Chemical Engineering Science 185 (2018) 141–148

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Chemical Engineering Science

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

Experimental and model studies of p–nitrophenol and phenol separation

in the bulk liquid membrane with the application of bond–graph method
Piotr Szczepański
Nicolaus Copernicus University in Toruń, Faculty of Chemistry, Gagarina 7, 87-100 Toruń, Poland

h i g h l i g h t s

Bond-graph model was formulated to elucidate the separation ability of the liquid membrane system.

Transport and separation of phenol and p-nitrophenol was analyzed.

The experimental verification of calculations results were carried out.

The effect of coupling between phenol and p-nitrophenol equilibrium distribution constants was elucidated.

Advantages of liquid membranes in separation are demonstrated.

a r t i c l e i n f o a b s t r a c t

Article history: A new method has been developed to describe the transport and separation of phenolic compounds in the
Received 4 October 2017 agitated bulk liquid membrane system (ABLM). The pseudo-thermodynamic network analysis was
Received in revised form 28 March 2018 applied to simulate the solution–diffusion transport of phenol (PH) and p–nitrophenol (PNP) with a fast
Accepted 3 April 2018
neutralization reaction in the stripping solution. The comparison of the experimental results in the sys-
Available online 5 April 2018
tem: PH, PNP aq. soln. (pH = 2)|cyclohexane|NaOH soln. (pH = 10) with the results of calculations indicate
that the model can be successfully applied for prediction of the time dependent PH/PNP separation char-
Keywords:
acteristics of the ABLM system under study. It was found that the separation PH/PNP factor attaining 50
Bond-graph modelling
Prediction of separation
was observed by experiments and calculations. The liquid membrane system can be considered as useful
Simultaneous liquid membrane transport for phenol removal from the mixture with PNP or PNP cleaning as the reagent for its specific applications.
Phenol and p-nitrophenol Ó 2018 Elsevier Ltd. All rights reserved.

1. Introduction liquid membranes (Boyadzhiev, et al., 1984; Boyadzhiev and

Transport and separation of various substances in the agitated
bulk liquid membrane systems composed of two aqueous phases
separated by an organic one is a typical example of practical appli-
cations of liquid membranes (Kislik, 2010). These membranes are
expected to be appropriate for treatment of aqueous wastes con-
taining phenol and phenolic compounds such as cresols,
chlorophenols, and nitrophenols (Arana, et al., 1999; Lin, et al.
2002; Correia and Carvalho, et al., 2003; Diaconu, et al., 2009a,
2009b, 2011; Szczepański and Diaconu, 2012a; Kargari, 2013).
For instance, the recovery of phenol by using emulsion liquid
membranes (ELM) (Gadekar, 1992; Correia Carvalho, et al., 2000;
Park, et al., 2006), supported liquid membranes (SLM) (Zha, et al.,
1994; Harriott and Ho, 1997; Venkateswaran and Palanivelu
2006), hollow fiber liquid membrane (HFLM) (Peretti, et al. 2001;
González–Muñoz, et al., 2003; Trivunac, et al., 2004) and bulk
E-mail address: piotrs@chem.uni.torun.pl
Alexandrova 1992; Cichy, et al., 2005; Diaconu, et al., 2009a,
2009b, 2011; Ng, et al., 2011; Szczepański and Diaconu, 2012a;
Ehtash, et al., 2014) with alkaline stripping solution was described
or reviewed by several authors.
The recovery of phenol and/or its derivatives from various aque-
ous phases is based on the difference in their w/o distribution coef-
ficients. In the case of liquid membranes exploiting the solution–
diffusion mechanism of operation, an additional differentiation
occurs due to the membrane transport kinetics (different interfa-
cial phenomena and diffusion characteristics). However, industrial
processing of chemicals results frequently in multicomponent
streams (Peretti, et al. 2001). Thus, the problem of ‘‘separation
between” becomes the key together with the ‘‘separation from”.
Note that only a few papers were published on the separation of
synthetic and real wastewater containing two, or more than two
phenolic compounds (Gadekar, 1992; Zeng, 1993; Ho, et al.,
1996; Harriott, et al. 1997; Arana, et al., 1999; Luan, et al., 2004;
Park, et al., 2006; Yu, et al. 2009). The results presented in these

