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Hyperbranched polymers: new selective solvents for extractive

distillation and solvent extraction

M. Seiler , D. Ko hler, W. Arlt


Technical University of Berlin, Institut fuer Verfahrenstechnik, Sekr. TK 7, Fachgebiet Thermodynamik und Thermische
Verfahrenstechnik, Strasse des 17. Juni 135, D-10623 Berlin, Germany
Received 26 June 2002; accepted 16 August 2002
Abstract
Ternary vapor/liquid (VLE), liquid/liquid (LLE) and solid/liquid/liquid (SLLE) equilibria of ethanol /water and
tetrahydrofuran (THF) /water solutions containing different kinds of hyperbranched polymers are presented. For the
system THF/water/hyperbranched polyester a remarkably distinct solutropic phenomenon is observed. Commercially
available hyperbranched polyesters and hyperbranched polyesteramides are found to be capable of breaking the
ethanol /water and THF/water azeotrope. The experimental results underline the potential of hyperbranched polymers
in the field of process engineering, especially as an entrainer for extractive distillation and as selective solvents for
solvent extraction. The non-volatility of hyperbranched polymers in combination with their remarkable separation
efficiency and selectivity enables new processes for the separation of azeotropic mixtures. The separation approaches
proposed might offer a potential for cost-savings in comparison with conventional separation processes.
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Hyperbranched polymers; Extractive distillation; Solvent extraction; Phase equilibria; Azeotropic mixtures
1. Introduction
Hyperbranched polymers are highly branched,
polydisperse, three-dimensional macromolecules
which, due to their unique structures and proper-
ties, have attracted increasing attention [1]. Unlike
dendrimers, the randomly branched hyper-
branched polymers can be synthesised via one-
step reactions and therefore, represent economic-
ally promising products for large-scale industrial
applications
1
. Most of their applications are based
on the nature and the large number of functional
groups within a molecule. These functionalities
allow for the tailoring of their physical and
chemical properties and thus provide a powerful

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Corresponding author. Tel.: /49-30-314-22646; fax: /49-
30-314-22406
E-mail address: m.seiler@vt.tu-berlin.de (M. Seiler).
1
Companies such as the Perstorp Group (Perstorp,
Sweden), DSM Fine Chemicals (Geleen, The Netherlands)
and Hyperpolymers (Freiburg, Germany) are already
producing hyperbranched polymers on a large scale.
Currently, Perstorp synthesises hyperbranched polymers,
known as Boltorn products, on a ton-scale for 12 a/kg.
Separation and Purification Technology 30 (2003) 179/197
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tool to design hyperbranched polymers for a wide
variety of applications [1]. Since structural perfec-
tion is not a strict prerequisite for most biomedical
applications [2], even the area of life science,
which*/concerning dendritic macromolecules*/
until recently seemed to be reserved for the
perfectly structured dendrimers, appears to be a
promising field for new applications of hyper-
branched polymers [2/5].
An area of application that, until now, has
remained unconsidered in scientific discussions is
the field of process engineering. Since the polarity
of hyperbranched macromolecules can be adjusted
by controlled functionalisation of the end groups,
selective solvents (consisting of either pure hyper-
branched polymers or fractions of hyperbranched
additives) can be tailored [1]. The remarkable
selectivities and capacities of hyperbranched poly-
mers in combination with their low melt viscosity,
high solubility and thermal stability can be utilised
for the optimisation of a number of separation
processes. Only recently, the authors suggested the
use of hyperbranched polymers as entrainers for
extractive distillation and as selective solvents for
liquid/liquid extraction [4,6/9]. Furthermore, the
potential for using hyperbranched polymers for
the purification of chemical wastewater by means
of hyperbranched self-stabilising emulsion liquid
membranes, as selectivity- and capacity-increasing
solvent additives for absorption processes as well
Nomenclature
Latin letters
K distribution coefficient (/)
M molecular weight (kg/kmol)
P pressure (Pa)
S selectivity (/)
T temperature (K)
w weight fraction (/)
x liquid phase mol fraction (/)
y vapor phase mol fraction (/)
Greek letters
a separation factor (/)
b separation efficiency (/)
g activity coefficient (/)
Subscripts
0 pure substance
i component i
Superscripts
V vapor phase
L liquid phase
Abbreviations
VLE vapor/liquid equilibrium
LLE liquid/liquid equilibrium
SLE solid/liquid equilibrium
SLLE solid/liquid/liquid equilibrium
DB degree of branching
THF tetrahydrofuran
PG hyperbranched polyglycerol
ED 1,2-ethanediol
wt.% mass percent, weight percent
M. Seiler et al./Separation and Purification Technology 30 (2003) 179/197 180
as stationary phases for preparative chromatogra-
phy was demonstrated [4].
This paper focuses on the separation of azeo-
tropic mixtures using commercially available hy-
perbranched polymers. Ternary vapor/liquid and
liquid/liquid equilibria of azeotropic systems
containing hyperbranched polymers are presented.
Based on the underlying thermodynamic phenom-
ena the separation of ethanol /water by means of
extractive distillation
2
as well as the separation of
tetrahydrofuran (THF)/water by means of solvent
extraction
3
are discussed and compared with
conventional industrial separation processes.
2. Experimental
2.1. VLE measurements by means of headspace gas
chromatography
Headspace gas chromatography (HSGC) [10]
represents an experimental approach, which com-
bines a headspace sampler and a gas chromato-
graph in order to determine the composition of a
vapor phase. If the vapor phase is in equilibrium
with a liquid or solid phase, vapor/liquid equili-
bria (VLE) or solid/vapor equilibria (SVE) can be
measured and thermodynamic information such as
partial pressures, activity coefficients as well as
interaction parameters can be obtained [11/13].
In this work, HSGC was used for VLE mea-
surements of ternary ethanol /water mixtures con-
taining different kinds of hyperbranched polymers.
The chosen experimental approach is accurately
described in [14].
2.2. LLE, SLLE and g
i

measurements
The phase behaviour of the ternary system
hyperbranched polyester/THF/water was ana-
lysed by phase separation experiments as well as
by visual cloud-point measurements according to
the experimental procedure described in [14].
Activity coefficients at infinite dilution, g
i

