Fuel 281 (2020) 118593

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Bioprocess intensification for isopropanol, butanol and ethanol (IBE) T

production by fermentation from sugarcane and sweet sorghum juices
through a gas stripping-pervaporation recovery process
Eloísa Rochóna, , Gastón Cortizoa, María Inés Cabota, María Teresa García Cuberob,c,
⁎

Mónica Cocab,c, Mario Daniel Ferraria, Claudia Lareoa

a
Depto. Bioingeniería, Facultad de Ingeniería, Universidad de la República, J. Herrera y Reissig 565, CP 11300 Montevideo, Uruguay
b
Department of Chemical Engineering and Environmental Technology, School of Industrial Engineering, University of Valladolid, Dr. Mergelina, s/n, 47011 Valladolid,
Spain
c
Institute of Sustainable Processes, Dr. Mergelina s/n, 47011 Valladolid, Spain

ARTICLE INFO ABSTRACT

Keywords: Butanol and isopropanol are important commodity chemicals with a variety of applications. One of the main
Butanol obstacles for biobutanol production by IBE (isopropanol–butanol–ethanol) fermentation is the intensive energy
Gas stripping consumption for product recovery by conventional distillation due to low butanol titer in fermentation broth
IBE fermentation caused by butanol toxicity to cells. In the present study, butanol production by batch IBE fermentation coupled
Pervaporation
to an in situ gas stripping-pervaporation process to recover the butanol is proposed using Clostridium beijerinckii
Sugarcane
DSM 6423 and a mixture of sugarcane-sweet sorghum juices as substrate. Gas stripping was used to continuously
Sweet sorghum
remove butanol from the fermentation broth, followed with pervaporation to further concentrate butanol. The
strategy used allows alleviating butanol inhibition and to recuperate a condensate containing high butanol
concentration (559 g/L). A kinetic model describing butanol production by IBE fermentation was developed.
Kinetic parameters and experimental data were used to estimate the energy consumption of the sugarcane-sweet
sorghum IBE production process. It was found that although the IBE production process showed less energy
consumption (15%) than the butanol production process by ABE (acetone-butanol-ethanol) fermentation, a
substantial improvement is still necessary for the process to be energetically/economically attractive.

1. Introduction The microorganism best known as natural IBE producer is Clostridium

beijerinckii DSM 6423 [3,4,7,8].
There is growing interest in the production of chemicals and fuels Major challenges in biobutanol production are the cost of the raw
from renewable resources due to climate change, global warming and material and the intensive energy consumption in product recovery
energy security [1]. n-Butanol is a four-carbon alcohol known both as stages of the entirely IBE production process [9–11]. Sugarcane and
an advanced biofuel and as a commodity chemical. It can be produced sweet sorghum are crops whose juices contain high amounts of soluble
through acetone-butanol-ethanol (ABE) or iso- fermentable sugars, and many essential nutrients for microbial growth
propanol–butanol–ethanol (IBE) fermentation in which a solvent mix- [8,12]. Both, mainly sugarcane, are currently used for fuel bioethanol
ture is produced. The co-production of acetone in the ABE process is not production in Uruguay. Furthermore, a residue (bagasse) is produced
desirable because is corrosive to rubber engine parts and has poor fuel when juices are extracted, which can be burnt for steam production to
properties [2]. Butanol production through ABE fermentation has also meet the energy demand of industrial processes [13,14]. The low bu-
been considered economically risky due to a potential oversupply of tanol concentrations that are reached in the fermentation broth due to
acetone [3]. Alternatively, isopropanol can be produced instead of cellular toxicity or product inhibition, requires a high energy con-
acetone by some Clostridium species. Isopropanol is an important sumption in the product recovery [15–17]. Alternative separation
commodity chemical with a variety of applications and the solvent technologies have been studied to coupled butanol production with an
mixture produced by fermentation (IBE) can be used as a fuel [4–6]. in situ extraction method to mitigate butanol inhibition [18–20], such as

⁎
Corresponding author.
E-mail address: merochon@[Link] (E. Rochón).

