Zdravko Kravanja, Miloš Bogataj (Editors), Proceedings of the 26th European Symposium on

Computer Aided Process Engineering – ESCAPE 26

June 12th -15th, 2016, Portorož, Slovenia © 2016 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/B978-0-444-63428-3.50126-0

Intensified Separation Processes for the Recovery

and Dehydration of Bioethanol from an Actual
Lignocellulosic Fermentation Broth
Carlo-Edgar Torres-Ortegaa, Ben-Guang Ronga*
a
Department of Chemical Engineering, Biotechnology and Enviromental Technology,
Universitiy of Southern Denmark, Campusvej 55, DK-5230 Odense M, Denmark
* Corresponding author :bgr@kbm.sdu.dk

Abstract
Bioethanol from fermentation of lignocellulosic feedstock is a potential gasoline-
substitute or partial substitute due to its fuel similarities. Regarding the whole
bioethanol production process, separation and purification represent a technical
challenge because of the dilute stream obtained, besides the presence of an ethanol-
water azeotrope. In the real production situation, the actual lignocellulosic fermentation
broth consisted of a set of representative components involved in every production step.
Thus, the mixture consisted of gas, liquid, and both soluble and insoluble solids. This
was separated in four sub-streams of interest destination: CO2 for algae growing,
bioethanol as transportation biofuel, stillage for water recovery, and insoluble solids for
energy recovery. The process simulator Aspen Plus V8.0 was used to simulate two
starting configurations consisting of one single bioethanol recovery and two types of
dehydration sections. Due to the nature of the mixture, the separation train consisted of
different types of units, making the intensification a non-trivial task. Therefore,
alternatives were proposed consisting of intermediate condensers, thermal couplings,
side-column sections and divided wall column (DWC) to reduce the number of
equipment and evaluate their total annual cost (TAC). It was found that some
alternatives achieved moderate TAC savings (~20 %) with respect to the starting cases
besides reducing the number of equipment. The novelty of this work was the synthesis
and design of intensified alternatives for the separation process of an actual
lignocellulosic fermentation broth.
Keywords: Actual fermentation broth, recovery and dehydration, bioethanol, rigorous
simulation, DWC

1. Introduction
Analyzing the energy situation in Europe, the transport sector accounts for more than
30% of the total energy consumption, and it is 98% dependent on limited and unevenly
distributed fossil fuels. Therefore a diversification of primary energies for fuel
production is necessary. Biomass is the world’s fourth largest energy source; moreover,
it is a carbon-neutral renewable resource, environmental benign and capable to drive
rural development and energy security. Bioethanol from fermentation of lignocellulosic
feedstock is a potential gasoline-substitute or partial substitute due to its fuel
similarities. Regarding the whole bioethanol production process, separation and
purification represent a technical challenge because of the dilute stream obtained,
containing 5 to 10% (w/w) of bioethanol, besides the presence of an ethanol-water
728 C.E. Torres-Ortega and B.-G. Rong

azeotrope at 95.63% (w/w) that must be overcome, aspects that have been extensively
studied as a simplified water and ethanol mixture, (Errico et al., 2013) among others.
However, in the real production situation, the actual lignocellulosic fermentation broth
consisted of a set of representative components involved in every production step, i.e.
feedstock such as cellulose, xylan, ash; pretreatment and neutralization such as
ammonia, HMF, furfural, sulfates; and fermentation such as xylitol, CO2, ethanol, etc.
Therefore, the simulation of a rigorous fermentation stream can generate new separation
sequences closer to the real problem.

