Chemical Engineering and Processing 87 (2015) 81–87

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Chemical Engineering and Processing:

Process Intensification
journal homepage: www.elsevier.com/locate/cep

Pervaporation composite membranes for ethyl acetate production

Anastasia Penkova a, *, Galina Polotskaya a,b , Alexander Toikka a
a
St. Petersburg State University, Department of Chemical Thermodynamics & Kinetics, Universitetsky pr. 26, Peterhof, St. Petersburg 198504, Russia
b
Institute of Macromolecular Compounds, Russian Academy of Sciences, Bolshoy pr. 31, St. Petersburg 199004, Russia

A R T I C L E I N F O A B S T R A C T

Article history: This paper continues research on the physicochemical features of nanocomposites of poly(2,6-dimethyl-
Received 11 July 2014 1,4-phenylene oxide) (PPO) and fullerene C60 with the purpose of using them as a selective layer of
Received in revised form 22 October 2014 composite membranes in pervaporation coupling esterification of acetic acid with ethanol to produce
Accepted 22 November 2014
ethyl acetate. The C60–PPO/MFFC composite membranes containing up to 3 wt%C60 were prepared in this
Available online 25 November 2014
work. SEM was employed in visualizing the internal morphology of the membranes. The nature of the
interaction between PPO and C60 molecules in composite was studied by NMR. TG analysis reveals the
Keywords:
fact of increasing thermal destruction point of the membrane due to certain structural changes of the PPO
Pervaporation
Hybrid process
matrix upon incorporation of the C60 molecules. Transport properties of composite membranes with a
Polymer membranes selective layer containing up to 3 wt%C60 were studied in the pervaporation of the quaternary mixture:
PPO ethanol, acetic acid, ethyl acetate, and water in order to identify the availability of their use in the hybrid
Fullerene process “esterification + pervaporation”. The strong permeability enhancement due to the introduction of
C60 particles in the PPO network was observed whereas the selectivity was almost steady. The best
complex of transport properties was obtained from the 2%C60–PPO/MFFC membrane.
ã 2014 Elsevier B.V. All rights reserved.

!
1. Introduction CH3 COOH þ C2 H5 OH CH3 COOC2 H5 þ H2 O

The increase in industrial applications of pervaporation using

membrane separation technology is due to the numerous
advantages of this method. In some cases to enhance performance
of chemical synthesis or technological production, the pervapora-
tion can be involved in engineering design of hybrid processes
[1–3]. One of the perspective hybrid processes is combining
esterification and pervaporation for the purpose of esters
production. Esterification of carboxylic acids and alcohols is a
typical example of an equilibrium-limited reaction that produces
ester and water as products. Nearing reaction equilibrium, the
conversion is generally low and increases cost by using an excess of
reactant for the shifting from equilibrium [4]. Accordingly,
removing reaction products in the course of the reaction inhibits
chemical equilibrium. Therefore, removing the ester or water by
pervaporation is a useful technology for ester synthesis reaction.
The reaction studied for the application of pervaporation is an
esterification of acetic acid with ethanol to produce ethyl acetate
and water:
* Corresponding author. Tel.: +7 812 428 48 05.
E-mail address: a.penkova@chem.spbu.ru (A. Penkova).
In our previous work we studied a similar case involving the
synthesis of methyl acetate [5]. The fundamentals of esterification
facilitated by pervaporation are presented in the paper [6].
To isolate one of the reaction products, either ester or water,
different types of polymer membranes can be used [5]. In the
majority of known cases, hydrophilic membranes have been
applied, which promote the release of water from the reaction
vessel (tank) [7–15].
The removal of the ester, not water, is economically viable
because the ester elimination not only diverts the reacting system
from equilibrium, but also promotes the separation of an
important industrial solvent from the reaction mixture. For ester
separation, membranes based on hydrophobic materials such as
polydimethylsiloxane are often used [16–18]. Use of PDMS
membranes is not always efficient because these membranes
require the procedure of PDMS cross-linking and show low
selectivity.
In our previous works [19–22] dense membranes based on poly
(2,6-dimethyl-1,4-phenylene oxide) (PPO) modified by fullerene
C60 (up to 2 wt%) were developed and studied in the pervaporation
of mixtures containing species that are reagents and products of
ethyl acetate synthesis. The conditions of the pervaporation