,
were determined by means of the gas/liquid
chromatography as described in [15].
2.3. Materials
2.3.1. Hyperbranched polymers
Table 1 lists the hyperbranched polymers used.
Perstorp Speciality Chemicals AB, Sweden, pro-
vided aliphatic hyperbranched polyesters, known
as the Boltorn family. The Boltorn samples used
(Boltorn H20 and Boltorn H3200) are hydroxyl
functional hyperbranched polyesters (see Fig. 1a),
which are produced from polyalcohol cores and
hydroxy acids. The hyperbranched structures are
formed by polymerisation of the particular core
with 2,2-dimethylol proponic acid (Bis-MPA) [16].
Boltorn H3200 represents a hyperbranched ali-
phatic polymer (Boltorn H30), whose hydroxyl
functionalities are esterified with saturated fatty
acids.
DSM, Netherlands, provided hyperbranched
polymers, known as the Hybrane family. Hybrane
S1200 and Hybrane H1500 are hyperbranched
polyesteramides
4
. The structures are illustrated in
Fig. 1b and c, respectively.
2
Presented by M. Seiler at the international conference on
Distillation and Absorption in Baden-Baden, Germany, 2002.
3
Presented by M. Seiler at the Fachausschusitzung fu r
Thermische Zerlegung, Adsorption und Extraktion in Bingen/
Rhein, Germany, 2002.
Table 1
Hyperbranched polymers used in this work
Sample Molecular weight
(g/mol)
M
w
/M
n
Provider
Boltorn H20 M
w
/2100 1.3 Perstorp
Boltorn H3200 M
w
/10500 1.6 Perstorp
Hybrane S1200 M
n
/1200 5 to 10 DSM
Hybrane H1500 M
n
/1500 5 to 10 DSM
, For further details see also [16,22].
4
The chemical name of Hybrane S1200 is 2,5-furandione,
dihydro-, polymer with 1,1?-iminobis[2-propanol] and of
Hybrane H1500 1,3-isobenzofurandione, hexahydro-, polymer
with 1,1?-imino-bis[2-propanol].
M. Seiler et al./Separation and Purification Technology 30 (2003) 179/197 181
2.3.2. Solvents
Ethanol and tetrahydrofuran (THF) were pro-
vided by Merck (Germany) with a purity greater
than 99.8 mol%. The solvents were used as
delivered. Distilled water was degassed and re-
peatedly filtered using a 0.02 mm Millipore filter in
order to remove dust.
3. Results and discussion
3.1. Hyperbranched polymers as selective solvents
for extractive distillation
Due to the large number of functional groups,
hydroxyl functional hyperbranched polymers
show a remarkable solubility in polar solvents
such as water or ethanol. As recently described
[14], the extent of inter- and intramolecular
hydrogen bond formations for these polymer
solutions is the dominating factor for a solvent
activity and therefore, determines partition coeffi-
cients and separation factors. Since the synthesis
of hyperbranched polymers allows for the tailoring
of properties such as solubility, solution viscosity,
selectivity and capacity, the authors analysed the
potential of using hyperbranched polymers as an
entrainer for the separation of azeotropic mix-
tures.
3.1.1. Vapor/liquid equilibria of hyperbranched
polymer/ethanol /water solutions
Figs. 2 and 3 as well as Table 2 show experi-
mental VLE results for ternary ethanol /water
mixtures containing different kinds of hyper-
branched polymers: hyperbranched polyestera-
mides (Hybrane H1500 and Hybrane S1500) and
a hyperbranched aliphatic polyester (Boltorn
H20). The influence of hyperbranched polymers
on VLE and separation factor of the ethanol /
water system is compared with the influence of
the conventional entrainer 1,2-ethanediol (Figs. 3
and 4). In Figs. 2 and 3, the binary ethanol /water
VLE is given by NRTL calculations (see solid line)
using parameters from the DETHERM database
[17]. As shown in [14] the NRTL calculations are
in good agreement with recommended experimen-
tal data for the binary ethanol /water VLE. All x,
y-diagrams are presented on a pseudo-binary
basis, i.e. the weight fraction of the binary
ethanol /water solution amounts to
w
ethanolwater
/1/w
entrainer
for hyperbranched
polymers or 1,2-ethanediol as an entrainer and is
split up according to the binary mol fractions
plotted (x
ethanol
/x
water
/1).
For small concentrations of the used hyper-
branched polymers (w
polymer
5/20 wt.%), the inter-
actions between polymer and water and between
polymer and ethanol, are approximately of the
same intensity. Due to good polymer solubility,
intermolecular solvent/polymer interactions seem
to dominate over polymer/polymer and intramo-
lecular polymer interactions. However, for
w
polymer
5/20 wt.%, the hyperbranched polyester-
Fig. 1. Structural details of the examined polymers; (a)
hyperbranched polyester Boltorn H20, (b) hyperbranched
polyesteramide Hybrane H1500, (c) hyperbranched polyester-
amide Hybrane S1200.
M. Seiler et al./Separation and Purification Technology 30 (2003) 179/197 182
amides Hybrane H1500 and Hybrane S1200, as
well as the hydroxyl functional hyperbranched
polyester Boltorn H20, do not have a strong
impact on the solvent activities and therefore,
they do not affect the vapor/liquid equilibrium
and the separation factor of the ethanol /water
system at 363.15 K.
For polymer concentrations above 20 wt.% and
x
ethanol
/0.2, the extent of intermolecular interac-
tions between the individual hyperbranched poly-
mer and water increases, leading to a larger molar
vapor fraction of ethanol in comparison with the
binary ethanol /water VLE (see Fig. 2 and Table
2). As far as the hyperbranched polyesteramide
Hybrane S1200 is concerned, a polymer concen-
tration larger than w
polymer
/40 wt.% results in
breaking the azeotrope of the ethanol /water
system. At x
ethanol
/0.89 (the azeotropic concen-
tration of the binary ethanol /water system at
363.15 K), the ethanol concentration in the vapor
phase y
ethanol
and hence the separation factor
a
ethanol,water
increases with increasing concentra-
tion of Hybrane S1200 until the maximum amount
of polymer is dissolved. The ethanol-rich systems,
containing a comparable amount of Hybrane
H1500 or Boltorn H20, show a molar vapor
fraction of ethanol considerably smaller than
that of Hybrane S1200 (see Figs. 2 and 3). Even
though Hybrane H1500 and Boltorn H20 break
the azeotrope at high polymer concentrations
Fig. 2. Experimental VLE results for the systems hyperbranched polyester /ethanol /water and hyperbranched polyesteramides /
ethanol /water for different polymer concentrations at T
equilibrium
/363.15 K; hyperbranched polyester: Boltorn H20, hyperbranched
polyesteramides: Hybrane S1200 and Hybrane H1500.
M. Seiler et al./Separation and Purification Technology 30 (2003) 179/197 183
(w
BoltornH
2
0
]/0.5; w
HybraneH1500
]/0.7), it can be
concluded from Fig. 2 that, due to a comparatively
low polymer polarity, Hybrane H1500 and Bol-
torn H20 do not show such a clear interaction
preference for water as the hyperbranched poly-
esteramide Hybrane S1200. This explanation cor-
responds to polymer/water interactions, which*/
in contrast to Hybrane S1200*/are much weaker
for the hyperbranched polymers Hybrane H1500
and Boltorn H20.
Both the solubility behaviour of the individual
polymer and the number of functional groups
(particularly the functional groups on the surface)
of a macromolecule seem to determine the separa-
tion factor of the respective ternary system.
The ease of ethanol /water separation by means
of distillation as well as the efficiency of an
entrainer can be evaluated with the help of the
separation factor and the separation efficiency.
They are defined as follows:
separation factor
a
ethanol;water

