Renewable and Sustainable Energy Reviews 64 (2016) 518–530

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Renewable and Sustainable Energy Reviews

journal homepage: www.elsevier.com/locate/rser

Lignocellulosic bioethanol: A review and design conceptualization

study of production from cassava peels
Ademola Adekunle n, Valerie Orsat, Vijaya Raghavan
Bioresource Engineering Department, McGill University, Canada

art ic l e i nf o a b s t r a c t

Article history: The importance of lignocellulosic biomass as important bioresources that can be utilized in many forms
Received 4 July 2015 has increased in the last few decades. Cassava peels, a lignocellulosic biomass discarded during cassava
Received in revised form processing, are commonly found in the tropics and several other countries around the world due to the
9 March 2016
popularity of cassava as an important calorie source. Interestingly however, a lot of energy deprived, oil
Accepted 26 June 2016
Available online 7 July 2016
dependent countries are also amongst the highest producer of this biomass. Hence, this review explores
the suitability of cassava peels as a lignocellulosic biomass substrate for the production of bioethanol.
Keywords: Special consideration to the properties of the biomass drive the conceptualized plant design while
Cassava peels conditions for optimal production and salient economic considerations are discussed. A cellulosic bior-
Lignocellulosic
efinery of this type is expected to help in harnessing the presently improperly managed agricultural
Bioethanol
processing byproduct with a view to reducing dependence on fossil fuels, which are totally non-re-
Wastes
Renewable energy newable and have damaging effects on the environment especially in developing countries.
Process design & 2016 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 518
1.1. Current status . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 519
1.2. Potential of Cassava Peel as a feedstock for bioethanol production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 520
2. Design of a bioethanol generation plant using Cassava Peel as a feedstock . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 521
2.1. Storage of biomass. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 521
2.2. Pre-treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 523
2.3. Hydrolysis and fermentation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 523
2.4. Extraction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 525
2.5. Optimal conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 526
3. Economic considerations. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 527
4. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 527
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 528

1. Introduction economically sustainable, has led to a quest for renewable sources

The use of cheaply available fossil feedstock for cooking and
heating, as well as in the production of many beneficial products
was a turning point discovery for mankind. However, the realiza-
tion that the supply of the fossil feedstock is limited, and the fact
that the products are not environmentally, ecologically or
n new technologies adapted to biofuels are ongoing in several parts
Corresponding author.
E-mail address: ademola.adekunle@mail.mcgill.ca (A. Adekunle).
of energy globally in recent years [1]. The discovery of biofuels has
helped a great deal in alleviating some of the problems identified
with fossil fuels such as global warming as well as provide income
and employment opportunities in rural areas.
First generation biofuels were produced from food crops and
were usually blended with fossil-fuel-based fuels for use in ex-
isting internal combustion engines. However, the developments of
of the world. This generation of biofuel has been commercialized

