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Ian David Lockhart Bogle and Michael Fairweather (Editors), Proceedings of the 22nd European

Symposium on Computer Aided Process Engineering, 17 - 20 June 2012, London.


2012 Elsevier B.V. All rights reserved

Enhanced bioethanol dehydration in extractive


dividing-wall columns
David J-P. C. Suszwalak,a,b Anton A. Kissa
a

AkzoNobel Research, Development & Innovation, Process Technology ECG,


Zutphenseweg 10, 7418 AJ Deventer, The Netherlands, Tony.Kiss@akzonobel.com
b
Ecole Nationale Suprieure de Chimie de Mulhouse (ENSCMu), Mulhouse, France

Abstract
The industrial production of anhydrous bioethanol requires energy demanding
distillation steps to overcome the azeotropic behaviour of ethanol-water mixture. This
study proposes a novel distillation technology for enhanced bioethanol dehydration, by
extending the use of dividing-wall columns (DWC) to energy efficient extractive
distillation (ED). A classic sequence of two distillation columns and the alternative
based on DWC are optimized using the state of the art sequential quadratic
programming (SQP) method. A mixture of 85 %mol ethanol is dehydrated using
ethylene glycol as mass separating agents. The results of the rigorous simulations
performed in Aspen Plus show that energy savings of 10% are possible for the novel
process intensification alternative based on DWC, while using less equipment units as
compared to the conventional ED configuration.
Keywords: Dividing-wall column, extractive distillation, energy savings, bioethanol

1. Introduction
Bioethanol is considered as one of the most promising biofuel alternative to counteract
the shortage of fossil fuels. Current industrial fermentation processes usually lead to the
production of diluted bioethanol in the range of 5-12 %wt ethanol that needs to be
further concentrated to purities up to 99.0-99.8 %wt according to the international
standards (EN 15376, ASTM D 4806). A so-called preconcentration stage concentrates
bioethanol up to 92.4-94 %wt (Vane, 2008; Huang et al., 2008). A second step requires
further dehydration of ethanol to concentrations above the azeotropic composition of
95.6 %wt. Distillation methods such as extractive distillation (ED) are the current
option of choice despite their high energy costs. Usually ED is performed in a sequence
of two conventional columns, one separating ethanol and one recovering the solvent.
An innovative solution to overcome the drawback of energy intensive distillation is
using advanced process intensification and integration techniques, such as dividing-wall
column (DWCs) that leads to CapEx savings of 30% and up to 40% less OpEx (Asprion
and Kaibel, 2010; Dejanovi et al., 2010). In this work, we investigate the application of
a novel extractive dividing-wall column (E-DWC) configuration as the key separation
unit to enhanced bioethanol dehydration, from 85 %mol ethanol (93.5 %wt, average
purity of a pre-concentrated stream) to the required standard purity. Ethylene glycol is
used as mass separating agent. A head-to-head comparison between an optimal
conventional sequence and the optimized DWC alternative is made possible using the
strong sequential quadratic programming (SQP) method available in Aspen Plus. Our
results clearly show that significant energy savings of 10% are possible while using less
equipment units as compared to the conventional extractive distillation configuration.

D. J-P. C. Suszwalak and A. A. Kiss

668

2. Problem statement
Most of the water present in the diluted ethanol/water mixture (5-12 %wt) from the
fermentation step has to be removed so that bioethanol can be used as fuel additive
(purity equal or higher than 99.0-99.8 %wt). Simple distillation is used, but the purity of
the bioethanol product is limited to maximum 95.6 %wt due to the presence of a binary
azeotrope with water. To reach the desired purity current industrial processes involve
pervaporation, adsorption, pressure-swing distillation, extractive and azeotropic
distillation, or a combination of these. The problem of all these methods is either the
high energy requirements or the high equipment costs leading to penalties in the
operating costs and long payback times. Considering the high demand of bioethanol,
new alternatives are needed to reduce these costs. To solve this problem, we propose
here a novel extractive distillation alternative based on DWC.

