C H A P T E R

19
Novel bioethanol production processes
and purification technology using
membranes
Alessandro Senatorea, Francesco Dalenab, Angelo Basilec,*
a
Chemistry and Chemical Technologies Dpt., University of Calabria, Rende, Cosenza, Italy; bDepartment
of Environmental and Chemical Engineering Dpt., University of Calabria, Rende, Cosenza, Italy; cITM-
CNR, c/o University of Calabria, Rende, Cosenza, Italy
* Corresponding author. e-mail address: a.zarli@nextchem.it

1. Introduction The development of new technologies to pro-

Increasing of oil prices and polluting emis-
sions, as well as the Security Act and the U.S. En-
ergy Independence of 2007, led the American
scientific society, and immediately after the
entire scientific community, to search for a new
kind of fuel with low environmental impact,
which could meet the needs of the world from
both an energetic and a renewable point of
view [1].
The massive use of this nonrenewable fuel,
due to the rapid industrial development is
strictly connected to the prediction that by
2040e50 the fuel demand in the world will
exceed the availability [2]; in addition, fossil
fuels are primarily responsible for the emission
of CH4, N2O, and CO2 (the so-called greenhouse
gases (GHG)), which contribute to the global
warming [3e6].
duce biofuels with low environmental impact is
one of the greatest scientific efforts of this cen-
tury. Based on the raw material and on the work-
ing process carried out on it, biofuels can be
classified as primary (natural gases) or second-
ary biofuels (ethanol, biodiesel, biooil, biogas,
or charcoal), and these, as a result, can be subse-
quently classified into first, second, or third gen-
eration (Fig. 19.1).
At the moment, primary biofuels are easily
converted into energy thanks to industrial plants
that operate on a wide range of scales, from few
kilowatts to hundreds of megawatts [7]. The sec-
ondary biofuels can be instead mainly converted
through three different processes: (i) chemical
(biomass into liquid fuels), (ii) thermochemical
(combustion, gasification, and pyrolysis), and
(iii) biochemical process (fermentation) [7,8],
through which various type of biofuels such as

Catalysis, Green Chemistry and Sustainable Energy

https://doi.org/10.1016/B978-0-444-64337-7.00019-7 359 Copyright © 2020 Elsevier B.V. All rights reserved.
360 19. Novel bioethanol production processes and purification technology using membranes
FIGURE 19.1 Schematic representation of the division class of biofuels.
hydrogen, ethanol, methanol, diesel, and many
others can be obtained. Among the many, from
both an economic and a productive point of
view, ethanol has been chosen as a possible alter-
native candidate, to satisfy the global energy de-
mand of the transport sector [8a].
Usually, one of the most important methods
of industrial ethanol production is carried out
by a process that comes from the oil industry
that foresees the acid-catalyzed hydration of
ethylene [2], as shown in the following chemical
reaction:
H3 PO4
C2 H4 þ H2 O ! CH3 CH2 OH
But today, ethanol, also known as bioethanol
and concurrently produced from plantations
rich in easily fermentable sugars such as sugar-
cane, corn, wheat, and sugar beet [2a], is a very
interesting molecule from both a chemical and
physical point of view [4e6].
From a chemical point of view, ethanol is a
molecule (with a molecular weight of 46.07 g/
mol and a density of 0.789 g/cm3) with an ethyl
group linked to a hydroxyl group, which makes
it a polar molecule really versatile to be mixed
both with water and many organic solvents
([6a]) [4e6]. Moreover, for its physicochemical
properties, ethanol has been widely studied as
a good fuel substitute for internal combustion
(IC) engines (i.e., the spark-ignition or the
IV. Selected examples and case history
compression-ignition engine) to be used alone
or in mixtures with gasoline or diesel, where
the slowdown in its development on a global
scale is mainly due to the production costs
([2a]; [6b]; [9]; [9a]).
One liter of ethanol affords 66% of the energy
provided by the same amount of gasoline;
moreover, being an alcohol, ethanol is an inter-
esting oxygenated molecule with a high latent
heat of vaporization (840e855 kJ/kg), a low ce-
tane number (5e20), and a high octane number
(99e107), which allows it to not take part in the
preignition process of the engine and to be
burned with a shorter time and a higher
compression ratio if compared to a fossil fuel
([4e6,9]; [6b]; [2a]). A typical gasoline fuel has
a heat of vaporization of about 380e400 kJ/kg,
a cetane number of 8, and an octane number
of about 82e92 ([9b]). Furthermore, ethanol
has a higher evaporation enthalpy (1177 kJ/
kg, at 60 C) compared to gasoline (348 kJ/kg,
at 60 C) [9]; Lynd, 1996). All these data are sum-
marized in Table 19.1, while Table 19.2 summa-
rizes the main advantages and disadvantages of
this molecule as a fuel.
Due to the chemical structure of the molecule,
which contains a hydrophilic head and allows
miscibility with water, ethanol could be used in
vehicles in the pure form or in a mixture with
gasoline, where the advantages of this mixtures
 1. Introduction 361
TABLE 19.1 Ethanol combustion characteristics compared to fossil fuels.

Property Unit Ethanol Gasoline Diesel

Density (at 20 C) g/cm 3

0.79 0.75 0.82
Octane number e 99e107 82e92 e
Cetane number e 5e20 8 48

Latent heat of vaporization kJ/kg 840e920 380e400 375

a
Type of motor e e SI engine CIa engine
References e Kukoyi et al., 2015; [9b]; [9b] [10]
Gangult et al., 2011
a
CI, compression ignition; SI, spark ignition.

are the substantial lowering of hydrocarbons, ni-
trogen oxides (NOx), and carbon monoxide (CO)
emissions with respect to the gasoline fuel alone
[9b]. Moreover, also if a high amount of water
must be avoided due to engine problems, hy-
drous ethanol with a water content of about
6.8% has been tested with good results in a
four-stroke engine ([9c]). Today, different blends
of ethanol with gasoline called “E” blends are
used in SI engines as well as flex-fuel vehicles.
The code used to identify a mixture of this kind
consists of a letter “E”, followed by a number
that identifies the percentage of ethanol in the
mixture [4e6,11]. Studies on different blends
from E5 to E85 up to a 100% pure ethanol
solution show how density, octane number,
and latent heat of vaporization increase with
the ethanol concentration, while the heating
value decreases [9b]. The E85 blend also in-
creases thermal efficiency, while there is
observed a decrease in hydrocarbons, CO, and
NOx emissions. The reduction of NOx, in par-
ticular, has been attributed to a reduction in
flame temperature, confirmed by a reduction in
exhaust temperature ([9b]; [9c]). With pure
ethanol or oxygenated fuel, NOx slightly in-
creases again, due probably to the advanced
combustion that leads to a higher temperature
and inecylinder pressure ([9b]; [9c]). The perfor-
mances of the engine are mainly observed in

TABLE 19.2 Schematization of advantages and disadvantages of ethanol as a biofuel.