http://dx.doi.org/10.1016/j.rser.2016.06.064
1364-0321/& 2016 Elsevier Ltd. All rights reserved.
 A. Adekunle et al. / Renewable and Sustainable Energy Reviews 64 (2016) 518–530
in several economies with an average of 859,000 barrels produced
daily as of 2012 [2]. However, there are concerns amongst en-
vironmentalists, food technologists and other scientists regarding
first generation biofuels [1]. The limitations identified for first
generation biofuels include their competition for land and water
that could have been used for food, their need for government
subsidies without which competition with petroleum products
would be impossible and the fact the net greenhouse gas emis-
sions associated with their production approaches that of fossil
fuels [3].
The reasons highlighted above have led to the use of waste
biomass for fuel production, where residues of crop cultivation
(stem, peels, leaves), crops which are generally not used for food
as well as industrial wastes are employed in the production of
biofuels. The fuels thus produced are termed second-generation
biofuels and are produced by the release of the sugar locked in the
lignin, hemicellulose and cellulose matrix of the feedstock. This
sugar is then processed into bioethanol using the same methods
used for first generation biofuel production. Examples of second-
generation biofuels are cellulosic ethanol and Fischer–Tropsch
fuels [4].
1.1. Current status
Generally speaking, bioethanol is a liquid biofuel, which can be
produced from several feedstock and through several conversion
methods. It is an attractive energy source because of its renew-
ability, as well as its ability to reduce particulate emissions in
compression-ignition engines [5]. The high octane number,
broader flammability limits, higher flame speed and vaporization
heats are particular characteristics of this liquid which enables it
to compete with fossil fuels on an efficiency level [6]. However,
bioethanol's disadvantages include its high corrosiveness, low
flame luminosity and vapor pressure and miscibility with water.
The total production of ethanol fuel surged to 84.6
109 L in 2011
with the United States accounting for 62.2% of the global
Glucose Fermentation
Yeast
First Generation Biofuel Pathway
Lignocellulosic Glucose
Biomass
Fermentation
Carbon Dioxide
Second Generation Biofuel Pathway
Fig. 1. First and second bioethanol processing steps.
519
production and followed by Brazil with 21.1
109 L [7]. Both
countries exploit corn and sugar cane respectively for their bioe-
thanol production. The top 10 nations producing bioethanol use
them as a blend and as such cannot be referred to as totally oil
independent, however the gains from bioethanol usage span the
economic, environmental and energy nexus [8,9]. A typical case
study can be seen in Brazil [10] where the production of bioe-
thanol is with an energy balance of at least 9:3, there was no
significant change in land use, a GDP increase by as much as 35%
and a greenhouses gases reduction by as much as 86% [10] were
recorded. In general, the reduction in importation dependency,
increase in local jobs, agricultural developments have positive
implications for the economic development of bioethanol produ-
cers. The environmental gains will also include proper sanitation
and the reduction of wastes contamination (where agro-residues
are used) while the security stemming from the renewability, re-
liability of this energy source are one of the many reasons for
encouraging research into the production, commercialization and
adoption of bioethanol production.
Second-generation bioethanol is produced from the treatment
of lignocellulose biomass, which is comprised of lignin, cellulose
and hemicellulose [3]. These polysaccharides are hydrolyzed into
sugars — mostly pentose and hexoses — which are then fer-
mented by the enzymes of specific organisms into ethanol. It can
thus be inferred that the difference between the first-generation
and second-generation biofuels is the hydrolysis of lignocellulosic
plant material into sugars. Fig. 1 shows the different pathways for
the production of the first-generation and second generation
biofuels [11]. It is pertinent to note that not only is the cost profile
for obtaining the feedstock for the second generation bioethanol
less than that of the first generation bioethanol, it also does not
require agricultural intensification as it is mainly supported
through by-products. It has often been said that second generation
biofuels are produced from biomass in a more sustainable fashion,
which is truly carbon neutral or even carbon negative in terms of
its impact on atmospheric carbon dioxide concentrations [12].
Bioethanol
Recovery
Distillation
Carbon Dioxide
Saccharification
(Hydrolysis)
Bioethanol Recovery and
Bioethanol
Distillation
520 A. Adekunle et al. / Renewable and Sustainable Energy Reviews 64 (2016) 518–530
Three different categories have been established for the clas-
sification of the sources of lignocellulosic biomass for ethanol
production [4]
 Forest residues: This includes wood and straw from paper and
pulp production
 Dedicated agricultural crops and short rotation crops such as
switch grass Panicum virgatum L. and Miscanthus
giganteus.
 Secondary or tertiary wastes such as municipal solid wastes, food
from processing industries and animal manure.
Lignocellulosic biomasses have been noted to have environ-
mental and productivity benefits over the agricultural crops uti-
lized in the first generation biofuel production process. An ex-
ample is seen in the short rotation crop, Miscanthus, which can
yield up to 40 Mg ha  1 y  1, whereas the yield for corn feedstock
may be as low as 7 Mg ha  1 y  1 after due consideration of the
starch content of the total mass produced [13]. In terms of energy
balance, second-generation biofuel feedstock has been docu-
mented to have a very high ratio of output when combusted to
input (i.e., planting, drying, fossil fuel usage, etc.), as analyzed by
[13]. The carbon balance output to input ratio of the feedstock for
second-generation feedstock is also very high, further emphasiz-
ing its ability to reduce atmospheric carbon dioxide. Harvey [14]
reported the very high carbon balance ratio of 53:1 for Miscanthus,
which implies that Miscanthus absorbs 53 parts of carbon from the
environment for every one part of carbon input. Several studies
have shown that most forms of lignocellulosic biomass are able to
sequester large amounts of carbon dioxide underground. Mis-
canthus for example is able to sequester 7–9 Mg C ha  1 in the soil
for the first 4 years after cultivation [13]. It has been noted that
lignocellulosic ethanol has a higher emission savings when com-
pared to bioethanol from starch. Ryan [15] showed that for every
1000 L of lignocellulosic bioethanol there is an approximately
2.6 Mg carbon dioxide emission savings, whereas only 0.4 Mg of
carbon dioxide are saved when producing bioethanol from starch.
It has also been highlighted that the combustion of cellulosic
ethanol produces 75% less carbon dioxide compared to 60% re-
duction for first-generation bioethanol [16]. This calculation takes
into account the full-life cycle emission from the growing of the
crops to the combustion. The reduction of fertilizer use for the
crops specified for bioethanol production as well as increased
carbon sequestration of the plants grown specifically for second-
generation biofuels is a major contributing factor to this phe-
nomenon. However it is critical to state that the Brazilian su-
garcane (Saccharum officinarum L.) ethanol has the largest carbon
savings of all because of the efficiency of the process of producing
it. These distilleries utilize sugar cane bagasse and straw as a
source of electricity and heat generation and as such are self-
sustaining, which translates to zero-dependence on fossil fuels,
which would have otherwise reduced its carbon savings [13].
Despite all the challenges associated with second generation
biofuels such as cost of technology: [17,18], environmental de-
gradation: [19,20], biomass availability, limited flexible vehicle
development [21] and supply chain, continuous progress are being
recorded annually. This promises a positive future for the com-
mercial development and deployment of such fuels, especially
given the active research and development that is occurring. The
private sector is leading research by funding many initiatives to
improve the efficiency of the conversion process, especially in
terms of the development of enzymes. This is especially true for
traditionally fossil fuel companies such as Exxon, Chevron, Shell,
BP, ConocoPhilip who contributed an upward of $2 billion towards
research and development [22].
There are several conversion processes for the extraction of
bioethanol from biomass. These can be broadly classified as
mechanical, thermochemical and biological conversion processes
[12,22]. However for the purpose of this review, the biological
conversion process will be discussed, as it focuses on the organic
content extraction more than other conversions methods [23].
However it is important to note that there is still a need for more
research and developmental work to be done before this process is