[Link]
Received 27 April 2020; Received in revised form 25 June 2020; Accepted 29 June 2020
0016-2361/ © 2020 Elsevier Ltd. All rights reserved.
E. Rochón, et al. Fuel 281 (2020) 118593

liquid–liquid extraction [21], gas stripping [22,23], pervaporation swept with O2-free N2 (Linde, Uruguay), over the headspace of the
[24,25], and flash vacuum [26]. bioreactor, followed by sterilization at 121 °C for 15 min. When it
Among butanol recovery methods, gas stripping and pervaporation reached room temperature, 1% (v/v) of filter-sterilized buffer and mi-
are the most promising alternatives, and both have advantages and neral P2 stock solutions and a commercial vitamin complex solution
disadvantages. Gas stripping allows the removal of volatiles from the (Dispert ®, 1% (v/v)) were added. The P2 buffer and mineral solutions
fermentation broth, does not requires chemicals or membranes, its contained: K2HPO4 50 g/L, KH2PO4 50 g/L, ammonium acetate 220 g/L
operation is simple and does not harm the culture [16,27–29]. Its main and MgSO4·7H2O 20 g/L, MnSO4·H2O 1 g/L, FeSO4·7H2O 1 g/L, NaCl
disadvantage is its low selectivity [30]. Pervaporation is a separation 1 g/L, respectively. The vitamin complex solution composition was:
process in which a feed solution is in contact with one side of the thiamine mononitrate 0.12 g/L, riboflavin 0.020 g/L, pyridoxine hy-
membrane, and the permeate is removed as a low-pressure vapor on the drochloride 0.020 g/L, calcium pantothenate 0.061 g/L, niacinamide
other side. The driving force is given by a vacuum system on the 0.61 g/L, and excipient qs. The bioreactor was inoculated with 8% (v/
permeate side [19,31,32]. It presents high selectivity and less energy v) highly active, motile cells and the fermentation was carried out at
requirement [18,30]. The main disadvantage of pervaporation is the 150 rpm and 35 °C. Samples were withdrawn at regular intervals for
operating cost due to membrane fouling when used as an in-situ ex- sugars, products, and optical density analysis.
traction method because of the presence of cells, residual sugars and The fermentation with in situ gas stripping was conducted in the
other components of the fermentation broth. While sugar conversion bioreactor containing 1.5 L of the medium. The experimental set-up is
could be improved by extracting butanol with an in-situ extraction detailed by Rochón et al. [41].
method, obtaining higher butanol concentrations with low energy
consumption remains the challenge. By using both methods, their ad- 2.1.3. Repeated-batch fermentations
vantages could be combined and enhanced. In the present study, an Repeated-batch IBE fermentations of the industrial juices were
integrated in situ gas stripping-pervaporation process is proposed, performed in bottles of 250 mL with 100 mL of medium. The industrial
where gas stripping is used to continuously remove butanol from fer- juice mixture was diluted to reach a total sugar concentration of
mentation broth, followed by pervaporation to further condense bu- 55–60 g/L and supplemented with yeast extract (1 g/L). The pH was
tanol. adjusted initially to 6.0 ± 0.1. The medium was swept with O2-free N2
The energy consumption of several industrial processes has been over the headspace of the bottles. It was sterilized at 121 °C during
successfully modeled and predicted using computer simulations. 15 min. On cooling to room temperature, 1% (v/v) of filter-sterilized P2
Various researchers have reported models for butanol production by stock solutions and vitamin complex Dispert® were added, followed by
ABE fermentation using Aspen Plus software from different raw mate- inoculation with 8% (v/v) highly motile cells. The bottles were in-
rials such as sugarcane, sugar cane molasses, and corn [33–38]. Some cubated in an orbital shaker (Infors HT Ecotron, Switzerland) at
researchers have specifically studied the use of energy of the butanol 150 rpm and 35 °C. At the end of each batch fermentation (48 h), 8 mL
