Renewable and Sustainable Energy Reviews 66 (2016) 631–653

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Renewable and Sustainable Energy Reviews

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

Second generation bioethanol production: A critical review

H.B. Aditiya a,b,n, T.M.I. Mahlia a,e, W.T. Chong b, Hadi Nur c, A.H. Sebayang b,d
a
Department of Mechanical Engineering, Universiti Tenaga Nasional, 43009 Kajang, Selangor, Malaysia
b
Department of Mechanical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia
c
Centre for Sustainable Nanomaterials, Ibnu Sina Institute for Scientific and Industrial Research, Universiti Teknologi Malaysia, Johor Bahru, Malaysia
d
Department of Mechanical Engineering, Medan State Polytechnic, 20155 Medan, Indonesia
e
Faculty of Integrated Technologies, Universiti Brunei Darussalam, Jalan Tungku Link, Gadong BE1410, Brunei Darussalam

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

Article history: It is a popular fact that the world's dependency on fossil fuel has caused unfavourable effects, including
Received 1 April 2015 lessening crude oil reserve, decreasing air quality, rising global temperature, unpredictable weather
Received in revised form change, and so on. As the effort to promote sustainability and independency from fossil fuel, bioethanol
12 February 2016
is now favoured as the blend or fossil petrol substitute. However, the feedstock functionality of first
Accepted 4 July 2016
generation bioethanol production is restricted due to its edibleness since it would clash the feeding
purpose. Second generation bioethanol production fulfils the impractical gap of first generation since it
Keywords: employs non-edible feedstock sourced from agriculture and forestry wastes. Lignocellulosic and starchy
Second generation materials in them are convertible to fermentable sugars that are able to be further processed, resulting
Bioethanol production
anhydrous bioethanol as the end product. This paper critically reviews the existing variance of second
Agricultural waste
generation bioethanol production methodologies, namely pre-treatment, hydrolysis, fermentation and
Lignocellulosic biomass
Starch biomass distillation, as well as the worth of second generation production for future reference. The discussions in
this paper are also fit as the fundamental for feasible planning of second generation bioethanol pro-
duction plant.
& Published by Elsevier Ltd.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 632
2. Second generation bioethanol production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 633
2.1. Pre-treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 633
2.1.1. Biological pre-treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 633
2.1.2. Chemical pre-treatment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 634
2.1.3. Mechanical pre-treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 635
2.1.4. Physicochemical pre-treatment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 636
2.2. Hydrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 636
2.2.1. Enzymatic hydrolysis of lignocellulosic biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 636
2.2.2. Enzymatic hydrolysis of starchy biomass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 638
2.3. Fermentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 639
2.4. Distillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 641
2.4.1. Adsorption distillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 642
2.4.2. Azeotropic distillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 642
2.4.3. Chemical dehydration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 644
2.4.4. Diffusion distillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 645
2.4.5. Extractive distillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 645
2.4.6. Membrane distillation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 647

n
Corresponding author at: Department of Mechanical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia.
E-mail addresses: aditharjon@siswa.um.edu.my (H.B. Aditiya), chong_wentong@um.edu.my (W.T. Chong).

http://dx.doi.org/10.1016/j.rser.2016.07.015
1364-0321/& Published by Elsevier Ltd.
632 H.B. Aditiya et al. / Renewable and Sustainable Energy Reviews 66 (2016) 631–653

3. The future of second generation bioethanol production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 648

4. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 650
Acknowledgement. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 650
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 650

