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Emerging techniques in bioethanol production:

from distillation to waste valorization
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Cite this: DOI: 10.1039/c8gc02698j

Mohsen Gavahian, a Paulo E. S. Munekata,b Ismail Eş,c Jose M. Lorenzo, b

Amin Mousavi Khaneghah d,e and Francisco J. Barba *f

Ethanol production from biomass, especially waste biomass, and the use of such ethanol as fuel can
reduce fossil fuel consumption and ameliorate the hidden costs of burning fossil fuels such as its environ-
mental impact. However, bioethanol production suffers from several limitations such as being energy-
intensive and generating a sizeable amount of waste. This review briefly describes the aspects related to
bioethanol production and focuses on both theoretical and practical approaches for process improve-
ments. Several green emerging distillation techniques, such as ohmic-assisted hydrodistillation, mem-
brane-assisted distillation, and heat integrated techniques, are shown to be energy-saving alternatives to
the conventional distillation processes. Besides, a number of valuable components, such as pectin and
Received 24th August 2018, bioactive compounds (e.g., phenolic compounds), have been recently isolated from the waste materials
Accepted 7th December 2018
of bioethanol plants through various environmentally friendly valorization methods. These emerging dis-
DOI: 10.1039/c8gc02698j tillation and extraction techniques can be integrated to evolve a greener bioethanol production process in
rsc.li/greenchem the future.

Introduction production.2 Although bioethanol is currently produced world-

wide, the United States and Brazil are the world’s leading
The consumption of fossil-based fuels in the transportation bioethanol producing countries, responsible for more than
sector, which accounts for 60% of total world-wide fuel con- 80% of global production3 (Fig. 1). The United States is the
sumption, has inevitably increased. Consequently, it has main ethanol producer in the world with an estimated pro-
increased the safety concerns linked to environmental impact duction of more than 15 000 million of gallons per year, which
due to carbon dioxide (CO2) and carbon monoxide (CO) emis- accounts for more than half of global production, while esti-
sions.1 In this context, replacing fossil fuels with biofuels is an mated production of Brazil is more than 7000 millions of
indispensable solution to reduce environmental impact. gallons per year.4
Bioethanol is a sustainable alternative to reduce the consump- One of the main operations to obtain fuel-grade ethanol is
tion of crude oil and its environmental impact. Basic pro- the distillation of fermented broths. Distillation is an energy-
perties of bioethanol such as higher heats of vaporization, intensive consuming operation, which separates ethanol from
higher flame speed, and higher octane number, in comparison fermented broths and accounts for a relevant share of bioetha-
with gasoline, are some of the main reasons to encourage its nol production cost, particularly for conventional distillation/
dehydration operation.5 It is worth mentioning that one of the
main characteristics of conventional distillation columns is
a
Product and Process Research Center, Food Industry Research and Development the recovery of ethanol with low energy efficiency, which is
Institute, No. 331 Shih-Pin Rd., Hsinchu, 30062, Taiwan, Republic of China limited by the azeotrope formed with water.6 Due to the impor-
b
Centro Tecnológico de la Carne de Galicia, rúa Galicia no. 4, Parque Tecnológico de tance of distillation in the processing of ethanol, several envir-
Galicia, San Cibrao das Viñas, Ourense, Spain onmentally friendly and energy saving approaches have been
c
Department of Material and Bioprocess Engineering, School of Chemical
proposed to improve this operation. Most of the strategies are
Engineering, University of Campinas (UNICAMP), Campinas, São Paulo, Brazil
d
Department of Food Science, Faculty of Food Engineering, University of Campinas based on the physicochemical properties of the ethanol–water
(UNICAMP), Campinas, São Paulo, Brazil mixture and the equipment configuration such as heat inte-
e
Department of Technology of Chemistry, Azerbaijan State Oil and Industry grated distillation,7 membrane-assisted vapor stripping8 and
University, Baku, Azerbaijan feed-splitting.9
f
Nutrition and Food Science Area, Preventive Medicine and Public Health, Food
Another important aspect of bioethanol processing is the
Science, Toxicology and Forensic Medicine Department, Faculty of Pharmacy,
Universitat de València, Avda. Vicent Andrés Estellés, s/n, 46100 Burjassot, València, generation of residues. Although residues generated from
Spain. E-mail: Francisco.barba@uv.es bioethanol processing can be reused as alternative fuel in the

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Fig. 1 Bioethanol production around the world in 2017. https://www.statista.com/statistics/281606/ethanol-production-in-selected-countries/

(accessed on 2018/09/19).

bioethanol process to reduce processing costs,10 the loss of storage conditions. Afterward, carbohydrate molecules are
high-added value compounds with potential biological activity extracted or exposed for further extraction through some pre-
also occurs. Moreover, compounds with biological activity, treatments. The type of raw material and pretreatment con-
such as flavonoids and anthocyanins, are discarded as ditions determine the amounts of fermentable sugars after the
contaminants.11 pretreatment step (Fig. 3). Fig. 3 illustrates that all of these raw
Therefore, the search for alternative processing tools to materials require almost the same fermentation and ethanol
improve productivity/reduce energy demand and valorization concentration processes.
of residues generated from bioethanol production are impor- However, bioethanol producers can apply different
tant advances for the current bioethanol scenario. This review approaches to release sugars, which yield different co-pro-
focuses first on energy-saving strategies to improve energy use ducts. For instance, sugar can be directly extracted from sugar-
during the distillation of fermented broths to obtain bioetha- cane, and the residual bagasse can be used as a boiler fuel as
nol and second, on the use of environmentally friendly a source of extraction energy.
approaches for the recovery of compounds with potential When corn is used as the raw material, it should be ground
bioactivity. and hydrolyzed by using appropriate enzymes to convert starch
molecules into fermentable sugars that are required for
ethanol production, whereas corn oil, protein, and fiber can be
The overall process of bioethanol recovered from residues for valorization processes. When the
production raw material is cellulosic biomass, either thermal, acidic, or
enzymatic hydrolysis of cellulose and hemicellulose should be
Ethanol can be produced from any materials containing sugar performed to release sugar molecules, which are further fer-
molecules (e.g., sugarcane, corn, sugar beet, rice straw, sweet mented to ethanol. On the other hand, lignin and other wastes
sorghum, and algae) (Fig. 2 and 3). Generally, this process can can be used as an energy source for extraction or can be valor-
be divided into three distinct steps, namely: preparation of the ized to produce value-added products.16
fermentable sugar-containing solution; fermentation of the In many processes, large amounts of biomass fibers might
sugar-containing solution leading to ethanol production; and be kept for conversion into simple sugars molecules through
finally by recovering and concentrating the ethanol from the hydrolytic reactions. The production of bioethanol can be con-
fermented solution12–15 (Table 1). ducted by different types of processes: batch, fed-batch, and
It should be noted that several parameters, including the continuous processes. The batch fermentation process is com-
type of raw material and conversion technology, can affect the posed of several components such as hydrolysate (source of
overall process of ethanol production. Once the sugar-contain- fermentable sugars), nutrients, and yeasts to be fed into a bio-
ing biomass arrives at the bioethanol factory, required precau- reactor before starting the process. Differently, in the fed-batch
tions are taken to protect the biomass against bacterial con- process, these materials can be progressively added along the
tamination and undesirable early fermentation by controlling fermentation period. Finally, the continuous input of ingredi-

