ARTICLE

pubs.acs.org/EF

Energy Requirements for Butanol Recovery Using the Flash

Fermentation Technology
Adriano P. Mariano,*,, Mohammad J. Keshtkar, Daniel I. P. Atala, Francisco Maugeri Filho,||
Maria Regina Wolf Maciel, Rubens Maciel Filho, and Paul Stuart

cole Polytechnique de Montr
eal,
NSERC Environmental Design Engineering Chair, Department of Chemical Engineering, E
Montreal, QC, Canada

Laboratory of Optimization, Design and Advanced Control (LOPCA), School of Chemical Engineering,
University of Campinas (UNICAMP), Campinas, SP, Brazil

Center of Sugar Cane Technology (CTC), Piracicaba, SP, Brazil

Laboratory of Bioprocess Engineering, School of Food Engineering, University of Campinas (UNICAMP), Campinas, SP, Brazil

ABSTRACT: Acetone
butanol
ethanol (ABE) facilities have traditionally presented unattractive economics because of the large
energy consumption during recovery of the products from a dilute fermentation broth (13 g/L butanol). This problem results
from the high toxicity of butanol to microorganisms that catalyze its production. Flash fermentation is a continuous fermentation
system with integrated product recovery. The bioreactor is operated at atmospheric pressure and the broth is circulated in a closed
loop to a vacuum chamber where ABE is continuously boiled o at 37 C and condensed afterward. With this technology the beer
achieved a concentration of butanol as high as 30
37 g/L. This paper studies the energy requirements for butanol recovery using the
ash fermentation technology and its eect on the energy consumption by the downstream distillation system. Compressors are
used to remove the vapors from the ash tank, thus maintaining the desired vacuum. The heat recovery technique of vapor
recompression is used to reduce energy requirements. With this technique the heat generated by the compression and partial
condensation of the vapors provides the energy for boil up (heat of vaporization) in the ash tank. Thus the energy requirement for
the ash fermentation is essentially the electrical power demanded by compressors. Energy for recirculation pumps accounts for
approximately 0.5% of the total energy consumption. Small increments in butanol concentration in the beer can have important
positive impacts on the energy consumption of the distillation unit. Nonetheless, the energy use of the recovery technology must be
included in the energy balance. For a fermentation with a wild-type strain, the total energy requirement for butanol recovery (ash
fermentation distillation) was 17.0 MJ/kg butanol, with 36% of this value demanded by the ash fermentation. This represents a
reduction of 39% in the energy for butanol recovery in relation to the conventional batch process. In the case of a fermentation with a
hyper-butanol producing mutant strain, the use of the ash fermentation could reduce the energy consumption for butanol recovery
by 16.8% in relation to a batch fermentation with the same mutant strain.

1. INTRODUCTION
Butanol is highly toxic to microorganisms that catalyze its
production, and for this reason less than 13 g/L of butanol is
produced during batch fermentation. For the sake of comparison,
in the ethanol fermentation the yeast cells tolerance to ethanol is
approximately ten times greater. Therefore, typical acetone

butanol
ethanol (ABE) fermentation has been plagued by the
use of dilute sugar solutions as substrates, large process volumes,
high downstream process costs due to intensive energy requirements for recovery of low concentrations of ABE in the beer, and
large quantities of wastewater.
A solution to these problems can be addressed by using genetic engineering techniques to develop strains that could
tolerate higher concentrations of butanol and sugar.1,2 Another
option is the use of technologies designed to remove butanol
continuously from the fermentation broth (integrated recovery technologies). The product recovery reduces the eect
of product inhibition and allows an increase in the substrate
concentration which results in a reduction in process streams,
and higher productivity. With either approach (biological and
r 2011 American Chemical Society

technological) the energy eciency of the process is expected to

be enhanced.
Product-recovery technologies are designed to remove ABE
from the bioreactor liquid as the fermentation is ongoing and the
ABE-depleted stream is returned to the bioreactor or, in the case
of an in situ products removal technology, the fermentation
broth never leaves the bioreactor. Product-removal techniques
include gas stripping, liquid
liquid extraction, membrane-based
methods (pervaporation, perstraction), and adsorption. All these
techniques have advantages and disadvantages in terms of
capacity, selectivity, fouling, clogging, scale-up, operational simplicity, and energy requirement. A comparison among some of
them can be found elsewhere.1,3
8
As a commodity, butanol production cost is mainly aected by
feedstock price. Economic modeling studies show that feedstock
price (sugar cane juice in Brazil) could account for 60% of the
Received: February 22, 2011
Revised:
April 12, 2011
Published: April 12, 2011
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Figure 1. Flash fermentation technology.

