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J.chem.Technol.biotechnol.(2005)80 189-197 BLM Fenol

J.chem.Technol.biotechnol.(2005)80 189-197 BLM Fenol

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 Journal of Chemical Technology and Biotechnology J Chem Technol Biotechno
80
:189–197 (2005)DOI: 10.1002/jctb.1178
Extraction and pertraction of phenol throughbulk liquid membranes
Wojciech Cichy,
1
ˇ Stefan Schlosser
2
and Jan Szymanowski
1
1
Institute of Chemical Technology and Engineering, Poznan University of Technology, Pl Sklodowskiej-Curie 2, 60-965 Poznan, Poland
2
Department of Chemical and Biochemical Engineering, Slovak University of Technology, Radlinskeho 9, 81237 Bratislava, Slovakia
Abstract: The extraction and pertraction of phenol through a bulk liquid membrane (BLM) with Cyanex
923, Amberlite
LA-2 and trioctylamine (TOA) as carriers were studied. Cyanex
923 was selected asthe best carrier for pertraction. The distribution coefficient of phenol for solvents with carrier and pure
n
-alkanes, the individual mass-transfer coefficient at the extraction interface and the initial flux of phenolthrough the extraction interface (
  J 
Fo
) decreased in the order: Cyanex
923
>
Amberlite
LA-2
>
TOA
>>
pure
n
-alkanes. The opposite order was observed for the value of the mass-transfer coefficient inBLM and the maximum flux of phenol through the stripping interface (
  J 
Rmax
). At constant driving forcesthe maximum fluxes through the extraction and stripping interfaces were similar when amine carrierswere used. However,
Rmax
was lower than
Fo
for Cyanex
923. Although the kinetics of stripping was therate-determining step, the flux of phenol was significantly higher than in pertraction with amine carriers.The adsorption of the carrier at aqueous phase/membrane interfaces was probably responsible for therapid and slow transfer of phenol through the extraction and stripping interface, respectively.
2004 Society of Chemical Industry
Keywords:
phenol; extraction; pertraction; bulk liquid membranes; Cyanex
923; trioctylamine; Amberlite
LA-2
NOTATION
 A
Interface surface area (m
2
)
c
Concentration (gdm
3
)
D
Diffusion coefficient (m
2
s
1
)
D
Distribution ratio
D
a
Distribution ratio in the absence of carrier
 J 
Flux density (molm
2
s
1
)
k
Individual mass-transfer coefficient (ms
1
)
 K 
a
Dissociation constant (moldm
3
)
 K 
d
Dimerization constant (dm
3
mol
1
)
 K 
ex
Extraction constant (dm
3
mol
1
)
n
Degree of association
Time (h)
Phase volume (m
3
)S Extractant (carrier)
ν
Kinematic viscosity (m
2
s
1
)
Subscripts
F Feed phasemax Maximum flux of phenolM Membrane phaseo Initial valueR Stripping solutionMF Interface on the feed sideMR Interface on the strip side
Superscripts
T Overall concentration of component* Equilibrium valueWith overbar Organic phaseWithout overbar Aqueous phase
INTRODUCTION
Phenol and its derivatives are toxic pollutants,frequently found in surface and tap waters, andin aqueous effluents from various manufacturingprocesses.
1
As a consequence, they are listed in theUS Environmental Protection Agency priority list of pollutants and in the 76/464/EEC Directive of theEuropean Union, related to dangerous substancesdiscarded into the aquatic environment.Solvent extraction is the most often used techniqueto recover phenol (p
 K 
a
=
9
.
98) in its neutral form.
2
The use of simple organic solvents, such as benzene,heptane, toluene, methylisobutyl ketone, diisopropylether,isopropylether,methyl
tert 
-butylether,isopropylacetate, etc, is now limited due to the highhydrophilicity and solubility of these solvents inaqueous streams and/or their toxicity. The useof various basic and solvating reagents, including
Correspondence to:ˇ Stefan Schlosser, Department of Chemical and Biochemical Engineering, Slovak University of Technology,Radlinskeho 9, 81237 Bratislava, SlovakiaE-mail: schlosser@cvt.stuba.skContract/grant sponsor: Polish Scientific Committee; contract/grant number: DS 32/044/2004Contract/grant sponsor: VEGA; contract/grant number: 9136/02
Received 15 December 2003; revised version received 23 June 2004; accepted 13 August 2004
 )Published online 8 December 2004
2004 Society of Chemical Industry.
J Chem Technol Biotechnol 
0268–2575/2004/$30.00
189
 