purification stages. Mariano et al. [17] have evaluated flash fermenta- of the culture were taken and inoculated into a bottle containing 92 mL
tion technology whereas Cai et al. [39,40] evaluated the use of energy of fresh medium (8% v/v). Two sets of repeated-batch fermentations
of a gas stripping-distillation, gas stripping-pervaporation-distillation were carried out.
and two stage pervaporation-distillation processes. However, there are
no energy evaluations for the butanol production by IBE fermentation 2.1.4. Pervaporation assays
from sugarcane and sweet sorghum juices reported in the literature to Pervaporation assays were done with a polydimethylsiloxane
the authors’ knowledge. (PDMS) membrane with a total surface area of 50 cm2 (Pervatech BV,
In this work, butanol production by batch IBE fermentation coupled the Netherlands). The feed solution was heated to 70 °C and circulated
to an in situ gas stripping-pervaporation process to recover the butanol at a flow rate of 50 mL/min. The pressure on the permeate side was
was evaluated using C. beijerinckii DSM 6423 and a mixture of industrial maintained at ~2 kPa by a vacuum pump IDP-3 (Agilent Technologies,
sugarcane-sweet sorghum juices as substrate. Repeated-batch fermen- USA) monitored by a vacuum gauge. The permeated vapor was con-
tations were also carried out. A kinetic model describing butanol pro- densed at −6 °C in vacuum traps immersed in a refrigerated circulating
duction by IBE fermentation was developed. The kinetic parameters bath.
obtained and the experimental data of raw material composition, batch An IBE aqueous solution with the same condensate composition as
and repeated-batch fermentations and purification stages, were com- that obtained from a batch fermentation of sugarcane-sweet sorghum
bined into a model to estimate the energy consumption of the in- juices coupled with in situ gas stripping using C. beijerinckii DSM 6423,
tegrated process using Aspen Plus software. was used as the feed solution. A schematic diagram of the integrated
reactor set up is shown in Fig. 1. Samples of both retentate and
2. Materials and methods permeate were withdrawn every 3 h until 20 h and every 48 h until 38 h
for solvent analysis.
2.1. Experimental assays
2.1.5. Analytical methods
2.1.1. Medium, microorganism and inoculum preparation Isopropanol, butanol and ethanol from the gas stripping assays,
A mixture of industrial sugarcane and sweet sorghum juices, 75 and batch, repeated-batch fermentation and fermentation with in situ gas
25%, respectively, provided by Alur-Bella Union, Uruguay, was utilized stripping, both in the fermentation broth and in the gas stripping con-
as culture medium. The microorganism used was C. beijerinckii DSM densate, were measured with a gas chromatograph (GC, Shimadzu GC-
6423. The inoculum preparation using the industrial sugarcane-sweet 2010) equipped with a flame ionization detector and a fused silica
sorghum juices is described elsewhere, as well as the composition of the column (RTX®-Wax, 30 m long, 0.5 μm film thickness and 0.32 mm
juices used [41]. ID,Restek). Limit of quantification (LOQ) was 0.1 g/L. Sugars were
determined by HPLC (Shimadzu, Kyoto, Japan) using an Aminex 87-H
2.1.2. Batch fermentation without and with in situ gas stripping column (Bio-Rad Europe GmbH) at 45 °C, 0.01 N sulfuric acid as eluent
Fermentation experiments were performed in a 5 L-bioreactor at a flow rate of 0.3 mL/min and a refractive index detector (RID).
(Infors HT, Switzerland) containing 2.5 L of industrial juices diluted to Isopropanol, butanol and ethanol concentrations from pervapora-
reach a total sugar concentration of 60 g/L (expressed in glucose tion assays were determined by HPLC using an Aminex 87-H column
equivalents) and supplemented with yeast extract (1 g/L). The pH was (Bio-Rad Europe GmbH) at 30 °C, 0.01 N sulfuric acid as eluent at a
initially adjusted to 6.0 ± 0.1 with NaOH 1 M, and the medium was flow rate of 0.6 mL/min and a refractive index detector (RID, Waters