K
ethanol
K
water

(y
ethanol
=x
ethanol
)
(y
water
=x
water
)
(1)
separation efficiency b
a
with entrainer
ethanol; water
a
without entrainer
ethanol; water
(2)
In Fig. 4 the separation factor a
ethanol,water
and
the separation efficiency b are depicted as depen-
Fig. 3. Inuence of hyperbranched polyesteramides (Hybrane), hyperbranched polyester (Boltorn), hyperbranched polyglycerol and
the conventional entrainer 1,2-ethanediol on the ethanol /water VLE at T
equilibrium
/363.15 K.
M. Seiler et al./Separation and Purification Technology 30 (2003) 179/197 184
Table 2
Summary of the experimental VLE headspace results for the systems listed below
I II III IV V VI
II a IIb IIc III a III b IV a IV b IV c IV d V a V b V c
x
ethanol
y
etha-
nol
x
etha-
nol
y
etha-
nol
x
etha-
nol
y
etha-
nol
x
etha-
nol
y
etha-
nol
x
etha-
nol
y
etha-
nol
x
etha-
nol
y
etha-
nol
x
etha-
nol
y
etha-
nol
x
etha-
nol
y
etha-
nol
x
etha-
nol
y
etha-
nol
x
etha-
nol
y
etha-
nol
x
etha-
nol
y
etha-
nol
x
etha-
nol
y
etha-
nol
x
etha-
nol
y
etha-
nol
x
etha-
nol
y
etha-
nol
T/363.15 K
0.0230 0.2458 0.1001 0.4485 0.1005 0.4314 0.0996 0.3979 0.1999 0.5225 0.2001 0.5043 0.2008 0.5191 0.1994 0.4782 0.2028 0.4824 0.1492 0.4038 0.1997 0.5026 0.1998 0.4621 0.1992 0.4303 0.4001 0.6480
0.1000 0.4394 0.2995 0.5949 0.3000 0.6135 0.3010 0.6450 0.2998 0.5708 0.3999 0.6367 0.3993 0.6269 0.4028 0.6289 0.4033 0.6391 0.3949 0.6392 0.4000 0.6120 0.3999 0.5883 0.4004 0.5874 0.6989 0.7936
0.1998 0.5195 0.5989 0.7337 0.6005 0.7659 0.5959 0.8273 0.4160 0.6179 0.5996 0.7306 0.6002 0.7261 0.6005 0.7428 0.6050 0.7629 0.5489 0.7504 0.5999 0.7095 0.6000 0.7045 0.6032 0.7142 0.8002 0.8622
0.3002 0.5665 0.8482 0.8845 0.8504 0.9107 0.8512 0.9420 0.5987 0.7054 0.8002 0.8565 0.8013 0.8412 0.8001 0.8593 0.7020 0.8272 0.6995 0.8440 0.7998 0.8323 0.8001 0.8390 0.7999 0.8519 0.8511 0.8967
0.4002 0.6078 0.9507 0.9588 0.9498 0.9672 0.9428 0.9771 0.8018 0.8274 0.9010 0.9204 0.8503 0.8776 0.8500 0.8874 0.8003 0.8917 0.8332 0.9212 0.8499 0.8689 0.8500 0.8732 0.8496 0.8861 0.9018 0.9285
0.5010 0.6521 0.9021 0.9046 0.9509 0.9541 0.9000 0.9101 0.8999 0.9192 0.8498 0.9133 0.9009 0.9560 0.9000 0.9082 0.8999 0.9120 0.8999 0.9196 0.9495 0.9587
0.6005 0.7005 0.9500 0.9507 0.9292 0.9575 0.9007 0.9447 0.9511 0.9807 0.9499 0.9487 0.9501 0.9498 0.9498 0.9550
0.7035 0.7564 0.9513 0.9706 0.9482 0.9747 0.9731 0.9913
0.8004 0.8210 0.9724 0.9832 0.9701 0.9860
0.9011 0.9042
0.9476 0.9473
0.9763 0.9753
I, ethanol /water; II, ethanol /water /ethanediol; II a, 20 wt.% ED; II b, 40 wt.% ED; II c, 70 wt.% ED; III, ethanol /water /Boltorn H20; III a, 20 wt.% Boltorn H20;
III b, 50 wt.% Boltorn H20; IV, ethanol /water /Hybrane S1200; IV a, 40 wt.% Hybrane S1200; IV b, 60 wt.% Hybrane S1200; IV c, 70 wt.% Hybrane S1200; IV d, 80
wt.% Hybrane S1200; V, ethanol /water /Hybrane H1500; V a, 40 wt.% Hybrane H1500; V b, 60 wt.% Hybrane H1500; V c, 70 wt.% Hybrane H1500; VI, ethanol /water /
PEG, 70 wt.% PEG; ED: 1,2-ethanediol, PEG: Poly(ethylene glycol).
M
.
S
e
i
l
e
r
e
t
a
l
.
/
S
e
p
a
r
a
t
i
o
n
a
n
d
P
u
r
i
f
i
c
a
t
i
o
n
T
e
c
h
n
o
l
o
g
y
3
0
(
2
0
0
3
)
1
7
9