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Fig. 2 Schematic representation of the “generation” steps during bioethanol production using different renewable resources.

Fig. 3 A schematic representation of bioethanol production from three common sources: corn, sugarcane, and cellulosic biomass.

ents and constant removal of fermentation products from the 6–72 h, respectively. However, optimization studies carried out
bioreactors are the main operation characteristics of continu- to determine the appropriate temperature and fermentation
ous processes. In order to enhance fermentation efficiency, the time depend on several parameters including yeast species,
cell density can be maintained at high levels by recycling or cell density, and composition of the hydrolysate. The concen-
immobilizing yeasts to enhance their activity, which can result tration of ethanol in the fermented biomass is usually
in high concentration of ethanol in the fermented broth.16 expected to be between 8 and 14%. Higher concentrations of
The typical fermentation temperature and fermentation ethanol in the broth can inhibit the activity of yeasts and nega-
time for bioethanol production are about 25–30 °C and tively affect the process. Once the fermentation stage is over,

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Table 1 The typical techniques involved in bioethanol production from crops and their conventional by-products13–15

Typical process energy

Plant type Harvest technique Plant material conversion to sugar source

*,1Sugarcane Cane stalk cut, mainly from field Crushing, soaking, chemical process Heat electricity
(Saccharum officinarum) molasses
*,2Sugar beet (Beta Beets harvested while foliage left on the Sugar extraction Animal feed fertilizer
vulgaris) field
**,2Corn (Zea mays) Starchy parts harvested while stalks left on Starch separation milling, conversion to Animal feed
the field sugar by enzyme application
**,2Wheat (Triticum) Starchy parts harvested while stalks left on Starch separation milling, conversion to Animal feed
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the field sugar by enzyme application

,2
** Potatoes (Solanum Potatoes harvested while foliage left on the Washing, cooking, starch separation, Animal feed industrial
tuberosum) field conversion to sugar by enzyme application use
***,3Grasses (several Grass cut with regrowth Sacarification Heat electricity animal
species) feed bio-plastics
***,3Trees (several Full plant above ground harvested Cellulose conversion to sugar by enzymatic Heat electricity animal
species) hydrolysis (sacarification) feed bio-plastics
****,3Crop residue, Collected, separated, and cleaned to extract Sacarification Heat electricity animal
Forestry waste material with high cellulose content feed bio-plastics
1 2 3
Crops: * Sugary. ** Starchy. *** Cellulosic. **** Waste biomass. Typical process energy source: Crushed cane (bagasse). Fossil fuel. Lignin
and excess cellulose. 4 Sugar conversion to alcohol: Fermentation and alcohol distillation.

the ethanol is recovered by distilling the fermented broth. et al. (2012) discussed the crucial considerations for cost-
However, conventional distillation concentrates ethanol up to effective production of bioethanol from algae. For instance,
its azeotropic point with water (around 95% ethanol), which is using enzymatic saccharification and salt-tolerant yeasts to
also known as “hydrous” or “hydrated” ethanol. The continu- eliminate the desalting stage was highlighted by authors.18
ous dehydration of azeotropic ethanol produces “anhydrous”
alcohol (99.6% ethanol). Distillation also produces a residual
flow known as vinasse, which can be valorized as a by-product. Emerging energy saving distillation
The valorization of residual flows and materials includes
technologies
the traditional valorization practices (such as animal feed pro-
duction or soil fertilization) and the innovative approaches As distillation is one of the most energy-consuming steps in
(Fig. 4) such as bioactive compound recovery.17 Khambhaty the ethanol production,19 many researchers proposed several

Fig. 4 Some of the value-added compounds that have been successfully extracted from bioethanol waste through green valorization techniques.