1. Introduction agricultural industry waste comes from oil palm industry [20].
From the amount of waste generated, Malaysia could sustain the
Transportation sector, inevitably, contributes the rise of petro- national ethanol supply to support the fossil fuel demand and
leum consumption the most, which closely linked to harmful en- reduce the environmental harmful impact. Although replacing
vironment impacts. The world's consumption of fossil fuels by tropical forests with oil palm plantations is responsible for the
transportation sector accounts for 60%, which consequently con- large amounts of carbon released into the atmosphere, utilising oil
tributes to the massive pollution generation to the environment palm waste might contribute to reducing the carbon emission. But
[1]. Moreover, global transportation sector contributes 19% of the sustainability issue is still there since the net CO2 emission
carbon dioxide (CO2) which about 8 kg CO2/gallon petrol, and lifecycle, from both direct and indirect land use, tends to exceed
more than 70% of carbon monoxide (CO) [2,3]. Malaysia, as one of the safe limit. Capital investment in second generation production
rapidly developing countries in the South East Asia, appears to indeed seems highly risky. However, it has been strongly sug-
grow a similar pattern in pollution generation in its transportation gested that every little investment in the first generation pro-
sector. As reported in Compendium of Environment Statistics 2013 duction should be gradually allocated to the second generation
by Department of Statistics (DoS) Malaysia [4], in year 2012 production development for the future readiness. Also, experts
transportation sector in Malaysia contributed the most of the at- have forecasted that second generation production will replace
mosphere pollutions by 68.5%. In the same year, transportation first generation in the near future [21]. Similarly in biodiesel,
sector degraded the air quality by emitting 1.78 million-tonnes of Malaysia has shown the interest in second generation of biodiesel
CO, 226.2 ktonnes of NO2, 14.4 ktonnes of SO2 and 4.6 ktonnes of production from various non-edible feedstock as contribution in
particulate matters. Moreover, 6.5% and 5.1% of CO and SO2 the renewable energy demand for the compression engine ve-
emissions increased respectively from 2011 to 2012, while 4.5% hicles [9–11,22,23].
increment occurred on both NO2 and particulate matters emis- The quality of bioethanol produced is majorly dependent on
sions. One of the solutions in reducing environmental impact is by the production routes. As bioethanol production in general con-
using biofuel to replace fossil fuel. Simply, biodiesel is used to
sists of several sequential procedures, namely pre-treatment, hy-
replace diesel whereas bioethanol used to replace petrol. Study on
drolysis, fermentation and distillation, each of the stage is bran-
biodiesel production and performance have widely been con-
ched and each branch will give different results in ethanol quality
ducted as can be found in refs [5–13]. However, study on second
as well as overall production cost. Moreover, the current available
generation bioethanol production is still limited.
technologies enrich the possibilities in bioethanol production
Bioethanol is a renewable and sustainable liquid fuel that is
routes. For instance, a study showed that acid hydrolysis by sul-
expected to have a promising future in tackling today's global
phuric acid gives sugar conversion efficiency of 76% for cellulose to
energy crisis and the worsening environment quality. In 2011, the
glucose, and 90% from hemicellulose to xylose [24]. The type of
world's bioethanol production was stated to be above 100 billion
source of sugar also determines the quality of ethanol produced
litres and was expected to increase up to 3–7% p.a in the year
from fermentation, as the same author claimed that glucose can be
2012–2015, which shows that bioethanol is already being seen as
fermented into ethanol with efficiency about 75%, while 50% with
one preferable alternative energy source to substitute the fossil
xylose [24]. Another example is comparison between mechanical
fuel [14]. Bioethanol is not a new energy source since it has been
used extensively in Europe and the United States early 1900s, but and acid pre-treatment. Mechanical pre-treatment is indeed con-
it was ignored due to its high production cost compare to petrol. venient and conventional, but it consumes high energy to run.
The bioethanol production was then continued due to the oil Meanwhile, acid pre-treatment, another common pre-treatment
crisis in 1970s [15]. With its high octane number of 108, bioe- method to increase the feedstock surface area, tends to corrode
thanol becomes a favourable fuel internal combustion engine to production equipment [25]. The selected method from the avail-
prevent engine knocking and early ignition, thus leads to high able technologies will give different outcome, advantage and dis-
antiknock value [16]. Although it has 68% lower energy content advantage from the overall production process. This leads to the
compared to petrol, bioethanol's high oxygen content makes the importance of bioethanol production method selection, especially
combustion cleaner and results lower emission of toxic sub- for a country to initiate or implement national second generation
stances [17]. Bioethanol also helps to reduce CO2 emission up to bioethanol prospect as its renewable energy industry sector. In
80% compared to using petrol, thus promotes a cleaner en- addition, to regulate second generation bioethanol policies gov-
vironment for the future [18]. The criteria of the bioethanol to ernment requires a thorough study of the available production
substitute, or to be blended with, petrol is prescribed under technologies to determine the viable route for the country.
ASTM D4806 standard, which sets the quality requirements of This paper provides a critical and complete review on second
bioethanol for spark-ignited engine [19]. generation bioethanol production through the accessible existing
The development of second generation bioethanol production methods. Generally ethanol production comprises pre-treatment,
may not be as advanced as the first generation production. How- hydrolysis, fermentation and distillation to achieve anhydrous
ever, looking at the feedstock's availability, second generation ethanol as the end product, and this paper describes the available
holds a gigantic potential if implemented nationally. For instance, technologies for each production stage. This paper also discusses
as the world's second largest oil palm producer, Malaysia gen- production methods from lignocellulosic and starchy biomass,
erates excessive oil palm wastes of which are usually unprocessed results, advantages and disadvantages of the technologies from
and thrown. It is recorded that 85.5% of the total nation's compilation of reported works.
 H.B. Aditiya et al. / Renewable and Sustainable Energy Reviews 66 (2016) 631–653 633