Advantages Disadvantages

Oxygenated molecule Miscibility with water

High latent heat of vaporization (840 kJ/kg) Lower vapor pressure
Low cetane number (8)
High octane number (100)

Effects
Preventing self-ignition in IC Initiation in engines at cold temperatures is difficult
Burning at high compression ratio
Burning almost completely

IV. Selected examples and case history

362 19. Novel bioethanol production processes and purification technology using membranes
torque experiments that show how it increases
with increasing the compression ratio [11a].
There is a lot of literature on ethanol blends
that, based on a search done on ScienceDirect
with the keywords “ethanol fuel blends,” shows
an increase of about 9.5% from 2000 until 2018
(Fig. 19.2). In the same period, another inter-
esting search with the keywords “bioethanol
fuel” shows how the scientific interest and the
term bioethanol as a fuel are slowly taking the
upper hand over ethanol (Fig. 19.2).
At the moment, data updated to 2017 reveal
that the United States and Brazil represent the
major countries involved in bioethanol pro-
duction mainly from corn and sugarcane
(Table 19.3), with, respectively, 58% (15.8 billions
of gallons) and 26% (7.06 billions of gallons) of
the global ethanol production (Fig. 19.3), fol-
lowed by Europe and China [11b].
Several efforts are being carried out to opti-
mize the process of conversion of ethanol, and
today, an appropriate separation technology is
required. At the moment, distillation, the pro-
cess which separates liquid compounds of a
mixture exploiting the different volatility of
each component through selective boiling and
condensation points, is the main technique
FIGURE 19.2 Scientific articles on ScienceDirect found with the keywords “ethanol fuel blends” and “bioethanol Fuel,”
from 2000 to 2018.
IV. Selected examples and case history
used in industrial plants, but membrane separa-
tion technologies are gradually catching on in
biorefining and bioenergy production, due to
the low energy consumption, greater separation
efficiency, reduced number of processing steps,
and high quality of the final product [11c]. In
the second part of this chapter, various aspects
of membrane reactor (MR) technology will be
considered and discussed by referring to both
the ethanol and bioethanol reforming reactions
to produce pure hydrogen.
2. The bioethanol production process
Based on the chemical composition of the
initial feedstock, the pretreatment, technology,
and cost-effectiveness of processes vary widely.
In any case, it is really important that the fermen-
tation processes have a good suitability for pro-
ducing bioethanol.
The costs and yields of the final product are
mainly affected by (i) content of lignin in the
biomass; (ii) type and variety of sugars to be fer-
mented; (iii) costs for the collection and storage
of low density lignocellulose materials [12].
 2. The bioethanol production process 363
TABLE 19.3 Bioethanol production costs.

Ethanol from corn Ethanol from sugarcane

Type of process Dry grind Melle-Boinot

Feedstock costs ($/L) 0.21 0.012

Costs on the plant ($/L) 0.109 0.048
Gain from by-products ($/L) 0.068 0
Total production costs ($/L) 0.25 0.06

Ethanol yield (L/tons of feedstock) 403.66 100

Ethanol price ($/L) 0.40 0.20
References [11], [2a] [11e], [2a]

The main steps involved in the bioethanol
production process are the pretreatments, hy-
drolysis, fermentation, and purification, where
the fermentative processes are a common point
among all the three generations of feedstock
(Fig. 19.4).
The whole process involves the biochem-
ical conversion of simple sugars into ethanol
through enzymes produced by microorganisms:
the so-called cellulases that are also respon-
sible for the hydrolysis of cellulose [13]; these
enzymes are able to convert only pentose and
hexoses sugars [14,15]. The problem with
feedstock that contains a lot of lignin is the
expense of pretreatments, which serve to elimi-
nate its structure and free the sugars that will
be fermented by the enzymatic treatment. This
removal improves significantly the effect

FIGURE 19.3 AFDC data of global ethanol production, from 2007 to 2017.

IV. Selected examples and case history

364 19. Novel bioethanol production processes and purification technology using membranes
FIGURE 19.4 Schematic repre-
sentation of the various steps of
fermentative process.
of enzymatic hydrolysis, improving process
yield.
Experimental data show that hydrolysis car-
ried out without pretreatment lowers the yield
by about 20%, whereas yields after pretreat-
ment often exceed 90% [16]. The simple sugars
produced during hydrolysis are subsequently
transformed into ethanol during enzymatic
fermentation. The limiting aspect of the fermen-
tation process is the self-by-product inhibition,
which is the inhibition of yeast cell enzymes
from its product, bioethanol, at high concentra-
tions [17]. This problem is usually overcome by
the removal and recovery of ethanol during its
production through distillation process, also if
genetic techniques are trying to produce yeasts
that are increasingly resistant to this type of
self-inhibition [13]; [13a].
2.1 Pretreatment
Pretreatment is one of the key steps involved in
bioethanol production processes, capable of
altering the size, structure, and chemical composi-
tion of the starting biomass; it is really crucial to
make the polysaccharides to be fermented easily
accessible by chemicals and enzymes of other steps
and to guide the yield and the cost-effectiveness of
the whole process (indeed, it represents about 18%
of the total cost of the whole transformation pro-
cess) [18,19]; [19a]; [20]. The choice of pretreat-
ments is linked to a number of important criteria,
such as (i) ethanol yield; (ii) best lignin removal
treatment; (iii) limitation in the production of prod-
ucts that inhibit the fermentation enzymes; (iv)
minimization of GHG; and (v) minimization of
toxic by-products [18,21,22]. According to these
criteria, pretreatment can be divided into
(i) physical, (ii) chemical, (iii) physicochemical,
and (iv) biologic (Fig. 19.5).
IV. Selected examples and case history
i Physical pretreatment. The main techniques
that take into account physical principles are
mechanical chipping, grinding, milling, or
uncatalyzed steam explosion
(autohydrolysis) and liquid hot water
pressure (Table 19.4) [23,24]. In any case, the
main purpose of this treatment is to reduce
the particle size of the cellulosic/
lignocellulosic raw material, to obtain smaller
particles having a larger surface area, which
makes sugars easily accessible for other
industrial steps [24,25]. Usually, the
maximum particle size obtained after a
chipping treatment is about 10e30 mm, while
it is of about 0.2e2 mm after a milling or
grinding process [4e6,20,22]. The optimal
particle size range seems to be about
4e8 mm, which increases the subsequent
extraction yield up to 7.5% ([22a];[3]). So at
the end of this process, the cellulose degree of
polymerization decreases with a partial break
of the chains of both lignin and cellulose
[25,26].
ii Chemical pretreatment. Taking advantage of
different acidic, basic, or oxidizing chemicals,
different effects can be obtained on the
lignocellulosic materials. The most common
and useful methods toward feedstock with a
high lignin content are alkaline, ozonolysis,
peroxide, and wet oxidation treatments,
while to improve the solubilization of
hemicelluloses, treatments with diluted
acids such as H2SO4, are preferred
for their efficiency [26a].
iii Physicochemical pretreatment. A series of
physicochemical reaction conditions such as
humidity, temperature, and pH deeply affect
the solubilization of lignocellulosic
compounds, since it is the most sensitive
fraction. Hemicelluloses, for instance, become
 2. The bioethanol production process 365