W Cichy, S Schlosser, J Szymanowski
different alkylamines (eg Amberlite
LA-2, Alamine
336),
3
tributylphosphate, trialkylphosphine oxides
47
and trialkylphosphine sulfide
8
,
9
is now preferred.Classical extraction is sometimes connected withthe formation of a third phase and/or emulsification.As a result, phase disengagement problems mayoccur and can cause significant contamination of aqueous streams with chemicals and even stopthe continuous process. An emulsion is oftenformed in the stripping of phenol from loadedorganic phases with alkaline aqueous solutions asextractants, including commercial trialkylphosphineoxides. Such reagents contain some acidic substanceswhich after neutralization form strongly surface-active salts. These problems can be eliminatedusing pertraction through liquid membranes ormembrane-based solvent extraction in hollow fibercontactors. Although these processes also have somelimitations, including lower mass-transfer coefficientsand problems with stability of hollow fiber modulesin contact with solvent
10
they seem to be naturalsuccessors to traditional extraction.The transport of phenol through liquid membranescan be studied in contactors with a bulk liquid mem-brane (BLM). The advantage of these contactors istheir relative simplicity, the possibility of experimentaldetermination of concentrations in all three phases,and the possibility of visual observation of interfacesand phases. For a BLM with a lower density than thatoftheaqueousphase,theuseofH-typecontactors
11
,
12
is very convenient because all three phases can bestirred in such a way that identical hydrodynamicconditions at both interfaces can be reached.The aim of this work was to compare differentextractants/carriers, such as Cyanex
923, triocty-lamine (TOA) and Amberlite
LA-2, in the extractionand the transport of phenol through a BLM. Theadditional aim was to study the effect of the purifi-cation of Cyanex
923 from acidic substances uponthe extraction and pertraction performance and themass transfer. In previous work
13
it was found that thereagent exhibited atypical adsorption behavior at themembrane/alkaline strip phase, and the stripping stepwas significantly slower than extraction.
THEORY
At pH values above 4 for TOA and Cyanex
923 andabove5.5forAmberlite
LA-2,thestudiedextractants(carriers) form 1:1 complexes with phenol (PhOH):
7
PhOH
w
+
S
(PhOH)S
(
1
)
the bar denoting the organic phase, hereafter calledthe membrane phase. Simultaneously the physicalextraction of phenol into the membrane phase andthen the association of phenol, at least to the dimer,have to be considered. At pH
>
8, dissociation of phenol also occurs.The dissociation will be further important in theBLM experiments at the stripping interface, as thecomplex is decomposed and phenol is effectivelystripped.When the physical extraction and association of phenol to a dimer is considered, then the followingmass balance equations can be formulated:[PhOH]
T
=
[PhOH
·
S]
+
D
a
[PhOH]
w
+
nK 
d
(
D
a
)
n
[PhOH]
n
w
(
2
)
[S]
T
=
[S]
+
[PhOH
·
S]
(
3
)
The results of the BLM experiments are welldescribed by the model used by Boyadzhiev andAtanassova
14
for
-lysine recovery and by Schlosserand Sabolov´a
11
for the pertraction of butyric acid.The following assumptions were taken into accountin the development of a mass-transfer model in thetwo-compartment cell with a bulk liquid membrane:(i) fast chemical reactions of the formation anddecomposition of the complex phenol–carrier atthe interfaces, which means that diffusional mass-transfer in boundary layers is important;(ii) all three phases are well mixed and hydrodynamicconditions at both interfaces in the membrane areidentical, so
k
MF
=
k
MR 
=
k
M
;(iii) equilibrium at both interfaces;(iv) volumes of the feed, membrane, and the strippingphases do not change;(v) concentration of undissociated phenol in thestripping solution at the interface R/M (strippingsolution/membrane phase) is practically zero,whichmeansthattheconcentrationofthecomplexin the membrane at the strip interface is close tozero, as well.The resulting model equations are as follows:d
c
F
d
=
k
F
k
M
 A
F
(
D
F
c
F
c
M
)
F
(
k
F
+
k
M
D
F
)(
4
)
d
c
M
d
=
k
M
 A
M
k
F
 A
F
(
D
F
c
F
c
M
)
 A
(
k
F
+
k
M
D
F
)
c
M
(
5
)
d
c
d
=
k
M
 A
c
M
(
6
)
where for the concentration of the permeate in themembranephasethefollowingequationcanbewrittenfrom the material balance:
c
M
=
F
(
c
Fo
c
F
)
c
M
(
7
)
The initial flux of phenol through the extractioninterface and the maximum flux of phenol through thestripping interface were estimated from the followingequations:
 J 
Fo
=
F
 A
F
d
c
F
d
(
8
)
 J 
Mmax
=
 A
d
c
d
(
9
)
190
J Chem Technol Biotechnol 
80
:189–197 (2005)
 