2. Second generation bioethanol production bonds of the starch react with water molecules and dissolved. As
the result, the gelatinization of starch occurred. However, this
2.1. Pre-treatment occurrence is undesirable in the bioethanol production since gel is
an undesirable medium for the whole procedures.
The principle objectives of pre-treatment process to begin the In lignocellulosic materials, pre-treatment is commonly func-
biofuel production are (i) as the physical material's size reduction tioned as deformation of the rigid components, which structured
method [26], (ii) provision of the components exposure (hemi- of lignin, cellulose and hemicellulose; and resulting in the de-
cellulose, cellulose, starch) as prior to hydrolysis to yield improved gradation of the crystallinity degree, which is required as the
reducing sugars [27], (iii) provision of better hydrolysis access for adequate condition prior hydrolysis. Physical reduction pre-treat-
the enzymes to hydrolyse the carbohydrate into fermentable su- ment (mechanically) alone is also suitable for the lignocellulosic
gars in the subsequent enzymatic hydrolysis method [28] and (iv) material. However, with an additional method, by chemical pre-
reduction of crystallinity degree of the cellulose matrix [29]. It is treatment for instance, would deliver a smoother condition for
frequently emphasised that pre-treatment process is highly hydrolysis as the following stage. The combination would also
recommended as it gives subsequent or direct yield of the fer- bring out a better yield of reducing sugars at the end of hydrolysis.
mentable sugars; prevents premature degradation of the yielded Refaat [32] explored various types of the pre-treatments in bioe-
sugars; prevents inhibitors formation prior hydrolysis and fer- thanol production from the typical lignocellulosic material
mentation; lowers the processing cost; and lowers the demand of (Table 1). The wide choices of pre-treatment method for lig-
conventional energy in general [30,31]. nocellulosic material are to bring up the amorphous form of the
In the typical starchy agricultural waste, physical size reduction celluloses, so that enzymes in hydrolysis stage can efficiently
as the result of the pre-treatment is sufficient. This approach is consume them and resulting more sugar monomers at the end of
usually done by any simple mechanical pre-treatment since star- the process [29]. It requires more effort to attain complex sugars
chy material distinctively provides easier direct access to hydro- (carbohydrate) in the lignocellulosic materials to be converted into
lysis (enzymatically through amylases). With reduced size of the sugar monomers. Table 1 sums the available pre-treatment
starch (e.g. starch milling with fine powder as the end pre-treat- methods can be used in the production [32]. These pre-treatment
ment product) an easy hydrolysis method (e.g. heating the starch methods are categorically specified under biological pre-treat-
with water) can be opted as the method to hydrolyse the starch, ment, chemical pre-treatment, physical pre-treatment and physi-
although the ethanol yield may be varied according to the other cochemical pre-treatment.
stages' method and procedure in the overall production. This
phenomenon is possible due to the nature of the starch that 2.1.1. Biological pre-treatment
comprises direct long chains of glucose forming polysaccharide as Biological pre-treatment employs microorganisms to perform the
the complex form of sugar. Starch is also soluble in water. As the pre-treatment task. The employed microorganisms in this method
starch is mixed with water and presence of heat, the hydrogen specifically possess the capability to degrade the lignocellulosic