3. Results and discussion


This section describes the results of the conventional and DWC alternative for the
extractive distillation of bioethanol. Aspen Plus simulations were performed using the
rigorous RADFRAC unit with RateSep (rate-based) model, and explicitly considering
three phase balances. The feed stream considered in this work comes from the preconcentration stage of bioethanol and consists of 85 kmol/hr (3915.9 kg/hr) ethanol and
15 kmol/hr (270.2 kg/hr) water thus having a near azeotropic composition (93.5 %wt
ethanol). The target purity was selected to be over 99.8 %wt ethanol in order to comply
with all bioethanol standards. No hard constraint was set on the purity of water. The
head-to-head comparison of the conventional system and the A-DWC system is possible
by using the same feed conditions and the same purity/recovery constraints. The classic
and novel alternatives described hereafter were optimized in terms of minimal energy
demand using the state of the art sequential quadratic programming (SQP) method.
Backed by a solid theoretical and computational foundation, the SQP method has
arguably become the most successful method for solving nonlinearly constrained
optimization problems This can be linked in Aspen Plus to the minimization of the heat
duty of the sequence, constraint by the required purity and recovery of the bioethanol
product, and using several optimization variables: total number of stages, feed location,
solvent flowrate, reflux ratio, liquid and vapor split. NRTL and UNIQUAC property
methods can be used due to the presence of a non-ideal mixture containing polar
components. Both methods were successfully used in the past, practically leading to
very same results (Kotai et al., 2007). In this study the NRTL property method has been
used for both the classic sequence and the DWC alternative.

Ethanol

Water

Ethanol

Water

Solvent

Solvent
DC2

DC1

Feed

Feed

DC1
BTM

Ethylene
glycol

Ethylene Glycol

Figure 1. Two-columns extractive distillation sequence (left) and DWC alternative (right)

Enhanced bioethanol dehydration in extractive dividing-wall columns

1.0

1.0

DC1

0.9

DC2

0.9
0.8

Molar fraction / [-]

0.8

Molar fraction / [-]

669

0.7
0.6
Ethanol

0.5

Water

0.4

Ethylene glycol

0.3

0.7
Ethanol

0.6

Water

0.5

Ethylene glycol

0.4
0.3

0.2

0.2

0.1

0.1
0.0

0.0
0

10
Stage / [-]

15

20

10
Stage / [-]

15

20

Figure 2. Composition profiles in DC1 and DC2 (two-columns ED sequence)

Extractive distillation performs the separation in the presence of a miscible, high


boiling, relatively non-volatile component that forms no azeotrope with the other
components in the mixture. Ethylene glycol (EG) remains the most common entrainer
used in the extractive distillation of ethanol-water (Ravagnani et al., 2010). Therefore,
EG is used as mass separating agent for both the conventional and E-DWC sequences.
Note that the ternary mixture ethanol-water-glycol presents a single binary azeotrope
and no liquid phase splitting.
The conventional direct sequence presented in Figure 1 (left) consists of two column
shells, two condensers and two reboilers. Ethylene glycol is a high boiling solvent hence
it is being added on a stage (3) higher than the feed stage (13) of the ethanol-water
mixture. Due to the presence of the EG solvent the relative volatility of ethanol-water is
changed such that their separation becomes possible. Pure bioethanol is collected as top
distillate product of the first distillation column (DC1), while the bottom product a
mixture of ethylene glycol and water is being fed to the second distillation column
(DC2). High purity water by-product and ethylene glycol are obtained as top distillate
and bottom product of DC2, respectively. DC1 consists of 17 stages whereas DC2 has a
total number of 16 stages with the feed located on stage 7 (stages are numbered from the
top to the bottom). The EG solvent recovered here is typically recycled back to the first
distillation unit (DC1). Figure 2 presents the composition profiles along the two
distillation columns. These results confirm that ethylene glycol is a feasible entrainer
allowing an excellent separation of ethanol-water. Despite quite high investments costs
required for 2 columns, 2 reboilers and 2 condensers, this classic sequence has the key
advantage of being flexible as DC1 and DC2 can be operated at different pressures
this not being possible in a DWC configuration. However since both DC1 and DC2
operate at atmospheric pressure, the use of a DWC seems to be an attractive alternative.
Figure 1 (right) shows the conceptual design of the proposed E-DWC that is in fact a
split shell column with divided overhead section and common bottoms section (Yildirim
et al., 2011). In this column the solvent is separated as single bottom product, while two
distillate products are collected on each side of the wall ethanol and water,
respectively. Since there is no off-shelf DWC unit in the currently available process
simulators, two coupled RADFRAC units (called prefractionator and DWC) were used
in Aspen Plus, as the thermodynamically equivalent of the E-DWC. The resulting
flowsheet consists of two column shells, two condensers but only one reboiler. The
Aspen Plus model of the direct sequence is used as the starting point of the E-DWC
simulation. The results of the direct sequence simulation provide in fact the initial
estimates for the number of trays, feed tray locations, liquid and vapor split. Figure 3
plots the temperature and liquid composition profiles in the E-DWC, while the key
parameters of the optimal design are presented in Table 1.