Extraction and pertraction of phenol
The slope of the linear part of the time dependenceof 
c
, calculated from experimental data, is taken asd
c
/
d
.
EXPERIMENTAL METHODS
The following carriers were used as deliveredwithout any purification: Cyanex
923 (Cytec,Canada), trioctylamine (TOA) (Fluka, Germany) andAmberlite
LA-2 (Fluka, Germany). Cyanex
923contained trialkyl (C
6
, C
8
) phosphine oxides as theactivecomponentsandthehighpurityofthisindustrialreagent was recently demonstrated.
15
The reagentcontains,however,smallamountsofdialkylphosphinicacids that were observed on a gas chromatogram,but only after sample derivatization. This impuritycauses an atypical change of the interfacial tensionand formation of emulsions when the aqueousphase contains sodium hydroxide. Dialkylphosphinicacids were removed by gentle shaking of Cyanex
923 solution several times with fresh portions of 2kmolm
3
aqueous NaOH solution. The purificationwas stopped when the formation of a haze duringshaking was not observed.TOA had a purity better than 99%. Amberlite
LA-2 contained
-dodecyl-
 N 
-(1,1,3,3,5,5-hexamethyl-hexylamine) as the active substance.
n
-Alkanes (dodecane fraction, Slovnaft, Slovakia),purified by zeolite adsorption, were used as diluents.Their composition was as follows: aliphatic hydrocar-bons—99.8% (
n
-C
10
: 7.18%,
n
-C
11
: 32.39%,
n
-C
12
:33.11%,
n
-C
13
:26.84%and
n
-C
14
andhigherhomolo-ges: 0.28%) and aromatics: 0.03%. The compositionof the membrane phases and their characteristics areshown in Table 1. Viscosities of organic phases weredetermined by an Ubbelohde capillary viscometer.Extraction experiments were carried out at roomtemperature. Phases of various ratios were mechan-ically shaken for 3h and the content of phenol wasdetermined in the aqueous phases. The concentrationof phenol in the aqueous feed was changed from 1 to
Table 1.
Physical and transport properties of membrane phases(solvents): distribution coefficient of phenol
D
(at equilibrium phenolconcentration in the feed 0
.
8gdm
3
, and pH
F
=
4), kinematicviscosity of the membrane
ν
M
, and diffusion coefficient of thecarrier–phenol complex in the membrane phase
D
at 25
C calculatedby Wilke–Chang equation
16
Membranephase
ν
M
×
10
6
(m
2
s
1
 )
DD
×
10
10
(m
2
s
1
 )
D
·
D
×
10
10
(m
2
s
1
 )
 n
-Alkanes 1.60 0.124 14.2 1.70
.
4moldm
3
 TOA in
 n
-alkanes2.03 1.35 3.8 5.10
.
4moldm
3
LA-2 in
 n
-alkanes2.22 2.20 3.8 8.40
.
4moldm
3
Cyanex
923in
n
-alkanes2.30 42 4.7 197.4
10gdm
3
, and the pH of the feed was above 2 andvaried up to 11.In membrane experiments the aqueous feeds con-tained phenol (pure, POCh, Poland) (0
.
5–2gdm
3
),Na
2
SO
4
(
0
.
1kmolm
3
)
with pH values in the range1.2–6.0 (adjusted with H
2
SO
4
). The aqueous receiv-ing phase contained NaOH (0
.
05–2kmolm
3
). Theconcentration of the carrier in the membrane phasewas 0
.
4kmolm
3
.BLMexperimentswerecarriedoutat25
Cinatwo-compartmentcontactordesignedbySchlosser
11
,
12
andalso described in previous work.
13
The membranephase was mixed with Teflon disc mixers (29mmin diameter, distance between the center of discand interface 12mm) rotating in the same directionwith an adjustable frequency set at 120 min
1
in thecurrent experiments. Interfaces were stable up to afrequency of the membrane phase mixers of about135 min
1
. Aqueous feed and stripping phases weremixed by magnetic Teflon rod mixers (diameter 5mmand length 25mm) at a frequency of 95 min
1
. Asfound for the transport of citric acid and zinc,
17
thepermeate flux reached a steady state value betweenfrequencies from about 90 to 130 min
1
. Above thisvalueinterfacesbecameunstableandthetransportrateincreased due to the increase in the interfacial area.Volumes of phases were equal to: feed
F
=
310cm
3
, membrane
M
=
90cm
3
, stripping solution
=
130cm
3
. Interfacial areas were equal to:
A
F
=
21
.
53cm
2
,
A
=
20
.
19cm
2
.The content of phenol in the aqueous phaseswas determined spectrophotometrically using a (spec-trophotometer UNICAM 8625, UK). Samples werediluted with NaOH (0
.
1moldm
3
) to adjust the pHto well above the p
 K 
a
, and the content of phenolatewas determined at 270nm. The concentration of phe-nol in the organic (membrane) phase was determinedafter stripping of phenol into alkali solution where itwas analyzed spectrophotometrically.
DISCUSSION AND RESULTSLiquid/liquid equilibria and extraction of phenol
Initial screening experiments showed that each of the extractants considered could be used to recoverphenol from aqueous acidic and neutral solutions.Phenol could be efficiently stripped from the loadedorganic phase with NaOH (0
.
2moldm
3
). However,stable emulsions were formed in the stripping step inthe system containing Cyanex
923. The formationof emulsions was also observed in extraction whenthe concentration of phenol in the aqueous feed wasabove 2gdm
3
. Centrifuging was necessary to achieveseparation of phases. This negative effect was notobserved in systems containing amines and when thepurifiedCyanex
923wasused.Thus,thecommercialCyanex
923 had to be pre-washed with an alkalinesolution before use. However, it is necessary to pointout that the purification did not change the extractionabilities of the reagent.
 J Chem Technol Biotechnol 
80
:189–197 (2005)
191

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