Table 1
Different pre-treatment methods for lignocellulosic materials in bioethanol production [32].

Pre-treatment method Main effects Advantages Disadvantage/limitations

Ammonia fibre explosion
Increases accessible surface area
Low formation of inhibitors
Not efficient for biomass with high
(AFEX)
Removes lignin and hemicelluloses to an lignin content
extent
High cost of large amount of ammonia
Ammonia recycled percola-
Removes lignin
Highly selective delignification
High energy consumption
tion (ARP)
Alkali
Removes lignin and hemicelluloses
High digestibility
Long residence times

Increases accessible surface area
High lignin removal
Irrecoverable salts formation
Biological pre-treatment
Degrades lignin and hemicellulose
Low energy consumption
Low rate of hydrolysis
Concentrated acid
Hydrolyses both hemicelluloses and
High glucose yield
Acid recovery is mandatory
cellulose
Reduction in the operational costs due to
Equipment corrosion
moderate operation temperature
Generation of inhibitory compounds

Low formation of degradation products

No enzymes are required
Diluted acid
Hydrolyses hemicelluloses
Less corrosion problems than concentrated
Generation of degradation products

Renders cellulose more amenable for a acid due to high temperature
further enzymatic treatment
Low formation of inhibitors
Low sugar concentration exit stream

Alters lignin structure
Ionic liquids
Reduces cellulose crystallinity
High digestibility
Large-scale application still under

Removes lignin
Green solvents investigation
Mechanical
Reduces cellulose crystallinity
No formation of inhibitors
High power and energy consumption
Organisolv
Hydrolyses lignin and hemicelluloses
Pure lignin recovery
High cost

High digestibility
Solvents need to be drained and
recycled
Ozonolysis
Reduces lignin content
No formation of inhibitors
High cost of large amount of ozone

Mild operational conditions needed
Steam explosion
Causes lignin transformation
Cost effective
Generation of inhibitory compounds

Causes hemicelluloses solubilisation
Higher yield of glucose and hemicelluloses
Partial hemicellulose degradation

Incomplete disruption of the lignin-
carbohydrate matrix
Supercritical fluid
Increases accessible surface area
Cost effective
Does not affect lignin and
technology
No formation of inhibitors hemicelluloses

Very high pressure requirements
Wet oxidation
Removes lignin
Low formation of inhibitors
High cost of oxygen and alkaline
catalyst
634 H.B. Aditiya et al. / Renewable and Sustainable Energy Reviews 66 (2016) 631–653