https://doi.org/10.1016/j.ces.2018.04.007
0009-2509/Ó 2018 Elsevier Ltd. All rights reserved.
142 P. Szczepański / Chemical Engineering Science 185 (2018) 141–148
Nomenclature
List of symbols
A contact area between the membrane and external
solutions (cm2)
DS
ðjÞ
diffusion coefficient of S = PH, PHNa, PNP, PNPNa
and NaOH in the membrane (m), feed (f) or strip-
ping solution (s) (cm2/s)
JS flux of S (mol/cm2s)
.
k1,PC k1,PC extraction an re–extraction rate constant (cm/s) at
the f|m inteface
k2,PC re–extraction rate constants (cm/s) at the m|s
interface
ðjÞ
l thickness of membrane or diffusion layers (cm) for
j = f, m and s
li
ðjÞ
thickness of sub–layer (local diffusion distance)
(cm) for j = f, m and s
n(j) number of sub–layers for j = f, m and s
ðjÞ
PS permeability coefficient of S (cm/s)
ðjÞ
½PCb concentration of PC = PH or PNP in the bulk solu-
tion phase, for j = f and m (mol/cm3)
ðjÞ
½PCi local concentration of PC = PH or PNP for j = f and m
(mol/cm3)
papers indicate that the liquid membrane processes are an efficient
method for the pertraction of phenol (Boyadzhiev, et al., 1984;
Boyadzhiev and Alexandrova 1992; Zha, et al., 1994; Correia and
Carvalho, et al., 2003; González–Muñoz, et al., 2003; Trivunac,
et al., 2004; Cichy, et al., 2005; Venkateswaran and Palanivelu
2006; Ng, et al., 2011; Ehtash, et al., 2014), o–nitrophenol (Zeng,
1993; Yu, et al., 2009), and p–nitrophenol (Tompkins, et al. 1992;
Peretti, et al. 2001; Yu, et al., 2009; Szczepański and Diaconu,
2012a).
The referenced practical methods should be optimized which
needs some predictive models for solution–diffusion separations
as mediated by liquid membranes. It concerns mainly the pro-
cesses occurring in closed systems with fluxes changeable in time
and separation characteristics. The most widespread description
method exploits the so–called ‘‘resistances–in–series model”
(Tompkins, et al. 1992; Urtiaga et al., 1992; Trivunac, et al.,
2004; Reis, et al., 2007) used also for analyzing membrane based
extraction and integrated membrane based extraction–stripping
processes (Rodriguez, et al., 1997; Lazarova, et al., 2002; Vajda,
et al., 2003; González–Muńoz, et al., 2004; González–Muńoz,
et al., 2005; Asimakopoulou and Karabelas 2006; Shen, et al.,
2009). Alternatively, more advanced methods of thermodynamic
network analysis (TNA) can be applied for this purpose
(Szczepański and Wódzki, et al., 2013; Szczepański, et al., 2014).
It should be mentioned that in the practical applications of the
TNA, the method of equivalent electrical circuits (Peusner, 1986)
and the bond–graph method (Oster et al., 1971) are used alterna-
tively. For example, both the network simulation (which exploiting
the symbols and theory of electrical circuits) and the bond–graph
methods have been successfully applied in the studies of
biophysics of membrane phenomena (Oster et al., 1973;
Schnakenberg, 1981; Imai, 1989, 1996; Imai, et al., 1989;
Mikulecky, 2001) and the properties of synthetic membranes
(Srivastava and Mehta 1980; González–Caballero, et al., 1988;
Paterson, 1988; Horno, et al., 1989, 1990, 1994; Wódzki et al.,
1995, 2004; Simon et al., 1996; Castilla, et al., 1996, 1997a,