total variable operating cost. The remaining value is made up of

utilities costs.9 Thus the overall energy consumption during
recovery is also an important operating cost factor. For this
reason, during the selection of an integrated recovery technology,
the energy consumption must be a key decision factor and can be
used as a ranking parameter.7
In our previous works we demonstrated the technical feasibility of the ash fermentation technology to recover ABE from
the bioreactor.10,11 This integrated ABE fermentation involves
operating the bioreactor at atmospheric pressure while the broth
is circulated in a closed loop to a vacuum chamber where ABE is
continuously boiled o. With this technology, a signicant improvement of productivity was observed, and the beer achieved a
concentration of butanol as high as approximately 30 g/L. These
good results prompted us to further investigate this technology as
to its energy requirements and its eect on the energy consumption by the downstream distillation system. These studies are
presented in the next sections.

2. METHODOLOGY
The principles of the ash fermentation process are presented
in the scheme shown in Figure 1. The fermentation broth of a
continuous fermentor circulates through a vacuum ash tank.
The partial vaporization of water and fermentation products that
takes place in the ash tank generates a vapor phase rich in
solvents (ABE) and an ABE-depleted liquid stream. The vapor is
subsequently condensed and combined with the beer stream and
then sent to distillation. The ABE-depleted liquid stream returns
to the fermentor, which is operated at atmospheric pressure.
Temperature in the fermentor and in the ash tank is set to
37 C. Vacuum is regulated in order to keep constant the amount
of broth vaporized.

In the ash tank, fermentation broth boils at low pressure

(6.4
6.8 kPa) and an equilibrium mixture of fermentation
products (ABE, organic acids, and CO2 and H2) and water is
taken overhead. Compressors remove these vapors, thus maintaining the desired vacuum. The heat recovery technique of
vapor recompression is used to reduce energy requirements12
(Figure 2). In this integrated system, the rst compressor
compresses the vapor to 0.3 atm. At this pressure the vapor
can be passed through the shell side of a shell-and-tube heat
exchanger and heat is exchanged with the fermentation broth
present in the ash tank. The ow rate of the fermentation broth
through the heat exchanger is set in order to allow temperature a
maximum increase of 0.5 C. This restriction is necessary due to
the strong sensibility of the microorganism activity to temperature variations. Most of the vapor (80%, mass basis) condenses
in the heat exchanger, providing the energy for boil up (heat of
vaporization) in the ash tank. The condensed fraction is
pumped at low energy cost to atmospheric pressure and sent
to distillation. The remaining vapor is compressed to 1.5 atm in a
second compressor and a subsequently partial (30%, mass
basis) condensation suces to meet the total reboiler duty of one
of the distillation columns (acetone column). Afterward, the
remaining vapor stream is completely condensed by heating the
beer stream from the fermentor. Noncondensables (CO2 and
H2) are sent to an absorber column in order to recover carried
ABE. The pressure in the rst compression stage (0.3 atm) is the
minimum value demanded by the heat exchanger of the ash tank
to meet its heat duty requirement. Pressure drop in each heat
exchanger is assumed to be 0.14 atm (2 psia). Compressors
isentropic eciency is considered to be 0.72.
Until the shutdown of the commercial butanol fermentation
facilities in the 1980s, the separation of the fermentation
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Figure 2. Vapor recompression heating system. Heat integration between the recompressed ABE-enriched vapor stream from the ash tank and the
reboiler of the acetone column, and fermentation beer stream (stream conditions refers to scenario 2, Table 1).