/
1
9
7
1
8
5
Fig. 4. Separation factors and separation efciencies for ethanol /water mixtures containing hyperbranched polyesteramides (Hybrane
S1200 and Hybrane H1500), hyperbranched polyester (Boltorn H20), hyperbranched polyglycerol and 1,2-ethanediol; T
equilibrium
/
363.15 K unless otherwise indicated in the legend; note that the line segments between the experimental points represent only a guide
for the eyes and no calculated results.
M. Seiler et al./Separation and Purification Technology 30 (2003) 179/197 186
dent on the pseudo-binary liquid ethanol mol
fraction
5
.
Among the studied polymers, the hyper-
branched polyesteramide Hybrane S1200 is the
most promising candidate as an entrainer in the
field of extractive distillation. As can be seen from
Fig. 4, for x
ethanol
B/0.7 and polymer concentra-
tions of 70 wt.%, the recently introduced hyper-
branched polyglycerol [14,7] and the conventional
entrainer 1,2-ethanediol show the best separation
efficiency, whereas for the more non-polar Hy-
brane and Boltorn products the relatively smaller
extent of attractive intermolecular water/polymer
interactions results in separation efficiencies com-
parable with those of 40 wt.% ethanediol. Never-
theless, in the important azeotropic ethanol /water
concentration range, the separation efficiency
curve of Hybrane S1200 shows a large slope for
polymer concentrations ]/70 wt.%, resulting in a
remarkable separation efficiency of b(x
ethanol
/
0.9, T/363.15 K) /2.4 for w
HybraneS1200
/0.8.
In comparison to ethanediol or hyperbranched
polyglycerol, the maximum separation efficiency
of Hybrane S1200 is observed at larger ethanol
concentrations (x
ethanol
:/0.95), at which the se-
paration efficiency of Hybrane S1200 reaches the
magnitude of the conventional entrainer ethane-
diol.
From Fig. 4 it can be concluded, that the
influence of the conventional entrainer 1,2-etha-
nediol and the hyperbranched polyesteramide
Hybrane S1200 on the separation factor
a
ethanol,water
is almost of the same magnitude,
whereas the hyperbranched aliphatic polyester
Boltorn H20 as well as the suggested polymeric
entrainer poly(ethylene glycol)
6
(see Table 2)
exhibit a rather modest effect on the separation
factor with only very limited use in the field of
extractive distillation.
Advantages of using the hyperbranched poly-
esteramide Hybrane S1200 or the hyperbranched
polyglycerol instead of 1,2-ethanediol as entrainer
might become evident when focusing on possible,
competing operation steps for the entrainer regen-
eration. In the case of a non-volatile macromole-
cular entrainer, the problem of an entrainer-
polluted overhead product of the extractive dis-
tillation column does not exist and a variety of
separation steps can be used for the entrainer
regeneration (i.e. the separation of the columns
bottom product) as described in the following
section.
3.1.2. Regeneration of hyperbranched
macromolecular entrainers
The entrainer recovery in a conventional ex-
tractive distillation process is mostly carried out
using another countercurrent distillation column.
Unlike this conventional process, the regeneration
of non-volatile entrainers such as hyperbranched
polymers allows for the use of other unit opera-
tions.
As described below, hyperbranched polymers
can be separated from low boiling substances like
water by means of a stripping column, appropriate
thin-film evaporators, dryers or even crystallisers
when applicable.
Conventional distillation for the separation of a
binary mixture consisting of a non-volatile entrai-
ner and a volatile component is not feasible, since
the non-volatility of a component would lead to a
break down of the columns counterflow. A
possibility to circumvent this problem is the
operation of a stripping column (charge reflux
fractionator) without a rectifying section and
reflux. A heated inert gas can be fed into the
bottoms of the stripper and guided through the
column in countercurrent to the entrainer rich
feed, resulting in a concentrated entrainer-bottom
product and a solvent (water) rich overhead
product.
Thin-film evaporators represent another alter-
native for an effective, thermally gentle and
continuous recycling of a non-volatile entrainer.
5
For the b-calculations the separation factor of the binary
ethanol /water system at 363.15 K was determined using the
NRTL-model with parameters from the DETHERM database
[17].
6
Based on only a few VLE data, Al-Amer suggested
poly(ethylene glycol) as promising polymeric entrainer for the
ethanol /water separation by extractive distillation [18]. Own
experimental VLE results for the system ethanol /water /
poly(ethylene glycol) can be seen in Table 2. Poly(ethylene
glycol) was obtained from Polysciences (Warrington, USA)
with a molecular weight of M
w
/400 g/mol.
M. Seiler et al./Separation and Purification Technology 30 (2003) 179/197 187
Depending on the viscosity of the solution, falling-
film evaporators or*/for higher viscosities*/ro-
tary thin-film evaporators appear to be suitable.
Although the hyperbranched polymer melts show
comparatively (to other polymers) low viscosities,
it might be advantageous to install a refuse worm
at the rotory end of the thin-film evaporator such
as those used for the stripping of epoxy resins or
the degassing of polyolefins.
Hyperbranched polymers can also be recycled
by convection drying, using a spray dryer, a thin-
film evaporation dryer or a belt dryer. Crystal-
lisation/precipitation, which is dependent on the
underlying solid/liquid equilibrium of the poly-
mer-solvent system, could also represent an inter-
esting regeneration alternative.
The recovery options described for a non-
volatile entrainer are competing unit operations,
which have to be thoroughly assessed with regard
to their investment and operation costs. A com-
parison with conventional separation processes for
azeotropic mixtures shows, that the remarkable
separation efficiencies of hyperbranched polymers
as well as the variety of energetically promising
recycling options for the entrainer offer consider-
able potential for process and economic optimisa-
tions.
Therefore, it can be concluded that hyper-
branched polymers such as the polyesteramide
Hybrane S1200 or the hyperbranched polyglycerol
described in [14] represent promising entrainers or
entrainer additives for the ethanol /water separa-
tion by means of extractive distillation.
3.2. Hyperbranched polymers as selective solvents
in liquid/liquid extraction
Solvent extraction is a separation process, which
is in competition with distillation. However, due to
its low energy consumption, solvent extraction is
gaining notice. Solvent extraction is often applied
if the mixture components exhibit low or high
boiling points and thus distillation must be carried
out under a costly low temperature or a vacuum
operation. It is also applied if the mixture is a close
boiling or an azeotropic system, if the components
Fig. 5. Experimental LLE results for the system acetylated hyperbranched polyglycerol /THF/water at T
equilibrium
/295.15 K [14]; ,