1997b; Moya, et al., 1999, 2001, 2015a, 2015b, 2016, 2017,
Ceynowa et al., 2001; Szczepański, et al., 2012b, 2013, 2014). How-
ever, up till now, no predictive models for the separation of pheno-
lic compounds has been presented in the literature.
ðjÞ
½PCNab concentration of neutralized PCNa = PHNa or
PNPNa in the bulk stripping solution phase, (mol/
cm3)
ðjÞ
½PCNai local concentration of neutralized PCNa = PHNa or
PNPNa in the stripping solution (mol/cm3)
ðsÞ
½NaOHb concentration of NaOH in the bulk stripping solu-
tion phase, (mol/cm3)
ðsÞ
½NaOHi local concentration of NaOH in the stripping solu-
tion (mol/cm3)
SC PH
PNP separation coefficient
ðjÞ
fSgi local capacitance for S = PH, PHNa, PNP, PNPNa,
NaOH and j = f, m or s
t time (s)
V ðjÞ overall volume (cm3)
ðjÞ
Vi volume of sub–layer (cm3)
aðmjfÞ
PC equilibrium distribution coefficient for PC = PH or
PNP
Superscripts
j = f, m, s indices for feed, membrane, and stripping solution
m|f and m|s membrane|feed and membrane|stripping solution
interface
In this paper, therefore, the system for the experimental sep-
aration of phenol (PH) from the mixture with p–nitrophenol
(PNP) and its theoretical description based on bond-graph
method is presented. The method is aimed at the numerical sim-
ulation for the prediction of the system separation ability
between PH and PNP. The experimental system is conventional,
i.e. it is composed of the simplest liquid membrane (agitated bulk
liquid membrane, ABLM) with no extractant/carrier in which PH
or PNP separation results from their solubility and/or diffusion
differences. On the other hand, the real conditions for modelling
and predicting separations are additionally represented by exper-
imental ABLM characteristics (volumes, composition, and pH of
the feed and/or striping solution, temperature, areas, etc.) which
should be taken into account when constructing any predictive
model.
2. Theoretical model
All the fundamental formulations necessary for network mod-
elling were described in previous papers (Wódzki, et al., 2004;
Szczepański, et al., 2012b, 2013, 2014) and the theory was refer-
enced therein. The formulation of: (i) the phenomenological model,
(ii) compartmental model, (iii) network model, and (iv) mathemat-
ical description usually represented by a set of ordinary, coupled,
differential equations, are common stages of network modelling.
The transport of undissociated phenolic compounds (PC„PH
and PNP) through BLM is driven by the prompt reaction with a
strong base (e.g. NaOH) occurring at the membrane–stripping solu-
tion interface. The overall process of pH and/or PNP pertraction can
be divided into five steps described and commented in details in
previous papers (Szczepański, et al., 2014) and marked also in
Fig. 1, i.e.:
(1) diffusion of PC from the bulk feed solution to the feed|mem-
brane (f|m) interface region,
(2) permeation of PC across the interface, from the aqueous to
the organic phase,
(3) transport of PC across the liquid membrane diffusion layers
at the membrane|feed (m|f), and membrane|stripping solu-
tion (m|s) interfaces,
 P. Szczepański / Chemical Engineering Science 185 (2018) 141–148 143