components of the feedstock to amorphous form [33,34]. The typical to be the most suitable for the commercial scale application [54].
microorganisms used as the liberator of the complex lignocellulosic Chemical pre-treatment is approachable due to its likability: che-
structure are brown rot, soft rot and white rot fungi [35]. Brown rot mical substances are easier to be obtained, cheaper and does not get
type is able to degrade cellulose, while both soft and white rot are affected by the technological development (unlike enzymes, the
able to degrade both cellulose and lignin [34]. From all these fungi engineered enzymes cost more than the traditional enzymes), less
types, white rot fungi type is known as the most favourable biolo- hassle in storage and chemical substances are mostly durable with
gical pre-treatment agent. The ability of the fungi to degrade the the proper storage. The chemical substances degrade the walls of
lignocellulosic structure lies on the hydrolytic system and lig- lignocellulosic and the complex carbohydrate chain of starch
ninolytic system, which are responsible in producing hydrolases for through direct chemical reaction that only requires less energy (in
polysaccharide liberation and in breaking the lignin structure, re- heat form), although it takes more time and produces comparatively
spectively [36]. lesser sugar yield (for alkali pre-treatment) [27].
Biological pre-treatment is favourable due to its sustainability There are several common acids used in acid pre-treatment, for
to the environment. During the process, biological pre-treatment
instance, hydrochloric acid, phosphoric acid, nitric acid, and sul-
only requires mild condition, which means no excessive energy
phuric acid as the most popular to be used in lignocellulosic ma-
addition is needed. The built-in ability of the fungi to degrade
terial; also several organic acids such as peracetic acid, maleic acid,
lignocellulosic wall makes this process requires no additional
lactic acid and acetic acid [32,55]. In general, acid pre-treatment
chemical substance. Therefore this approach is safe from any
can be performed by two methods: concentrated acid pre-treat-
harmful effects. However, pre-treating the lignocellulosic feed-
ment and dilute acid pre-treatment. In concentrated acid pre-
stock by this method results in a slower production rate. Hence
this approach is unfavourable for the big-scale industry. To lessen treatment, only shorter time and mild temperature are required to
the unfavourableness, this pre-treatment method is useful in de- yield the sugar monomers [56]. This method is also able to pro-
livering more potential of the feedstock if another pre-treatment duce monosaccharides by degrading the polysaccharide's glycosi-
method is paired with biological pre-treatment [33]. dic linkages. In the practice, concentrated acid has drawbacks as it
As a study of fungal pre-treatment for saccharification of su- forms inhibitors, easily corrodes the production equipment and
garcane bagasse into sugars, Deswal et al. [37] employed white rot inclines the sugar monomer degradations tendency [32,57]. In
type fungi, which are Pleurotus florida, Coriolopsis caperata RCK
2011 and Ganoderma sp. rckk-02. The saccharification was further Table 2
Reported biological pre-treatment research on different lignocelullosic materials.
proceeded by hydrolysis from crude celullase produced from
brown rot fungus Fomitopsis sp. RCK2010. Resulted from this study, Fungus employed Material Ref.
the lignin component from sugarcane bagasse was degraded 7.91%,
5.48% and 5.58% by Pleurotus florida, Coriolopsis caperata RCK 2011 Aspergillus awamori Sugarcane trash [39]