2. Base process alternatives for bioethanol recovery and dehydration

The fermentation broth was generated after treating a hybrid lignocellulosic feedstock
consisting of wheat straw, scot pine and switchgrass by dilute acid (DA) pre-treatment
and simultaneous saccharification and co-fermentation (SSCF). The compositions,
conditions and yields were obtained from the literature. Table 1 presents the
components considered for the feed stream.
Table 1. Composition of the complete fermentation broth stream (% wt.)
Complete broth stream Grouped broth components
NH3 0.01%
O2 0.01% Gases 4.21%
CO2 4.19%
Ethanol 4.40% Ethanol 4.40%
H2O 66.74% H2O 66.74%
Glucose 0.60%
Xylose 0.55%
Extractive 1.51%
Soluble Lignin 0.30%
HMF 0.21%
Furfural 0.02%
Lactic Acid 0.14% Soluble solids and impurities 14.51%
Xylitol 0.04%
Glycerol 0.01%
Succinic Acid 0.02%
(NH4)2SO4 10.57%
NH4 acetate 0.49%
DAP 0.06%
Cellulose 2.65%
Xylan 1.68%
Insoluble Lignin 3.88%
Protein 0.95% Insoluble solids 10.15%
Ash 0.92%
Microorganisms 0.04%
Tar 0.03%
Total mass flow rate: 479165 kg/h
For the aforementioned lignocellulosic fermentation broth, two sequences were
considered as starting points for the analysis, Fig. 1. The recovery subsection is
common for both sequences (left side), and it mainly consists of a centrifuge filter E-1
Intensified Separation Processes for the Recovery and Dehydration of
Bioethanol from an Actual Lignocellulosic Fermentation Broth 729

to remove the insoluble solids (D), followed by a distillation column E-2 that separates
the gases (A) and a pre-concentrated stream on bioethanol (B) at the top, and most of
the water and soluble solids as a bottom stream (C). After the distillation column, a set
of flashes E-3 and E-4 separate the A from B, and B is concentrated until reach 90%
(wt.) purity on bioethanol. A scrubber, E-5, is used to recover any bioethanol losses
with the gases. Regarding the dehydration section (right side), there are two different
ways how the solvent is recovered. The upper section (right side) Fig. 1 depicts an
extractive distillation column using glycerol as solvent in order to break the azeotrope
and obtain the bioethanol at a purity of 99.5% wt., E-6. After breaking the azeotrope,
the glycerol is recovered through the combination of a flash and a stripper, E-7 and E-8.
Unlike the previous case, the sequence from the lower section (right side) Fig. 1 uses a
distillation column, E-7, in order to recover the glycerol. Both solvent recovery
alternatives produce a stream of the glycerol of 99% (wt.) purity.

Fig. 1 Original_Rec&Dehyd. Left side describes the bioethanol recovery, and right side,
upper (flash and desorber) and lower (distillation) sections, describe the dehydration of
bioethanol and solvent recovery.

3. Synthesis of Intensified Sequences

The objective of the synthesis analysis was to replace the flashes that separates the
distillation columns in order allow direct interconnection between each other. Four
possibilities were explored to replace the functionality of the flashes: using an extra
vertical column section together with a condenser, Fig. 2(a); using an extra vertical
column section together with a thermal coupling, Fig. 2(b); and finally replace them
with a side rectifier, Fig. 2(c). A thermodynamically equivalent sequence (equivalent in
energy consumption) to Fig. 2(c) can be rearranged as a DWC, Fig. 2(d) (Rong and
Errico, 2012) and potentially reduce capital cost.

Fig. 2(a) No flashes: Condenser Fig. 2(b) No flashes: Thermal Coupling

730 C.E. Torres-Ortega and B.-G. Rong

Fig. 2(c) No flashes: Side Column Fig. 2(d) No flashes: DWC

4. Rigorous Design
The process simulator Aspen Plus V8.0 was used to perform the rigorous simulation of
the separation systems. The thermodynamic package NRTL, Henry gaseous
components, together with physical data from NREL for the components not included in
the Aspen database were implemented, (Humbird et al., 2011). The design equations for
the equipment as well as the utility costs were taken from textbooks. (Turton et al.,
2009). The sequences’ TAC values (Total Annual Cost) were evaluated according to the
modular methodology of Guthrie (Turton et al., 2009) considering 5 years as time for
recovering the investment and the CEPCI 2014 index. Equation 1 depicts how TAC was
calculated.