2
E. Rochón, et al. Fuel 281 (2020) 118593

Fig. 1. Schematic diagram of the integrated process: batch fermentation-gas stripping-pervaporation.

Fig. 2. Simplified block diagram of the isopropanol, butanol and ethanol production from sugarcane and sweet sorghum juices.

2414). Ji =
W
In each sample, the total permeate mass was measured. Since all the A t (1)
permeates presented phase separation, the mass of each of the phases
was also measured using an analytical balance.
To evaluate the pervaporation performances, the partial permeation Separation factor =
( )1
y
y

flux of a given component (Ji) and the separation factor were defined ( )
1
x
x (2)
and calculated according to the following equations [42]:
where W is the weight of the permeated condensate (g), A is the PDMS
membrane area (m2) and t is the operating time (h). x and y are the

3
E. Rochón, et al. Fuel 281 (2020) 118593

Fig. 3. Glucose, biomass and butanol concentration profiles during a batch

fermentation of the industrial juices. Experimental (symbols); simulated (lines).

Table 1
Kinetic model parameters.
Parameter Unit Value

−1
µm h 0.23
Ks g/L 2.0

YX/S g/g 0.09

YP/S g/g 0.22

Kp g/L 9.7
−1
kd h 0.03

a 2.1
2
R X – 0.97
2
R S – 0.99
2
R P – 0.99

2 2 2
R X, R S, R P are coefficient of determination for Eq. (1), Eq. (2) and Eq. (3), respectively [14].

mass fractions of a given component (isopropanol, butanol or ethanol)

in the retentate and permeate samples of the pervaporation system,
respectively.