FIGURE 19.5 Schematic representation of types of pretreatment processes and some examples.

more soluble in water at temperature higher fermentation inhibitors during the process
than 150 C, favoring the extraction of xylan [29]. However, some improvements must be
[13,27]. The most used pretreatment of this made before they can be used in industrial
type is the CO2 explosion, which is able to processes, such as faster growth times and
separate the hemicelluloses, reducing the removal of natural competitors, making it a
length of the polymer chains of glucosidic very expensive and precarious balance [29a].
fractions into simpler sugars. These Other disadvantages are the low rate of
treatments, often used with recovery of hydrolysis and the long pretreatment times
chemical solvent, can improve the yield on (between 4 and 8 weeks) compared to other
lignocellulosic raw material [28]. pretreatment technologies [30,31]. Table 19.4
iv Biologic pretreatment. Biologic pretreatment is a presents various types of pretreatments, both
treatment that has a great potential in the with the advantages and disadvantages for
industrial processes of the future, for its high each of them.
yield and low environmental impact. In this
Currently, the combination among the biologic
process, microorganisms such as fungi
pretreatment (usually in the form of ready-made
(white-, brown-, and soft-rot fungi) and
enzymes) and the other methods seems to be the
bacteria, or enzymes extracted from them, are
best choice to reduce the whole process time and
mainly used to degrade the lignin structure of
to improve ethanol yield [36]. An example can
the plant, which results in (i) a very low
be made coupling the enzymatic hydrolysis
energy requirement; (ii) no release of toxic
with ozonolysis, where the rate of enzymatic
compounds; and (iii) no generation of

IV. Selected examples and case history

366 19. Novel bioethanol production processes and purification technology using membranes

TABLE 19.4 Some examples of various types of pretreatment according to the starting feedstock (LCB) and the
advantages and disadvantages for each of them.

Pretreatment
Category Method Advantages Disadvantages Ref.

Physical Milling Cost effective High energy input, inability to remove lignin [21,32]
that restricts the access of the enzymes to
cellulose and inhibits cellulases
Extrusion Operate at high solids loadings, High energy consumption, effect is limited [21,32]
low production of inhibitory when no chemical agents are used, mostly
compounds, short time effective on herbaceous type biomass
Chemical Acid Short retention time, lignin and Concentrated acid process is corrosive and [21,32]
hydrolysis hemicellulose are removed dangerous. Requires specialized nonmetallic
constructions, formation of inhibitors at low
pH
Alkaline Removes lignin and a part of the Low digestibility in softwoods, large [21,32,33]
hydrolysis hemicellulose, decrease in the amounts of water requires for washing
polymerization degree
Organosolv Produces low residual lignin High capital investment, handling of harsh [21,32,34]
substrates that reduce unwanted organic solvents, formation of inhibitors
adsorption of enzymes and
allows their recycling and reuse
Ionic liquid Low vapor pressure designer Costly, complexity of synthesis and [21,32,35]
solvent, working under mild purification, toxicity, poor biodegradability,
reaction conditions and inhibitory effects on enzyme activity
Oxidation Lower production of by- Cellulose is partly degraded, high cost [21,32]
products
Physicochemical Steam Less expensive than other pre- Excessive degradation of the physical and [21,32]
explosion treatment methods and chemical properties of cellulose and release
chemical-free of inhibitors
Liquid hot High recovery and lower High energy input, removes mainly [21,32]
water formation of inhibitory hemicellulose
pretreatment components
Ammonia Reduces the lignin fraction, short Costly, does not significantly solubilize [21,32]
fiber retention time, no formation of hemicellulose, ammonia must be recycled
expansion some inhibitory by-products after the pretreatment to reduce the cost and
protect the environment; much less effective
for softwood
Biologic Microbial Lignin degradation, low energy Slow reaction time [21,32]
treatment requirement, chemical-free, mild
conditions