∑ (1)

5. Results and Discussion

Before proceeding with the TAC calculations, the fulfilling of the design specifications
was verified in all the sequences, that is, recoveries and purities of bioethanol and
glycerol. For the case of the options: No flashes_Condenser and No flashes_Thermal
coupling, the target purities were not achieved. No flashes_Condenser option did not
preconcentrate the bioethanol stream at the purity expected, around 60 % instead of 90
% wt, thus the performance of the downstream process was drastically decreased
compromising the final product purity. The alternative No flashes_thermal coupling
achieved without many complications the bioethanol purity specification in the
dehydration section; however because the thermal coupling implies a mass exchange,
between the recovery and extractive distillation columns, a significant amount of
glycerol, as liquid stream, went back to the recovery column and the stream C. This loss
of glycerol in stream C prevented of achieving the glycerol purity required. Moreover, it
is worthy to consider that the additional equipment and utilities required to separate the
lost glycerol from water also has to overcome the challenge of organic matter soluble in
both, water and glycerol. If a vapor stream would have been chosen instead of liquid
from the extractive distillation to the recovery column, a lower purity of bioethanol
would be achieved in the dehydration section. The use of vertical internal column
sections did not properly replace the functionality of the flashes.
On the other side, the options No flashes_side column and No flashes_DWC, adding a
parallel external and internal column sections, satisfied the design specifications.
Moreover, these additional column sections did not only replace the functions of the
flashes but even exceed them. Also it is believed that the fact operating pressures of
flashes intended to replace were similar to column the recovery column should ease the
Intensified Separation Processes for the Recovery and Dehydration of
Bioethanol from an Actual Lignocellulosic Fermentation Broth 731

column section replacement with not increment in the energy consumed. Although No
flashes side column presented relevant improvements in the performance (TAC values),
still there is the inconvenient of having additional equipment separating the recovery
column from the extractive distillation column, thus preventing a direct combination
and further intensification of both. Regarding the TAC values, the No flashes DWC
systems achieved the highest TAC savings with respect to the original sequences, 20.85
% and 21.42 %, flash and desorption, and distillation solvent-recovery units,
respectively, Fig. 3. The difference in TAC values among the sequences with side
rectifier (side column) and DWC are negligible for both solvent-recovery technologies;
however, the extra advantage of reducing the number of equipment makes DWC
sequences more attractive for intensification purposes. The main contributors to the
TAC value reduction were related to the reduction in the compressor used to recover the
ethanol in the absorption column and an important reduction in heating costs. Regarding
the capital costs reduction in the separation units by the removal of flashes, it was only
slightly reduced as the new DWC was bigger than the original one.

Fig. 3. TAC values for the original sequences and alternative ones fulfilling the design
specifications. SC stands for side column, Distil for distillation and desorp for
desorption.
The description of the flowsheets and key design parameters of the most profitable
alternative sequences is depicted in Fig. 4.
732 C.E. Torres-Ortega and B.-G. Rong

Fig. 4. No flashes: DWC_Rec&Dehyd. The numbers in circles represent the number of

theoretical stages in every column section. Left side describes the bioethanol recovery
and right side, upper (flash and disrober) and lower (distillation) sections describe the
dehydration of bioethanol and solvent recovery.

6. Conclusions
Two separation sequences consisting of a bioethanol recovery and dehydration section
of an actual lignocellulosic fermentation broth were analyzed; afterwards alternative
systems were proposed in order to reduce the number of equipment and to obtain
savings regarding the TAC values (Total Annual Costs). The most profitable alternative
sequences obtained among 20.85 % and 21.42 % savings in USD/year with respect to
the original cases. Moreover, as the distillation columns are now directly connected,
further possibilities of intensification are possible to implement.
Finally, since a synthesis point of view, it was proved that the replacement of separation
units, in this case the flashes, by DWC (internal column sections) might represent a
feasible alternative when the separation units operate at relatively similar pressure. By
doing so, the TAC value can be reduced and the system be intensified, that is, reduced
in the number of units.

References
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Bioethanol Separation. Part 1: Extractive Distillation with Simple Columns. Ind. Eng.
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Worley, M., Sexton, D., Dudgeon, D., 2011. Process design and economics for
biochemical conversion of lignocellulosic biomass to ethanol. Tech. Rep. NREL.
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