products (ABE) was carried out in a series of ve continuous

distillation columns, with the last two responsible for the separation of butanol from water.13 Therefore, this design was
adopted in the present study (Figure 3). In addition to the
proven utilization of this system in the past, distillation is a
mature technology and widely applied in the biofuel industry,
and accepted in terms of scale-up and operability.6 Solvents
(ABE) are removed from the beer in the beer column (45 stages;
feed in stage 1; stages are numbered from the top down) after
being heated to 112 C. The stillage contains most of the broth
water content, acetic and butyric acid, cells, and remaining sugars.
The overhead vapor from the beer column is separated in a series
of four distillation columns operated under dierent pressures in
order to allow heat integration. In the top of the acetone column
(30 stages; feed in stage 15), 99.5 wt % acetone is obtained and
the fermentation gases (CO2 and H2) are sent to an absorber
column (10 stages; feed in stage 10) in order to minimize the
losses of ABE in the distillation unit. The acetone column is
operated at 0.7 atm so that low pressure steam can be used in the
reboiler (it should be noted that for a process with the ash
fermentation, the total reboiler duty of the acetone column can
be met by partial condensation of the recompressed ABEenriched vapor stream from the ash tank). The bottom stream
of the acetone column is fed to the ethanol column (40 stages;
feed in stage 10), which operates at 0.3 atm. Vacuum operation
reduces the reux needed to produce the 85 wt % ethanol
overhead product and allows the total reboiler duty to be met
by condensing the overhead vapors from the beer column in the
ethanol column reboiler. A two-column distillation system in conjunction with a decanter is used to separate the heterogeneous

binary butanol/water azeotrope. The bottom stream of the

ethanol column is added to a decanter in conjunction with the
top streams from the water and butanol columns. In the decanter,
butanol phase separates from the aqueous phase and rises to form
an upper layer. The water-rich phase is reuxed to the water
column (10 stages; feed in stage 1), whose bottom (water)
contains less than 0.05 wt % butanol. The butanol-rich phase is
reuxed to the butanol column (10 stages; feed in stage 1), which
produces a 99.5 wt % butanol product. The water and butanol
columns and the decanter are operated at atmospheric pressure.
Solvent loss for the gas stream accounts for 1.7, 0.2, and 1.4% of
the total amount of acetone, butanol, and ethanol, respectively.
By employing vapor recompression heating, the energy requirement for the ash fermentation is essentially the electrical
power demanded by the compressors. Energy for recirculation
pumps accounts for approximately 0.5% of the total energy
consumption. The energy for vaporization is obtained from the
heat generated during compression of the vapors. Thus, it is very
intuitive that the greater the amount of fermentation broth
vaporized in the ash tank, the greater the energy consumption
necessary to compress the vapors. Having this in mind, the rst
step in the evaluation of the energy requirements was to determine
the eects of operating variables related to the ash tank (inlet ow
rate of the ash tank and pressure) on the amount of fermentation
broth vaporized in the ash tank. In the same manner, the eects
on the concentrations in the fermentor were also analyzed. These
studies were carried out using a mathematical model that simulates
the fermentation and the vaporization in the ash tank.
In the computational simulation, fermentation starts up in
batch mode (500 m3 fermentation volume) with initial sugar
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Figure 3. Downstream distillation unit (stream conditions refers to scenario 2, Table 1).

concentration of 60 g/L and after 17 h (the time butanol

concentration in the fermentor achieves 6 g/L) the continuous
feed of medium (50 m3/h) and the recirculation of the broth
through the ash tank are initiated (inlet ow rate of the ash
tank varying between 200 and 350 m3/h). Equations 1
3 were
used to determine the concentrations of biomass, substrate, and
products in the fermentor:
dX
F PU
Fr
rX

X Xr
dt
V
V

dS
F PU
Fr
F0
rS

S Sr S0
dt
V
V
V

dPi
F PU
Fr
r Pi

Pi Pr;i
dt
V
V

where i stands for butanol, acetone, ethanol, butyric acid, and

acetic acid.

The kinetic models (rx, rs, and rpi) were experimentally

determined by Mulchandani and Volesky14 based on the following assumptions: (1) carbon substrate (glucose) limitation only;
(2) no nitrogen and nutrient limitation; (3) product inhibition;
(4) acetic and butyric acid are intermediate metabolites and
are reduced to acetone and butanol, respectively; (5) acetone
and butanol are also synthesized directly from carbon substrate; (6) ethanol is synthesized from carbon substrate only;
(7) fermentation is performed at optimal temperature of
37 C and optimal pH of 4.5 under anaerobic conditions; (8)
all the cells (Clostridium acetobutylicum ATCC824) are
metabolically active and viable. Integration of eq 1 to 3 was
carried out by the fourth order Runge
Kutta method using a
Fortran code.
The modeling of the ash tank was based on the isothermal
and isobaric evaporation model15 and a multicomponent system
(water, butanol, acetone, ethanol, acetic acid, and butyric acid)
was considered. Saturation pressures were calculated by Antoines
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Table 1. Scenarios Considered for the Energy Consumption