Fig. 1. Compartmental model of the solution-diffusion pertraction in an agitated bulk liquid membrane system (ABLM) with postulated concentration profiles in particular
diffusion layers: PNP – p-nitrophenol, PNPNa – sodium p-nitrophenolate, PH – phenol, PHNa- sodium phenolate.

(4) re–extraction of PC from the liquid membrane associated fluxes (J, mol/cm2s) of PH and PNP, and their sodium salts (PHNa,
with prompt neutralization of PC to PCNa in the stripping PNPNa) are defined by the phenomenological linear transport
solution, coupled with the diffusion of a neutralizing agent equations (from i sub–layer to i + 1 sub–layer):
(NaOH) across the diffusion layer in the stripping solution
ðfÞ
at the (m|s) interface, DPC ðfÞ ðfÞ
J i!iþ1
PC ¼ ðfÞ
ð½PCi  ½PCiþ1 Þ for PCPH or PNP ð1Þ
(5) diffusion of PCNa across the diffusion layer at the (m|s) li
interface to the bulk phase of the stripping solution.
ðsÞ
The simultaneous transport of PH and PNP unionized species DPCNa ðsÞ
J i!iþ1
PCNa ¼ ðsÞ
ð½PCNai
occur in a system in which feed (f) and stripping (s) aqueous solu- li
tions (volumes V(f) and V(s)) are separated by hydrophobic liquid ðsÞ
membrane of a volume V(m). The contact area between the mem-  ½PCNaiþ1 Þ for PCNa PHNa and PNPNa: ð2Þ
brane and adjacent liquids equals A. It was assumed that PC dif-
with NaOH flux:
fuses through aqueous solutions and liquid membrane diffusion
ðfÞ ðfÞ ðsÞ
layers with constant diffusion coefficients equal to DPH or DPNP , iþ1!i DNaOH ðsÞ ðsÞ
ðsÞ ðsÞ ðmÞ ðmÞ J NaOH ¼ ðsÞ
ð½NaOHiþ1  ½NaOHi Þ ð3Þ
DPHNa or DPNPNa , and DPH or DPNP respectively. The diffusion layers li
in the aqueous solutions (between the bulk phase of the feed (fb)
and strip (sb) and the f|m or m|s interface) are divided into n(f), For PH and PNP the interfacial extraction and re–extraction
and n(s) diffusion sub–layers (Wódzki, et al., 2004) whereas n(m) fluxes (mol/cm2s) are defined as follows:
diffusion sub–layers and one large central volume (mb, intensive
n  ½PC1 =aPC Þ for PC PH or PNP
ðmÞ ðmjfÞ
agitated sink phase) in the liquid membrane is established. The J fPCn !m1 ¼ k1;PC ð½PCðfÞ ð4Þ
process of extraction (R1,PH, R1,PNP) at the f|m interface and reex-
traction (R2,PH, R2,PNP) at the m|s interface with the fast neutraliza- Jm
PC
n !s1
¼ k2;PC ½PCðmÞ
n for PC PH or PNP ð5Þ
tion reaction (R3) in the receiving solution take place as typical
where k1;PC and k2;PC (cm/s) and aPC denote kinetic constants and
ðmjfÞ
stages. The liquid membrane diffusion layers are characterized by
ðmÞ equilibrium distribution coefficients for a given PC (between the
the capacitances of phenolic compounds fPC  PH; with
PNPgi
subscripts from i = 1 to k (k = 10) and from k + 1 (k + 1=11) to n membrane and aqueous feed phase). Because the fast and irre-
(n = 20) whereas the capacitance marked with subscript b denote versible neutralization reaction in the stripping solution was
n !s1
the liquid membrane sink phase. For simplification of PC diffusion assumed, the input fluxes of PHNa and PNPNa are equal to Jm PC