http://dx.doi.org/10.1016/j.cep.2014.11.015
0255-2701/ ã 2014 Elsevier B.V. All rights reserved.
82 A. Penkova et al. / Chemical Engineering and Processing 87 (2015) 81–87
experiment and the C60–PPO composite preparation were identical
to the applied conditions in this paper. These membranes are
selective to the ester and exhibit a good separation factor but low
flux in the separation of binary and multicomponent mixtures
containing ethyl acetate. For example, in the works [20–22], using
the dense PPO membrane in the pervaporation of a four-
component mixture with equimolar ratio of reagents—16.7 mol%
of acetic acid, 16.7 mol% of ethanol, 33.3 mol% ethyl acetate and
33.3 mol% water (18.9 wt% acetic acid, 14.6 wt% ethanol, 55.2 wt%
ethyl acetate and 11.3 wt% water)—led to the permeate containing
81.6 wt% ethyl acetate. However, the flux was only 0.059 kg/m2,
which is insufficient for a hybrid process on an industrial scale.
Thus, establishing high selective properties in dense membranes
based on PPO make them promising for use in ethyl acetate
production. However, low permeability is a significant disadvan-
tage. Flux is largely determined by the thickness of a membrane,
which is about 60 mm in the case of dense PPO membranes.
Improving the fluxes is possible by decreasing membrane
thickness: it may lead to the increase of fluxes but simultaneously
causes a deterioration of the mechanical properties. One of the
ways to preserve the mechanical characteristics may be the
development of composite membranes.
In this paper we continue research on the structure and
physicochemical properties of the C60–PPO nanocomposites (up to
3 wt%) for use in membrane technology, e.g., as a selective layer of
composite membranes. The transport properties of composite
membranes with different concentration of C60 were investigated
in pervaporation of a four-component mixture—ethanol, acetic
acid, ethyl acetate, and water—to identify their prospective use in
the hybrid process “esterification + pervaporation”. In studying
pervaporation of quaternary mixtures, the results of experiments
on the separation of binary mixtures water–ethanol and water–
ethyl acetate were taken into account [19,21].
2. Experimental
2.1. Materials
PPO with a molecular weight of 172,000 and intrinsic viscosity
1.58 dl/g (Brno, Czech Republic) and fullerene C60 of 99.9% purity
(NeoTechProduct, Research & Production Company, Russia) were
used for the work. Ethyl acetate, ethanol, acetic acid, toluene, and
chloroform were purchased from Vecton (Russia). The MFFC
microfiltration fluoroplastic composite hydrophobic membrane
(Vladipor, Russia) was composed of a porous fluoroplast F42L layer
on polypropylene support; the pore size was 0.05 mm, with a total
porosity of 80%.
2.1.1. Preparation of composites
The C60–PPO composites were prepared by mixing solutions of
PPO in chloroform (2 wt% PPO) and fullerene C60 in toluene (0.14 wt
% C60) in amounts that provided the required content of fullerene in
the composite (up to 3 wt% C60). The resulting solution was allowed
to stand for 3–4 days for interactions to take place between the
polymer and fullerene C60 molecules. Next, the composite solution
was sonicated for 40 min and filtered to remove dust contami-
nants.
2.1.2. Membrane preparation
Dense membranes based on PPO and composites C60–PPO with
the thickness 60 mm were obtained by casting a 8 wt% polymer