cloud points; I, concentration according to LLE measurements; hyperbranched acetylated polyglycerol: M
n
/6500 g/mol, M
w
/M
n
/
2.1, degree of branching/0.56.
M. Seiler et al./Separation and Purification Technology 30 (2003) 179/197 188
to be separated are thermally sensitive or if the
mixture contains a key component of low concen-
tration.
Hyperbranched polymers exhibit many proper-
ties, which allow for their application as selective
solvents in solvent extraction. Large selectivities,
remarkable loading capacities for certain key
components per mass polymer, low vapor pres-
sures, comparatively low melt and solution visc-
osities, as well as thermal and chemical stability
are only some of their characteristics [14].
A system of industrial importance is the azeo-
tropic mixture of THF and water. THF is pro-
duced by dehydrocyclisation of 1,4-butanediol in
the presence of an acid catalyst. The key step in
purification is the breaking of the THF/water
azeotrope [19]. Generally, this is achieved by two-
pressure (low/high pressure) distillation, extractive
distillation or azeotropic distillation.
In the following sections, new process ap-
proaches for the THF/water separation using
hyperbranched polymers as extractive solvents
are derived from LLE measurements.
3.2.1. Liquid/liquid equilibria of hyperbranched
polymer/THF/water solutions
Only recently [14], we discussed the potential of
using hyperbranched polymers as selective solvents
in the field of solvent extraction by presenting the
ternary phase diagram of the system THF/water/
acetylated hyperbranched polyglycerol at 295.15 K
(see Fig. 5). THF and water form a minimum
boiling azeotrope containing 94.2 wt.% of THF at
0.1 MPa [19]. However, as can be seen from Fig. 5,
when extracting THF from water by means of
acetylated hyperbranched polyglycerol (M
n
/6500
g/mol, M
w
/M
n
/2.1, degree of branching/0.56)
the width of the miscibility gap at 295.15 K as well
as the selectivity values are not large enough to
break the THF/water azeotrope. Even though the
solubility of acetylated hyperbranched polygly-
cerol in water is sufficiently small, the water
solubility in the polymer and hence the water
concentration in the polymer rich phase is too
large for surpassing the THF/water azeotropic
concentration at T/295.15 K [14].
Fig. 6. Experimental LLE, SLLE and SLE results for the ternary system hyperbranched polyester/tetrahydrofuran/water at
T
equilibrium
/321.15 K. LLE measurements, cloud point measurement, SLLE measurements, SLE measurements.
M. Seiler et al./Separation and Purification Technology 30 (2003) 179/197 189
The extractive separation of THF and water by
means of a hyperbranched macromolecular sol-
vent requires a polymer, which*/in contrast to the
acetylated hyperbranched polyglycerol */shows a
higher selectivity and a lower water absorption.
Such a polymer represents the commercially avail-
able hyperbranched polyester Boltorn H3200.
In Figs. 6 and 7 the ternary phase behaviour of
the system THF/water/Boltorn H3200 is de-
picted at 321.15 and 334.15 K in the presence of
a vapor phase. At both temperatures, a broad area
of immisciblity originates from the binary system
Boltorn H3200/water. At 321.15 K (Fig. 6) and
high polymer concentrations, the LLE turns into a
solid/liquid/liquid (SLLE) and a solid/liquid
(SLE) equilibrium, depending on the polymer
concentration. This is due to the melting tempera-
ture of Boltorn H3200 (T
melt,H3200
/333 K), which
is larger than the system temperature of 321.15 K.
Moreover, as indicated by the slope of the tie-
lines, a solutropic effect of remarkable distinctness
was found. Only a few systems such as toluene/
water/acetone and n-butyl acetate/water/ace-
tone show solutropic behaviour [20]. In the case
of the ternary system THF/water/Boltorn H3200
the solutropic effect is accompanied by an inver-
sion of the water rich phase and the polymer rich
phase. This can be explained by discussing the
solubility of THF in both liquid phases and the
resulting change of the phase densities in depen-
dence on THF concentration.
At low THF concentrations of the LLE region,
the polymer rich phase represents the upper liquid
phase and the water rich phase represents the
lower liquid phase. With increasing THF concen-
tration, for both system temperatures (Figs. 6 and
7), the THF solubility in the polymer rich phase is
higher than in the polymer lean phase leading to a
negative slope of tie-lines. When approaching the
THF concentration in the polymer rich phase of
around 50 wt.%, a change in THF distribution can
be observed. Any further addition of THF results
in an increasing enrichment of THF in the polymer
lean phase. Therefore, the negative slope of tie-
lines decreases until the solutropic point, where a
horizontal course of the tie-lines can be observed,
corresponding to equal THF concentrations in
both liquid phases (see Figs. 6 and 7). The location
Fig. 7. Experimental LLE results for the ternary system hyperbranched polyester /tetrahydrofuran/water at T
equilibrium
/334.15 K;
I, concentration according to LLE measurements; cloud points.
M. Seiler et al./Separation and Purification Technology 30 (2003) 179/197 190
Table 3
Summary of experimental LLE, SLLE, SLE and cloud point results for the systems THF/water /hyperbranched polyester Boltorn H3200 at T/321.15 K and T/334.15
K
Polymer rich phase Polymer lean phase
LLE SLLE LLE SLLE Cloud points SLE
w
THF
w
polymer
w
water
w
THF
w
polymer
w
water
w
THF
w
polymer
w
water
w
THF
w
polymer
w
water
w
THF
w
polymer
w
water
w
THF
w
polymer
w
water
T /321.15 K
0.2290 0.7589 0.0121 0.1274 0.8652 0.0074 0.1434 0.0014 0.8553 0.0747 0.0005 0.9248 0.7479 0.1883 0.0638 0.0373 0.0005 0.9622
0.3107 0.6757 0.0136 0.1409 0.8500 0.0091 0.1948 0.0011 0.8041 0.0856 0.0008 0.9136 0.7802 0.1461 0.0737 0.0535 0.0004 0.9461
0.3873 0.5947 0.0180 0.1418 0.8506 0.0076 0.2652 0.0031 0.7317 0.0887 0.0032 0.9081 0.8032 0.1179 0.0789 0.0541 0.0005 0.9454
0.4611 0.5173 0.0216 0.3218 0.0019 0.6763 0.8200 0.1004 0.0796
0.5046 0.4722 0.0232 0.3660 0.0014 0.6325 0.8290 0.0879 0.0831
0.5162 0.4584 0.0255 0.4105 0.0019 0.5876 0.8386 0.0746 0.0868
0.5399 0.4327 0.0274 0.5035 0.0049 0.4916 0.8509 0.0445 0.1046
0.5529 0.4212 0.0259 0.5803 0.0002 0.4195
0.5596 0.4132 0.0272 0.6408 0.0073 0.3519
0.5776 0.3920 0.0304 0.7240 0.0002 0.2758
0.6171 0.3468 0.0361 0.7652 0.0065 0.2283
0.6431 0.3199 0.0370 0.7939 0.0108 0.1953
0.6597 0.3031 0.0372 0.8483 0.0196 0.1321
T/334.15 K
0.1008 0.8940 0.0052 0.0763 0.0010 0.9226 0.7030 0.2401 0.0569
0.2665 0.7204 0.0131 0.1319 0.0012 0.8669 0.7219 0.2144 0.0637
0.3019 0.6850 0.0131 0.1546 0.0013 0.8441 0.7618 0.1646 0.0736
0.3740 0.6100 0.0159 0.1901 0.0005 0.8093 0.7781 0.1414 0.0805
0.4740 0.5013 0.0247 0.2847 0.0024 0.7129 0.7930 0.1214 0.0856
0.5298 0.4382 0.0320 0.4022 0.0010 0.5968 0.7992 0.1121 0.0887
0.5893 0.3801 0.0306 0.5637 0.0040 0.4323 0.8090 0.1018 0.0892
0.6237 0.3425 0.0338 0.7061 0.0119 0.2820 0.8276 0.0732 0.0992
0.6470 0.3195 0.0335 0.8088 0.0514 0.1398 0.8305 0.0664 0.1031
M
.
S
e
i
l
e
r
e
t
a
l
.
/
S
e
p
a
r
a
t
i
o
n
a
n
d
P
u
r
i
f
i
c
a
t
i
o
n
T
e
c
h
n
o
l
o
g
y
3
0
(
2
0
0
3
)
1
7
9