2.2. Process models

The modified Monod kinetic model with terms of product inhibition

and bacterial death [14] was used in this study to describe microbial
growth, substrate consumption and butanol production of an IBE fer-
mentation. Therefore, the equations below were developed as follows:
a
dX µm S P
= X 1 kd X
dt Ks + S Kp (3)
a
dS µX µm S P X
= = 1
dt YX / S Ks + S Kp YX / S (4) Fig. 4. Solvents and acetic and butyric acid concentrations for repeated-batch
fermentations of C. beijerinckii DSM 6423 at 48 h using a mixture of industrial
µm S
a juices of sugarcane and sweet sorghum. a) set 1: b) set 2.
dP µ X YP / S P YP / S
= = 1 X
dt YX / S Ks + S Kp YX / S (5)
determination, R2.
−1
where X is the dry cell weight (g/L), µ is the specific growth rate (h ),
µm is the maximum specific growth rate (h−1), S is the growth-limiting
substrate concentration (g/L), Ks is the substrate saturation constant (g/ 2.3. Simulation methodology
L), kd is the specific cell death rate (h−1), P is the butanol concentration
(g/L), Kp is the product concentration at which no cell growth occurs 2.3.1. Process description
(g/L), a is the degree of product inhibition (–), YX/S is the biomass yield The facility processes 490 000 t of sugar cane and sweet sorghum
coefficient (g/g) and YP/S is the butanol yield coefficient (g/g). per year (annual production in Uruguay) and works 180 days (24 h per
Parameter estimation was carried out using global optimization day) per year since the crop is seasonally available. Isopropanol, bu-
tools presented in MATLAB® software (MathWorks, Nattick, MA, USA). tanol and ethanol purities were defined as 99.5% (w/w), 99.8% (w/w),
The objective function was defined with the method of maximum- and 88.4% (w/w), respectively. The solvent mixture presents a water
likelihood to minimize the differences between the experimental data concentration of ~0.5% which, according to literature, could be di-
obtained and the results of the model predictions. Fitting accuracy of rectly used as a fuel [6]. In this way, the process could be evaluated as
the models was evaluated through analysis of coefficient of either butanol or IBE production process. The simulated process can be

4
E. Rochón, et al. Fuel 281 (2020) 118593

Table 2
Repeated-batch fermentation parameters of C. beijerinckii DSM 6423 at 48h.

Set 1 Set 2

Batch number Butanol productivity (g/L h) IBE productivity (g/L h) X (g/L) Batch number Butanol productivity (g/L h) IBE productivity (g/L h) X (g/L)

1 0.13 0.19 1.7 1 0.13 0.19 1.7

**
2 * * 2 0.18 0.27 2.5
3 0.17 0.25 3.3 3 0.08 0.12 2.7
4 0.18 0.25 1.9 4 0.15 0.21 2.1
** **
5 0.13 0.29 5 0.18 0.26
6 0.21 0.32 2.8 6 0.15 0.26 1.4
7 0.20 0.28 3.2 7 * * 0.3
** **
8 * * 8 * *

* Not calculated. Butanol and IBE concentration produced at the end of the batch was less than 0.05 g/L, and 0.15 g/L, respectively.
** Not measured.