Studies
scenarios
I

III

IV

VI

S0 (g/L)

100

150

150

170

170

150

fermentation volume (m3)

500

500

750

500

750

750

strain
a

II

C. acetobutylicum ATCC824. b C. beijerinckii BA101.

equation and activity coecients were calculated by the

UNIQUAC model.
Six scenarios were set in order to assess the energy requirements for the ash fermentation and the subsequent distillation
unit. They dier from each other in terms of substrate concentration, fermentation volume (dilution rate), and microbial strain
(Table 1). For each scenario, the necessary vacuum in the ash
tank able to balance the trade-o between minimum vaporization
of fermentation broth and high sugar conversion (98%) was
initially determined using the above-described mathematical
model (eqs 1
3). In the simulated fermentations, the fresh
medium fed to the fermentor had a ow rate of 50 m3/h and the
inlet ow rate of the ash tank was 300 m3/h. For scenario VI
another microbial strain was considered. C. beijerinckii BA101 is a
hyper-butanol producing mutant strain able to produce 25.3 g/L
ABE (19.7 g/L butanol, 5.0 g/L acetone, 0.6 g/L ethanol).16 To
obtain this same level of solvents production, the values of the
parameters k7, k10, k15, and k11 of the kinetic model were changed
to 0.65, 0.02, 1.9, and 0.045, respectively (the reader is referred to
Mulchandani and Volesky14 for identication of parameters).
These alterations were necessary because the kinetic model
originally describes the typical ABE production level of a wildtype strain (11 g/L butanol, 5.0 g/L acetone, 1.5 g/L ethanol).
For each scenario shown in Table 1, the energy requirements
(energy for compressors and reboilers of distillation columns) were
calculated by process modeling in Aspen Plus 7.1. The complete
process represented in Figures 1
3 was simulated in Aspen
Plus incorporating the results (operating conditions and
steady-state concentrations) obtained with the simulations of
the fermentation in Fortran (eqs 1
3 and ash calculation).
For this, a stoichiometric reactor model (RStoic) was used to
simulate the fermentor in Aspen Plus, considering the following reaction equations:
C6 H12 O6 H2 O f C3 H6 O acetone 3CO2 4H2 4
C6 H12 O6 f C4 H10 O butanol 2CO2 H2 O

C6 H12 O6 f 2C2 H6 O ethanol 2CO2

C6 H12 O6 f C4 H8 O2 butyric acid 2CO2 2H2

C6 H12 O6 2H2 O f 2C2 H4 O2 acetc acid 2CO2 4H2

8
C6 H12 O6 1:1429NH3 f 5:7134CH1:8 O0:5 N0:2 biomass
0:2857CO2 2:5714H2 O
9
For each reaction equation, fractional conversions of glucose
were assigned. In this manner, the same values of consumed

Figure 4. Vapor
liquid equilibrium (VLE) of n-butanol/water binary

mixture at atmospheric pressure (T-xy diagram) and at 50.07 C (P-xy
diagram). Data (lines) obtained from Aspen Plus simulator and validated
by experimental data (circles and squares). ASPEN 1 (black lines): default
UNIQUAC parameters available in the simulator. ASPEN 2 (gray lines):
UNIQUAC parameters reported by Fisher and Gmehling.20

substrate and produced solvents and biomass previously determined from eqs 1
3 were obtained in the Aspen Plus simulations. This procedure enabled the simplied reactor model
used in the Aspen simulator (eqs 4
9) to reproduce the steady
state concentrations values generated by a mathematical model
that incorporates a sophisticated experimental kinetic model
(eqs 1
3), including a nonlinear product inhibition model.
The input data for the ash calculation in Aspen Plus were
temperature (37 C) and vapor fraction. The latter was obtained
from the Fortran calculations.
Properties for biomass (CH1.8O0.5N0.2) were obtained from
the NREL database.17 The energy demanded by the equipment
(MJ/h) was divided by the mass ow rate (kg/h) of butanol at
the bottom of the butanol column to get the specic energy
requirement (MJ/kg butanol) for butanol purication.
Design specications and operating conditions used in the
simulation of the distillation unit were based on the optimum
congurations determined by Luyben18 and van der Merwe.19
The nal setup used here aimed the conciliation between capital
(minimum number of trays) and energy (minimum reux ratio)
costs. For this, design specications were fed to the simulator in
terms of recovery or purity for a specic compound in either the
top or bottom sections. The design spec/vary feature of Aspen
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Figure 5. Eects of the inlet ow rate of the ash tank (Fc) on