solution on a cellophane surface. The solvent was removed by
evaporation at 40  C; the membrane was separated from the
substrate and dried in a vacuum oven at 40  C up to the constant
weight.
Composite membranes were prepared by casting 2 wt% PPO (or
C60–PPO) solutions in chloroform on the surface of an MFFC
support consisting of a fluoroplast F42L layer and polypropylene
base. To create a selective layer with 4–6 mm thickness, 0.03 ml of
polymer solution per 1 cm2 of the membrane was split. Then, the
composite membrane was dried in a vacuum oven at 40  C up to
constant weight.
2.2. Characterization
2.2.1. Nuclear magnetic resonance (NMR)
NMR spectra were recorded at the Center of Magnetic
Resonance of the St. Petersburg State University using a
BrukerAvance III spectrometer operating at a magnetic field
strength of 9.39 T, corresponding to Larmor frequency of
100.6 MHz for 13C nuclei. Experiments were carried out using
Bruker wide-bore 3.2 mm MAS probe. Chemical shifts are
referenced relative to the low field signal of adamantane at
38.48 ppm. Two types of experiments were applied to both PPO
and C60–PPO samples: (i) direct polarization of 13C with high power
1
H decoupling at a MAS rate of 5 kHz; and (ii) cross-polarization
from 1H with spinning sideband suppression (CP TOSS) using
contact pulse durations of 2 ms at a MAS rate of 7 kHz.
2.2.2. Thermal gravimetric (TG) analysis
Thermal degradation measurements of the membrane samples
were performed at the Resource Center of Thermal Analysis and
Calorimetry of St. Petersburg State University using TG 209 F3 Iris
Thermo-microbalance (Netzsch) at a heating rate of 10  C min and
airflow of 50 ml/min.
2.2.3. Scanning electron microscopy
Scanning electron microscopy (SEM) micrographs were
obtained with a microscope Zeiss Merlin SEM. Membranes were
submerged in liquid nitrogen for 5 min and fractured perpendicu-
larly to the surface. The prepared specimens were uncoated and
the fracture surfaces and sides membranes were observed under
the SEM microscope using secondary electrons at 1 kV.
2.2.4. Swelling study
Two types of dry non-porous membranes from PPO and from
fluoroplast F42L were immersed in liquid at 20  C and atmospheric
pressure for 7 days. At definite intervals, the swollen membranes
were taken out from the weighing bottles, carefully wiped with
filter papers to remove residue liquid on the membrane surface,
and then quickly weighed. The experiment was carried out until
the swollen membranes obtained a constant weight that indicated
a state of sorption equilibrium. Then, the membranes were placed
in a vacuum box at 40  C for 7 days to control the weight of the dry
membranes. The liquids under the study were water, ethanol,
acetic acid, and ethyl acetate. The degree of the swelling was
calculated by the following equation:
Ms  Md
Sw ¼  100 (1)
Md
where Ms is the weight of a swollen membrane in equilibrium state
and Md is the weight of a dry membrane.
2.2.5. Pervaporation test
Pervaporation properties were studied using a laboratory cell
with an effective membrane area of 14.8 cm2 at 20  C with stirring.
A downstream pressure of <101 mmHg was maintained. The
permeate was collected in a liquid nitrogen trap, weighed, and then
analyzed by gas chromatography. A gas chromatograph “Chroma-
tec Crystal 5000.2” (Russia) with thermal conductivity detector
was used.
 A. Penkova et al. / Chemical Engineering and Processing 87 (2015) 81–87 83