IV. Selected examples and case history

 2. The bioethanol production process
hydrolysis increased by a factor of five following
a 60% removal of the lignin from wheat straw.
Enzymatic hydrolysis yield increased from 0%
to 57% as lignin decreased from 29% to 8% after
ozonolysis pretreatment [12,37].
2.2 Hydrolysis
In the hydrolysis step that follows the pre-
treatment phase, a depolymerization reaction is
carried out in water by enzymes or acids, to
break down the long cellulosic and hemicellulo-
sic chains that are reduced to smaller units (a
mixture of pentose and hexose monomers) [38].
This hydrolysis process is critical to obtain a
good yield in ethanol, since the quality of the hy-
drolyzate drastically affects the fermentation
process [39]. The yield of this step is also closely
related to the previous pretreatment step that
produces the hydrolysable substrate of a given
purity that is important for both the final yield
and price. In the second-generation feedstock,
for instance, can be obtained up to five sugars
(glucose, galactose, mannose, xylose, and arabi-
nose) that are much more complex to hydrolyze
than that obtained from the first-generation feed-
stock (i.e., glucose) [38].
In the acid hydrolysis treatment, the sub-
strates are treated with mineral acids (i.e.,
H2SO4 and HCl) for a period of time at a specific
temperatures, to break down the cellulose and
hemicelluloses chain into more easily ferment-
able sugars, as described in the equation [3]:
ðC6 H10 O5 Þn þ H3 Oþ þ H2 O/ nC6 H12 O6
(19.1)
Disposal cost and control of acid concentra-
tion are the main problems deriving from acid
hydrolysis [39]. On the other hand, the enzy-
matic treatment, carried out by cellulose and
hemicellulase enzymes, appears to be more se-
lective, without inhibitory by-products and
applicable to milder experimental conditions,
but too expensive to be used in industrial pro-
cesses [39e42]. There are mainly three kinds
IV. Selected examples and case history
367
of cellulase enzymes suitable for the hydrolysis
process: endo-1,4-b-glucanase (EDG; EC 3.2.1.4),
cellobiohydrolase (CBH; EC 3.3.1.91), and
b-glucosidase (BGL; EC 3.2.1.21).
The cellulose reduction in glucose occurs in
three steps: (i) at first, EDG begins the break by
attacking the amorphous regions of the polymer,
forming a new lower molecular weight chain,
more accessible for cellobiohydrases (cello-
drexin); (ii) CBHs are the enzymes responsible
for the breaking of b-1,4-glycosidic linkages start-
ing from the ends of the chain and leading to the
formation of the cellobiose; (iii) BGL hydrolyzes
the cellobiose units into glucose [42a]; [27,43].
The enzymatic hydrolysis reaction of the cellu-
lose is schematized in Fig. 19.6.
Several microorganisms can produce cellulose
enzymes such as Clostridium, Cellulomonas, Erwi-
nia, Thermonospora, Bacteriodes, Bacillus, Ruminococ-
cus, Acetovibrio, and Streptomyces. Also, several
fungi are involved in the production of cellulases
such as Trichoderma, Penicillium, Fusarium, Phaner-
ochaete, Humicola, and Schizophillum sp. [42].
These aforementioned species are enzymes that
specifically hydrolyze cellulose, but in a good
fermentation process of lignocellulose substrates,
other enzymes are added. In fact, Xylanase, Glucu-
ronidase, Acetylesterase, and b-xylosidase attack spe-
cifically hemicellulose to reduce it into glucose,
galactose, mannose, xylose, and arabinose [27].
The enzymatic hydrolysis is influenced by
various experimental conditions. Temperature
and pH are the main factors, but also the concen-
tration of the substrate or the load of the cellu-
lase. It has been reported [27a] that the optimal
conditions in which cellulase enzymes act are
at a temperature of 40e50 C and pH of 4e5.
2.3 Fermentation process
The fermentation step has a key role in the con-
version of monomeric units of sugars into ethanol
through a yeast, as in the following reaction:
C6 H12 O6þyeast / 2 C2 H5 OH þ 2 CO2 (19.2)
368 19. Novel bioethanol production processes and purification technology using membranes

FIGURE 19.6 The enzymatic hydrolysis reaction of cellulose.

Saccharomyces cerevisiae is the most used yeast
for this process, which for the conversion uses
glucose, mannose, and fructose processed
through the EmbdeneMeyerhof pathway
(EM) of glycolysis, and galactose through the
Leloir pathway (LP) [27b]. Several experi-
ments have been tried over the years, to be
able to convert another of the most common
sugars in plants: xylan that has been recently
fermented by new interesting genetically
modified yeasts [10].
The fermentation process requires glucose or
other simple sugars that are phosphorylated to
glucose-6-phosphate, and subsequently con-
verted into pyruvate (3C) via the Embdene
MeyerhofeParnas (EMP) pathway through
some intermediates. Anyway, to be fermented,
cellulose must first be hydrolyzed [44].
Glucose / Glucose 6phosphate/Pyruvate
(19.3)
Hemicellulose is instead converted into xylose,
via the pentose-phosphate pathway (PPP), which
produces fructose-6-phosphate, which through
the EMP pathway is converted into pyruvate.
Xylose / PPP pathway/Fructose6
phosphate/EMP pathway /Pyruvate (19.4)
Although yeasts are the main microorganisms
used in the fermentation process, there are other
types of organisms capable of fermenting
pentose and hexose both separately and simulta-
neously: bacteria and fungi [44a] [11].
For example, some of the bacteria capable
of fermenting xylose in ethanol are Bacillus, Kleb-
siella, Thermoanerobacter, Aeromonas and Escheri-
chia Coli while some fungi are Neurospora
Zygosaccharomyces, Monilia, and Rhizopusfor
[44a] [4e6]. Table 19.5 shows some examples of
microorganisms and the optimal experimental
conditions for the maximization of the yield of
ethanol.

IV. Selected examples and case history

 2. The bioethanol production process 369
TABLE 19.5 Different yields of ethanol in some of main yeasts, bacteria, and fungi.

Sugar Ethanol
Temperature Fermentation concentration yield
Microorganism ( C) pH time (h) (g/L) (g/L) Reference

Yeasts Saccharomyces Cerevisiae 30 5.5 65 280 130.12 [45]

3013
Saccharomyces cerevisiae 35 5.0 96 80 39 [21]
BY4742
Bacteria Zymomonas Mobilis 30 6.5 18 117 30.4 [46]
NRRL 806
Zymomonas Mobilis 30 4.0 44 200 99.78 [47,48]
ZMA7-2
Fungi Aspergillus oryzae 694 First aerobic 5.0 24 50 24.4 [48a]
step)
30
Second 5.0 144
anaerobic step)
30
Rhizobium javanicus First aerobic 5.0 24 100 33 [48a]
2871 step)
30
Second 5.0 72
anaerobic step)
30

As can be seen from the results shown in the ta-
ble, a great look is given to Saccharomyces cerevisiae
and the bacterium Zymomonas mobilis (respec-
tively, 130.12 and 99.78 g/L in ethanol yield).
Moreover, these two strains both give good re-
sults for high ethanol yield (90%e97% of the
theoretical one) and high ethanol tolerance, up
to about 10% (w/v) in fermentation medium [49].
2.4 Integrated processes
In addition to pretreatment, the other two
steps that require economic sources are hydroly-
sis and fermentation; in these cases, both the con-
centration of initial products and ethanol yield
are economically feasible when the final yield ex-
ceeds at least 40 g/L of bioproduct [49a]. The
two methodologies that integrate these two
production processes (hydrolysis and fermenta-
tion) to increase their yield and reduce their costs
are SHF (where enzymatic hydrolysis and
fermentation occur separately) and simulta-
neous saccharification and fermentation (SSF)
(where both of the steps occur simultaneously).
In both the cases, one of the most expensive
but profitable processes in terms of yield, the
enzymatic hydrolysis is performed by cellulase
that breaks down cellulose chains into two
glucose molecules [50]. In the first separate pro-
cess (SHF) the hydrolysis is carried out before
the fermentation process, which in turn is
divided into two phases, one in which the
simplest hexose sugars are fermented to ethanol
and a second phase for the fermentation of xy-
loses [12]. The advantage of this technique is to
control separately the two processes, each with