fermentation parameters determined in a simulated fermentation with
the following operating conditions: F0 = 50 m3/h, S0 = 150 g/L,
V = 500 m3, Pash = 6.51
6.56 kPa, and amount of fermentation broth
vaporized in the ash tank equal to 5% of Fc.

Plus was used to hold these specications by varying the distillate

rate and reux ratio. Number of stages and feed location were fed
to the simulator and manually optimized to obtain better values
for reboiler duty.18,19 Columns were simulated using the RadFrac
model available in the Aspen Plus simulator and it was assumed
that column trays have a uniform Murphree eciency of 0.6.
Thermodynamic properties of the system were determined by
the UNIQUAC activity coecient model for the liquid phase and
the Hayden-OConnell model for the vapor phase. Having in
mind that the accuracy of the amount of butanol recovered in the
ash tank is given by a good representation of the thermodynamics characteristics of the vapor
liquid equilibrium of the
n-butanol/water system, validation of the equilibrium calculations was carried out using experimental data available in the
literature. Using the default UNIQUAC parameters available in
the Aspen Plus simulator, vapor
liquid equilibrium data at 1 atm
(T-xy diagram) were accurately predicted. However, at vacuum
conditions (P-xy diagram), the same precision was not observed,
mainly for the liquid phase at the region of interest (dilute
butanol concentrations) (Figure 4). For this reason, in the simulations the UNIQUAC parameters determined by Fisher
and Gmehling20 were used. The values of the parameters are
A12 = 506.31, A21 = 128.55, r1 = 0.92, r2 = 3.4543, q1 = 1.4,
q2 = 3.052 (1 = H2O; 2 = butanol). With these parameters a
better representation of the vapor
liquid equilibrium data at
vacuum conditions was observed.

3. RESULTS AND DISCUSSION

The eects of the inlet ow rate of the ash tank (Fc) on
fermentation parameters were determined in a simulated fermentation with the following operating conditions: F0 = 50 m3/h,
S0 = 150 g/L, V = 500 m3, and amount of fermentation broth
vaporized in the ash tank equal to 5% of Fc (vaporization rate
met by keeping Pash between 6.51 and 6.56 kPa). As the amount
of fermentation broth that circulates through the ash tank
increased (from 200 to 300 m3/h), more butanol was recovered.
Consequently, the concentration of butanol in the fermentor