widely adopted. The biological conversion process employs the
uses of enzymes to break down the cellulose for the subsequent
production of ethanol from the lignocellulosic material. The lig-
nocellulose in the biomass is fractionated into sugars, which are
then fermented into ethanol, or other solvents, as desired. This
process [15] is the basis for the cassava peel biofuel plant con-
ceptualized in this review. The structural units of cellulose,
hemicellulose and lignin are the main components of lig-
nocellulosic biomass and the conversion of these materials to
ethanol is more complex than the methods applied to pure starch
feedstocks (Naik et al., 2010). The major processes include a pre-
treatment of the biomass, which extracts the xylose from the
hemicellulose and lignin. The xylose is processed to ethanol while
the lignin is further treated to produce other fuels. The crystalline
cellulose remaining after the pre-treatment process is then broken
down to glucose by an enzymatic hydrolysis process. The ethanol
produced can be blended with gasoline, as is being done in several
OECD countries in order to produce oxygenated fuel, and lower
hydrocarbons, which will eventually reduce greenhouses gas
emissions.
1.2. Potential of Cassava Peel as a feedstock for bioethanol
production
Cassava is a very important food crop in the tropics. It is a very
good source of calories and also a very good source of income, as
cassava-producing countries export its products. Nigeria, Brazil
and Thailand are, in descending order, the largest producers of
cassava in the world. Nigeria in fact produces more than 53 million
tonnes per year of cassava and more than ten products that can be
derived from the cassava roots. In processing these food products,
the biomass that is left behind includes peels, leaves and roots, and
in almost all cases, this biomass is not used for any economical
purposes [24]. Apart from the roots that may be used for re-
planting and as a fertilizer, the peels are usually disposed of in-
discriminately, thus leading to environmental degradation and
thus provides an opportunity for bioethanol production. In the
best cases, the current uses of cassava peels include potential re-
placement for maize in animal feed especially for animals. How-
ever, the drawback of this is that due to their low ( o6%) protein
content [25], it is not recommended beyond a certain level in
animal feed. Regardless, the considerable effort that has been put
forth to process these peels into feeds for ruminants has been
hindered by the presence of anti-nutrients such as hydrocyanic
acid, tannic acid, oxalate, etc. [26]. Moreover, the lack of estab-
lished process for utilizing these feed as well as industrialization of
animal feed production in cultivation areas mean that a large
percentage of these cassava peels are simply discarded-. Several
research articles have examined the possibility of cellulosic etha-
nol production and the results have been positive except for
concerns that the amount of biomass produced cannot sustain the
production of bioethanol for commercial usage [23]. They also
noted that the inexpensive nature of the base raw material will
further improve its suitability for this purpose. The choice of
feedstock for bioethanol production in this case depended on the
combination of its availability, cost, and competition between its
present uses. The composition of the peel of the sweet cassava
variety ADP 3(4) which is one of the most widely grown in Nigeria
(the highest producer in the world), is shown in Table 1; further
emphasizing the suitability of this product for biomass production.
 A. Adekunle et al. / Renewable and Sustainable Energy Reviews 64 (2016) 518–530
Table 1
Composition of the sweet cassava variety ADP 3(4).
Category
Organic Content Carbohydrate
Protein
Fat
Crude fiber
Ash
290
270
Production (million tonnes)
250
230
210
190
170
150
1990 1995 2000 2005 2010
Year
Fig. 2. World cassava production 1993–2014.
The availability, supply chain of cassava peels is tied into that of
cassava processing. From the latest data available, the world pro-
duction of cassava was over 230 million tonnes annually as at the
end of 2013, representing over 61% increase over the last two
decades [27]. With the peels making up about 5% of the total
weight of the cassava root and this percentage likely increase to
about 10–20% due to inefficiency in peeling, [28] it is easy to cal-
culate that the waste produced totals would be over 14 million
tonnes annually and as world production continues to increase
(Fig. 2), this potential continues to increase. The supply chain of
the cassava peels for bioethanol production will tap into a typical
supply chain of cassava [29] as it moves from the producers to the
processors. From the farming field, a supply is usually generated to
either large or small scale industrial processors with a small
overall percentage being done on a subsistence level. In order to
sustain the level required for the adequate generation of bioe-
thanol, the major supply levels for the plants will be the peels that
can be collected from the large or small scale processors and
bioethanol production cycles can be planned for based on the
production activities of the established processing plants. In ad-
dition, a further stream of raw materials can be generated when
incentives are given to the subsistence level producers who are
generally in the lower income cadre and who by bagging an
otherwise dumped by-product, can generate further income. The
details of such a supply chain is represented succinctly in Fig. 3.
These two positive outlook on the availability and supply chain
enhances the bioethanol producing potential of cassava peels
commercially. Biologically, this process is also improved by the
relatively easy hydrolysis of the biomass as well as the high dry
matter content [30]. This potential has been examined in previous
works where as much as 8% [31] increase in yield was obtained
when the unpeeled cassava roots were used vis a vis the peeled
roots and this result is similar to the 8.5% yield obtained when
cassava peels were directly explored for bioethanol production
[32]. However 60.2% yield [23], 70% yield [33] and as much 83%
yield [34] can be obtained when the process is optimized. At a
density of 0.2511 g/cm3 f[35] for cassava peels, this corresponds to
approximately at least 114 L of bioethanol per ton of cassava peels
using the worst case scenario. As production from the peels alone
521
(w/w)
73%
6%
3%
5%
7%
Fig. 3. A supply chain for the supply of cassava peels as feedstock to the bioethanol
plant.
does not stress the food supply balance, it is a better alternative to
producing from the cassava pulp itself. In addition since devel-
oping countries where energy crises are particularly acute also
2015
tend to rely heavily on agricultural production, they
have access to a potentially large source of organic waste such as
the cassava peels. Thus the possibility for a successful break-
through in the usage of the cassava wastes is highlighted by the
fact that the countries with the highest production are also some
of the countries with one of the most acute energy shortages as
depicted in Fig. 4.
2. Design of a bioethanol generation plant using Cassava Peel
as a feedstock
The direct needs of a biorefinery plant spans from storage of
the raw materials to actual characterization of the produced bio-
ethanol. As a biological conversion of biomass will be adopted for
this conceptualized design. A review of the available methods for
each critical design step is done followed by a proposal of an op-
timal process step taking into consideration the characteristics of
the cassava peels.
2.1. Storage of biomass
Biomass generally does not flow as natural oil or gas would,
absorbs moisture and may degenerate in storage leading to a loss
of energy. This stage is thus as important as almost all the stages of
the bioethanol production. It is generally important that the sto-
rage facility be well designed to keep this biomass in good con-
dition and be easily accessible, either for delivery or actual usage
without requiring extra cost in labor or energy input. The chal-
lenges that usually need to be addressed during storage planning
include planning for storage as most lignocellulosic biomass are
low-value, high volume products and as such will require large
storage spaces. Dry matter loss also needs to be prevented, and
long term safety needs to be ensured [36]. However, one inter-
esting characteristics of cassava is that it can be grown all year
round and this removes the seasonal availability and extreme
storage space requirement problems from the supply chain
thereby enabling the development of a robust storage model.
In general storage location options for biomass can span from
on-field [37–40] to intermediate [37,41,42] to plant-site storage
location options [42,43] and sometimes a multi-biomass storage
solution [41]. However in most cases, what is chosen is usually the
lowest possible cost solution, which without proper consideration,
may have a negative effect on the total system cost [44]. An
522 A. Adekunle et al. / Renewable and Sustainable Energy Reviews 64 (2016) 518–530