description, equivalent graph modules in a membrane
, and stripping solution were applied (Szczepański, et al.,
2014). It was assumed also that extraction and re–extraction of
PH and PNP occur between the f10 and m1 or mn and s1 sublayers
and are described by unimolecular reactions represented by graphs
R1,PH, R1,PNP and R2,PH, R2,PNP (Fig. 2). The interfacial phenomena pro-
cesses are characterized by kinetic rate constants k1,PC, k1,PC and
k2,PC (with PC = PH or PNP) for a forward and reverse process of
R1,PC and irreversible R2,PC, respectively. Because the conditions
for extraction and reextraction processes are different the respec-
tive values of re–extraction kinetic rate constant at the f|m
(k–1,PC) or m|s (k2,PC) interfaces are not equal (k–1,PC – k2,PC). Very
fast neutralization reaction R3 coupling the re–extraction fluxes
n !s1 2 !s1
of pH and PNP (J m PC ) and diffusional fluxes of NaOH, (J sNaOH
1 !s2
and PCNa (J sPCNa ) at the m|s interface. The full graph for the simul-
taneous pertraction of PH and PNP is presented in Fig. 2.
From the full graph, one can derive the mathematical descrip-
tion of all the local capacitances (concentrations in mol/cm3)
located along the permeation pathways. The local input and output
, feed (Eq. (5)). In Table 1 the set of differential equations and other trans-
port characteristics describing the properties of the membrane sys-
tem are presented.
3. Model calculations and experimental results
The equations derived from bond–graph analysis, the opera-
tional parameters (volumes, contact area, initial concentrations,
etc.), and other characteristics listed in Table 1 were used in model
calculations. Taking into account some data reported by Arana
et al. (1999), the thickness of interfacial diffusion layers (l(j), j = f,
s, m) was assumed to be 2.5  103 cm. In the pertraction process,
both PH and PNP diffuse throughout the aqueous and liquid mem-
ðfÞ ðmÞ ðsÞ
) brane diffusion layers with diffusion coefficients (DPC , DPC , DPCNa ,
PC = PH or PNP) the values of which (Table 1) were evaluated by
applying Wilke–Chang equation (Reid and Sherwood 1966). The
diffusion coefficient of NaOH at 0.01 mol/dm3 concentration
ðsÞ
(DNaOH = 2.0  105 cm2/s) reported by Noulty and Leaist (1984),
was applied for calculations.
144 P. Szczepański / Chemical Engineering Science 185 (2018) 141–148
Fig. 2. Network for the pertraction of phenol and p-nitrophenol.
Equilibrium distribution constants for PH (aPH ) and PNP (aPNP )
ðmjfÞ
were determined experimentally as described below. Kinetic con-
stants k1,PC and k2,PC (PC = PH or PNP) for interfacial permeations
were adjusted by fitting the calculated data to the experimental
ones.
The fourth–order Runge–Kutta method (Berkeley Madonna pro-
gramme v. 8.1) was applied to solve the differential equations from
Table 1. The time dependent concentrations of the transported spe-
cies as the basic results of calculations were then used for calculat-
ing the separation coefficients (SC PH
PNP ) according to Eq. (6).
ðsÞ ðfÞ
½PHNab ½PNPb
SC PH
PNP ¼ ðfÞ ðsÞ
½PHb ½PNPNab
3.1. Reagents
The p–nitrophenol (PNP), phenol (PH), cyclohexane, hydrochlo-
ric acid, and sodium hydroxide solutions as well as cyclohexane
(analytical grade, supplied by POCh, Gliwice, Poland) were used
in the pertraction experiments. The NaOH was used for preparing
the stripping solution (s), while hydrochloric acid was used for
the pH adjustment of the feed phase (f).
3.2. Partition coefficients
Distribution coefficients for PH and PNP between cyclohexane
and aqueous solutions were determined by solvent-solvent extrac-
tion method at 25 ± 1 °C from their mixture. 20 cm3 of aqueous PH
and PNP solutions of concentrations in the range from 1  104 up
to 0.01 mol/dm3 (pH = 2 adjusted by HCl) were shaken over 24 h
with 20 cm3 of cyclohexane. It should be noted that the solubility
of PH in the aqueous solutions is much higher than the solubility
ðmjfÞ of PNP (Jaoui, et al., 2002). Therefore only the influence of high
PH concentration (from 0.01 M up to 0.5 M) on PNP distribution
was additionally investigated.
PH and PNP concentrations in the aqueous phases before and
after extraction were analyzed by the UV spectroscopy method
(described below). The mass balance rule was applied for calcula-
tion the concentration of PC in the organic phase. The following
equation was used for equilibrium distribution coefficient
evaluation:
aðmjfÞ ¼ aPC ¼ ½PCðorg:Þ ðaq:Þ
PC eq: =½PCeq: ; PC ¼ PH; PNP ð7Þ
ð6Þ
3.3. Extraction kinetics and pertraction experiments
The kinetics of PC extraction from their 1:1 equimolar mixture
into cyclohexane was studied in the half–cell system used in the
pertraction experiments (Szczepański, et al., 2014). The pertraction
experiments were carried out in the experimental ABLM set up
described in previous paper (Szczepański, et al., 2014) with the
contact area equals 17 cm2. The system was composed of two
aqueous solutions of 200 cm3 each and the liquid membrane of
150 cm3 cyclohexane. All these phases were agitated at the rate
of 375 rpm. The system was thermostated at 25 ± 0.1 °C.
The initial feed concentration was 2.027  104 mol PH/dm3
and 1.995  104 mol PNP/dm3. The solution was acidified
(pH ffi 2) by adding 1 M soln. of HCl. The initial NaOH concentration
in the stripping solution was 0.01 M. The time dependent concentra-
tions of PNP or PNPNa and PH or PHNa in aqueous solutions were
determined using a UV–Vis spectrophotometer (UV–2101PC Shi-
madzu). The PNP absorbances were measured at wavelengths 317
(PNP) and 404 nm (PNPNa). The PH concentrations were determined
in alkalized samples at 510 nm after the reaction with 4–aminoan-
tipyrine and K3Fe(CN)6 (Ettinger, et al., 1951).
 P. Szczepański / Chemical Engineering Science 185 (2018) 141–148 145

Table 1
Mathematical model and data for model calculations.