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energy-saving techniques, including heat integrated, mem- conventional distillation processes. Dias et al.22 evaluated the
brane-based, feed-splitting, and ohmic-assisted distillation impact of a double-effect distillation system in a conventional
methods, to overcome this issue7–9,19–28 (Table 2). However, it bioethanol plant. The study considered the combined use of
should be noted that further studies are required to examine the sugarcane extract and bagasse in the production of
the sustainability and the exact energy demands of these newly ethanol. The authors observed that replacing the conventional
proposed techniques. Other relevant aspects are the necessity distillation by the double-effect system, an increase of 26% of
to improve the consistency of process variable units and to bioethanol production would be obtained by using only 10%
establish appropriate benchmarks among green technologies. of sugarcane bagasse as fuel in the system. In a further study,
A comprehensive comparison of traditional energy-saving Dias et al.7 simulated and evaluated the impact of three
methods, including vapor recompression, multiple heat-inte- thermal integration configurations to reduce energy demand
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grated columns, and heat integration systems, was previously for bioethanol production from sugarcane. The most efficient
conducted by Collura et al.29 Therefore, this section mainly cogeneration system was the Biomass Integrated Gasification
focuses on the novel energy-saving techniques for bioethanol Combined Cycle (BIGCC) in comparison with the current
production. system used in the Brazilian bioethanol industries (Rankine
Cycle) with either backpressure steam turbine or condensing
Heat integrated distillation steam turbine. The authors also stated that a double-effect dis-
The concept of heat integrated distillation consists of improv- tillation system could reduce the consumption of steam.
ing the use of energy initially applied to the distillation However, a limitation highlighted by the authors is the lack of
system. The system configuration used to achieve improved specific equipment to distillate bioethanol by the BIGCC
energy-saving distillation varies according to the strategy. It system.
was reported that this technique could reduce the energy con- Biotechnological production of butanol has recently
sumption of biofuel production by up to 40%.7,21,22 attracted the attention of researchers since it was shown to be
Researchers also explored the possibility of reducing energy a potential biofuel.33 The conventional biotechnological
consumption by using various devices (e.g., heat exchangers, approach for butanol production comprises the fermentation
heat pumps, multiple-effect columns, and adiabatic columns). performed by mesophilic solvent-producing strains such as
Although this approach is considered of great value to reduce Clostridium saccharobutylicum, C. beijerinckii, and
the demand for fossil fuels and the environmental impact of C. acetobutylicum.34 ABE, which refers to the mixture of
industrial operation, major theoretical and experimental acetone, butanol, and ethanol, is the product of this fermenta-
advances are still necessary to increase its feasibility.32 tion process which can be used as a biofuel. However, a low
Studies carried out over the last few decades have strength- concentration (15–30 g l−1) of this valuable mixture in the
ened the role of such technology as a relevant alternative in fermented biomass makes the recovery of ABE an energy-inten-

Table 2 A summary of recently proposed energy-saving approaches for bioethanol distillation

Technique Key findings Ref.

1
Heat integrated Replacing the conventional distillation with the double-effect system, an increase of 26% in Dias et al.22
distillation bioethanol production would be obtained by using only 10% of sugarcane bagasse as fuel in Dias et al.7
the system
2
Heat integrated distillation can reduce the distillation cost Diaz & Tost21
2
Membrane-based The membrane system concentrated ethanol solution from 10 to 60% Liu et al.20
2
technologies The proposed membrane system concentrated ethanol from 10 to 91% Ueno et al.8
2
Vinyltriethoxysilane-g-silicalite-1/PDMS/PAN was used to manufacture a membrane which Yi and Wan28
could increase the ethanol concentration to about 60%
2
A carbon nanotube/PDMS membrane was developed which enhanced the ethanol concen- Xue et al.27
tration to 38%
2
A PDMS membrane increased the ethanol concentration to about 85% Song, Oh and Bae26
2
A PDMS membrane and carboxymethyl cellulose increased the ethanol concentration to Nigiz and Hilmioglu30
about 80% and 98.9, respectively
2
A NaA zeolite membrane increased the ethanol concentration to about 99.5% Wei, Tsai, and Weng25
2
A polyethyleneimine (PEI)/sodium alginate (SA) membrane yielded ethanol with the concen- Li et al.31
tration of 90%
3
Feed-splitting Feed-splitting system to reduce energy consumption Tavan & Shahhosseini9
3
Ohmic-assisted OAHD was run in the multiple-distillation mode and yielded ethanol with the concentration Gavahian et al.24
distillation of 84%. It was superior in terms of process control, process time and consumed energy.
4
OAHD successfully increased the ethanol concentration of fermented broth Gavahian, Farahnaky &
Sastry19
3
OAHD successfully increased the ethanol concentration from 10 to 50%. The proposed Gavahian, Farahnaky, &
method saved both distillation time and distillation energy in comparison with the electric Sastry23
mantle heater energy source.

Feedstock: 1 Sugarcane. 2 Diluted alcohol. 3 Azeotropic mixture. 4 Industrial fermented corn broth.