ARTICLE

lowered, which represents a signicant reduction in the product

inhibitory eect. Biomass concentration increased, resulting in
higher conversion of substrate, elevation of productivity, and
greater concentration of butanol in the stream sent to distillation
(Figure 5). The amount of fermentation broth vaporized also
increased. Thus, the vaporization of more water was necessary in
order to enhance fermentation performance. Butanol productivity (up to 8 g/L 3 h) reported in our previous work11 was
signicantly greater than the values shown in Figure 5. This is
due to the fact that the cell retention system with a microltration
module present in the previous design was here withdrawn. This
design change was aimed at operational simplicity and cost
reduction by elimination of the use of membranes. Nevertheless,
productivity values reported here (1.8
3.6 g/L 3 h) largely
surpass the usual value obtained from a conventional batch
process (0.5
0.6 g/L 3 h).
The eects of the ash tank pressure (Pash) on fermentation
parameters were determined in a simulated fermentation with
the following operating conditions: F0 = 50 m3/h, S0 = 150 g/L,
V = 500 m3, and Fc = 300 m3/h. The more vacuum was applied in
the ash tank, the greater was the amount of broth vaporized
(varied from 1.5 to 30 m3/h). This variation was more intense
than that observed with the manipulation of Fc (from 9.6 to
14.5 m3/h). For this reason, fermentation parameters exhibited
greater perturbations in the range of the evaluated pressures.
And, as expected, the energy consumption for condensation
was positively correlated to the amount of broth vaporized
(Figure 6). It is also important to note that the nal butanol
concentration (concentration in the stream sent to distillation)
reached a maximum (30 g/L) at a vaporization rate of 15 m3/h.
By increasing vaporization rate above this value, no alteration
in the nal butanol concentration was observed. Butanol
selectivity,7 a measure of the preferential removal of butanol over
other components present in the mixture such as water, was 20.
For the six scenarios shown in Table 1, the minimization of the
energy requirements for the ash fermentation was achieved by
manipulation of Fc and Pash. These two operating variables were
regulated aiming at the minimization of the amount of fermentation broth vaporized, respecting the chosen constraint of sugar
conversion (equal to 98%). Such high substrate conversion was
only obtained when Fc was set to 300 m3/h and, for this reason,
only the pressure in the ash tank was manipulated in order to
minimize vaporization. It should be noted that the range of the
substrate concentration chosen (100
170 g/L) was considerably higher than the typical maximum concentration found in
conventional batch processes (60 g/L).
Performance parameters of the ash fermentation for the six
scenarios are shown in Table 2. When substrate concentration in
the feed was elevated from 100 to 150 g/L, more vaporization
was necessary in the ash tank in order to meet the desired
conversion (comparison between scenarios I and II). On the
other hand, vaporization could be reduced by increasing the
fermentation volume (or decrease of dilution rate) (II compared
to III; and IV to V). In the fermentation with the hyper-butanol
producing strain (scenario VI), intensication of vaporization
was also necessary (comparison between scenarios III and VI).
To determine which scenario provides the better energy
eciency to the process, the energy requirement for the distillation unit must be included in the balance. As a previous analysis,
the energy consumption by distillation was determined as a
function of butanol concentration in the fermentation beer (here
the reboiler duty of the acetone column was met by low pressure
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Figure 6. Eects of pressure in the ash tank (Pash) on fermentation parameters determined in a simulated fermentation with the following operating
conditions: F0 = 50 m3/h, S0 = 150 g/L, V = 500 m3, Fc = 300 m3/h.

Table 2. Performance Parameters of the Flash Fermentation Considering the Scenarios Presented in Table 1
scenarios
I

II

III

IV

VI

ash tank pressure (kPa)

6.49

6.47

6.53

6.47

6.50

6.45

volume of fermentation broth vaporized (m3/h)

8.20

18.5

13.9

24.1

20.9

26.7

butanol productivity (g/L.h)

butanol yield (g/g)

1.8
0.18

3.0
0.20

2.1
0.21

3.6
0.22

2.5
0.22

3.2
0.33

ABE yield (g/g)

0.29

0.34

0.35

0.36

0.37

0.43

butanol concentration in the fermentor (g/L)

5.6

6.9

7.8

7.9

8.3

10.3

ABE concentration in the fermentor (g/L)

8.20

10.5

11.9

12.4

13.0

12.8

butanol concentration in the recovered (g/L)

81.8

69.4

91.6

67.0

77.3

82.1

fraction of produced butanol recovered by the ash (%)

75.3

84.9

81.2

88.0

86.2

90.0

nal concentration of butanol (g/L)

17.9

30.0

31.0

36.3

37.1

48.6

biomass concentration (g/L)

energy gain obtained from the heat integration scheme shown in Figure 2 (MJ/kg butanol)

6.60
4.1

12.6
5.5

10.6
4.1

16.6
5.5

14.4
4.6

14.9
4.5

energy requirement for ash fermentationa (MJ/kg butanol)

4.8

6.0

4.4

6.5

5.5

5.4

energy requirement for distillationb (MJ/kg butanol)

17.5

10.9

11.0

9.5

9.3

8.0

total energy requirement (MJ/kg butanol)

22.3

17.0

15.4

16.0

14.8

13.4

stillage to butanol ratio (m3/m3)

54.3

32.3

31.3

26.7

26.2

21.0

Electrical power demanded by compressors and recirculation pumps. b Reboilers.

steam). For the dierent concentrations of butanol considered in

this analysis, concentrations of solvents followed the proportion
3:6:0.5 (A:B:E). Concentrations of acetic and butyric acid were
equal to 1.0 and 0.5 g/L, respectively. The amount of energy
required per unit of butanol recovered decreases as the concentration of butanol in the beer stream increases (Figure 7).
The energy consumption asymptotically approaches 9 MJ/kg
butanol as butanol concentration increases in the fermentation beer. It should be noted that the energy is greatly aected
in the range of butanol concentrations (8
13 g/L) found in
conventional fermentations. Thereby, a concentration increment of as little as 1 g/L may have great eects on the energy
consumption.