grouped into juice treatment, fermentation with in situ gas stripping, stripping during and post-fermentation and pervaporation are detailed
butanol or IBE recovery, and wastewater treatment. A detailed de- in Sections 3.3 and 3.4. The amount of product remaining in the bior-
scription of juice treatment, inoculum development and wastewater eactor, not recovered by gas stripping after fermentation or by perva-
treatment stages was already done for ABE fermentation in a previous poration, results in product loss. The economic justification for in-
work [43]. corporating a specific stage for its recovery could depend on the scale of
Both sugarcane and sweet sorghum are sent to the industrial plant in industrial plant. If it is not recovered, more substrate will be needed to
trucks. The transport energy consumption was estimated as 21 MJ/t reach the determined production. For this reason, the in-situ recovery
from data reported for a sugarcane ethanol production facility in processes can be complemented by incorporating the conventional
Uruguay (average distance 20 km) [44]. The material is transported to process known as end of pipe [46]. In some works, in which various in-
the mill by a conveyor belt. Water is added, the bagasse is separated situ removal methods are compared, it is assumed that all processes
from the juice and sent to the boiler for steam generation. The pH is have the same annual production and substrate consumption, but the
adjusted to 7 by adding lime. The juice is heated at 105 °C by using two production will vary depending on the recovery efficiency of the pro-
heat exchangers. Then the juice is clarified in another tank where cess used. However, to achieve a good economy, it should be considered
flocculant is added. The clarifies juice is sent to the fermenters which that all products are recovered at some stage of the process [47].
are subsequently inoculated by a direct transfer of a culture of C. bei- Based on the separation efficiencies obtained experimentally in this
jerinckii DSM 6423. Each seed train consists of bioreactors operating in work, not all the butanol, nor the rest of the solvents, are recovered
batch mode for 24 h at 35 °C. In the IBE fermentation stage, the in- after gas stripping and pervaporation. To solve this, it was considered
oculated cells are reutilized for a period of no more than 288 h, in they were sent to another distillation column to remove most of the
accordance to the results found in the repeated-batch fermentations water and other components present in the fermentation medium. It
(section 3.2). Fermenters of 1700 m3 are used, a typical size of Uruguay then goes through various stages of distillation to achieve the desired
facility. RYield reactor type was used in the simulation. The fermenter purity of butanol. For these stages, an estimated energy consumption
temperature is kept constant at 35 °C by pumping 2% of the medium was considered from the data reported by Mariano et al. [17] and Vane
through an external heat exchanger [13]. Initial sugar concentration is and Alvarez [48].
fixed in 60 g/L to avoid substrate inhibition. Each fermentation pre-
sents a duration of 84 h achieving a sugar consumption of 95% and a 2.3.2. Process simulation
biomass, isopropanol, butanol and ethanol concentrations of 5, 4, 15 The process was simulated using Aspen Plus® software (Aspen
and 1 g/L, respectively. Gas stripping starts at 24 h when butanol Technologies Inc., Cambridge, MA version V8.8). The Aspen Plus model
concentration is approximately 5 g/L (butanol separator factor: 9). The of the butanol/IBE production plant was developed based on the results
off gasses (CO2/H2) are then recycled at a flow rate of 0.4 vvm (volume obtained in our laboratory for fermentation, gas stripping and perva-
of gas/volume of medium min) and pass through the culture broth until poration stages presented in this work. Besides, values from expert
the fermentation is completed. Gas stripping is continued after the consultations were utilized in the clarification stage. Butanol and IBE
fermentation is finished to recover butanol remaining in the fermen- production scenarios were compared. Fig. 2 shows a simplified flow
tation broth. The fermented broth is centrifuged to separate bacterial diagram of the process.
cells. Cells are reused in the next batch. Due to the complexity of the process, two Aspen Plus® methods were
Regarding IBE purification section, it consists of a holding tank to used to simulate the thermodynamic properties of the components. The
store the recovered condensate containing the IBE products which is non-random two liquid method, Haiden ÓConell (NRTL-HOC) was used
then concentrated by a pervaporation stage (butanol separator factor: in most of the process as it is the most suitable to evaluate the com-
50). The energy consumption of the pervaporation was calculated as ponents properties (help from Aspen Plus® V 8.8; [37]). To model the
reported by Vane [45]. The remaining water is removed by a series of decanter used in the butanol purification stages, a variable of the uni-
five distillation columns and a decanter. The first distillation column versal quasi-chemical method (UNIQUAC) called UNIQ2 was used as it
separates an ethanol/isopropanol/water mixture from a butanol-water is adequate to predict liquid–liquid separations (help from Aspen Plus®
mixture. The ethanol/isopropanol/water mixture is sent to another V8.8; [48]).
distillation column where ethanol is separated from the top of the
column. The isopropanol/water mixture is sent to a third distillation 3. Results and discussion
column which separates isopropanol. Other two distillation columns
and a decanter separate the butanol/water mixture into butanol and 3.1. Fermentation model
water.
It is widely known that the application of many of the recovery Batch fermentation studies of C. beijerinckii DSM 6423 were per-
technologies allows only part of the desired product to be recovered. formed with the industrial juices. The Eqs. (1)–(3) fitted well to the
The separation efficiencies of the recovery section, both for gas experimental data (Fig. 3). The model allowed to describe biomass

5
 E. Rochón, et al.

retentate; c) solvent concentration on the permeate side.

profile in the feed; b) solvent flux as a function of their concentration in the
Fig. 5. Performance of the pervaporation process. a) solvent concentration

6
Table 3
Comparison of the solvent concentration obtained in the condensate by ABE and IBE fermentations using different two-stage separation processes.
Strain Substrate Fermentation strategy Strategy Acetone (g/L) Isopropanol (g/L) Butanol (g/L) Ethanol (g/L) Total solvents (g/L) Refs.

C. acetobutylicum JB200 Glucose Batch with immobilized cells Two stage gas stripping 94.0 na 420.3 18.0 532.3 [9]
C. acetobutylicum JB200 Glucose Fed batch with immobilized cells Gas stripping- pervaporation 91.5 na 521.3 10.1 622.9 [18]
C. acetobutylicum ABE 1401 Glucose Fed batch with immobilized cells Gas stripping- pervaporation 169.9 na 482.5 54.2 706.7 [39]
C. acetobutylicum ABE 1201 Glucose Continuous Two stage pervaporation 304.6 na 451.9 26.0 782.5 [40]
C. acetobutylicum ABE 1201 Sweet sorghum bagasse Batch Gas stripping-salting out 203.5 na 520.3 23.8 747.6 [53]
C. beijerinckii DSM 6423 Sugarcane-sweet sorghum Batch Gas stripping- pervaporation na 140.0 558.9 10.0 712.4 This study

na: not applicable.