Fig. 4. Cassava peel bioethanol potential. (A) Energy poor countries. (B) Cassava producing countries.

analysis of the three dominant options has shown that indeed the
lowest cost storage method is the most efficient solution although
care has to be taken as this option increases health safety and
technological risks [44]. The eventual storage option also has im-
plications for the net energy and emissions of the produced lig-
nocellulosic ethanol. Depending on the goal of the storage as re-
gards moisture i.e. wet or dry storage, the options available for
lignocellulosic biomass storage can be silages, bail silage, indoor
large round/square bales, covered large round/square bales, un-
covered large round/square bales [45,46] or frozen [47]. Dedicated
crops such as grass crops are easily stored in bales which can ei-
ther be large round bales (LRB) or large square bales (LSB) [45].
The cost of storage in these types are generally low and although
handling is quite manageable for both uncovered platforms and
platforms, the critical downside is that they presents problems in
the high loss of dry matter and quality [36]. Moreover, the un-
covered forms can create health hazards and open fires from self-
ignition and hence it is generally discouraged if other options can
be explored with the same means [44]. On the other hand, al-
though steel and concrete bins are expensive to build, they are the
more suitable for ground/chopped biomass pellets because they
present the lowest dry matter and quality loss [36]. Therefore for
biomass with 50% to 70% moisture content, anaerobic storage in a
silage is recommended as the conditions in the silos can engender
a self-preserving environment [48]. Even for dedicated biofuel
crops, silage has been shown to result in a density and
 A. Adekunle et al. / Renewable and Sustainable Energy Reviews 64 (2016) 518–530
composition for stored biomass that are generally attractive to
biofuel producers [49]. Another option for storage involves LRBs in
low-moisture silage which can be utilized when the crops are
dried to or have a moisture content of 30–50% and are wrapped in
low density polyethylene (LDPE) [50,51].
Cassava peels have a moisture content of between 68–75%
depending on variety [52] and as can be confirmed from a review
cassava peel biomass characteristics in storage [52] the optimal
process for storage of this lignocellulosic biomass would be silage
which can be done after proper drying and chopping. Under the
anaerobic conditions of the silos, the effect of microorganism ac-
tion altogether present a combined and storage and pretreatment
benefits which requires less energy, costs [53] and which affords
easy handling [36]. Therefore for this process step, the peels col-
lected from the cassava root processing plants can be subjected to
a few treatments and stored in silos. However due to the presence
of cyanide in the peels, they are should first be soaked for at least
5 h to allow for effective removal of the contaminants [54]. In
preparation for storage, the peels can be dried with an industrial
desiccator before being chopped and ground by a hammer mill as
this will increase the surface area of the peels for subsequent
chemical reactions, reduce dry matter loss [36] as well as increase
the cellulose digestibility during pre-treatment. This is in adapting
the centralized-storage chopping/milling pattern which has been
described as the least expensive particulate size reduction method
[55]. The ground biomass can be stored in a typical concrete or bag
silo, which for example can have a horizontal orifice and an ex-
panded flow pattern for the discharge of materials and literature
shows that a recommended safe moisture content for storage will
be 10–12% [28]. An easy method of assessing the bulk solid char-
acteristics depending on the particle sizing and other behaviors
can be adapted from similar tests [56] as this can further improve
operations and the biomass handling for bioethanol production.
2.2. Pre-treatment
Pretreatment of biomass for the reduction of biomass recalci-
trance is a necessary step for bioethanol production [57]. This step
is vital in order to increase the availability of sugars that can be
biologically hydrolyzed. Biological hydrolysis is supported by lit-
erature due to the advantages it offers in higher yield and energy
input requirements. [58]. The polysaccharides in the lig-
nocellulosic biomass needs to be broken down into the corre-
sponding monosaccharides in order to increase availability for
hydrolysis. Therefore, cassava peels need to be pretreated in order
to unlock its cellulose and hemicellulose component [59] which
makes up more than 50% of its dry weight (Table 2) [60]. Pre-
treatment is also responsible for a reduction in the degree of
polymerization (DP) as it affects enzymatic hydrolysis yield which
can see an increase up to 200% [61]. There is always a need to
ensure that adequate sugars are formed, carbohydrate loss and
Table 2
Average proximal composition of cassava peels.
Parameters Percentage
Dry matter 30.13
ASH 7.00
Crude protein 3.5
Crude fiber 10.0
Ether extract 12.00
Neutral detergent fiber 52.00
Acid detergent fiber 25.00
Acid detergent lignin 11.00
Cellulose 14.00
Hemicellulose 27.00
523
formation of inhibitory products are avoided while cost effec-
tiveness is retained [62]. In general, the most common pretreat-
ments methods used in lignocellulosic bioethanol production are
classified into three: dilute acid pretreatment, hydrothermal pre-
treatment and alkaline pretreatment [58]. A summary of the
comprehensive literature review [58,62–99] of the commonly
available and leading methods was done in this study and is pre-
sented in Table 3. However as reviewed in literature, the key fac-
tors necessary for choosing an effective pretreatment of a lig-
nocellulosic biomass include substrate type [73,100], digestibility
aim [101], level of sugar degradation [68], level of inhibitors pro-
duced, costs, waste residues produced, fermentation compatibility
and power requirements [68]. The results of this important step
has implications for the other stages of the process. Particularly,
the factors that define a particular pretreatment method can be
classified into two broad categories. The first category are those
fact with a positive correlation i.e. increase in these factors is a
positive development e.g., the degree of polymerization [94],
available surface area [68]. The second category of factors have a
negative correlation, i.e. a reduction in these factors is better for
the process e.g. lignin formation or removal [102], hemicellulose
content [103], particle size [62] and other factors like porosity, cell
wall thickness [68]and change in accessibility with conversion
[103].
Next to the biomass storage option, if not properly managed,
this process step has the propensity to increase the setup costs for
a bioethanol processing plant. For the cassava peel process, a
catalyzed steam explosion is preferred over the LHW pretreatment
which requires more water and energy requirement and is
therefore unfavorable for commercial scale development. In
making this selection, energy availability and water requirements
in the cultivating areas of cassava, with the potential of commer-
cialization, are the predominant factors. In the proposed process
design, the ground cassava peel can unloaded and subsequent
delivery into a pressure chamber for a catalyzed steam explosion
(CSE) treatment. The CSE procedure is proposed for the cassava
peel pretreatment as it has been shown in literature that the ad-
dition of the catalyst during this step can lead to a significant in-
crease in sugar yields [104]. In this procedure, steam at high
temperature is introduced into the reactor for about 5 min (usually
at a temperature of about 433 K at a pressure of 1.5 MPa). The
subsequent rapid reduction in pressure causes an expansion of the
lignocellulosic matrix, thereby leading to a separation of individual
fibers [13]. A dilute acid sulfuric acid catalyst can employed as it is
inexpensive and can also reduce the xylose content by as much as
90% [6,105], all of which have positive effects on ethanol yield. The
end of the exposure marks the end of the cassava peels pre-
treatment stage and this is a very important stage ensure an op-
timal yield of ethanol yield [106].
2.3. Hydrolysis and fermentation
The next stage after the exposure of the cellulose accomplished
by the pre-treatment stage, is hydrolysis. In this stage, the cellu-
lose is completely broken to reducing sugars and glucose [62].
There are two leading hydrolysis categories are acid (dilute and
concentrated) hydrolysis and enzymatic hydrolysis [107]. It is the
residence time and acid concentration that basically distinguishes
the two options for acid hydrolysis [106]. For enzymatic hydrolysis,
cellulose enzymes are produced or acquired for the breakdown of
the exposed cellulose [62]; the hydrolysis option with great po-
tential for cost reduction and technological improvements [108]. A
literature review of these available options as well as bibliographic
analysis of the options is summarized and presented for easy re-
ference in Fig. 5. Although the CBP process is the most preferred
process with the best efficiency, the simultaneous saccharification
524 A. Adekunle et al. / Renewable and Sustainable Energy Reviews 64 (2016) 518–530