Time evolution of local concentrations of phenolic compounds, PC„PH or PNP, (mol/cm3∙s)

Feed solution (f) Stripping solution (s)
ðfÞ b !f 1 ðfÞ ðsÞn !s1 s1 !s2 ðsÞ
d½PCb =dt ¼ JfPC A=V b d½PCNa1 =dt ¼ ðJm
PCNa  J PCNa ÞA=V 1
ðfÞ b !f 1 1 !f 2 ðfÞ ðsÞ i1 !si si !siþ1 ðsÞ
d½PC1 =dt ¼ ðJ fPC  J fPC ÞA=V 1 d½PCNai =dt ¼ ðJsPCNa  JPCNa ÞA=V i i ¼ 2 . . . ðn  1Þ
  sn !sb

ðfÞ
d½PCi =dt ¼ f i1 !f i
J PC
f i !f iþ1
 JPC
ðfÞ
A=V i i ¼ 2 . . . ðn  1Þ d½PCNaðsÞ
n =dt ¼ sn1 !sn
JPCNa  J PCNa A=V nðsÞ
  ðsÞ ðsÞ
n !sb
d½PCnðfÞ =dt ¼ J fPC
n1 !f n n !m1
 JfPC A=V ðfÞ
n
d½PCNab =dt ¼ J sPCNa A=V b

Membrane (m)
  ðmÞ m !mkþ1
ðmÞ
ðmÞ ðmÞ k !mb
n !m1
d½PC1 =dt ¼ J fPC  Jm
PC
1 !m2
A=V 1 d½PCb =dt ¼ Jm
PC  JPCb A=V b
ðmÞ mi1 !mi mi !miþ1
ðmÞ ðmÞ m !m m !m
ðmÞ
d½PCi =dt ¼ JPC  JPC A=V i i ¼ 2 . . . ðk  1Þ and i ¼ ðk þ 2Þ . . . ðn  1Þ d½PCkþ1 =dt ¼ J PCb kþ1  JPCkþ1 kþ2 A=V kþ1
ðmÞ k1 !mk k !mb ðmÞ ðmÞ mn1 !mn mn !s1 ðmÞ
d½PCk =dt ¼ ðJ m
PC  Jm
PC ÞA=V k d½PCn =dt ¼ ðJPC  JPC ÞA=V n

Fluxes (mol/cm2∙s)
Feed solution (f) Stripping solution (s)
b !f 1 ðfÞ ðfÞ ðfÞ s !s ðsÞ ðsÞ ðsÞ
JfPC ¼ 2P PC ð½PCb  ½PC1 Þ a J PCNa
i iþ1
¼ P PCNa ð½PCNai  ½PCNaiþ 1 Þ
f i !f iþ1 ðfÞ ðfÞ ðfÞ siþ1 !si ðsÞ ðsÞ ðsÞ
JPC ¼ P PC ð½PCi  ½PCiþ 1 Þ J NaOH ¼ P NaOH ð½NaOHiþ1  ½NaOHi Þ
i ¼ 1 . . . ðn  1Þ i ¼ 1 . . . ðn  1Þ
n !sb ðsÞ ðsÞ
J sPCNa ¼ 2P PNPNas ð½PCNaðsÞ
n  ½PCNab Þ
a

b !sn ðsÞ ðsÞ

J sNaOH ¼ 2P NaOH ð½NaOHb  ½NaOHðsÞ
n Þ
a

f|m interface m|s interface

n !m1
JfPC ¼ k1;PC Að½PCðfÞ
n  ½PC1 =aPC Þ
ðmÞ ðmjfÞ
Jm
PC
n !s1
¼ k2;PC A½PCnðmÞ

Membrane (m) Definitions

m !miþ1 ðmÞ ðmÞ ðmÞ ðfÞ ðfÞ ðfÞ ðmÞ ðmÞ ðmÞ
JPCi ¼ P PC ð½PCi  ½PCiþ 1 Þ, P PC ¼ DPC =li ; P PC ¼ DPC =li
k !mb ðmÞ ðmÞ ðmÞ ðsÞ ðsÞ ðsÞ ðsÞ ðsÞ ðsÞ
i ¼ 1 . . . ðk  1Þ and i ¼ ðk þ 1Þ . . . . . . :ðn  1Þ J m
PC ¼ 2P PC ð½PCk  ½PCb Þ a P PCNa ¼ DPCNa =li ; P NaOH ¼ DNaOH =li ; cm/s
m !m ðmÞ ðmÞ ðmÞ ðfÞ ðfÞ ðmÞ ðmÞ ðsÞ ðsÞ ðfÞ ðfÞ ðm ðm ðsÞ ðsÞ
JPCb kþ1 ¼ 2P PC ð½PCb  ½PCkþ 1 Þ a li ¼ l =n; li ¼ 2l =n; li ¼ l =n; cm V i ¼ li A; V i ¼ li A; V i ¼ li A
ðfÞ ðfÞ ðfÞ ðmÞ ðmÞ ðmÞ
V b ¼ V  l A; V b ¼ V  2l A;
ðsÞ ðsÞ
V b ¼ V ðsÞ  l A; cm3
sn !sb
J output
PCNa ¼ J PCNa mol/cm s
2