IV. Selected examples and case history

370 19. Novel bioethanol production processes and purification technology using membranes

its own temperature, which in the case of Saccha- Another integrated process based on SSF tech-
romyces cerevisiae and cellulases are, respectively, nology is the consolidate bioprocessing (CBP).
32 and 50 C [12a]; [12]. Temperatures above Which integrate the two processes, producing
32 C would lose yeast vitality, while the best cel- also the enzyme required for the whole process
lulases activities are usually between 45 and [12b] (Fig. 19.8).
55 C [12] (Zhao et al., 2012; [12c]). An implemen- Another excellent example of integrated pro-
tation of this method is called SHCF (separate cess is introduced and discussed in the next
hydrolysis and cofermentation), where both section.
pentose and hexose sugars are fermented simul-
taneously in a single-step process (Zhao et al.,
2012). A disadvantage of the enzymatic hydroly-
3. MR concept and technology
sis is the inhibition of the same cellulosic en-
zymes from high concentrations of glucose; this
A very important example of an integrated
problem is usually solved by increasing enzyme
process is the membrane reactor (MR). It is an en-
concentration, but a new method has been devel-
gineering device in which both reaction and sep-
oped with the SSF patented by Gauss et al., in
aration of one or more products occur
1976 [12,51]; [51a]. This method is used to
simultaneously. The separation is performed by
convert cellulose into ethanol, allowing simulta-
a membrane that is integrated with the reactor,
neous hydrolysis and fermentation into a single
in which the reaction takes place. There are
reactor (Fig. 19.7) where glucose is rapidly con-
different configurations of MRs. For example, a
verted into ethanol without leading to the afore-
simple configuration of MR is shown in
mentioned accumulation problems.
Fig. 19.9 with two concentric tubes: the catalyst
This process requires a compromise between
is allocated in the inner part of the tube contain-
the functionality of the enzyme and the vitality
ing the membrane (generally, it is the membrane
of the yeast, so temperatures of 37 C and pH
itself), whereas the membrane works as a selec-
above 5 are mainly used [50]. As an example,
tive barrier for the chemical species considered.
the final ethanol concentration in an SSF process,
The main application of the product removal
which uses wheat straw as raw material, gives a
from the reaction zone as it is produced is in
yield of 40 g/L starting from a concentration
reversible reaction. This is due to Le Chatelier-
of hexose and pentose sugars greater than
Braun principle (“If an external force leads to the
70% [12].
separation as a specified component from a system

FIGURE 19.7 From LCB to ethanol in SHF and SSF fermentation process.

IV. Selected examples and case history

 3. MR concept and technology 371

FIGURE 19.8 Differences among SSF, SSCF, and CBP processes.

at equilibrium, this system adjusts so as to minimize The thermodynamic equilibrium constant is

the effect of the applied force”), for which a product as follows:
removal leads to an enhancement of the reaction
½Cc ½Dd
efficiency. Keq ¼ (19.6)
From a chemical point of view, in an MR, ½Aa ½Bb
removing a species produced during the reaction and determines the maximum conversion of the
from the reaction zone reduces the reverse reac- reaction.
tion rate, which improves the overall conversion In particular, if the compound C is considered
rate of reactants [52]. to be the hydrogen molecule, the concept is well
If we consider a generic reversible reaction: shown in Fig. 19.10A, with Fig. 19.10B for a
aA þ bB ¼ cC þ dD (19.5) generic reversible and exothermic reaction.

FIGURE 19.9 Conceptual scheme of a membrane reactor configuration.

IV. Selected examples and case history

372 19. Novel bioethanol production processes and purification technology using membranes
FIGURE 19.10 Conceptual difference of a traditional reactor (A, left side) and a membrane reactor (B, right side).
In the case of a traditional (or conventional)
reactor, TR (Fig. 19.10A), the maximum limit of
the thermodynamic conversion, represented by
the red curve in both figures, makes it impossible
to have a chemical conversion higher than the
one suggested by the thermodynamic equilib-
rium. In the case of MRs, Fig. 19.10B, this limit
does not exist because the system is different
and thermodynamics is not applicable in the
same way like in a TR. In fact, the thermody-
namic equilibrium does not take place because
something is escaping from the system. So, in
the case of MRs, the system is an open structure
because part of the material (for example,
hydrogen, a product of the reaction) is escaping
through the membrane, and the maximum con-
version obtainable is higher than the previous
case, because of the Le Chatelier principle. In
other words, the reversible reaction is trans-
formed into an irreversible one. For example,
in Fig. 19.10A the maximum conversion at the
temperature X1 is around 50% (see X2 in the
thermodynamic curve); vice versa, at the same
temperature (X1) in Fig. 19.10B, the maximum
conversion is around 90% (see X3; see the curve
named “dynamic equilibrium”).
Anyway, from the figure, it is also clear that,
instead of working at the same temperature X1
to increase the conversion, an MR can work at
lower temperatures maintaining the same
IV. Selected examples and case history
conversion of a traditional reactor (see X2eX4).
Generally a compromise is chosen, so the
temperature is a bit reduced with a higher
reaction conversion with respect to a TR.
3.1 Main application opportunities of
using an MR
To extend the concept, there are also other
great opportunities in using MRs. Some of
them are resumed in Fig. 19.11, where four
different cases are considered. Two are related
to (1) the chemical conversion enhancement by
selective separation of a product of an equilib-
rium limited reaction and (2) conversion
enhancement by coupling of reactions. The other
two are related to (3) the reaction selectivity (to
be not confused with the selectivity of the mem-
brane), selectivity enhancement by selective
permeation of an intermediate product; and (4)
selectivity enhancement by dosing a reactant
through the membrane.
The first case is also called extractor mode: an
example is hydrogen selectively removed using
dense Pd-based membranes. Examples of chem-
ical reactions are water gas shift (WGS), steam
reforming of methane, steam reforming of alco-
hols (methanol, ethanol, etc.), decomposition of
H2S and HI, alkane dehydrogenation, etc.
 3. MR concept and technology 373

FIGURE 19.11 Main application opportunities of inorganic MRs: (1) conversion enhancement by selective permeation; (2)
conversion enhancement by coupling of reactions; (3) selectivity enhancement by selective permeation; (4) selective enhance-
ment by dosing of reactant.