The fluxes, J (kg/m2 h), were determined as an amount of liquid reveals some noticeable differences that are possibly due to
transported through the unit of the membrane area per hour. structural changes in the matrix upon incorporation of the
Pervaporation separation index (PSI) was calculated by the fullerene C60 molecules.
following equation: The effect of fullerene C60 additives in the PPO matrix on the
! thermal stability was determined by a TG analysis of the samples.
C pEA Fig. 2 demonstrates that thermal destruction of PPO films
PSI ¼ J  1 (2)
C fEA begins at 370  C, while thermal destruction of the C60–PPO
composite occurs at 420  C and rises dramatically, approximately
where CpEA is the concentration of ethyl acetate in the permeate,
in one point. This result can be explained as due to structural
CfEA is the concentration of ethyl acetate in the feed.
changes of the matrix upon incorporation of the C60 molecules. It is
Pervaporation experiments were carried out at least three times
known that fullerene C60 molecules are capable of strong
for each of membrane type to study the reproducibility and
intermolecular interaction because of many conjugate links in
calculate experimental errors.
the structure of C60 [26]. When C60 content exceeds 0.15 mol%,
opportunities for interaction between C60 and C60 molecules in the
3. Results and discussion
PPO–C60 system may increase, which leads to physical linking of
polymer chains [27].
3.1. Dense film characterization
SEM was applied in visualizing the internal morphology of
membranes. SEM micrographs of fracture surfaces perpendicular
The possibility of donor-acceptor binding between PPO and
to the membrane surfaces, so called cross-sections, are shown in
C60 molecules in composites was shown by IR spectroscopy,
Fig. 3. A pure PPO membrane (Fig. 3a) exhibited comparatively
luminescence, etc., in work [23]. In this work, the character of
uniform morphology. The structure of the 2%C60–PPO membranes
interaction between PPO and C60 molecules was investigated by
changed (Fig. 3b), which also proves that the formation of
nuclear magnetic resonance.
nanocomposites occurs through the interaction of the fullerene
The 13C NMR spectrum of neat Buckminster fullerene
C60 with polymer chains.
C60 (Fig. 1a) contains only a sharp single line with a chemical
shift of 142.68 ppm [24]. After incorporation into the PPO matrix,
3.2. Transport properties
its signal shifts ca. 1.2 ppm to the high-field and broadens (Fig. 1c).
This change indicates an interaction between fullerene molecules
The transport properties of membranes were studied in
and the polymer matrix, which slows down fast isotropical
pervaporation of mixtures of reagents and products of ethyl
reorientation of the former. However, other conclusions follow
acetate synthesis reaction (i.e., ethanol, acetic acid, water, and
from the spectrum of the C60–PPO sample obtained under cross-
ethyl acetate).
polarization (CP) conditions (Fig. 1e) in which 13C magnetization is
Table 1 lists the physical properties of substances under study,
developed due to energy transfer from 1H nuclei via a hetero-
which are called penetrants in pervaporation. Data on the
nuclear magnetic dipolar interaction and thus is sensitive to
solubility parameter (d) of substances can be used to predict the
internuclear distances and the mobility of molecules or functional
solubility of a polymer in these liquids [28]. According to the
groups involved [25]. It is evident that the C60 signal is small in
solubility theory [29], the less the difference in solubility
comparison with the signal in the direct 13C observation
parameters of polymer and penetrant |Dd|, the better the solubility
experiment (Fig. 1c). This observation might indicate an insuffi-
of the penetrant in the polymer. The solubility parameter of PPO is
cient interaction of the C60 molecules with the PCO matrix: they
equal to 18.2 (MJ/m3)1/2 [28]. In the case of ethyl acetate |Dd| is
are either rotating quickly or are relatively far from the vicinity of
equal to 0.1 and minimal. So, ethyl acetate solubility should be
protonated polymer fragments. Also, a comparison of the cross-
preferential for PPO compared to the other components of the
polarization spectra of the samples C60–PPO and PPO (Fig. 1d and e)
mixture.
[(Fig._1)TD$IG] To use the PPO selective properties with respect to the ethyl
acetate in the real process, we developed composite membrane
that ensures high performance of pervaporation. The composite
membrane consisted of a thin selective PPO top layer (4 mm)
[(Fig._2)TD$IG]