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sive process and research revealed that about 15 MJ-fuel is systems to recover bioethanol using glucose solution with
required to produce one kilogram of ABE.35 nutritional supplements for microbial fermentation or fermen-
In this context, Diaz & Tost21 proposed 4 processes of heat- ted broths from several sources of fermentable sugars. The
integrated distillation and assessed the energy consumption experiment performed by Yi and Wan28 tested a membrane
while conducting the fermentation process with several bioca- made of vinyltriethoxysilane (VTES)-g-silicalite-1/PDMS/PAN to
talysts. According to the results, the processes composed of separate ethanol from a fermented glucose solution and
four distillation columns and three distillation columns achieve a final ethanol content of 60.0 wt% (total flow of
needed a similar amount of energy (8–12 MJ-fuel per kg-ABE). 2.0 L min−1, at 35 °C, at 210 Pa, for up to 8 h). Xue et al.27 also
The authors also indicated that the double-effect system with observed a similar effect but with lower final ethanol concen-
four columns was the most economical process as the pro- tration: 38 wt%. The authors developed a carbon nanotube
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duction of 1 kilogram of ABE through this method only cost (CNT)/PDMS membrane that operated with a total flow of
0.12–0.16 USD which was cheaper than other studied 1.2 L min−1, at 60 °C, under pressure lower than 20 kPa, for up
methods. The authors also mentioned that ABE recovery from to 34 h.
dilute solutions by the double-effect system required 6–9 MJ The promising outcomes observed in these studies were
fuel per kg-ABE. Among all the studied methods, vapor com- also reported with the fermented broth obtained from more
pression system distillation required the lowest amount of complex fermentable sugar sources. The production and con-
energy, i.e., 5–7 MJ fuel per kg-ABE. centration of bioethanol from Jerusalem artichoke tubers were
Moreover, recovering ABE by the double-effect and vapor evaluated by Song, Oh and Bae.26 In this research, the fermen-
compression distillation needs a lower amount of energy as ted broth was pervaporated in the PDMS membrane (flow of
compared to integrated reactors. This research revealed that 1.8 L min−1 and pressure of 5 mmHg). The final ethanolic
the energy requirements for ABE production were 1.3 to 2.0- solution displayed an ethanol content of 85.3 wt%. A similar
fold greater than those of other biofuels, such as isobutanol ethanolic yield was obtained by Nigiz and Hilmioglu,30 who
and ethanol, whereas the energy efficiency of ABE production evaluated the fermentation of molasses. The authors obtained
was similar to that of isobutanol and ethanol production.21 80.0 wt% ethanol solution in the permeate of a PDMS mem-
brane. Similarly, Wei, Tsai, and Weng25 studied the use of a
Membrane technology commercial NaA zeolite membrane to pervaporate a rice straw
The mechanism involved in the recovery of ethanol from fermented broth. The authors reported a final ethanol concen-
aqueous solutions by membrane technology can be explained tration of 99.5 wt% with the following operational conditions:
by the higher partial pressure of ethanol concerning water. the total flow of 6 L h−1, the temperature of 100 °C, and
This difference favors the transport of ethanol from the fer- pressure of 5–7 bar.
mented broth to membrane pores. The processes have been Purified concentrated ethanolic solutions with >95 wt%
improved to accelerate the recovery of ethanol by reducing the ethanol are not easily dehydrated due to the azeotrope formed
pressure or gas flow in the permeate side of the membrane. with water. Under these conditions, the use of membranes
Under this condition, the transport of the target compound is focuses on removing water. Li et al.31 tested the efficiency of a
facilitated by a concentration gradient across the membrane, polyethyleneimine (PEI)/sodium alginate (SA) membrane to
which is known as pervaporation. The primary industrial concentrate a 90 wt% ethanolic solution. The authors observed
applications are dedicated to removing water from concen- that operating this membrane with a flow of 1.90 kg m−2 h−1,
trated ethanolic solutions due to the kinetic diameter of water at 80 °C, and the pressure of 100 Pa, the water content in the
and ethanol (0.32 vs. 0.57 nm, respectively).36 permeant had a concentration of 99.75 wt%. The experiment
The membrane composition plays a central role in the carried out by Nigiz, and Hilmioglu30 enhanced the ethanol
capacity to effectively separate ethanol from binary solutions concentration from 95 to 98.99 wt% by using a carboxymethyl
and fermented broths (from either glucose solutions or fer- cellulose membrane operating at 25 °C. In this study, the
mentable sugars extracted from natural sources). The study ethanol was produced by fermenting molasses.
carried out by Liu et al.20 revealed that a membrane composed Membrane-assisted vapor stripping. Vapor stripping is a
of ZSM-5 zeolites (Si/Al = 300) and polydimethylsiloxane technique involving the passage of vapor, usually from water
(PDMS) could yield an ethanolic solution of 60.0 wt% from a in the ethanolic solution of the fermented broth to volatilize
10.0 wt% solution (operating at 80 L h−1, 60 °C, and 2300 Pa). ethanol. After that, the vapor flow is separated into two flows:
Besides, the column was also tested for 1000 h wherein the one retentate and one permeate that contain either high or
ethanolic content of the permeate remained constant through- low ethanol concentration dependent on membrane pro-
out the testing period. Similarly, Ueno et al.8 using a silicate- perties. A limited number of configurations have been pro-
1 membrane obtained a more concentrated ethanolic solution posed so far: a batch and a continuous system.37
of 91.0 wt%. The authors fed the membrane system with a The experiment conducted by Vane et al.38 evaluated the
10 wt% ethanolic solution and observed the same efficiency recovery of ethanol from a 5 wt% ethanol solution in a com-
after 8 h of operation (total flow of 3 kg m−2 h−1 at 323 K). bined system with a stripping column and a hydrophilic mem-
Due to the complex composition of fermented broths, brane. The operation yielded ethanol-rich retentate vapor con-
many researchers proposed and evaluated different membrane taining 80 wt% of ethanol. In a further experiment, Vane

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et al.37 evaluated the efficiency to recover ethanol from a fer- 0.7–0.8. Furthermore, the authors compared the recovery of
mented broth (ethanol content of 35.9 wt%) as a function of IBE with alternative biofuels and reported that the energy
the vapor flow rate in the system. The separation was carried requirement of IBE was about 1.4–2.4 and 0.9–1.4 times
out using a membrane composed of hydrophilic cellulose greater than that of ethanol and isobutanol dehydration,
ester layer overcoated by silicone rubber after a vapor stripping respectively. According to the authors, biofuel recovery from
step. The authors observed that using vapor flows in the range the fermented broth through the heat-integrated distillation
of 0.02–0.06 kmol h−1, the concentration of ethanol in the method represents the highest energy efficiency.
retentate was around 90 wt%.
Vane et al.39 evaluated the recovery of ethanol, along with Feed-splitting
acetone and butanol, from the fermented broth in a mem- Feed splitting is a strategy to improve energy efficiency in a dis-
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brane filled with a hydrophilic cellulose ester layer overcoated tillation system. A heat exchanger is used to heat the feed flow
by silicone rubber after a vapor stripping stage. This system by cooling the bottom product flow.42 To the best of our knowl-
displayed the capacity to obtain an ABE-rich fraction (95 wt%) edge, only a single study explored, using process simulation,
wherein ethanol comprised around 10 wt% of the membrane the separation of azeotropic ethanol.
retentate. In addition, the authors also estimated that the pro- Tavan & Shahhosseini9 proposed a feed-splitting system to
posed system could reduce energy consumption by 25% in reduce the energy consumption in the recovery process of
comparison with a simple vapor stripping process. An interest- azeotropic mixtures such as the fermented broth of the biofuel
ing experiment conducted by Xue et al.27 evaluated the recov- industry. In this context, the authors employed Hysys process
ery of ABE in a membrane assisted vapor stripping system in simulation software and relevant optimization analysis. The
comparison with simple gas tripping pervaporation operation. proposed system could reduce energy consumption by 27% as
The experiment revealed that the condensate produced from compared to the conventional system. The authors concluded
the combined system contained 8.3–8.6 g L−1 of ethanol, while that the proposed feed-splitting process could be regarded as
the other two separation strategies produced condensates with an energy-saving alternative to the conventional ethanol–water
6.3–6.7 ( pervaporation) and 7.4–7.7 (gas tripping) g L−1 of azeotropic process.
ethanol.
Combining extractive and azeotropic distillation. Extractive Ohmic-assisted hydrodistillation
distillation is a technique which separates both close boiling The term ohmic-assisted hydrodistillation (OAHD) refers to a
point and azeotropic mixtures. The mechanism is simple: a system that consists of an ohmic heater and condenser sec-
miscible solvent (entrainer) is added and facilitates the separ- tions. While the former generates heat volumetrically (based
ation of one of the volatile components. Under these con- on the Joule’s law), the latter collects and cools down the
ditions, a simple distillation column can be applied to separ- vapor produced by the heating section.43 The major com-
ate the target component. Another similar approach is the ponents of the ohmic heater section are the power supply, elec-
azeotropic distillation of ethanolic solutions. This strategy is trodes, and a non-electroconductive chamber (flask). This
similar to that applied for extractive distillation of ethanolic simple design might be combined with other sections, such as
solutions, but the entrainer has a different purpose. The safety systems, variable transformers to control the input
entrainer forms an azeotrope with the target component power, frequency, and variable transformers, data acquisition
which is vaporized and obtained on the top of the distillation systems along with thermocouples, voltmeters and other
column. The other component is recovered in the bottom of sensors.44,45 Although the OAHD system was first proposed as
the distillation column. In a posterior conventional distillation an energy-saving tool for essential oil extraction,46 later
column, the target component and the entrainer can be research revealed its potential application for ethanol concen-
separated.40 tration.19 For instance, an OAHD equipment in the Ohio State
The term IBE, which is the abbreviation for isopropanol, University was updated from its primary design: OAHD system
butanol, and ethanol, is an emerging biofuel. However, the to recover essential oils.46 The condenser section of the distil-
concentration of this biofuel is more complicated and energy- lation system was modified to collect ethanol instead of essen-
intensive than conventional bioethanol distillation due to the tial oil. This approach successfully separated ethanol from a
presence of three binary azeotropes in the fermented broth, fermented corn feedstock source from a bioethanol plant and
i.e., ethanol, butanol, and isopropanol. To overcome this chal- enhances the ethanol concentration from 10% to 47%.24 The
lenge, Díaz and Tost41 designed and developed a novel distilla- authors found that OAHD can save up to 77% of the required
tion system, which operates based on a combination of azeo- energy in the ethanol distillation process.
tropic and extractive distillation. They also evaluated the pro- A further study of this research team explored the applica-
posed system by using computer software, i.e., Aspen Plus® bility of the OAHD technique in producing higher concen-
software, and observed that the recovery system needed 6.5–8.2 trations of bioethanol that can comply with the ASTM stan-
MJ-fuel per kg-IBE. Moreover, this new distillation technique dard.47 In this regard, Gavahian, Farahnaky, & Sastry23 com-
reduced the fuel requirement using steam compression distil- bined three consecutive processes of OAHD. According to the
lation to 3.4–4.1 MJ-fuel per kg-IBE. According to the results, authors, the proposed multiple effect arrangement enhanced
the energy efficiency of IBE dehydration was in the range of the concentration of ethanol from 10% to 50%, 76%, and 84%