Table 3
A summary of available pre-treatment methods.

Dilute Acid pretreatment (DAP) Hydrothermal pretreatment Alkaline pretreatment

General  Temperature range of 120–-210 °C 
Characteristic [64–67]  Liquid Hot Water (LHW) or Steam Explosion
 Acid 4 wt%; varying residence time
[64]  LHW: 160–240 °C water cooking, optimum
 Expensive special reactors, in-
expensive dilute acid use and neu-
tralization [64–67].
 Cellulose yield can be up to 88% [68]
Hemicellulose  Xylan hydrolyzed to fermentable  LHW: Water acidic OH  removal, mass transfer 
behavior glucomannan [81]
 High severity leads to less residual
xylan, low severity leads to xylose
[82–84].
 Increase in inhibitors due to the
formation of pseudo-lignin at high
severity [83]
Cellulose behavior  Crystallinity increases [61,94]
 Reduction in degree of polymeriza-
tion (DP) until leveling-off-degree
polymerization is reached [82,95].
Water (liquid/vapor), pressure, high temp
(SE) major types
under 220 °C [60], cellulose conversion yield
up to 96% [69],
 SE: High pressure treatment, and rapid reduc-
tion, 160–210 °C, 0.69–4.83[56] MPa, inexpen-
sive acid (catalyzed SE- CSE); Cellulose yield
may be similar to LHW [70]
 No special requirements or special require-
ments [71]
effect significant, time and temp. dependent,
less inhibitors produced [85–87]
 CSE: Similar to DAP [52]
 USE: Initial xylan removal increase and sub-
sequent reduction, increase in pseudo-lignin
[88–90]
 LHW: Increased crystallinity with severity, DP  AlB: Decrease in DP and increase in surface area,
reduces until a LODP like DAP [82,95], No
pseudo- lignin [52]
 CSE: Similar to DAP[52]
 USE: Cellulose least altered[96], increased crys-
tallinity up to 45% before reduction [97].
 NAOH or CA(OH)2 based (AlB) or ammonia based:
Ammonia Fiber Explosion Pretreatment (AFEX);
Ammonia Recycled Percolation (ARP); [72]
 Low temperature req, time, alkali load critical
factors, salt formation and incorporation can pose
a problem, expensive [57,73,74]
 AlB: Inexpensive lime preferred [57,75]. Cellulose
conversion yield up to 98% [76]
 AFEX: 40–180 °C, liquid anhydrous ammonia, high
pressure combined with swift reduction, not sui-
table for high lignin content [77,78]. Up to 97%
cellulose yield [79].
 ARP: fixed temp (140–210 °C), ammonium through
column reactor [77,80], cellulose yield up to 93%
[77]
AlB: Solubility and produced inhibitors lesser than
in DAP [91,92].
 AFEX: Minimal inhibitor production, lowest across
all classes [93].
 ARP: Delignification and solubilization, minimal
inhibitors [61].
increase in crystallinity, dilute alkali better results
[61,98],
 AFEX: Lowest impact on DP [61], decrystallisation
[61,99].
 ARP: Low impact on DP, crystanility index in-
creases [61,77]