The second case considers the coupling of
two different reactions in the two different
zones of the reactor: in one, for example,
hydrogen is produced and selectively trans-
ferred through the membrane to the other zone.
For example the WGS reaction in carried out
one side and the hydrogenation of benzene on
the other side. In this configuration, two
different reactions take place in the same reactor,
so energy can be transferred through the mem-
brane, if the two reactions are one endothermic
and the other one exothermic.
The third and the fourth cases related to the
selectivity enhancement of the reaction are
generally called distributor mode: it is impor-
tant for avoiding hot spots by dosing the
amount of a reactant; it also helps to extend
catalyst life. The reactant that could lead to un-
desirable or side reactions is added in a
controlled manner to the reaction zone. By its
gradual or distributed addition into the reactor,
its concentration in the reaction zone can be
kept at a low value along the reactor, and this
helps to prevent from its participation in the
undesirable reactions [53,54]. Examples of reac-
tions are partial oxidation, oxy-
dehydrogenation of hydrocarbons, oxidative
coupling of methane, etc.
There is also another case, called contactor
mode, where the membrane is the diffusion
barrier and is also catalytically active
(or intrinsically active). In this case, in the reac-
tion zone, the residence time is controlled by
tuning the pressure difference applied to the
membrane. Two cases can be distinguished:
- forced flow-mode, used with enzyme-
catalyzed reactions and oxidation of volatile
organic compounds;
- opposing reactant mode, used with partial
oxidations reactions.
To resume the main advantages of the inor-
ganic MR technology, considering for example
a pure hydrogen production, the main benefits
are as follows:
- chemical reaction and hydrogen separation
performed in only one system with a
consequent reduction of the capital costs;