/
1
9
7
1
9
1
of the solutropic point shows a slight temperature
dependence. For the equilibrium temperature of
321.15 K (Fig. 6) the solutropic point is located at
54 wt.% THF, whereas for the system temperature
of 334.15 K (Fig. 7) the solutropic THF concen-
tration amounts to 60 wt.% (see also Fig. 8). The
increased enrichment of THF in the lower polymer
lean phase also results in a decreasing density of
this phase. Hence, the densities of both liquid
phases approach each other leading to similar
phase densities in the solutropic area. For THF
concentrations above the solutropic point, the
THF solubility in the water rich phase is still
higher than in the polymer rich phase (positive
slope of tie-lines). Therefore, at around 65 wt.% of
THF, the density of the water rich phase falls
below the density of the polymer rich phase and
phase inversion is observed.
Apart from these thermodynamic phenomena, it
is noteworthy concerning the THF/water separa-
tion, that for both system temperatures all phase
compositions of the polymer rich phase indicate
the breaking of the atmospheric THF/water
azeotrope (see experimental results in Table 3 but
on polymer-free basis).
For the equilibrium temperatures of 321.15 and
334.15 K, the distribution of THF between the
polymer rich and the polymer lean phase is
depicted in Fig. 8. Below 50 wt.% of THF, for
both polymer solutions, the THF solubility in the
polymer rich phase is higher than in the water rich
phase. As can be seen for the Boltorn H3200
system, the THF solubility in the polymer rich
phase increases with the temperature. At the
solutropic point the diagonal is intersected, indi-
cating equal THF concentrations in both liquid
phases
7
. Above around 60 wt.% of THF, due to a
higher THF solubility in the polyester lean phase,
Fig. 8. Distribution of THF between the polymer rich and the polymer lean phase for ternary liquid/liquid equilibria of different
hyperbranched polymers in THF/water.
7
In the case of the hyperbranched polyglycerol solution, no
solutropic effect was measured. Therefore, the intersection with
the diagonal represents the critical point of the mixture which
can be estimated from Fig. 5.
M. Seiler et al./Separation and Purification Technology 30 (2003) 179/197 192
the THF concentration of the water rich phase is
larger than for the polymer rich phase. Eventually,
the critical point of the Boltorn H3200 mixture, at
which the THF concentration in both liquid
phases are equal, appears.
The preference of Boltorn H3200 for THF as
the preferred interaction partner can be recognised
from the activity coefficients at infinite dilution.
Activity coefficients at infinite dilution of a solute
i, g
i