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after the 1st, 2nd, and 3rd steps of OAHD, respectively. However, sugar beet matrix is influenced by pulsed electric fields.
the authors raised the safety concerns regarding the applica- According to the authors, the results support the application
bility of OAHD for the production of concentrated ethanol of pulsed electric field and also increase the possibility for the
(such as above 90%) as this involves distillation of a flammable valorization of sugar beet residues. Moreover, the potential of
compound which can lead to disaster due to ignition of high PEF for food waste and by-product valorization has been exten-
ethanol concentration feed in the case of generation of electri- sively described by several authors. For an interesting review
cal sparks during the OAHD process. However, it was demon- see the study by Puértolas and Barba.52
strated that the proposed method could save more than one-
third of both consumed energy and distillation time as com- High voltage electrical discharges
pared with the conventional hydrodistillation system. The The operation of high voltage electrical discharges consists of
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research also pointed out that OAHD is superior to convention- placing samples between electrodes and directly applying an
al distillation method regarding process control. electrical discharge for a short time. The samples are usually
submerged in aqueous solution for extraction purposes.52
Green extraction of bioactive products Although the mechanism of high voltage electrical discharges
During the bioethanol production process, great amounts of in the liquid medium remains partially explained, it is
wastes and by-products are produced. These materials are rich accepted that components are ionized leading to multipli-
sources of high-added value compounds, which can be used as cation of charge carriers and consequent energy transportation
potential food additives and/or nutraceuticals, among other to the sample matrix. In more detail, the process is initiated
applications.48 In this line, tremendous efforts have been with the formation of vapor channels that are formed between
made for new sustainable “green and innovative” technologies electrodes. Once the vapor channels are formed, the conduc-
in order to reduce extraction time, temperature, and the use of tivity increases. This condition increases the current and
an excessive amount of solvent, which in some cases can be reduces the voltage between electrodes. The whole process
toxic. Moreover, it is also possible to reduce water and energy occurs in few nanoseconds. The impact of high voltage electri-
consumption, as well as CO2 emission and carbon cal discharges on the structure is dependent on electrical dis-
footprint.49–51 The most commonly innovative green and non- charge intensity, frequency, time of operation, and tempera-
thermal technologies include electrotechnologies ( pulsed elec- ture, for instance. The integrity of membranes and complex
tric fields and high voltage electrical discharges),52 ultra- structures is impaired leading to fragmentation of the matrix
sound,53,54 microwaves,55–57 supercritical fluid extraction,58 and enhancing mass transfer.52,71
high pressure processing,59 supercritical CO2 and, gas-assisted Recently, pectin was extracted by high voltage electrical dis-
mechanical expression,60,61 enzyme-assisted extraction62 and charges from sugar beet pulp (residue generated from sucrose
solar energy,63 which attract considerable interest as alterna- extraction). The study revealed that the number of pulses, the
tive tools for “Green” processing.64–67 intensity of pulses, temperature and pH were relevant variables
to improve the recovery of pectin. The authors observed that
Pulsed electric fields pectin extraction was maximized by applying 100 pulses but
The use of pulsed electric fields can potentially enhance the no significant recovery yield was obtained with 200 and 500
recovery of bioactive compounds.68,69 The mechanism of PEF pulses. The optimization of pectin recovery revealed that pH =
treatment consists of the disruption of natural dipole between 1.5 and 2.0 maximized the extraction of pectin. Similarly,
two molecules that are trapping bioactive compounds. For pulse intensity and temperature were proportional to extrac-
instance, the average distance among membrane components tion yield wherein the highest yield was obtained with 40 kV
of living cells is increased, particularly those associated with and 90 °C, respectively. The authors observed that maximum
transport, due to the influence of the electric field. Likewise, extraction yield was 53.4% (13.5 g per 100 g DM) in the opti-
plant tissue can be disrupted, which facilitates the release of mized treatment.72
intracellular components.66,68 The control of processing con-
ditions is crucial to improving the yield of extraction. In this Enzyme-assisted extraction
sense, selecting the number of pulses, the intensity of field Enzyme-assisted extraction is an interesting strategy to recover
strength and energy input, time of treatment and temperature bioactive compounds from a complex matrix. The concept of
can be of great value to extract target compounds from a such a strategy relies on enzymatic degradation of the matrix
complex matrix.52 to facilitate the removal of target compounds. The use of cellu-
Although the amount of information related to the appli- lases, pectinases and other enzymes to disrupt cell walls to
cation of pulsed electric field as the extraction technique is recover phenolic compounds with antioxidant activity is a
limited, a promising result was obtained by Almohammed, common example of enzyme-assisted extraction.62 The control
Mhemdi, and Vorobiev70 who studied the extraction of fermen- relies on the characteristics of the matrix and optimum enzy-
table sugars for ethanol fermentation. The sugar-rich extract matic activity, which involves variables such as temperature,
obtained by pulsed electric field treatment (intensity of 450 pH, particle size and solvent/solid ratio.73–75
V cm−1 for 10 min) had 3.75 times more sugar than the extract Zykwinska et al.76 evaluated the effect of cellulases and pro-
obtained by a solid–liquid extraction, which suggests that the teases as a green approach to recover pectin from sugar beet