D. J-P. C. Suszwalak and A. A. Kiss

670

DWC side

Prefractionator side

200

1.0
Temperature DWC side

0.9

Temperature prefractionator side

0.8

160

Molar fraction / [-]

Temperature / [C]

180

140
120
100

80

Water

0.7

Ethylene glycol

0.6

0.5
0.4
0.3
0.2

Ethanol

0.1

60
0

10

15

20

0.0

Stage / [-]

10
Stage / [-]

15

20

Figure 3. Temperature and composition profiles in the E-DWC (dashed line used for the prefractionator side, while continuous line is used for the main DWC side)

The prefractionator consists of 16 stages with the bioethanol feed located on stage 13
while the extractive agent ethylene glycol is added on stage 3. The dividing-wall goes
down to stage 14 of a 20 stages main column. Remarkably, the temperature difference
between the two sides of the wall is very low, less than 20 C such conditions being
easily achievable in the practical application. Large temperature differences (above
50C) would require more attention, as equivalent configurations used for the
simulation are thermodynamically equivalent to a DWC only if the heat transfer across
the wall can be neglected. Moreover, it is worth noting that high purity and recovery is
obtained for all three products of the extractive dividing-wall column: ethanol and water
as top distillates, and EG solvent as recovered bottom product. The composition profiles
are very similar to the one observed for the classic sequence previously described. The
key difference is a larger column for the E-DWC as compared to the classic ED.
Table 2 presents a comparison of the reboiler and condenser duties for the conventional
two-column sequence versus the proposed E-DWC. The specific energy requirements
are 0.51 kW.h/kg for ED and 0.46 kW.h/kg bioethanol for E-DWC, respectively. Hence
energy savings of around 10% are possible with the E-DWC, as compared to ED.
Table 1. Design parameters of the optimized E-DWC
Design parameters
Reflux ratio pre-fractionator
Number of stages pre-fractionator
Feed stage pre-fractionator
Feed stage of extractive agent
Reflux ratio DWC
Number of stages DWC
Stage of the interconnection Liq1
Stage of the interconnection Vap1
Interconnection liquid flow
Interconnection vapor flow
Feed flowrate of extractive agent
Heat duty pre-fractionator
Heat duty DWC
Total heat duty
Operating pressure pre-fractionator
Operating pressure DWC
Ethanol recovery
Water recovery
Ethylene glycol recovery
Purity of ethanol recovered
Purity of water by-product
Purity of ethylene glycol (recycled)

Value
0.27
16
13
3
0.2
20
14
14
291
86
190
0
1819.52
1819.52
1
1
99.80
99.10
99.90
99.80 / 99.84
97.64 / 99.07
99.98 / 99.93

Unit
kmol / kmol

kmol / kmol

kmol/hr
kmol/hr
kmol/hr
kW
kW
kW
bar
bar
%
%
%
%wt / %mol
%wt / %mol
%wt / %mol

Enhanced bioethanol dehydration in extractive dividing-wall columns

671

Table 2. Comparison condenser and reboiler duty for extractive distillation

Condenser duty (kW)


Reboiler duty (kW)

Direct sequence ED
DC1
DC2
Total
-1200.62
-367.29
-1567.90
1402.43
605.39
2007.82

PreFrac
-1175.01
0.00

E-DWC
DWC
-205.09
1819.52

Total
-1380.10
1819.52

Note that the energy savings are lower than the usually reported values of 25-40%, due
to the fact that the conventional ED sequence was also optimized in this study. Much
higher savings are expected by comparing with data from an actual plant where the
process is not fully optimized.

4. Conclusions
This study successfully demonstrated the potential use of novel distillation alternative
based on extractive DWC, for enhanced bioethanol dehydration. The innovative process
proposed here is technically feasible, allowing the separation of high purity bioethanol
(over 99.8 %wt) according to the current standards (EN 15376, ASTM D 4806). The
use of E-DWC configuration leads to over 10% energy savings. Remarkable, only one
column shell is used while a reboiler is spared, as compared to the conventional ED
configuration. Based on these results, the use of E-DWC for ethanol dehydration is
particularly interesting in case of building new bioethanol plants. However, in case of
revamping existing plants the equivalent Petlyuk configuration should be considered.

Acknowledgements
The financial support given by AkzoNobel to David Suszwalak (ENSCMu, France)
during his MSc internship is gratefully acknowledged.

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