, provide information about the intermolecu-


lar energy between the solvent and the solute and
are used, in particular, for the selection of solvents
for extraction and extractive distillation [21]. For
two different temperatures, T/345.15 K and
T/357.17 K, activity coefficients of THF and
water infinitely diluted in the hyperbranched
polymer Boltorn H3200 were determined [15].
While g
water

increases from 0.17 (for T/345.15


K) to 0.21 (for T/357.17 K), g
THF

does not show


a significant temperature dependence (g
THF

/0.03
for 345.15 KB/T B/357.17 K).
The effectiveness of THF extraction by hyper-
branched polymer can be characterised by its
selectivity S, which is a measure of the ability of
the polymer to separate THF from water. For
solvent extraction, the selectivity, as defined in Eq.
(3), is of comparable importance to the separation
factor used in distillation.
S
THF;water

K
THF
K
water

w
L1
THF
w
L2
water
w
L2
THF
w
L1
water
L1:polymer rich phase; L2:polymer lean phase
(3)
Based on Table 3, in Fig. 9 the selectivity
S
THF,water
is plotted versus the weight fraction of
THF in the polymer rich phase. Unlike hyper-
branched acetylated polyglycerol, the Boltorn
Fig. 9. Selectivity vs. weight fraction of THF for liquid/liquid equilibria of different hyperbranched polymers in THF/water.
M. Seiler et al./Separation and Purification Technology 30 (2003) 179/197 193
H3200 system shows remarkable selectivities for
the THF/water separation, which gradually de-
creases with increasing THF concentration in the
polymer rich phase.
Therefore, it can be concluded that the hyper-
branched esterified polyester Boltorn H3200 meets
the requirements of an efficient extraction solvent.
Thus, new process approaches for the separation
of THF/water by means of a hyperbranched
polymer can be derived (see next section).
3.2.2. New process approaches for the THF/water
separation
Based on Fig. 6, the following three separation
processes could be suggested for separating a 50
wt.% THF/50 wt.% water mixture:
Fig. 10 shows a separation process on the basis
of azeotropic distillation. The first distillation
column separates the THF/water feed into water
as the bottom product and the azeotrope-close
THF/water mixture (w
THF
:/0.94) as the over-
head product. According to Fig. 10, the latter
stream is fed into the second atmospheric counter-
current distillation column, which is operated with
a THF-rich reflux. The reflux represents the upper
polymer-rich phase in a mixer-settler, whose con-
stant phase compositions could be guaranteed by
adjusting the liquid mixture at 321.15 K to that
specific tie-line, which leads to an upper liquid
phase characterised by w
THF
/0.540, w
polymer
/
0.433, w
water
/0.027 and a lower liquid phase
characterised by w
THF
/0.503, w
polymer
/0.005,
w
water
/0.492 (see also Fig. 6 and Table 3). Due
to the THF-rich reflux, the overall THF concen-
tration in the second distillation column is
larger than the azeotropic THF concentration
(w
THF
/0.942). Therefore, (in spite of the presence
of a second liquid phase and a resulting additional
mass transfer resistance) a water-free THF/Bol-
torn H3200 mixture can be received as the bottom
product and the minimum boiling azeotrope as the
overhead product. The bottom product is sepa-
rated e.g. by means of a thin-film evaporator into
the pure THF product and a highly concentrated
Fig. 10. Separation of THF/water by means of a hyperbranched polymer as extraction solvent; A1, A2: countercurrent distillation
column, B: mixer /settler, C: polymer /solvent separation unit (e.g. evaporator, dryer); Compositions: THF/polymer/water,
concentrations in wt.%.
M. Seiler et al./Separation and Purification Technology 30 (2003) 179/197 194
polymer solution
8
, which is conveyed at T/
333K
9
into the mixer-settler. In order to save the
reboiler of the column A1, a partial flow of the
THF vapor product could be fed into the bottom
of A1. The liquid mixture, consisting of the
regenerated polymer and the condensed overhead
product of the second distillation column, should
meet the phase composition criteria described
above, so that the lower polymer free, liquid phase
of the mixer-settler shows the same composition as
the initial THF/water feed solution. Therefore,
both streams, the lower liquid phase of the mixer-
settler and the THF/water feed, can be mixed in
accordance to the overall mass balance and sub-
sequently fed into the first distillation column (see
Fig. 10).
The second separation scheme, depicted in Fig.
11, represents a process with the same unit
operations as in Fig. 10. But since the unit
operations in Fig. 11 are arranged in a different
order and the solvent extraction is based on
another tie-line, the second separation scheme
(Fig. 11) might be energetically superior to con-
ventional extraction processes and to the separa-
tion scheme of Fig. 10. As can be seen in Fig. 11,
the first separation step represents the liquid-liquid
demixing of the THF/water feed, which is mixed
with the regenerated polymer, in a mixer-settler at
321.15 K. In this process another tie-line from Fig.
6 is chosen for the single step extraction, leading to
an upper liquid phase characterised by w
THF
/
0.461, w
polymer
/0.517, w
water
/0.022 and a lower
liquid phase characterised by w
THF
/0.322,
w
polymer
/0.002, w
water
/0.676. The latter water-
rich phase is separated by means of a small
atmospheric countercurrent distillation column,
which*/within two or three theoretical stages*/
leads to water as the bottom product and a THF/
8
Since the mixture in the mixer /settler must have a constant
composition, the overall mass balance determines the amount
