150 min), by using 35%
(v/v) Aliquat 336 and 0.5 M NaOH, the HFSLM system could extract
and recover arsenic ions from produced water up to 91% and 72%,
respectively. The concentration of arsenic in the stripping phase
is expected to be higher than that in the feed phase, showing the
expected advantage of liquid membrane for concentrating the tar-
get species for recovery. However, the performance of the HFSLM in
terms of the percentages of extraction and recovery of arsenic ions
reached a constant value after the 3rd-cycle operation, implying
that liquid membrane lost its stability due to both by pore foul-
ing and the leak of membrane solution from porous hollow fibers.
Therefore, at every third run, the hollow fiber module was cleaned
to avoid contaminant buildup, and liquid membrane was changed.
In addition, because a high feed flow rate might lower system sta-
bility from the leak of membrane solution so in this work feed flow
rate was fixed at 100 ml/min.
After the 9th run, the concentration of arsenic ions left in feed
solution of 0.1201 ppm was in accordance with the legislation dis-
charge of produced water by the Ministry of Industry, Thailand of
0.250 ppm as shown in Fig. 13.
Fig. 12. Plot of the percentages of the extraction and recovery of arsenic ions from
produced water against the number of runs through HFSLM at Aliquat 336 35% (v/v)
and 0.5 M NaOH. The flow rates of feed and stripping solutions were 100 ml/min.
Fig. 13. Plot of the concentrations of arsenic ions from outlet feed solution against
the number of runs through HFSLM at Aliquat 336 35% (v/v) and 0.5 M NaOH. The
flow rates of feed and stripping solutions were 100 ml/min.
333
Fig. 14. Plot of the concentration of arsenic ions in the recycling stripping solution
against the numbers of runs through HFSLM at Aliquat 336 35% (v/v) and 0.5 M NaOH.
The flow rates of feed and stripping solutions were100 ml/min.
4.4. Relation between the concentration of arsenic ions in the
recycling stripping solution and the numbers of runs through the
hollow fiber module
For an application to control the amount of discharge, high
arsenic concentration in the stripping solution is observed. Liq-
uid membrane and feed solution were changed every third run
but the outlet stripping solution was continued recycling through
the HFSLM. The results in Fig. 14 indicated that for every third run
(3nd, 6th and 9th runs), the concentration of arsenic ions in the
stripping solution increased and no change was observed after the
9th run. This may be because sodium hydroxide solution might
react with the intermediates which formed within liquid mem-
brane (Figs. 4 and 5, and Eqs. (4)–(6)) until no sodium hydroxide
solution left. Therefore, no difference in concentration gradient
between the feed and stripping solutions.
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-
nary amine, showed higher extractability and recovery of arsenic
ions than TOA, a tertiary amine, because it reacted with both dis-
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
The authors wish to thank the Thailand Research Fund (TRF),
the Office of Small and Medium Enterprises Promotion (OSMEP)
for granting a research fund. Sincere thanks also go to the Pearl Oil
Thailand Ltd. for supplying of produced water and fruitful infor-
mation. The supports from the Separation Technology Laboratory,
Department of Chemical Engineering, Faculty of Engineering as well
as the Graduate School, Chulalongkorn University are appreciated.
334 U. Pancharoen et al. / Journal of Alloys and Compounds 482 (2009) 328–334
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