Using the same wild-type strain and fermentation medium

considered in the present work, Votruba et al.21 obtained a beer
with 17.5 g/L ABE (11 g/L butanol, 5.0 g/L acetone, 1.5 g/L
ethanol) in batch fermentation. The energy requirement for
distillation in this case would be 28 MJ/kg butanol. This
separation would have very low energy eciency given that the
energy required for the complete production process could be
greater than the energy content of the product itself (the heat of
combustion of butanol is 36.2 MJ/kg). On the other hand, ash
fermentation employing this same strain achieved a maximum
beer concentration of 37.1 g/L butanol (scenario V), resulting in
an important reduction of 67% of the energy requirement for
distillation (9.3 MJ/kg butanol). It should be noted that not only
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Figure 7. Energy requirement for the distillation unit to achieve

dehydration (99.5 wt %) of n-butanol as function of butanol concentration in the fermentation beer. The heat integration scheme shown in
Figure 2 was not considered here.

the butanol concentration was responsible for the decrease in the

energy consumption. The heat integration scheme shown in
Figure 2 contributed with an energy reduction of 4.6 MJ/kg
butanol (Table 2). However, the energy use of the ash fermentation (4.4
6.5 MJ/kg butanol) must be included in this balance.
Thus, for the scenarios with the wild-type strain (I to V), the total
energy requirement for butanol recovery (ash fermentation
distillation) varied from 14.8 to 22.3 MJ/kg butanol. This
represents a maximum reduction in energy consumption of
47% in relation to the batch process.
Signicant improvement in energy eciency of the distillation
unit and reduction of specic stillage volume (m3 stillage/m3
butanol) were observed when feed sugar concentration increased
from 100 to 150
170 g/L (Table 2). For the decision on which
feed sugar concentration (150 or 170 g/L) would give ash
fermentation the better performance, another important parameter, the butanol concentration in the fermentor, was taken into
account. A problem found in long-time continuous ABE fermentation is the culture degeneration, which is the change of genetic
characteristics over cell generations, due to butanol toxicity. It
results in decline of solvent production over time, and a
concomitant increase in acid formation.22,23 For this reason, in
most of the studies that report stable continuous cultures the
solvent level did not exceed 10
13 g/L.24 Thus, scenario II
(S0 = 150 g/L, V = 500 m3/h) with a lower ABE concentration in the
fermentor (6.9 g/L butanol, 3.0 g/L acetone, 0.6 g/L ethanol)
was considered the better operation strategy for the ash fermentation when using a wild-type strain. This means that the use of
ash fermentation would result in a reduction of 39% on the energy
for butanol recovery in relation to the conventional batch process.
When the hyper-butanol producing mutant strain was used in
the ash fermentation (scenario VI), butanol concentration in
the stream sent to distillation was 48.6 g/L. It had a signicant
positive impact on the energy requirement for distillation, and for
this reason, the energy eciency of this scenario was better than
those with the wild-type strain. The total energy requirement for
scenario VI was 13.4 MJ/kg butanol. If this same mutant strain was
employed in a conventional batch fermentation, producing 25.3 g/L
ABE (19.7 g/L butanol, 5.0 g/L acetone, 0.6 g/L ethanol),16 the
energy requirement for distillation in this case would be 16.1 MJ/