Data for calculations:

ðmjfÞ ðmjfÞ
Experimental system: V(f) = V(s) = 200, V(m) = 150 cm3, A = 17 cm2, aPH = 0.159, aPNP = 0.0149
Initial concentrations, mol/cm3:
[PH](f) = 2.027  107, [PH](m) = [PNP](m) = [PHNa](s) = [PNPNa](s) = 0, [PNP](f) = 1.995  107, [NaOH](s) = 1  105
Literature data:
l(f) = 0.0025, l(s) = 0.0025, l(m) = 0.0025 cm,
ðfÞ ðsÞ ðmÞ ðfÞ ðsÞ ðmÞ
DPH = DPHNa = 1.15  105,DPH = 1.54  105, DPNP = DPNPNa = 1.07  105, DPNP = 1.43  105,
ðsÞ
DNaOH = 2  105 cm2/s
Adjusted values: k1,PH = 3.38  104, k2,PH = 9.64  104, k1,PNP = 7.32  105, k2,PNP = 6.13  104 cm/s
a
the coefficient equal to 2 means that the diffusion distance from the centre of edge diffusion sub-layers to the feed, stripping or membrane bulk phase equals to one half of
that between diffusion sub-layers.

4. Results and discussion

4.1. Partition coefficients

Into an organic phase only the undissociated species of phenolic

compounds are extracted. The results of experiments for PH and
PNP initial concentration ranging from 1  104 to 0.01 M at acidic
pH are presented in Fig. 3 as the plots of equilibrium concentra-
tions of PH and PNP in cyclohexane vs. the respective concentra-
tions in the aqueous solution. Thus, the slopes of the linear plots
represent the distribution coefficient aPC defined as the equilib-
rium concentrations ratios for PNP or PH. For the initial PH and
PNP concentrations studied, they attain 0.159 and 0.0149, respec-
tively. The confidence limits at the 95% level of significance are
0.148–0.170 (PH) and 0.0138–0.016 (PNP). These values are com-
parable with the literature data for phenol 0.1–0.19 and p–nitro-
phenol 0.0117–0.0162 (Leo, et al., 1971). The linearity of plots
(r 2PH ¼ 0:9990 and r 2PNP ¼ 0:9990) indicates the practical indepen-
dence of distribution coefficients on PH and PNP concentrations
and their presence in a mixture. However, for some higher concen-
trations of PH, i.e. in the range from 0.01 to 0.5 mol/dm3 one can Fig. 3. Distribution of phenol and p-nitrophenol between cyclohexane and water
observe that the distribution coefficient of PNP becomes for low initial aqueous concentrations (from 1  104 to 0.01 M).
146 P. Szczepański / Chemical Engineering Science 185 (2018) 141–148

dependent on PH concentrations according the following empirical

relationship:

aPNP ¼ 0:014  0:02  ½PHaq ð8Þ

Thus, according to Eq. (8), the phenol concentration dependent

distribution coefficient of PNP was introduced into the model in
Table 1 instead of its constant value when PNP is dissolved in a
more concentrated phenol solution.

4.2. Experimental pertraction results and model calculations

In the case of phenolic compounds pertraction and separation,

the following phenomena should be taken into account:

ðfÞ
(a) the PNP and PH removal from the feed, ½PNPb and
ðfÞ
½PHb ¼ f ðtÞ;
(b) the accumulation of neutralized PNP and PH in the stripping
ðsÞ ðsÞ
solution, ½PNPNab and ½PHNab ¼ f ðtÞ;
(c) time dependence of separation ability (separation factor), i.e.
SC PH
PNP = f(t) Fig. 5. Competetive extraction of pH and PNP in the system with cyclohexane. s-
concentration of pH in aqueous solution, O- concentration of PNP in aqueous
The calculations of the PNP or PH concentration in the feed and solution.