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pulp. The extraction of pectin was carried out at 50 °C for 4 h, tion of phenolic compounds from steam-exploded sugarcane
which yielded 4% pectin extract. The authors also evaluated bagasse. The authors obtained the highest yield of extraction
the composition of pectin and observed that sugar beet pectin (47.65 mg g−1), total phenolic content (29.11 mg GAE g−1),
was mainly composed of galacturonic acid (403 mg g−1) and flavonoid content (1.47 mg QE g−1), and ABTS radical scaven-
arabinan (103 mg g−1). Concha-Olmos and Zúñiga-Hansen77 ging activity (82.54 mg TE g−1) by carrying out the ultrasound
evaluated the recovery of pectin and pectic-oligosaccharides extraction at 40 W for 6 min. In addition, the optimized ultra-
from sugar beet pulp by the activity of Rohapect DA6L and sound extraction also produced extracts with the lowest
Macer8 FJ (commercial enzymes). Both enzymes produced minimum inhibitory concentration against Staphylococcus
extracts predominately composed of oligosaccharides with a aureus (1.875 mg mL−1) and Escherichia coli O157:H7
polymerization degree greater than 6. However, the study also (7.5 mg mL−1).
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revealed that Rohapect DA6L was the most effective to release Likewise, sugar beet molasses is a source of phenolic com-
pectic oligosaccharides (94.9% recovery of total pectin) in com- pounds (with antioxidant activity) which can be recovered by
parison with Macer8 FJ. Additionally, the authors also charac- ultrasound extraction.84 The ultrasound treatment maximized
terized the extracted pectin and observed that it was mainly the total phenolic recovery to 17.36 mg GAE per 100 mL extract
formed by low methoxyl pectin (which in combination with and total anthocyanin content to 31.81 mg per 100 g extract.
calcium forms low-calorie gels). Antioxidant activity (using ABTS radical scavenging activity
Likewise, a study conducted by Holck et al.78 revealed the assay) was also improved by ultrasound treatment wherein a
impact of lyase ( pH = 8, 50 °C, 15 h) and rhamnogalacturonan maximum of 16.66 mg TE g−1 was reported by the authors.
I lyase ( pH = 7.8, 60 °C, 2 h) on sugar beet pectin to extract pre- The authors optimized the solvent composition (1.55–1.72 mol
biotic oligosaccharides. The authors obtained and character- L−1 HCl and 57–63% ethanol), temperature (41–48 °C), and
ized homogalacturonans (7 compounds, recovery of 200 time requirement (66–73 min). The study also revealed that
mg g−1 pectin) and rhamnogalacturonide (6 compounds, main active compounds in sugar beet molasses were flavo-
recovery of 67 mg g−1 pectin). In addition, the authors also noids (e.g., catechin), phenolic acids (such as hydroxybenzoic
observed that the homogalacturonide fraction could be con- acid and syringic acid), and anthocyanins (e.g., cyanidin-3-O-
sidered as a promising prebiotic by inducing the regulation of rutinoside and delphinidin-3-O-glucuronide).
probiotics in vitro.
Microwave-assisted extraction
Ultrasound-assisted extraction The use of microwave technology is an emerging approach to
The propagation of ultrasound in a liquid medium causes a recover pectin and bioactive compounds.65 The fast heating of
phenomenon known as cavitation. Cavitation is the result of the extraction solvent is explained by the simultaneous ionic
ultrasound wave propagation in a liquid which reduces the conduction and dipole rotation of solvent molecules by the
pressure and leads to the formation of vapor cavities. The influence of the electromagnetic field. While ionic induction
eventual collapse of such cavities creates micro-jetting on the causes the migration of solvent molecules (friction), the dipole
surface of the matrix subjected to ultrasound treatment which rotation by means of continuous alignment and realignment
increases the interaction between the solvent and high-added of solvent molecules (4.9 × 109 times per s) increases the
value compounds from plant materials (e.g., pectin and bio- solvent temperature. The appropriate selection of solvents
active compounds), thus promoting their subsequent recov- depends on their capacity to dissipate energy to other mole-
ery.53,65 The main mechanisms associated with ultrasound cules, which is dependent on the dielectric constant. Water is
extraction are capillarity, detexturation, erosion, fragmenta- usually used for microwave-assisted extraction due to its
tion, and sonoporation. Moreover, these mechanisms are higher dielectric constant (78.3 at 20 °C) in comparison with
suggested to co-occur as a consequence of the matrix compo- other solvents such as ethanol and methanol (24.3 and 32.6 at
sition, structure, and ultrasound treatment conditions.79–81 20 °C, respectively). Three main strategies can be used (alone
The use of ultrasound to assist the extraction of bioactive or combined) to extract bioactive compounds from the matrix:
components from bioethanol processing was evaluated in a first, the use of a solvent (or a mixture) with high capacity to
previous study. Zheng et al.82 extracted potential bioactive absorb microwave energy; second, the use of a mixture formed
compounds from sugarcane bagasse by ultrasound (40 kHz). by a strong and weak microwave absorbing energy; and third,
The results obtained from the 30% hydroalcoholic fraction the use of a solvent that does not absorb microwave energy,
indicated that sugarcane bagasse contains phenolic com- while the matrix has a high dielectric loss.85
pounds with antioxidant activity (using DPPH, ABTS and Regarding the use of microwaves to recover high added-
ORAC assays) and inhibitory activity against sucrase and value compounds, Fishman et al.86 optimized the extraction of
maltase while reducing insulin resistance. The authors identi- pectin from sugar beet pulp. The experiment evaluated the
fied the main phenolic compounds in such a fraction: p-cou- impact of processing time (3–20 min), and pressure (25–75 psi)
maric acid, genistein, genistin, quercetin, and tricin 4-O-guaia- wherein the matrix was irradiated with 1200 W of microwave
col glyceryl ether-7-O-glucopyranoside. A similar experiment power at a frequency of 2450 MHz. The highest recovery of
was carried out by Juttuporn et al.,83 who explored the ultra- pectin (16.80%) was obtained by processing sugar beet pulp
sound technology (20–40 W, 3–9 min) to increase the extrac- for 10 min at 50 psi. The authors also argued that the mole-