and fermentation (SSF) process pathways when enzymatic hy-
drolysis is carried out appears to be the most explored option for
bioethanol production in recent years as can be seen from a con-
cise bibliographic information in recent years. This SSF is an ex-
ample of technological process improvement that has been
achieved with the eventual destination believed to be the con-
solidated bioprocessing (CBP) [62,108] although not much pro-
gress has been made in this regard. The separate hydrolysis and
fermentation (SHF) method, processes the hydrolysis and fer-
mentation at the optimal condition but the chance of con-
tamination, lower ethanol yield and the requirements for many
reactors has led to its wane in popularity [109] especially as it
relates to industrial applications. Industrial applications oriented
research has continued to show that when enzymatic hydrolysis is
the chosen option, a synergistic approach is preferred [109–111].
This approach involves supplementing the on-site produced cel-
lulase production with other enzymes and accelerants (e.g laccase,
feruloyl esterase) with results leading up to 61.2% increase for
glucose yield and 112.7% yield for ethanol [112]. The enzyme
loading requirement is also expected to reduce due to this sy-
nergistic protocol; all of which have benefits for the total cost of
the process [113].
As regards fermentation, the choice organism depends on the
pathway chosen. For example in SHF processes, engineered Zy-
momonas mobilis has been shown to be capable of carrying out this
process effectively [23]. However as recent literature as shown,
more industrial engineered strains of yeasts such as Saccharomyces
cerevisiae IPE005 [109] can carry out the simultaneous fermenta-
tion of the glucose and the ethanol with great efficiency thus
lending credence to the simultaneous hydrolysis and co-fermen-
tation (SSCF) as proposed by Lynd [108]. This industrial strain, a
result of the domestication of S. cerevisiae IPE003 using steam
exploded corn stover [114,115] was capable of increasing the
theoretical yield by as much as 84.5%. It was also noted to have a
better resistance to the common inhibitors such as furfural [116], a
better general performance than other S. cerevisiae [117–119] and
thus is a viable candidate for industrial usage. This is definitely a
better performance than other specific microbes including Z. mo-
bilis used to ferment cassava peels in previous studies.
Therefore with the specific characteristics of cassava peels in
mind especially as it relates to constrained amount of cellulosic
availability and ethanol yield, a proposed optimal process step for
bioethanol production is an adaptation of the SSCF option with
particular attention to the solid loading, pH, temperature and time.
However, care has to be taken to avoid problems with un-
necessarily high solid loading in the form of mixing, power re-
quirements [109,120]. It is proposed that the hydrolysis be started
at the optimal lead time of 24 h before the actual fermentation,
drawing conclusions from the observations of [109] from the
works of [118].
Thus in the conceptualized biorefinery, the pre-treated ground
cassava peel can now be pumped into a saccharification and fer-
mentation reactor using a centrifugal pump at a solid loading rate
of 20% and this marks the beginning of the pre-hydrolysis stage.
The synergistic enzymatic approach can be used as well as a
combination of different enzymes as prescribed by [23]. For ex-
ample the following can be combined: amyloglycosidases (60 IU
mL  1, SIGMA, Aldrich), amylase (3000 IU mL  1, SIGMA, Aldrich)
and cellulases (75 IU mL  1, SIGMA, Aldrich) added at a rate of
1 mL g  1 substrate and at 50 °C. For optimum conditions and
taking into factor the characteristics of cassava peels, the industrial
fermentation procedure will start after about 24 h of pre-hydro-
lysis. After the introduction of the fermentative organism to the
reactor, the reaction will be allowed to go on for about 144 h and it
is expected that this time period is sufficient for the process to be
completed [23,6]. Similar processes for fermentation and hydro-
lysis presented in literature on cassava peels had recorded increase
in ethanol yields by at least 70% [34].
 A. Adekunle et al. / Renewable and Sustainable Energy Reviews 64 (2016) 518–530 525

Fig. 5. Hydrolysis pathways for lignocellulosic bioethanol production and presence in literature.