PNPNa or PHNa in the stripping solution were carried out using

optimized rate constants (best fit procedure in Berkeley Madonna
Fig. 6. From the presented results, one can conclude that, despite
Programme) and presented in Fig. 4 as the continuous line. The
low distribution coefficient, the system effectively separates PH
experimental points correspond with two independent experimen-
from the mixture with PNP. The separation coefficient attains the
tal series (30 or 100 h of continuous process of pertraction).
value of ca. 50 after 100 h of transport, i.e. at 92% of pH recovery
In order to verify kinetic constants k1,PH = 3.38  104 cm/s and
from the feed solution. Note that the same coefficient for the
k1,PNP = 7.32  105 cm/s, additional extraction kinetics experiments
extraction process can attain the value equal to the ratio of distri-
of these compounds were carried out. Independently established
bution coefficients, i.e. ca. 10. Thus, if the liquid–liquid extraction
constants equals k1,PH = 2.44  104 cm/s and k1,PNP = 7.62 
process is replaced by the liquid membrane process, the low distri-
104/5 cm/s, i.e. they are comparable with these observed in per-
bution coefficients no longer present a problem for the phenol
traction experiments. The plots corresponding with the extraction
removal and PNP cleaning from that compound.
kinetics are presented in Fig. 5.
In the previous paper (Szczepański, et al., 2014), the influence of
The results indicated that, according to the physicochemical
interfacial extraction kinetics on PNP pertraction was additionally
properties of the liquid membrane system, phenol is preferentially
analyzed. For this purpose, the interfacial concentration ratio of
transported from the feed solution to the membrane and then to ðmÞ ðfÞ
the receiving solution in which neutralization reaction at the m|s transported PNP (½PNP1 =½PNP10 ) was calculated from TN model
interphase takes place. The overall separation effect is represented and compared with distribution coefficient value (i.e. 1.21 for
water/toluene system). It was found that the calculated values
by the time dependent separation curve (SC PH
PNP = f(t)) shown in

Fig. 4. Competetive pertraction of pH and PNP in the ABLM system with LM made
of cyclohexane. Two independent experimental series: feed solution d,s, - PH, . O Fig. 6. Separation factor SC PH
PNP for competetive pertraction of pH and PNP:
- PNP; stripping solution: jh-PH, N,4 - PNP. continuous line – calculated data, points – experimental data.
 P. Szczepański / Chemical Engineering Science 185 (2018) 141–148
depends on the liquid membrane volume and amounts only 20–25%
of its equilibrium value. Such results indicated that the ABLM system
for PNP pertraction in which toluene is used as the liquid membrane
phase cannot be described by a simple solution diffusion model with
interfacial processes at equilibrium. The same calculations were car-
ried out for the system presented herein (PH and PNP simultaneous
transport through cyclohexane as the liquid membrane). The inter-
facial concentration ratio values equals 75 and 91% for PH and PNP,
respectively. These values indicated that interfacial processes are
fast when compared with the diffusional ones. Therefore, in the con-
ventional resistance in series models, the equilibrium at the inter-
face can be assumed, especially for the phenolic compounds with a
lower distribution coefficient i.e. PNP.
5. Conclusion
It can be concluded that developed a new mathematical model
can be applied for description of the simultaneous pertraction and
separation of the PC in the ABLM system. Moreover, the bond-
graph model elaborated using known operation parameters (vol-
umes, concentrations, contact area) and physicochemical parame-
ters (distribution coefficients, diffusion coefficients) satisfactorily
well predicts the time-dependent concentrations of the PC as well
as the time dependent separation coefficient and takes into
account the effect of coupling between PH and PNP equilibrium
distribution constants.
The calculated and experimental data confirmed that PH can be
effectively separated from the mixture with PNP, i.e. the system
can be exploited for the PH recovery and/or for cleaning PNP from
PH. Moreover, the separation coefficients are significantly larger in
comparison to the classical liquid–liquid extraction processes. It
was also found that for low feed phase concentration (up to 0.01
M, i.e. typical for the liquid membrane systems applicability) the
effect of coupling between PH and PNP equilibrium distribution
constants is not observed.
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