and Ganoderma sp. rckk-02 respectively. After the enzymatic hy- Aspergillus terreus Sugarcane trash [39]
Ceriporiopsis subvermispora Corn stover [40,41]
drolysis from the crude cellulose, the reducing sugars concentra- Echinodontium taxodii Corn stover [43]
tions released were 303.33, 192.52 and 220.86 mg/g of substrate Echinodontium taxodii Softwood [45]
from Pleurotus florida, Coriolopsis caperata RCK 2011 and Gano- Echinodontium taxodii Hardwood [45]
derma sp. rckk-02 respectively, showing 1.5–2.4 fold higher than Fusarium concolor Wheat straw [44]
Irpex lacteus Corn stover [42,43]
the non-pre-treated sugarcane bagasse. Although the authors did
Phanerochaete chrysosporium Wheat straw [47]
not analyse the ethanol content through fermentation process, the Phanerochaete chrysosporium Rice straw [46]
presence of reducing sugars as the product of fungal pre-treatment Phanerochaete chrysosporium Cotton stalks [48]
indicates the potential for second generation bioethanol produc- Pleurotus ostreatus Corn stover [43]
tion. Another contribution in biological pre-treatment in bioetha- Pleurotus ostreatus Rice hull [50]
Pycnoporus cinnabarinus Wheat straw [47]
nol production research is by Millati et al. [38]. In their research, Pycnoporus sanguineus Cereal straw [49]
biological pre-treatment was commenced by employing Pleurotus Trichoderma reesei Sugarcane trash [39]
florida within period of 28 days on oil palm empty fruit bunch Trichoderma viride Sugarcane trash [39]
(OPEFB) and oat straw. The ethanol concentrations produced were
14.25% and 49.88% from OPEFB and oat straw respectively.
Table 2 shows the reported studies of biological pre-treatments Table 3
from different biomass sources with the employed fungi [39–50]. Reducing sugar yielded from biological pre-treatment of different lignocellulosic
Table 3 shows the results of biological pre-treatment on different feedstock.
lignocellulosic materials from the view of the yielded reducing
Fungus employed Material Reducing sugars yield Ref.
sugars content [37,41,45,48,51–53]. These reported studies in-
(mg/g)
dicate the interest of many researchers in utilising biological ap-
proach for pre-treatment process, hence widen the potential range Ceriporiopsis subvermispora Corn stover 233 [41]
of bioethanol production. It is noticed that there is utterly rare Coriolopsis caperata Sugarcane 192.52 [37]
report on biological pre-treatment of starchy materials. Utilising RCK2011 bagasse
Echinodontium taxodii Bamboo culms 100 [53]
the reported fungi as the pre-treatment agent to the starchy ma- Echinodontium taxodii 2538 China fir 60 [45]
terials is then strongly advisable as the additional research con- Echinodontium taxodii 2538 Chinese willow 175 [45]
tribution in second generation bioethanol production. Ganoderma sp.rckk-02 Sugarcane 194.86 [37]
bagasse
Iprex lacteus Wheat straw 120 [51]
2.1.2. Chemical pre-treatment
Phanerochaete Cotton stalks 55.6 [48]
Specific supporting chemical substances are expected to be ad- chrysosporium
ded in chemical pre-treatment. The purpose is the same: to guide Pleurotus florida Sugarcane 303.33 [37]
the lignocellulosic or the starchy materials into the better form for bagasse
hydrolysis process as the next sequence of the production series. Pleurotus ostreatus Rice hull 80 [45]
Pleurotus ostreatus Rice straw 118.5 [52]
Although there is no the absolute best method for pre-treatment Trametes versicolor Bamboo culms 98 [53]
stage, chemical pre-treatment (dilute acid pre-treatment) is believed
 H.B. Aditiya et al. / Renewable and Sustainable Energy Reviews 66 (2016) 631–653 635