IV. Selected examples and case history

374 19. Novel bioethanol production processes and purification technology using membranes
- conversion enhancement of equilibrium
limited reactions;
- higher conversions than TRs operating at the
same experimental conditions of MRs or, on
the contrary, the same conversion, but the
operatives are milder;
- improvement of both H2 yield and H2
selectivity;
- direct production of H2 with a very high
purity (in the case of dense Pd-based MRs).
3.2 Type of membrane used for inorganic
MRs
There exist many kinds of inorganic mem-
branes. Among them, particular attention is
paid to the dense Pd-based membranes because
of their full hydrogen perm-selectivity [55]. As it
is well-known, the hydrogen permeation
through dense Pd-based membranes follows a
solution-diffusion transport mechanism [56].
In the case of dense palladium (Pd) membrane,
it must be carefully stressed that at
T < 300 C the metal is exposed to a hydrogen
flow, so the embrittlement phenomenon takes
place in the metallic lattice after a few cycles
of a$b transitions of pure Pd [57e59]. These
transitions do not take place as a change of the
lattice structure: they only produce a dilatation
in the lattice. As a solution of this problem,
generally by alloying palladium with elements
such as silver, copper, or other metals, PdeH
phases show an increased reticular step and
FIGURE 19.12 Conventional multistage process for natural gas steam reforming and hydrogen separation/purification.
IV. Selected examples and case history
the ability of anticipating the reticular expan-
sion from hydrogen [60].
The behavior of dense Pd-based and porous
membranes has been studied since the 1960s,
when involved in MR applications for hydrogen
production, because the higher performance of
Pd membranes overcomes all the other materials.
This is due to both the high solubility of hydrogen
and the full perm-selectivity to hydrogen perme-
ation with respect to all the other gases.
4. MRs for bioethanol reactions to
produce pure hydrogen
Currently, most of the worldwide demand
for hydrogen comes from natural gas, which is
processed in TRs mainly via steam reforming
reaction, as well as partial oxidation and auto-
thermal reforming reactions. Today, 50% of
the global hydrogen is produced by natural
gas steam reforming reaction: although its
impact on the climate is considered quite nega-
tive due to the production of greenhouse gases,
it represents the most common process for the
production of hydrogen. The entire conven-
tional process to transform natural gas into
hydrogen involves four different systems:
one TR, two WGS TRs (high and low tempera-
tures), and a successive stage for the hydrogen
separation and purification, such as pressure
swing adsorption, preferential oxidation reac-
tors, membrane separation, etc. (Fig. 19.12).
 4. MRs for bioethanol reactions to produce pure hydrogen
From the point of view of the process intensifi-
cation strategy, a large number of scientific
works in this field evaluate the benefits in using
alternative solutions to the conventional pro-
cesses, such as the MRs for both producing
and simultaneously purifying hydrogen in
only one stage. In fact, using an MR, the four
systems reported in Fig. 19.12 are reduced to
only one.
During the last decades, MR technology has
been developed with the intention of producing
hydrogen based on ethanol as a renewable
source. As reported by Ref. [61] the number of
scientific studies per year focusing on hydrogen
production via ethanol steam reforming (ESR)
reaction combined with MR technology, with
respect to the total number of publications on
this field, with both TR and MR applications, is
dramatically increasing from time to time. The
same work also shows the various catalysts
and the percentage distribution of the principal
catalysts for ESR reactions in MRs. Among
others, Rh-, Ru-, Pd-, Pt-, Ni-, Co-, and Cu-
based ones are used in TRs and, in particular,
Ni and Ru-based catalysts are mainly used,
probably because they are cheaper than other
catalysts.
The catalysts performance evaluation has
been based on various parameters, such as H2
selectivity, ethanol conversion, and catalyst sta-
bility versus time. For example, following [51]
the catalysts used in ESR show, with respect to
the H2 selectivity on alumina supports, the order
of Co > Ni > Rh > Pt > Ru > Cu. Vice versa,
other researchers connecting the catalytic activ-
ity to the resistance of coke formation show
that the activity of metal-based catalysts has
the order of Rh > Co > Ni > Pd [62].
Anyway, also other chemical reactions, such as
preferential oxidation and autothermal reforming
of ethanol, are extensively used for hydrogen pro-
duction in MRs (see the recent [63]).
In fact, apart from the various kinds of cata-
lysts, recent papers [11,52,64e67] focused the
attention on ESR mainly considering the
IV. Selected examples and case history
375
influence of the feed molar ratio at low reaction
temperatures (400e450 C), using both porous
stainless-steel supported Pd-based and dense
self-supported PdeAg MRs.
In both types of supported and self-supported
inorganic membranes, the researchers pointed
out that higher pressures are able to favor the
so-called “shift effect” due to an increase of the
hydrogen permeation driving force. This results
in a greater removal of hydrogen from the reac-
tion zone to the permeate zone, as a COx-free
hydrogen stream.
To cite only a few examples [68,69] ESR reac-
tion was carried out with a steam-to-carbon molar
ratio in the range 3/1e12/1, using a supported
PdeAg MR packed with a RheLaAl2O3 catalyst.
At 700 C and 6.9 bar, this MR gives around 75%
hydrogen yield, while at 69 bar, it drops to 42%
due to an increase of methane yield.
Moreover, a PdeAg deposited on a porous
stainless-steel (PSS) membrane was studied by
Ref. [70] for performing the ESR reaction in the
MR. The membrane, prepared by the electroless
plating technique, was experimentally tested at
450 C, in the pressure range of 2.0e11.0 bar, us-
ing a CueZn/Al2O3 catalyst. A sweep gas
improved the H2 permeation driving force and
increased the H2 recovery.
In the field of oxidative ESR reaction [71], a
self-supported PdeAg MR was used. They
increased the oxygen content on the reaction
side (O2 over ethanol feed ratio > 1.3/1) and
confirmed that both H2 yield and H2 recovery
are reduced due to the fast oxidation reaction
of the hydrogen produced during the reaction.
At O2 on ethanol feed ratio equal to 0.6/1,
400 C, and 2.5 bar, w18% H2 yield and 30% H2
recovery is obtained.
The reaction of oxygen addition to ethanol
dehydrogenation was carried out by Ref. [72].
They used a laminated 25 mm PdAg membrane
foil and carried out the ethanol dehydrogenation
reaction at 350 C. It was observed that hydrogen
production decreases with increasing the oxy-
gen content in the feed. The researchers observed
376 19. Novel bioethanol production processes and purification technology using membranes
that, when oxygen is not supplied, the carbo-
naceous layer reduces drastically or does not
allow at all the hydrogen permeation. At oxy-
gen/ethanol feed ratio >1, the hydrogen perme-
ation is lowered by the oxidation reaction of
hydrogen, while at oxygen/ethanol feed
ratio <0.7, the carbonaceous layer is not fully
oxidized, but a constant hydrogen permeation
(and recovery) is obtained. Around 40% is the
best H2 yield.
Instead of using the highly expensive Pd-
based MR, other works on the ESR reaction
focused on the use of nonpalladium-based MR
to reduce the cost of palladium. As an example,
[73] carried out the ESR reaction at 350 C using
a silica-alumina composite MR, with a water/
ethanol feed ratio ranging between 3/1 and
13/1. Their membrane, prepared by chemical va-
por deposition technique, is not fully selective
to hydrogen permeation. In fact, it shows, at
350 C, a H2/CH4 selectivity ¼ 350, with an H2
permeance ¼ 108 mol/m2/s1/Pa1. At water/
ethanol feed ratio ¼ 3/1, H2 yield is more than
20%. This yield is improved as 10%e20% more
than that of a TR working at the same operating
conditions of an MR.
An important contribution to hydrogen pro-
duction carrying out the ESR reaction in an MR
technology is the one of [74], where a
nonpalladium-based MR for collecting hydrogen
with very low CO content (molar
concentration < 1%) is used. The membrane is
composed of SiO2 supported onto PSS and the
catalyst is RueSiO2. As a result, the stream
permeated through the membrane is rich in
hydrogen and CO, further converted via WGS
reaction to decrease the CO content under 1%
in the permeate side. At water/ethanol feed
ratio ¼ 5/1 and 600 C, the H2 recovery and the
H2 yield are 85% and 50%, respectively.
Concerning again the supported Pd-based
MRs, [47,48] obtained a complete ESR conver-
sion at 500 C, recovering a hydrogen stream
with a purity of 99.9%. These researchers used
a supported membrane in which a first layer of
IV. Selected examples and case history
palladium and gold were doubled on a PSS
support.
Yun et al. [75] were able to prepare an ultra-
thin supported Pd membrane (thickness 2 mm)
to be used in an MR for performing the ESR reac-
tion. In their work, high feed molar ratio, at mod-
erate experimental conditions (at 360 C; and
1 atm) resulted in a 70% ethanol conversion.