Fig. 1. 13C MAS and CP/MAS NMR spectra of nanocomposite 2%C60–PPO, (c) and (e),
respectively; 13C MAS and CP/MAS NMR spectrum of neat PPO, (b) and (d),
respectively; and (a) 13C MAS NMR spectrum of neat fullerene C60. Fig. 2. TG curves of PPO and 2%C60–PPO dense films.
84 A. Penkova et al. / Chemical Engineering and Processing 87 (2015) 81–87
[(Fig._3)TD$IG]

Fig. 3. SEM micrographs of cross-section of (a) PPO and (b) 2%C60–PPO dense films.

Table 1
Properties of substances.

Substance Mol. weight Density, g/cm3 Mol. volume, cm3/mol Viscosity, mPa s Solubility parameter, d,(MJ/m3)1/2
Ethanol 46.07 0.789 40.40 1.20 26.0
Acetic acid 60.05 1.049 119.10 1.15 25.7
Ethyl acetate 88.10 0.901 97.78 0.44 18.6
Water 18.02 0.998 18.07 0.89 48.1

deposited on a MFFC microporous support, which provides
mechanical strength and does not resist to penetrant transport.
The composite membrane was prepared with consideration to the
peculiarities of selective layer formation established in the work
[30,31].
Fulfilling the conditions necessary for casting PPO solution
1  [h]c  8, where [h] is an intrinsic viscosity (dl/g) and c the
polymer solution concentration (g/dl), assured the formation of
defectless membranes [31]. In our case, the value [h]
c = 1.58  2 = 3.16 was used.
Fig. 4 illustrates a cross-section of PPO/MFFC composite
membrane. The SEM micrograph shows the uniform structure of
the dense PPO top layer and that a part of the porous MFFC support
exhibited a spongy structure. Fig. 4 also demonstrates the excellent
adhesion of the selective top layer to the porous support. According
to SEM data, the thickness of the top layer is equal to 4 mm.
The transport properties of the PPO/MFFC composite mem-
brane were studied in pervaporation of quaternary mixtures of
various compositions. In the real hybrid process the reaction
mixtures with different concentrations of species can be obtained
[(Fig._4)TD$IG]
Fig. 4. SEM micrographs of cross-section of the PPO/MFFC composite membrane.
during reaction time. The compositions of feed and permeate in
pervaporation of a quaternary system using a PPO/MFFC composite
membrane are presented in Table 2. Data on performance as total
flux are also listed in Table 2.
The enrichment of the permeate by esterification products,
especially ethyl acetate, was established for all compositions. The
concentration of ethyl acetate in the permeates was much higher
than in the feed. The amount of water in the permeate increased
(except in Nos. 2, 5, and 7). The concentration of initial reagents
changes in the opposite way: the ethanol amount in the permeates
is less than in the feed (except No. 7), while acetic acid virtually
does not pass through the membrane. Such low permeability of
acetic acid in pervaporation of quaternary mixture was previously
observed in the hybrid processes “pervaporation + reaction” of
butyl acetate [32] and methyl acetate [5] synthesis.
Table 2 lists data on the total flux, which depends on the
composition of feed with definite regularity. The performance of
the PPO/MFFC composite membrane increases with an increase of
ethyl acetate content in the feed. An exception is feed No. 5, where
the decrease in performance may have occurred because of a high
water content in the feed.
A noteworthy result is that use of the composite membrane
leads to an increase in permeability and selectivity with respect to
ethyl acetate. The reason may be in the specific interaction
between components of the feed and the polymer of the support
(fluoroplast F42L). To confirm this assumption, the sorption of
films from fluoroplast F42L was determined. Equilibrium degrees
of swelling (Sw) of PPO and fluoroplast F42L in pure liquids are
presented in Table 3. Fluoroplast F42L is inert to water, and slightly
sorb ethanol and acetic acid, but has very high sorption with
respect to ethyl acetate (S = 103.4%). The data confirm that
hydrophobic interactions between the support and ethyl acetate
molecules may contribute to an improved separation factor of the
composite membrane PPO/MFFC containing fluoroplast F42L. It
significantly influences the pervaporative removal of ethyl acetate
from the quaternary mixture.
Previous works on dense film membranes [20–22] showed that
the addition of fullerene in a PPO matrix leads to a positive change in
the transport characteristics of membranes in pervaporation of the
quaternary reacting mixture with a composition close to chemical
equilibrium. These results are presented in Table 4. It is evident that
 A. Penkova et al. / Chemical Engineering and Processing 87 (2015) 81–87 85

Table 2
Data on pervaporation of quaternary mixtures using PPO/MFFC membrane.