2.4. Extraction Table 4. Distillation extraction protocols remains at the fore-front

The final extraction process is a very key step in bioethanol
production as it determines the qualitative and quantitative suc-
cess of the entire pathway. A succinct summary [121,122] of the
currently available azeotropic separation methods is presented in
of the separation and extraction of bioethanol although the best
distillation sequence and combinations is an open issue in re-
search [123]. Amongst several process options available, some-
times ranging from simple [124] to complex configurations [125], a
two column sequence can reduce cost by at least 10% [123] and as
526 A. Adekunle et al. / Renewable and Sustainable Energy Reviews 64 (2016) 518–530

such as been adapted for the design of this step. The adsorption

Most effective and most energy saving

Low separation capacity for bio- Expensive set-up, requires specialized

membrane pervaporation. Can be ei-
separation method has been recommended for this step based on

Membrane used can be inorganic,

ther vacuum PV or sweep gas PV.
the low energy requirement and the opportunity to utilize bio-

Solution-diffusion mechanism in
based adsorbents in this process.

expertize. Expensive sieves.

At the end of the cassava peel fermentation process, the mix-

polymeric or composite
Membrane separation
ture can be pumped into a series of distillers. In the first distilla-
tion column, the remaining carbon dioxide is given out as a gas
vapor, while the unreacted substrate including unfermented sugar
will be collected at the bottom. The ethanol, which is estimated to
be 37 wt%, can then be collected as a side stream which is fed into

process,
the second distillation column where the bioethanol will be re-
covered as a vapor stream. A scrubber installed in the first dis-
tillation column is responsible for the separation of the compo-
sorption of water from the wa-
Vapor adsorption or liquid ad-

sorbents can be bio-based or

nents. The alcohol produced at this stage is estimated to be at least

based adsorbents, expensive
Lower energy requirements.

95% in concentration. Drying in a bio-based molecular sieve ad-

ter ethanol mixtures. Ad-

sorption unit further treats this bioethanol and a component

splitter models this process. The bioethanol produced from this
molecular sieves

molecular absorption stage can be as high as 99.6% in concentra-

tion [6] and is pumped into storage tanks. There will be two flash
Adsorption

molecular,

separators; the first one will be between the pretreatment pres-

sure vessel and the hydrolysis chamber as this will be useful for
evacuating some water, xylose and some by-products. The second
flash separator will be installed after the fermentation reactor in
(simultaneous saccharification
Liquid-liquid extraction fer-

Combined with fermentation

and extractive fermentation-

Increase ethanol yield (65%),

Extensive expertize as it re-

38% less energy, 78% reduc-
tion in water consumption,

order to remove the carbon dioxide that is non-condensable.

lates to solvent selection,

2.5. Optimal conditions

mentation hybrid

During the entire production process, optimal conditions for

maximum yield of ethanol from the cassava peels need to be
maintained. Amongst several other, eleven process factors have
SSEF)

been identified as the major influencers of bioethanol production

from cassava peels [34]. The optimum level for the first three most
salt, a mixture of volatile liquid solvent and
such as liquid solvent, ionic liquid, dissolved

complex process and availability of solvents,

OD method þaddition of separating agent

dissolved salt, or hyperbranched polymer

significant factors have been statistically determined to increase

At least 95% purity, with the ionicliquid/
hyperbranched polymer: less energy re-

the ethanol yield from cassava peel to as much as 83% [34]. The
optimum level of the other factors have also been determined
after a careful review of literature [23,33,34,126,127] on the best
Extractive distillation (ED)

level for increased reducing sugar yield; where studies do not exist
possible contaminations

yet for optimum level determination specific to cassava peels, best

quirements than AD,

industrial values are adapted. This is summarized in Table 5.

There will be a constant need to evaluate the cassava peels
obtained for suitability at regular interval, this can be done
through standard methods [23,34,128]. These parameters will
provide information on the dry matter, ash, organic matter and
protein properties of the lignocellulosic biomass. At the end of the
distillation, the bioethanol needs to be evaluated in order to en-
Health and safety concern, ex-
trainers which changes volati-

sure that the bioethanol parameters conform to the alcohol fuel

Azeotropic distillation (AD)

OD methodþ addition of en-

lites and activity coefficient

parameters specifications e.g. as specified for the Brazilian ethanol

Simple set-up, efficient

fuel [129]. This will include analysis of the color, clarity, acidity,
pensive, high energy

Table 5
requirements

Optimal process factors for bioethanol production from cassava peels.

sepration

Rank Factors Recommended optimum point

1 Substrate concentration 69.82 g/L

2 Inoculum size 5.22% (v/v) (for 2 and 3 since SSCF is
Ordinary distilla-

Very simple pro-

3 Glucoamylase recommended
cess, no special
requirements

concentration
Boiling temp
Distillation methods summary.

differences

4 α-amylase concentration 24.74% (v/v)

Disadvantages Expensive
tion (OD)

5 Agitation speed of 100 rpm

fermentation
6 Temperature of pre- 50 °C
hydrolysis
6 pH of fermentation 5
Advantages

8 Time of fermentation 114 h

Process

9 Time of pre-hydrolysis 24
Table 4

Basis

10 pH of pre-hydrolysis 4
11 Temperature of fermentation 27 °C
 A. Adekunle et al. / Renewable and Sustainable Energy Reviews 64 (2016) 518–530 527