Fuel 281 (2020) 118593
E. Rochón, et al. Fuel 281 (2020) 118593

Table 4 time from 55 to 36 h and carried out seven repeated batches (257 h).
Energy consumption for butanol and IBE production from sugarcane-sweet Butanol concentrations in the range 1.5–8.6 g/L, IBE concentrations in
sorghum juices. the range 3.9–14.3 g/L, and IBE productivities in the range
Stages of the process Energy consumption 0.11–0.27 g/L h were reached, which were similar to those obtained in
Butanol production IBE production (GJ/ this work. In the present work, higher butanol and IBE concentrations
(GJ/m3 butanol) m3 IBE) were found in some batches using an industrial medium (10.5 and
16.7 g/L respectively).
Transport 0.85 0.65
Milling 1.26 0.97 Although more studies are needed to understand the changes in the
Clarification 9.91 7.58 metabolism of C. beijerinckii DSM 6423, the results showed that the cells
Inoculum development and 0.41 0.31 could be reused for a period of approximately 288 h (6 cycles of 48 h),
fermentation
saving operational costs due to the development of inoculum. Results
Recovery 29.63 22.66
Water treatment 0.32 0.25
were incorporated in the butanol plant model for the energy con-
Total 42.38 32.41 sumption estimation.

3.3. Fermentation with in situ gas stripping

production, sugar consumption and butanol production appropriately
(R2X = 0.97, R2S = 0.99, R2P = 0.99). The model parameters and coef- Batch fermentation coupled with butanol extraction by in situ gas
ficients of determination are presented in Table 1. stripping was performed to alleviate butanol inhibition. The average
The maximum specific growth rate (µm) and biomass yield (YX/S) solvent concentration obtained in the condensate after the use of gas
values determined by the model were similar to those obtained for C. stripping was: isopropanol 47 g/L, butanol 33 g/L, and ethanol 5 g/L.
acetobutylicum DSM 792 in a glucose-based medium (0.23 h−1 and Neither acetic nor butyric acids were detected in the condensate.
0.09 g/g, and 0.22 h−1 and 0.11 g/g, for C. beijerinckii DSM 6423 and C. The separation efficiency of gas stripping for isopropanol, butanol
acetobutylicum DSM 792, respectively) [14]. However, a higher butanol and ethanol was 53, 49 and 41% during the fermentation and 21, 32
yield (YP/S) was found, 0.22 and 0.19 g/g for C. beijerinckii DSM 6423 and 21% during 40 h of gas stripping post-fermentation, respectively.
and C. acetobutylicum DSM 792, respectively. To the authors’ knowl- The overall gas stripping separation efficiency for isopropanol, butanol
edge, there are no kinetic parameters for butanol production from an and ethanol was 63, 60 and 60%, respectively.
IBE fermentation using C. beijerinckii DSM 6423 reported in literature Other results of batch fermentations with in situ gas stripping have
for further comparison. These values were used in the calculations been reported by Rochón et al. [41].
corresponding to the design and operation of the bioprocess in the
fermentation section of the sugarcane-sweet sorghum juices based 3.4. Pervaporation assays
biobutanol plant model performed with Aspen Plus.
Since the one-stage butanol recovery process by in situ gas stripping
3.2. Repeated-batch fermentations is not efficient enough to concentrate butanol at a high level [14], in
this study it is proposed to use a second stage of recovery by perva-
The capacity of C. beijerinckii DSM 6423 to be reused in repeated- poration for further purification.
batch IBE fermentations of a mixture of industrial juices of sugarcane Fig. 5a and b show the solvent concentration profiles on the feed
and sweet sorghum was evaluated to determine if the cells could be side (gas stripping condensate as feedstock) of PDMS membrane and
reused after the end of a batch fermentation or if they degenerate due to solvents flux vs its retentate concentrations, respectively. Butanol con-
long exposure to butanol. An initial batch fermentation showed that the centration on the feed side decreased significantly from 36 to 13 g/L,
process finished at 48 h, when the total solvent concentration was isopropanol decreased from 46 to 31 g/L and ethanol scarcely per-
11.8 g/L and sugar conversion 72%. Solvents yield and productivity meated. This behavior was expected because of the selective separation
were 0.21 g/g and 0.21 g/L h, respectively. Therefore, repeated-batch of volatile organic compounds by the PDMS membrane [39].
fermentations were performed every 48 h. Final acids and solvents At the beginning of the pervaporation, butanol and IBE fluxes were
concentrations obtained for each of the fermentation sets are shown in 100 and 134 g/h m2, respectively, which decreased to 39 and 52 g/h m2
Fig. 4. Table 2 shows the biomass concentration and the butanol and after 38 h due to the decrease in their retentate concentrations.
IBE productivities obtained for each of the batches. Isopropanol and ethanol fluxes were lower (9–32 and 1–2 g/h m2, re-
A total solvents concentration in the range 7.4–16.7 g/L spectively). Separation factor for butanol varied in the range 50–78,
(4.1–10.5 g/L of butanol) was observed until the seventh batch fer- while isopropanol and ethanol values were stable at less than 6. The
mentation. IBE productivities were in the range 0.12–0.32 g/L h. Acetic hydrophobic characteristic of the PDMS contributed to the high se-
and butyric acids were also produced (1.6–2.2 and 0.2–0.5 g/L, re- lectivity for butanol and the low selectivity for isopropanol and ethanol.
spectively). Biomass concentration varied between 1.0 and 3.3 g/L. As Kieblich et al. [32] have studied in situ butanol removal from PBE (1,3-
expected, low cell motility was observed after 48 h. propanediol-butanol-ethanol) fermentation process by pervaporation
In the second batch of the set 1, very low solvents concentration was obtaining a separation factor of 40 with a PDMS membrane (Pervap
observed (< 1.5 g/L) possibly due to “acid crash” phenomenon. Acetic 4060) at 50 °C. They also reported a butanol flux of 517.3 g/m2 h and a
and butyric acids concentrations were higher (2.3 and 1.8 g/L, re- butanol concentration of 328 g/L when operated at 50 °C and a feed
spectively). From the seventh batch onwards, solvent production de- flow rate of 4 L/min at a feed butanol concentration of 11 g/L de-
creased significantly. Acetic acid concentrations were higher monstrating the potential of butanol removal by pervaporation.
(2.1–2.2 g/L) and no biomass growth was observed < 0.3 g/L). Xue et al. [18] have studied an integrated ABE fermentation-gas
Repeated-batch fermentations from a glucose-based medium (60 g/ stripping-pervaporation process. They reported that the performance
L) using C. beijerinckii DSM 6423 immobilized on natural sugarcane and efficiency of the membrane were greatly affected by the solvent
bagasse was recently reported by Vieira et al. [49]. They found that IBE concentrations in the retentate. However, a clear correlation between
production was not stable in repeated batches and that IBE yield gen- butanol concentration in the retentate and permeate was not observed
erally decreased throughout batches. Butanol concentrations decreased (Fig. 5c). This could be due to adsorption of butanol into the tube and
from 5.4 to 6.2 g/L to 1.1–2.6 g/L after three batches for fermentations membrane, and possibly desorption in different time periods. Permeate
of 55 h. This behavior was attributed to cell degeneration due to long average concentrations obtained were 140, 559 and 10 g/L of iso-
exposure to butanol. For this reason, they reduced the fermentation propanol, butanol and ethanol, respectively. Butanol and ethanol