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cular mass of extracted pectin was influenced by pressure and mechanisms, which can accelerate the extraction of valuable
temperature, particularly at mild pressure and low tempera- compounds, are more intense in moderate electric field. Both
ture. An interesting experiment was carried out by Peng et al.87 these techniques have been successfully used as a green
wherein ultrasound and microwave techniques were combined energy-saving technique for the extraction of bioactive com-
to extract pectin from sugar beet pulp. The authors optimized pounds from soybean slurry,92 rapeseed slurry,93 and rice
the extraction with a solid-to-solvent ratio of 1 : 30, at 92 °C, for bran,94 colored potato,95 and microalgae.96,97 Furthermore, a
37 min. The pectin extracted by the optimized method dis- proposed combination of ohmic heating and traditional
played higher average molecular weight, viscosity, emulsifying systems by Gavahian et al.46 has been successfully used for the
activity and stability than pectin extracted by a conventional extraction of bioactive compounds from thyme,43 mint,98–100
method. oregano,54 and citronella.101 This method has been shown to
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be a time- and energy saving approach for the extraction of bio-

Subcritical fluid extraction active compounds.44,45 A comprehensive review of this extrac-
The subcritical fluids are produced by combining pressure and tion approach showed that further studies on the sustainability
heating to obtain a saturated liquid with unique characteristics and safety aspects of OAHD are the prerequisite for its indus-
wherein temperature is held between atmospheric boiling and trial adaptation.45
critical points.88 The system also requires pressures high
enough to prevent liquid vaporization. Particularly for water Techno-economic evaluation
(temperature between 100 and 374 °C), its properties as a Techno-economic evaluation of emerging green technologies
solvent are improved: enhanced diffusion rate and reduced vis- in both distillation of ethanol and extraction of bioactive com-
cosity and surface tension which facilitates the extraction of pounds is of great interest to select the most appropriate
target compounds.89 approach due to the variety of raw materials and high added-
Subcritical fluid extraction was used by Sato et al.90 to value products. Although the amount of information about
recover neutral sugars (mainly arabinooligosaccharides and this topic is scarce, the current results available in the litera-
feruloylated arabino-oligosaccharides) and ferulic acid (free ture show a promising scenario for such technologies.
and ester form) from sugar beet fiber by two systems (batch Regarding the techno-economic evaluation of green distilla-
and flow systems). The experiment was carried out at tempera- tion technologies, Dias et al.102 compared the consumption of
tures between 160 and 180 °C for 5–15 min in both batch and energy (kW) between a conventional distillation and a double-
continuous systems. According to the authors, the highest effect distillation column. The integrated approach can reduce
extraction yields for neutral sugars (28.5 wt%) and total ferulic the energy consumption (hot utility demand) by using sugar-
acid (0.55 wt%) were obtained at 160 °C for 12 min in the cane bagasse as fuel. The authors also argued that additional
batch system. In the flow reactor system, the authors evaluated fermentable sugar could be obtained from the exceeding
the impact of extraction time (7–12 min), while the tempera- sugarcane bagasse, which could lead to increasing production
ture was set at 170 °C. The extraction yield of neutral sugars of ethanol. However, the surplus of electricity produced is
(27.3–27.7 wt%) and ferulic acid (0.52–0.54 wt%) was in the reduced from 33.0 to 13.5 kW h t−1 cane.
same range of results obtained by the batch system. In another study, Dias et al.7 obtained promising theore-
An interesting experiment combining ultrasound ( pre-treat- tical results about the use of double-effect, heat integration
ment) and subcritical water to extract pectin-related materials and co-generation systems for a bioethanol refinery. The study
and ferulic acid from sugar beet pulp was carried out by Chen, indicated that the most relevant reduction in hot utility
Fu, and Luo.91 The authors performed the ultrasound pre- demand was obtained by combining a double-effect column
treatment prior to subcritical water extraction: sonic frequency with thermal integration. In addition, electricity and bagasse
of 25 kHz at an ultrasonic intensity of 1 W cm−2 for 10 min. surpluses were obtained when the Rankine cycle was used in
The effect of pressure, temperature, time and solvent-to-solid the cogeneration system depending on the type of turbine
ratio on the extraction of pectin materials by subcritical water installed in the system. According to the authors, condensing
extraction was studied. The maximum yield of pectin-related steam turbine and back pressure steam turbine resulted in
materials (24.63%) was obtained by conducting the extraction electricity and bagasse surpluses, respectively. It is worth men-
at 10.7 MPa, for 30.49 min, at 120.7 °C and the solvent-to-solid tioning that authors also evaluated the cost of energy for the
ratio of 44.03. The authors also characterized the composition abovementioned system as well as for a Biomass Integrated
of extracted pectin, which was mainly composed of galacturo- Gasification Combined Cycle (BIGCC). Although no bagasse
nic acid (59.1%) and arabinose (21.6%). surplus was obtained in this configuration, the energy surplus
was enhanced and production cost was decreased.
Ohmic-assisted extraction Regarding the final price of ethanol, the theoretical evalu-
The terms ohmic heating and moderate electric field are used ation performed by Quintero et al.103 revealed the potential
to designate the electrical treatment of materials. While the economic benefit to produce ethanol from lignocellulosic raw
former profoundly increase the temperature of materials, the materials combined with a BIGCC system to co-regenerate
latter are usually performed at relatively lower temperatures.45 energy in the process. According to authors, the use of such a
In addition, electroporation and enhanced cell permeability system reduced the final cost of ethanol (for all lignocellulosic