No Feed, wt% 0.2% Permeate, wt% 0.3% Total flux, kg/m2 h

EA Ethanol Water Acetic acid EA Ethanol Water

1 80.1 7.5 2.6 9.8 92.6 4.2 3.2 1.1 0.2
2 73.7 11.8 10.1 4.4 92.0 3.5 4.5 0.76 0.08
3 58.2 31.6 2.6 7.6 87.9 8.5 3.6 0.53 0.07
4 54.9 4.5 0.3 40.3 93.9 2.9 3.2 0.39 0.01
5 55.2 14.6 11.3 18.9 85.9 5.6 8.5 0.37 0.01
6 38.1 21.1 1.1 39.7 78.1 14.6 7.3 0.14 0.01
7 17.9 8.6 35.2 38.3 67.4 20.5 12.1 0.093 0.003

surface; this fact can be confirmed by increasing the contact angle u

Table 3 of water (from uPPO = 91.2 to u2%C60–PPO = 94.4 ).
Swelling degree of PPO [21] and fluoroplast F42L.
Therefore, taking into account the positive influence of
Solvents Swelling degree, g/100 g polymer fullerene C60 additives in PPO and the high efficiency of
PPO Fluoroplast F42L membranes with a composite structure, further studies were
Ethanol 13.0 0.5 2.3 0.2
carried out with C60–PPO/MFFC composite membranes. The
Acetic acid 23.6 0.5 7.5 0.4 morphology of the C60–PPO/MFFC composite membrane was
Water 0 0 similar to that presented in Fig. 4. Good adhesion between the
Ethyl acetate 23.4 0.4 103 2 selective layer and the support was also observed.
The effect of the content of fullerene on the transport properties
of composite membranes with various concentrations of C60 in the
Table 4 top layer was studied in pervaporation of a reacting mixture whose
Pervaporation of the quaternary reacting mixture using PPO and 2%C60–PPO dense composition is close to chemical equilibrium (Table 4). The results
films [22]. are presented in Figs. 5 and 6.
Solvents Feed wt% 0.1% Permeate, wt% 0.1% Fig. 5 shows the change of content of the quaternary feed
PPO 2%C60–PPO
mixture after pervaporation through C60–PPO/MFFC composite
membranes containing 0.5, 2, and 3 wt% C60. The content of ethanol
Ethanol 14.6 8.6 8.8
Acetic acid 18.9 1.4 1.2
and acetic acid in the permeate is smaller than in the feed. This
Water 11.3 8.4 6.2 indicates that over the course of the synthesis, the initial reagents
Ethyl acetate 55.2 81.6 83.8 essentially remained in the reactor. The reaction products
penetrated through the membranes by different modes. The water
amount in the permeate decreased compared to the initial amount
for composite membranes containing only 0.5 and 2 wt% C60, but in
use of membranes modified by fullerene C60 leads to decreasing the case of 3 wt% C60, the water amount in the permeate increased.
water content and increasing ethyl acetate content in permeate. The The main component of the permeate is ethyl acetate. Its amount
increase of selectivity occurs due to decreasing the free volume [22] essentially increases in the permeate in comparison with the feed,
as a result of interaction between PPO and C60. The rise of flux occurs and a higher amount of ethyl acetate have been obtained through a
due to formation of additional sorption centers on the membrane 2%C60–PPO/MFFC membrane.
[(Fig._5)TD$IG]