of THF in the highly concentrated polymer solution. Generally,
a concentrated polymer solution containing about 10 wt.% of
THF appears desirable, since the viscosity of the concentrated
polymer stream as well as the energy input of the evaporator
have to be taken into account. Future work will focus on these
aspects of process optimization (see Section 4).
9
Boltorn H3200 is thermally stable up to 520 K. The
melting point of this semi-crystalline polymer is 333 K.
Fig. 11. Separation of THF/water by means of a hyperbranched polymer as extraction solvent, A1, A2: countercurrent distillation
column, B: mixer /settler, C: polymer /solvent separation unit (e.g. evaporator, dryer); Compositions: THF/polymer/water,
concentrations in wt.%.
M. Seiler et al./Separation and Purification Technology 30 (2003) 179/197 195
water mixture, similar in composition to the feed
solution, as the overhead product. The upper
polymer-rich phase of the mixer settler with
w
THF
/0.955/w
THF,azeotrope
/0.942 is fed into a
second distillation column. The bottom product of
this column, a THF/polymer mixture, is separated
(for instance by means of an evaporator or dryer).
The yielded polymer is added to the columns
overhead product (i.e. the low boiling azeotropic
THF/water mixture), so that the underlying tie-
line of the single step extraction is met and the
overall mass-balance is satisfied. When necessary,
additional polymer is added in order to reach the
selected tie-line. The THF/polymer separation is
realised in accordance with Fig. 10.
A third separation process is conceivable,
which*/apart from the separation of the upper
liquid phase of the solvent extraction in Fig. 11*/
is equivalent to the latter separation scheme. In
this third approach, the upper polymer rich phase
from the liquid/liquid extraction is separated by
means of (shear) crystallisation into a liquid THF
product and a solid phase, containing all water
and most of the polymer. The solid mixture is fed
into an extruder. Here, devolatilisation allows the
water/polymer separation, so that the polymer
can be recycled. Further research on the under-
lying solid-liquid equilibria will investigate the
feasibility of crystallisation for the THF/water
separation.
4. Conclusions and future work
Hyperbranched polymers represent a promising
class of highly selective macromolecules, which
can be used for the optimisation of a variety of
separation processes. Properties such as solubility,
capacity, selectivity, melt and solution viscosity,
thermal stability as well as glass transition tem-
perature can be tailored according to the indivi-
dual application. In this work the potential of
commercially available hyperbranched polymers
in the field of extractive distillation and solvent
extraction is demonstrated.
In contrast to Hybrane H1500 and Boltorn H20,
the hyperbranched polymers Hybrane S1200 and
hyperbranched polyglycerol exhibit remarkable
separation efficiencies for the ethanol /water sys-
tem. Both hyperbranched representatives, Hy-
brane S1200 and hyperbranched polyglycerol,
easily break the azeotropic phase behaviour of
the ethanol /water system due to selective interac-
tions with water. For x
ethanol
/0.3, a considerable
increase of the separation factor a
ethanol,water
was
observed when adding Hybrane S1200 or hyper-
branched polyglycerol to the ethanol /water solu-
tion. In case of Hybrane S1200 this increase
proved to be of the same magnitude as that of
the conventional entrainer 1,2-ethanediol, which
confirms the suitability of using Hybrane S1200 as
an entrainer or entrainer additive for the separa-
tion of azeotropic mixtures by extractive distilla-
tion.
Due to the use of a non-volatile entrainer, the
entrainer regeneration can be carried out by
stripping, evaporation, drying or crystallisation.
Moreover, the main column does not require a
section for the separation of the low boiling
component from the entrainer, since a polymeric
entrainer cannot pollute the columns overhead
product. Therefore, extractive distillation using
one of the suggested hyperbranched polymers as
entrainer indicate a potential for cost-savings in
comparison to conventional extractive distillation
processes.
The separation of the azeotropic system THF/
water by means of solvent extraction is also
studied. The hyperbranched aliphatic polyester
Boltorn H3200 is used as a solvent. Boltorn
H3200 exhibits a remarkable selectivity and capa-
city, which allows for the breaking of the THF-
water azeotrope by single stage extraction. The
purification of the extract and the raffinate can be
achieved by combining the extraction unit either
with distillation or crystallisation steps. For the
system THF/water/hyperbranched polyester, a
remarkably distinct solutropic phenomenon is
observed.
Future work will focus on evaluating the
suggested processes for separating azeotropic mix-
tures by means of hyperbranched polymers. AS-
PEN PLUS

simulations will be carried out to


energetically optimise the individual separation
approach and to discuss their advantages and
M. Seiler et al./Separation and Purification Technology 30 (2003) 179/197 196
disadvantages in contrast to conventional separa-
tion processes.
Acknowledgements
The authors would like to thank Perstorp
Speciality Chemicals AB for providing hyper-
branched aliphatic polyesters. Thanks especially
to B. Pettersson and H.C. Bjoernberg, Perstorp,
for useful discussions. We also appreciate the
support of Dr P.E. Froehling, DSM, who kindly
provided hyperbranched polyesteramides. Experi-
mental HSGC-assistance of Dipl.-Ing. A. Kavar-
nou is gratefully acknowledged.
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