pH, conductivity, halide ions etc. A flow of the steps for the pro-
posed cassava peel bioethanol plant is presented in Fig. 6.
3. Economic considerations
This review has focused on the possible use of cassava peels as
a feedstock for bioethanol production especially in those regions
suffering from acute renewable energy shortage. Usually, the
economic investments for bioethanol plants can range up to sev-
eral millions of dollars especially due to high set-up costs and
other materials procuring costs. However, recent studies have
shown that the costs per unit of biofuel produced are coming
down with constant technological improvements. They further
predict that these costs will further go down as the market for
biofuels continue to grow. Now, quite a few developing countries
continue to invest in commercial production and utilization of the
biofuels which could further reduce their dependence on fossil
fuels and diversify their energy sectors [130]. In spite of the pro-
found advantages of biofuel production and continued efforts of
various governments, it is interesting to note that the investments
have been rather low for various reasons as mentioned below
[130]:
 Poor Technology and Design of reactors and lack of
maintenance.
 Improper strategy adopted by promoters.
 Lack of responsible ownership and management.
 Governments failure in adopting proper policies for energy
production.
well as data on production costs [134] and current available date from
the Nigerian market [135,136]. A cost estimation analysis of a cassava
bioethanol plant was then carried out using Nigeria, the world largest
producer of cassava as a case study. With the annual production in
Nigeria estimated to be approximately 53 million tonnes in 2013, a
modest peel generation rate of 10% and utilization of 60% of these
peels for bioethanol production, we determined the nominal capacity
of a plant capable (at a yield of 9%- worst case scenario) of processing
the wastes to be approximately 34 kg/h of cassava peels. The equip-
ment, raw material acquisition/transportation, insurance and in-
dustrial materials for the process were estimated using values from
the cost description model. The bulk values for some baseline re-
quirements (enzymes, yeast e.t.c) as well as estimates on maintenance,
labor, co-product credit etc. were also estimated by prorating values
from this model per kg, adjusting for inflation by 18% (2006–2014) and
estimated yield before being used for the analysis. The raw materials
were adjusted to reflect the US $0.003 value of cassava peels (15% of
an average US $ 0.02 per kg cassava root market price), the con-
siderable cheaper natural gas cost of US $36.68 per 1000 kg natural
gas costs and the US $ 0.034 kW h  1 of electricity. The power costs
were adjusted to reflect the unstable energy situation in the country
where at least 69% of total electricity is provided by private generators
[135] and this substantially increased the power cost requirements.
However, the results (summarized in Table 7) of this analysis shows
that even the bioethanol cost price/L is 20% cheaper than the heavily
subsidized current gas price in Nigeria (US $0.5/L- March 2016). This
shows that the economic outlook for a bioethanol plant in such a
country is favorable and such an opportunity can be harnessed. Even
though this analysis is based on Nigeria, it can be easily duplicated for
other countries.

But, this situation is changing rapidly with advent of new tech-

nologies which have improved the efficiency of biofuel production
with the ever increasing markets. The governments have also started
changing the policies to help them reduce the dependency on fossil
fuels leading to excessive pollution and economic drain due to im-
ports of petroleum products. The future of bioethanol production of
any feedstock hinges on the following two factors:
4. Conclusions
Lignocellulosic biomass for the production of bioethanol has
been shown to be better than conventional sugar- and starch-
based raw material in several studies and this opens up the op-
portunity for the usage of cassava peels in producing countries.

(1) Economics - Cost and availability of raw materials, process Table 7

economics. Summary of cost analysis for a cassava peel bioethanol plant in Nigeria.

(2) Policies – Support available for the biofuel production Estimated annual production cassava peels (kg) 5,300,000.00
industry. Estimated available peels for bioethanol production 270,300.00
(kg)
The typical economic requirements for bioethanol production [131] Estimated annual bioethanol yield (L) 344,304.89

costs is shown in Table 6. It is clear from the table that majority of the Raw materials
financial resources is usually dedicated to the procurement of raw Cassava peels $ 23,850.00
Denaturant $ 2,782.14
materials. Cassava peels have an almost negligible economic value due
Enzymes $ 5,403.46
to its limited uses [132] and will lead to a reduction of the eventual Yeast $ 1,278.50
total cost of the raw materials. This economic aspect was tested using Other $ 1,329.42
values from a model created by [133] using a SuperPro Designer s as Utilities
Power $ 14,361.96
Table 6 Steam $ 13,546.16
The % of various factors for ethanol production. Natural gas $ 1,096.18
Cooling water $ 2,471.22
Cost structure %
Labor and supplies
Plant operations $ 2,779.46
Raw materials 56.5%
Maintenance $ 3,524.58
Utilities 11.5%
Insurance and administration $ 1,935.17
Chemicals 6.9%
Depreciation (5 years straight line) $ 31,608.00
Maintenance and insurance 0.6%
Subtotal $ 105,966.24
Wages and additions 2.4%
Coproduct credit $ (31,471.91)
Depreciation 5.9%
Net annual production cost $ 137,438.16
Fiscal charges 4.7%
Selling expenses 2.4% Price Analysis
Miscellaneous 1.2% Break even selling price $ 0.39 /L (20% cheaper)
Profit margin 9.1% Current subsidized gas price in Nigeria- March 2016 $0.5 /L
528 A. Adekunle et al. / Renewable and Sustainable Energy Reviews 64 (2016) 518–530
Fig. 6. Flow steps for a cassava peel bioethanol plant.
This work has reviewed the cassava peel bioethanol production
potential as well as several processes that exists for exploration
and has presented a viable process that can be so utilized. Also, an
adapted cost analysis has been used to show the probable profit-
ability of using this raw materials in bioethanol production. Al-
though some challenges associated with the industrial production
of bioethanol ranging from process synthesis, analysis, integration
are likely to be encountered, this study represents a stepping stone
towards adaptation and practical usage.
For developing countries which are able to explore this possi-
bility of production from cassava peels, it is recommended that
this process be integrated with the petrochemical industry in or-
der to ensure proper blending and to encourage proper profitable
pricing. The co-products of this refining process can also be ex-
plored in other to further drive down the costs of production
through commercial exploitation of the side products that are
formed/can be produced during ethanoic fermentation. An inter-
esting opportunity can also be the integration of an ethanol plant
with a power generation and/or biomethane/biohydrogen plant.
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