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E. Rochón, et al. Fuel 281 (2020) 118593

concentrations were similar to those reported by Xue et al. [18] for a was lower (12%).
similar process using ABE as feed solution. The results showed that the A mass balance of the overall process for biobutanol production
membrane was effective in recovering butanol if a high butanol con- from sugarcane and sweet sorghum juices was performed. Isopropanol,
centration feed was used. butanol and ethanol production were 2670, 9920 and 380 ton/year.
Table 3 presents the solvents concentration obtained by different Butanol and solvents yield of 25 and 32 g per kg of juices, respectively,
authors. The experimental results are compared with those obtained for were reached by IBE fermentation whereas 19 g butanol per kg of juices
ABE fermentation, since to authorś knowledge there is no data in the was obtained by ABE fermentation.
literature for IBE fermentation using a two-stage in situ recovery pro- Regarding the two scenarios evaluated, as it was expected, the energy
cess. The butanol concentration reached in this study (559 g/L) was the consumption was lower (23%) when the IBE mixture was considered as
highest and total solvent concentration was relatively high compared to the final product (Table 4). Calorific value (lower heating value) of the
those obtained by the other authors for ABE fermentation. Furthermore, IBE mixture was calculated as 26.1 GJ/m3 based on data reported by
to the authoŕs knowledge, total IBE concentration obtained (712 g/L) Yanowitz et al. [52] for an I:B:E mass solvent relation produced of [Link].
was the highest reported in the literature. The two-stage gas stripping- Unfortunately, both scenarios presented an energy consumption higher
pervaporation separation process provides a high IBE concentration than their calorific value, which suggests that improvements should be
and, therefore could be a more efficient promising system than con- made in the IBE production process from sugarcane-sweet sorghum
ventional systems. juices either by genetic engineering of the strain or by improvements in
The separation efficiency (solvent in permeate-solvent in retentate the fermentation and purification processes.
ratio) were 16, 82 and 8% for isopropanol, butanol and ethanol, re-
spectively. The losses of products could be mainly attributed to sam- 4. Conclusions
pling and solvent adsorption on tubes and membrane. In addition, it
should be noted that there are solvents present in the feed solution (31, The integrated gas stripping-pervaporation process utilized was
13 and 5 g/L of isopropanol, butanol and ethanol, respectively) at the successful in terms of condensate concentrations obtained (140, 560,
end of the pervaporation process (38 h). Longer times are required for and 10 g/L for isopropanol, butanol and ethanol, respectively). A
pervaporation assays in these conditions to achieve complete removal modified Monod kinetic model with terms of product inhibition and
of solvents. bacterial death showed satisfactory agreement with the experimental
data obtained with C. beijerinckii DSM 6423 in terms of cell growth,
3.5. Energy consumption sugar consumption, and butanol production which could be used in
models for the design and control of an IBE fermentation. C. beijerinckii
The energy consumption of an industrial plant that produces IBE DSM 6423 could be used in repeated-batch fermentations, saving op-
from the industrial sugarcane-sweet sorghum juices through a batch erational costs due to inoculum development although more in-depth
fermentation strategy was evaluated. Gas stripping was coupled to the studies are required in order to have a more predictable performance.
fermentation as an in-situ recovery technique followed by pervaporation Kinetic parameters and experimental data were used to estimate the
for further product purification. As already mentioned, experimental energy consumption of the sugarcane-sweet sorghum IBE production
results presented above were used throughout the simulation (kinetic process. It was found that although the IBE production process showed
parameters, batch and repeated batch fermentation, in situ gas stripping less energy consumption than the butanol production process by ABE
and pervaporation results). Since the kinetic model did not consider fermentation, a substantial improvement is still necessary for the pro-
neither isopropanol nor ethanol production, experimental yield values cess to be energetically/economically attractive.
obtained in the batch fermentation were used (Yisopropanol/S = 0.07 g/g,
Ybutanol/S = 0.26 g/g, Yethanol/S = 0.01 g/g) [8]. CRediT authorship contribution statement
The energy required by the process was covered by the energy
generated by burning the bagasse. Butanol and IBE recovery stages Eloísa Rochón: Conceptualization, Methodology, Validation,
presented the higher energy consumption of the process (Table 4). They Formal analysis, Investigation, Writing - original draft, Visualization.
presented an energy consumption of 29.63 and 22.66 GJ/m3, for bu- Gastón Cortizo: Validation, Investigation. María Inés Cabot:
tanol and IBE production process, respectively, which are higher than Validation, Investigation. María Teresa García Cubero: Resources,
the estimated value reported by Cai et al. [39] (20.1 GJ/m3butanol) for
Visualization, Supervision, Writing - review & editing. Mónica Coca:
ABE production with a similar recovery process (gas stripping-perva- Visualization, Supervision, Writing - review & editing. Mario Daniel
poration-distillation). Pyrgakis et al. [50] evaluated different scenarios
Ferrari: Conceptualization, Methodology, Validation, Visualization,
for butanol production through IBE fermentation with gas stripping Writing - review & editing. Claudia Lareo: Conceptualization,
coupled to adsorption/desorption and condensation methods. The sce-
Methodology, Validation, Formal analysis, Resources, Visualization,
narios consisted in three different product portfolios with adsorption as Supervision, Project administration, Funding acquisition, Writing - re-
the recovery method and one portfolio for IBE production with con-
view & editing.
densation as recovery method. They concluded that condensation was
not sustainable due to the high energy cost that is required for the re-
Declaration of Competing Interest
covery of alcohols. Grisales-Diaz and Tost [51] have recently reported
an alternative distillation system for IBE recovery with an energy re-
quirement between 5.3 and 6.6 GJ/m3IBE, which is approximately half of The authors declare that they have no known competing financial
that obtained in this work (11.8 GJ/m3IBE). This could probably be due interests or personal relationships that could have appeared to influ-
to the alternative efficient distillation system proposed in their work, ence the work reported in this paper.
which is a combination of azeotropic and extractive distillation.
Butanol production by ABE fermentation from sugarcane-sweet Acknowledgements
sorghum juices in a similar plant and process configuration was eval-
uated previously [43]. The total energy consumption of the butanol The financial support was provided by Agencia Nacional de
plant by IBE fermentation was 15% higher than that through ABE fer- Investigación e Innovación (ANII), Uruguay FSE 102720. The authors
mentation. One reason could be the higher energy consumption in the thank Alur SA for providing industrial sugary material and to Becas
distillation, since it involves more distillation columns. However, if the Iberoamérica (Santander Universidades) for the mobility scholarship of
IBE mixture is considered as the final product, the energy consumption Eloísa Rochón.

8
E. Rochón, et al. Fuel 281 (2020) 118593

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