Other interesting experimental results were ob-
tained by Ref. [76] using a very thin PdeAg layer
(4 mm) deposited on PSS to obtain a composite
membrane. With this membrane allocated in an
MR, packed with a cobased catalyst, at 500 C,
a 100% conversion and 70% H2 recovery were
obtained. At milder temperature conditions
(400 C), Ref. [77] reached a conversion of 98%
and an H2 recovery of 65%, even though its pu-
rity was around 95% (this was probably due to
the presence of pin-holes and microcracks on
the Pd layer formed under experimental
operations).
Lin et al. [78,79] used two kinds of supported
membranes, NiePdeAg (8 mm thick) and Pde
Ag (20 mm thick) in an MR. The best result in
terms of ethanol conversion is 80% using the Nie
PdeAg MR operated at 450 C and 3.0 bar.
To resume, part of the specialized literature
about ESR and/or Bio-ESR reactions in MRs in-
volves dense unsupported Pd-based MRs. For
example, Basile and coworkers used various
full hydrogen perm-selective unsupported Pde
Ag membranes (50 mm thick) [52,64,65,71,80e82]
in MRs for pure hydrogen production from ESR
or Bio-ESR reactions, and they obtained various
experimental results, depending on both the cata-
lysts and the operating conditions. Their best
experimental result was achieved using a syn-
thetic bioethanol mixture, using a cobased
catalyst at 400 C, which consisted of a
complete (100%) ethanol conversion and 90% of
H2 100% pure recovered in the permeate zone
of the MR.
Recently, various researchers started to
consider the need for coupling green processes
and bio-derived sources, so a growing attention
 4. MRs for bioethanol reactions to produce pure hydrogen
was paid to the hydrogen generation using biogas
[83]. As a versatile raw feedstock, biogas could be
considered an alternative to natural gas exploita-
tion, thereby helping to reduce the greenhouse
gas emissions. Its composition depends on the ty-
pology of residual biomass (sewage treatment
plants, industrial wastewater, among animal
waste, and so on) used during the various anaer-
obic digestion processes. Nevertheless, biogas
has main components of methane and carbon di-
oxide, including traces of H2S, NH3, hydrogen, ni-
trogen, oxygen, and steam.
Regarding the integration of biogas reform-
ing with MR technology, at this moment (year
2019), unfortunately, only a few works are pub-
lished in the specialized literature. For example,
Ref. [63] report the performance of a limited
number of applications in this interesting and
new research field. In their book chapter, the
authors show that only [84] used a supported
Pd/Al2O3 membrane (Pd layer of 7 mm) for car-
rying out the biogas steam reforming reaction
in an MR. These authors obtained at quite mod-
erate experimental conditions (450 C and
3.5 bar) a CH4 conversion around 30%, an H2
recovery of 70%, 96% in concentration. In
all the other cases, thick unsupported Pd or
PdeAg dense membranes were used, favoring
a recovery of a high-grade hydrogen stream
(nearly 100% in purity) with conversions
around 90% [85], but using high temperatures
(700 C).
The other recent literature in this field is more
concentrated on biogas steam reforming in TRs
[86e89] and, concerning the MRs development,
on methane/natural gas steam reforming reac-
tion [63].
Bioethanol is also produced using a large
number of other membrane technologies. In
fact, compared to other separation techniques,
the main attractions of membrane separation
processes in biorefining and bioenergy produc-
tion are a very low energy consumption, a very
IV. Selected examples and case history
377
high separation efficiency, a reduced number of
processing steps, and high quality of the final
product.
Among the specific membrane processes that
are of particular interest for biorefining and bio-
energy production, these can be cited: diafiltra-
tion (DF), membrane distillation (MD),
microfiltration (MF), nanofiltration (NF), perva-
poration (PV), and ultrafiltration (UF).
In particular, MF, UF, and NF use porous
membranes driven by hydrostatic pressure,
whereas PV uses nonporous membranes driven
by a chemical potential gradient, while MD
uses porous hydrophobic membranes driven
by a thermal gradient.
Examples of specific applications can be cited:
- Acetic acid production (MF, UF)
- Biodiesel production (MF, UF, NF)
- Bioethanol production (PV, MD)
- Biogas production (MF, UF)
- Biooil production (MF)
- Dehydration of bioethanol (PV)
- Enzyme recovery (MF, UF)
- Fermentation inhibitor removal (NF)
- Lignin and hemicellulose recovery (MF,
UF, UF)
The recent excellent review of [10] discusses in
detail and in-depth the current knowledge
regarding application of many of the cited mem-
brane technologies to biorefining and bioenergy
production. This paper also introduces pervapo-
ration membrane bioreactors (PVMBR) and mem-
brane distillation bioreactors (MDBR) as potential
integrated technologies for bioethanol produc-
tion. Among the various membrane techniques
to improve the operation of the ethanol-water
separation include MF of the broth before the
distillation (and PV, in a hybrid system) and MD.
Anyway, whereas the benefits of introducing
these techniques are well recognized, extensive
research is still needed to scientifically and
economically justify their applications. A
378 19. Novel bioethanol production processes and purification technology using membranes
tentative economic assessment demonstrates
that the application of process improvements
can lead to production cost savings of w11%
[10]. So, further research of the different alterna-
tives, preferably on pilot or large scale, appears
economically and technically justified [2].
In particular, the distillation through mem-
branes allows selective mass transport of specific
components from a mixture, making this tech-
nique useful in wastewater treatment, desalina-
tion of seawater, dairy processing, and
separating volatile components. The paper of
[39] is an excellent review that concentrates on
the discussion on the various aspects related
the bioethanol production. They consider criti-
cally the existing variance of second-generation
bioethanol production methodology. In the pa-
per, a section is entirely dedicated to MD tech-
nique, which holds several benefits: it works at
lower experimental conditions (T and P), perfect
theoretical separation, and fewer mechanical
property requirements. As drawbacks, MD is
impractical once it is installed on a commercial
scale, which is namely due to the heat loss and
module design that further expand the cost
inefficiency.
The biohydrogen can also be obtained using
an anaerobic membrane bioreactor (AnMBR).
In fact, another important field of hydrogen pro-
duction is the use of bioreactors. In this case, sci-
entists speak about “biohydrogen.”
Biohydrogen can be produced by several bio-
logic ways, for example, photodecomposition
of organic compounds by photosynthetic bacte-
ria (photofermentation), biophotolysis of water
using algae and cyanobacteria, and fermentative
hydrogen production from organic waste
streams.
Anyway, in all these cases, there is not com-
plete conversion, and there are low yield and
low generation rates. To bypass these drawbacks
the concept of a bioreactor combined with the
use of membranes seems to be the most prom-
ising solution. In this integrated system, mem-
branes separate liquid from biomass and retain
IV. Selected examples and case history
biomass effectively in the bioreactor with the
potential benefits for the bioprocesses where
product formation separation is desired simulta-
neously in a compact system.
An excellent review of these aspects was
recently proposed by Ref. [90] where recent
advances and emerging issues associated with
biohydrogen generation using MBR technology
are deeply and critically discussed. Several tech-
niques aimed at overcoming these barriers are
highlighted. Moreover, environmental and
economical potentials along with future research
perspectives are addressed to better drive bio-
hydrogen technology toward the necessary prac-
ticality and economical-feasibility aspects. The
main conclusion of the authors is “Considering
the practicality and economic feasibility of bio-
hydrogen generation with AnMBRs, technology
breakthrough must be sought to refine better perfor-
mances in terms of reduced energy consumption
and fouling; extract most of hydrogen from substrate
and scaling up of the long-term steady state
operation.”
5. Conclusion and future trends
As seen in this chapter, the choice of the right
raw material combined with the right produc-
tion process is a key objective of all researchers
in the sector.
Process optimization means obtaining bio-
ethanol productivity optimization reducing
costs. Currently the most used raw materials
for the production of bioethanol are the first-
generation feedstocks, but new technologies are
pushing toward a new direction: agricultural
and urban wastes. Production costs remain un-
competitive compared to those of the first gener-
ation, but bioethanol produced from wastes has
the great advantage of being independent of the
costs of the raw materials market. Furthermore,
the use of this type of raw materials will be one
of the resolutions of the problem of disposal of
urban waste. Looking further still, marine
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