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raw materials) from 0.578–0.767 (conventional distillation) to pound extraction from bioethanol residues has been carried
0.487–0.684 (BIGCC system) US$ per L. The authors also high- out. However, it is relevant to comment that important
lighted the importance of commercializing the surplus of elec- advances were reported for the green extraction technologies
tricity in the processing plant operating with the cogeneration discussed in this review. For instance, pilot scale studies about
approach in order to reduce the production cost of ethanol. It is pulsed electric field,108 high voltage electrical discharges,109
also important to mention that the final price for ethanol under and solvent-free microwave110 extractions were reported in the
such conditions can differ from other studies, as indicated by literature.
the authors. A similar conclusion was obtained by Rincón Although comparisons between green technologies are
et al.104 who estimated the influence of conventional, Biomass difficult due to the characteristics of each approach, selected
Steam Turbine (BST) and BIGCC systems on the production variables, production scale and amount of information avail-
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cost of ethanol. In addition to improving energy use, both able in the scientific literature, it is also important to highlight
technologies (BST and BIGCC) reduced the production cost of that some green technology can influence the total utility
ethanol from 0.51 US$ per L (obtained from the conventional requirement. For instance, Kunnakorn et al.106 proposed an
process) to 0.46–0.48 in the BST and 0.42–0.43 US$ per L in the azeotropic and membrane distillation of ethanol as a green
BIGCC system. It is important to note that such reductions are approach for conventional distillation. The authors estimated
also attributed to the commercialization of electricity surplus. higher energy consumption in azeotropic distillation than in
In the case of membrane assisted separation of ethanol– conventional and membrane distillation (18.20 vs. 8.18 and
water mixtures, the price for m2 is an important indicator 9.31 MJ kg−1 ethanol, respectively). Differently, Vázquez-Ojeda
regarding processing viability. An interesting approach to esti- et al.107 simulated and compared the utility cost of distilling
mate the net present value profits (indicates the time required ethanol in four systems: conventional, extractive distillation
to obtain a positive balance between inflow and outflow cash) and combining both technologies with the heat-integration
was used to evaluated the economic viability of such techno- approach. The most energy efficient distillation system was
logy. The study indicated that expensive membranes (costing obtained combining conventional and heat integrated
$1000 per m2) would not return a profit after a 20-year period. distillation.
Differently, the reasonable payback period of 4 years could be The use of green technologies in the distillation of ethanol
achieved by using $500 per m2 membranes, which can be pro- and extraction of bioactive compounds has potential to reduce
portionally reduced to 1 year as membrane price is reduced to the environmental impact to obtain both products but the
$100 per m2. The authors also argued that relevant investment investment to achieve such an operational condition is sub-
in membrane development (such as the production of thinner stantially higher than conventional process operation, which
and less expensive supports) is an important strategy to reduce comprises relatively simple equipment and systems. However,
the final price of membranes.105 prospective advances in the engineering and system design
The membrane technology was also related to lower energy may reduce the equipment cost to address this limitation.111
consumption in comparison with azeotropic distillation.106 Consequently, scaling up green technologies remains a
The operational cost in the azeotropic system was estimated to major challenge in the current scenario. For instance, more
be 0.350€ per kg ethanol in the configuration of one practical studies are necessary to estimate the operational conditions at
azeotropic distillation. Moreover, operational cost could be different scales and then perform experiments to evaluate the
improved to 0.550 and 0.742€ per kg ethanol by using two and real operational conditions, define suitable control systems,
three practical azeotropic distillation systems, respectively. and calculate the operational cost for heat-integration distilla-
Conversely, the operational cost for membrane technology was tion.32 A similar condition can be observed in membrane
estimated to be 0.168€ per kg ethanol and cost of conventional technology. This technology requires advances regarding mod-
distillation was estimated to be 0.157€ per kg ethanol. eling processing operation, development of materials with
The combination of approaches to carrying out bioethanol higher separation performance, reduced manufacture cost,
separation was also evaluated in the literature. For instance, enhanced ethanol extraction, and improved flux and resistance
Vázquez-Ojeda et al.107 evaluated the utility costs in an inter- against ethanol and temperature.112
esting approach wherein extractive distillation and energy inte- In addition, one can speculate about the potential mis-
gration were combined to improve the energy efficiency of match in demand between ethanol production and extraction
bioethanol separation from water. Two main outcomes were of bioactive compounds in an integrated biorefinery scenario.
obtained from this study. Energy integration was associated Since these processes explore different compounds from the
with reduced utility cost in both conventional and extractive same raw materials (fermentable sugar for ethanol production
distillation. In contrast, the cost associated with extractive dis- and other secondary compounds as bioactive agents) the
tillation was associated with higher values than those obtained ethanol and bioactive compound productivities are spectated
from conventional extraction. The authors concluded that con- to be proportionally influenced. This scenario is different from
ventional distillation with energy integration was the best pro- that usually observed for ethanol and sugar refineries.113
cessing condition to distill bioethanol. Nonetheless, the current scenario of green technologies, at
To the best of our knowledge, no techno-economic evalu- least at a theoretical level, supports further development of
ation of industrial-scale green technologies for bioactive com- such approaches and related technological advance to obtain

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both ethanol and bioactive compounds. At the practical level, members of the MARCARNE network, funded by CYTED
membrane technology is the most advanced strategy among all (ref. 116RT0503).
green options for ethanol distillation due to important
advances in the development of materials and separation
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