Fig. 5. Content of quaternary mixture in feed and in permeate in pervaporation using 0.5%C60–PPO/MFFC, 2%C60–PPO/MFFC, and 3%C60–PPO/MFFC membranes, 25  C.
86 A. Penkova et al. / Chemical Engineering and Processing 87 (2015) 81–87
[(Fig._6)TD$IG]
Fig. 6. Dependence of total flux and pervaporation separation index (PSI) on
fullerene E60 content in the top layer of E60–PPO/MFFC membranes for
pervaporation of the quaternary mixture 18.9 wt% acetic acid, 14.6 wt% ethanol,
55.2 wt% ethyl acetate, and 11.3 wt% water, 25  C. The size of dots includes the range
of experimental errors.
Fig. 6 shows the dependence of total flux and pervaporation
separation index on the fullerene content in the top layer of the
E60–PPO/MFFC membranes in pervaporation of the quaternary
reacting mixture.
The data show that an increase in the fullerene C60 content in
the top layer increases the total flux. The composite membrane
with 3%E60–PPO selective layer has the best permeability.
The efficiency of the membranes was evaluated using the
pervaporation separation index (PSI) determined by Eq. (2) as a
product of total flux on the separation factor of ethyl acetate. The
dependence of PSI on fullerene content in the top layer of
the E60–PPO/MFFC membranes is also presented in Fig. 6. The
pervaporation separation index increases with the rise of C60
content up to 2 wt% C60 and then decreases in the case of the 3%
C60–PPO/MFFC membrane.
Thus, it was established that the best transport properties can
be obtained by using the 2%C60–PPO/MFFC membrane in
pervaporation of the system with ethyl acetate synthesis.
4. Conclusions
The suggested character of binding in C60–PPO compositions
was verified by nuclear magnetic resonance study. 13C MAS and CP/
MAS NMR spectra of C60–PPO nanocomposites show a slight
interaction between the C60 molecules and the PCO matrix. TG
analysis reveals that increasing the temperature of the membrane
results in thermal destruction due to certain structural changes of
the matrix upon incorporation of the C60 molecules.
E60–PPO/MFFC composite membranes with a thin selective
layer containing up to 3 wt% C60 placed on the surface of an MFFC
porous support were developed. The study of pervaporation of the
quaternary reacting system ethyl acetate–ethanol–water–acetic
acid shows that composite membranes possess high permeability;
moreover, the E60–PPO/MFFC membranes exhibit higher selectiv-
ity with respect to ethyl acetate compared to the composite
membrane unmodified by fullerene. The optimum content of
fullerene in the selective layer is equal to 2 wt% C60. Pervaporation
tests show that the 2%E60–PPO/MFFC composite membrane has a
maximal pervaporation separation index and is promising for use
in real hybrid processes (esterification + pervaporation). The RU
patent fixes the preparation method of composite membranes
with a fullerene-containing selective layer [33]. The invention is
related to the producing composite membranes with fullerene-
containing polymer selective layer intended for ester separation in
hybrid process of alkyl acetate production. Proposed method
consists in formation of the selective polymer top layer on the
MFFC support that is microfiltration membrane from copolymer
fluoroplast F42L and polypropylene base. Selective layer is the
composite of fullerene C60 and PPO. Selective layer is formed by
coating 2% solution of C60–PPO composite onto the surface of
microporous support; and finally composite membrane is dried.
Acknowledgments
The authors acknowledge St. Petersburg State University for a
research grant (12.38.257.2014). The chapter on the PV separation
process was carried out within the span of the grant of Russian
Foundation for Basic Research (RFBR project 12-03-00522a). The
authors are also grateful to the Resource Center of Thermal
Analysis and Calorimetry, the Interdisciplinary Resource center for
Nano technology, and the Resource Center of Magnetic Resonance
of the St. Petersburg State University for help in this study.
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