ARTICLE

kg butanol. Thus, in a fermentation with a mutant strain, the use

of the ash fermentation could reduce the energy consumption
for butanol recovery by 16.8%. The gain in this case was lower
than that of the fermentation with the wild-type strain because
the mutant strain is able to produce more butanol and for this
reason vaporization was intensied in order to recover a greater
amount of butanol (Table 2).
When compared to the batch process, the use of the ash
fermentation would result in reduction of process and wastewater streams and smaller fermentors with higher productivity.
Moreover, less energy would be spent for sterilization of a more
concentrated sugar solution. On the other hand, the operation
complexity and the total project capital cost would increase in
relation to a batch process, as additional equipment such as the
ash tank, compressors, heat exchangers, and recirculation
pumps is required.
In relation to other recovery technology options, the energy
requirement for butanol recovery using ash fermentation and
distillation was lower than that reported for in situ gas stripping in
conjunction with distillation (21.8 MJ/kg butanol).5 The same
authors reported the energy consumption for other separation
systems, such as adsorption distillation (8.1 MJ/kg butanol)
and pervaporation distillation (13.8 MJ/kg butanol). Matsumura et al.25 reported the energy requirement for a separation
system combining pervaporation using a liquid membrane with
distillation (7.4 MJ/kg butanol to concentrate butanol from 0.5
to 99.9 wt %) and a membrane separation system using both a
liquid membrane and a hydrophilic membrane (6.5 MJ/kg
butanol to concentrate butanol from 0.5 to 95 wt %). Based on
these reports and on the studies presented in this paper, it is
unquestionable that ash fermentation and gas stripping are less
energy ecient than adsorption and membrane-based processes.
However, it should be noted that the comparison of energy
requirements for dierent technologies must be looked at with
caution as process-specic details such as butanol production
basis (substrate concentration and fermentation yield), butanol
concentration in the beer (microorganism strain), and heat
integrations are not entirely available for the other studies and
are very likely to dier from those of the present study.

4. CONCLUSIONS
With the ash fermentation technology, high conversion of
concentrated sugar solution into ABE can be obtained, resulting
in high productivity and a more concentrated fermentation beer.
For dierent fermentation conditions (substrate concentration,
dilution rate, and microbial strain), two operating variables of the
ash tank, inlet ow rate and pressure, must be regulated in order
to ensure the desired sugar conversion. These two variables regulate the amount of fermentation broth vaporized, minimization of which is crucial to enhance the energy eciency of the
ash fermentation.
Small increments in butanol concentration in the beer can
have important positive impacts on the energy consumption of
the distillation unit. Nonetheless, the energy use of the recovery
technology must be included in the energy balance. For a fermentation with a wild-type strain, the total energy requirement for butanol recovery (ash fermentation distillation) was
17.0 MJ/kg butanol, with 36% of this value demanded by the ash
fermentation. This represents a reduction of 39% in the energy
for butanol recovery in relation to the conventional batch
process. In the case of a fermentation with a hyper-butanol
2354

dx.doi.org/10.1021/ef200279v |Energy Fuels 2011, 25, 23472355

Energy & Fuels

producing mutant strain, use of the ash fermentation could
reduce the energy consumption for butanol recovery by 16.8% in
relation to a batch fermentation with the same mutant strain.

AUTHOR INFORMATION
Corresponding Author

*E-mail: adrianomariano@yahoo.com.br. Mail: Av. Albert

Einstein 500, CEP 13083-852, Campinas, SP, Brazil. Telephone:
5519-3521-3958. Fax: 5519-35213965.

ACKNOWLEDGMENT
We thank Fundac-~ao de Amparo a Pesquisa do Estado de S~ao
Paulo (FAPESP) (Contract grant 2007/00341-1) for the nancial support.
NOMENCLATURE
A = Heat-transfer area, m2
Aij = Parameter for GE (molar Gibbs energy) for the UNIQUAC
activity coecient model (cal/mol)
AA = Acetic acid
ABE = Acetone
butanol
ethanol
BA = Butyric acid
F0 = Fresh broth ow rate (continuous feed), m3/h
Fc = Inlet ow rate of the ash tank, m3/h
Fpu = Fermentor beer ow rate (beer), m3/h
Fr = Flash tank liquid outlet ow rate (liquid stream depleted in
ABE), m3/h
NREL = National Renewable Energy Laboratory (USA)
Pash = Flash tank pressure, kPa
Pi = Fermentor product concentration, g/L
Pr = Product concentration in the ash tank liquid outlet ow, g/L
q = Molecular area parameter for the UNIQUAC activity
coecient model, Q = Heat, MW
r = Molecular volume parameter for the UNIQUAC activity
coecient model, S = Fermentor substrate concentration, g/L
Sr = Substrate concentration in the ash tank liquid outlet ow, g/L
S0 = Substrate concentration in fresh broth, g/L
X = Fermentor biomass concentration, g/L
Xr = Biomass concentration in the ash tank liquid outlet ow, g/L
U = Overall heat-transfer coecient, W/m2 K
V = Fermentation volume, m3

ARTICLE

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