regard to this matter, dilute acid pre-treatment is used for the cutting the aromatic structure in lignin. From a study of alkaline
better conduct. Dilute acid pre-treatment leads to the same out- pre-treatment of sugarcane bagasse, C2H4O3 gives better digest-
come as the concentrated acid pre-treatment which to yield the ibility enhancement for the enzyme to hydrolyse the sugarcane
sugar monomers, although it behaves differently than con- bagasse than H2O2 as the oxidising agent [72]. In a recent research,
centrated acid pre-treatment. Typically, dilute acid pre-treatment Toquero and Bolado [62] compared the results of four different
can be performed through different paths: batch process with low pre-treatments of wheat straw: dilute NaOH with autoclave, dilute
temperature (less than 433 K or 160 °C) and high substrates HCl with autoclave, thermal autoclaving, and alkaline peroxide
loading (ranges 10–40 w/w%); and continuous process with high (NaOH with H2O2). After 72 h of hydrolysis, it was found that al-
temperature (more than 433 K or 160 °C) and low substrates kaline peroxide pre-treatment yielded the most glucose and xy-
loading (ranges 5–10 w/w%) [31]. Pre-treatment with dilute acid lose of 31.83 g/L and 13.75 g/L respectively. Ethanol with con-
does not require acid recovery with negligible acid loss [32]. centration of 17.37 g/L was observed after fermentation by Pichia
Dilute acid pre-treatment is popular in bioethanol production stipitis in 24 h. The effectiveness of using ozone in enhancing sugar
from lignocellulosic biomass. From a research of Bermuda grass yield has also been reported, as it produced sugar of 88.6% from
pre-treatment, 204.1 mg/g of reducing sugars was produced per wheat straw than 29% from the non-ozonised, although this
biomass weight basis by employing 1.2 wt% dilute sulphuric acid at method is infeasible from the economic perspective [32,73].
121 °C and 60 min [58]. Another bioethanol production attempt Organosolv is also seen as one chemical pre-treatment that
from inedible sources was conducted by taking silver grass as the dissolves lignin in the lignocellulosic biomass. This method is
feedstock through dilute acid pre-treatment [59]. After 30 min of performed by mixing organic solvent with inorganic acid as the
dilute acid pre-treatment at 121 °C, the silver grass produced 70– catalyst, such as HCl or H2SO4. Since the typical organic solvents,
75% xylan sugars and 64.3% theoretical ethanol was able to be for instance ethanol, methanol, phenol, acetone, triethylene glycol
extracted after 48 h of fermentation. Rice straw was also pre- and ethylene glycol, are combustible, this pre-treatment method
treated by dilute acid in a study by ref [60]. The acid pre-treated must be performed under extreme safety care [74]. A study by Li
rice straw drew 9.71 g/L of glucose, which was uplifted to 11.45 g/L et al. [75] revealed bioethanol production with quality of 93% by
of glucose after it underwent enzymatic hydrolysis by cellulase organosolv pre-treatment using acetone and phosphoric acid from
from Trichoderma reesei. This study yielded 52.75% of theoretical lignocellulosic biomasses. Although its effectiveness in producing
ethanol from the combination of acid pre-treatment with enzy- high quality bioethanol, this method is considered to be in-
matic hydrolysis, compared to acid pre-treatment alone of which dustrially impractical due to high solvents cost [74].
yielded 11.26%. Study on acid pre-treatment of durian seed was Pre-treatment method using ionic liquid fractures the non-
performed also in the conduct of second generation bioethanol covalent structure between hemicellulose, lignin and cellulose, as
production from starchy material [61]. The study utilised 0.6% di- caused by the strong hydrogen bond acceptors of the ionic liquid
lute sulphuric acid and 5 w/v% substrate loading beforehand the contained in chloride [76]. It is reported that the most effective
enzymatic hydrolysis, and it yielded 23.66 g/L of reducing sugars. ionic liquids are 1-allyl-3-methylimidazolium chloride and 1-bu-
At the end of this study, the ethanol quality was recorded as 51.2% tyl3-methylimidazolium chloride [77]. In comparison with dilute
of theoretical value. acid pre-treatment, ionic liquid pre-treatment showed 16.7-fold of
While acid pre-treatment is good in degrading mostly hemi- enzymatic hydrolysis enhancement from switchgrass, as ionic li-
cellulose component in the lignocellulosic biomass, alkali pre- quid gave more exposed surface area, lesser crystallinity of cellu-
treatment breaks more lignin component into a better accessible lose and lesser lignin obtained [78]. Although the effect of the
form for hydrolysis afterward [32]. In alkali pre-treatment, NaOH suitability with enzymes and fermentation microorganism is still
and lime (Ca(OH)2) are found as the most frequent alkaline solu- under investigation, Ionic liquid pre-treatment is considered as a
tion to be used in alkali pre-treatment, as performed in several green, sustainable method [32].
researches [62–67]. NH4OH (ammonia) is also commonly em-
ployed as the pre-treatment agent in the attempt to produce 2.1.3. Mechanical pre-treatment
second generation bioethanol [62,63,68]. According to the men- Another path to pre-treating the biomass is by mechanical pre-
tioned references, these alkali substance are chosen for their treatment, where the size of biomass is physically reduced
specialty in degrading mostly lignin compound. In lignocellulosic through cutting, chopping or material breaking method. Likewise
material, NaOH gives better internal surface by swelling it and any other pre-treatment method, mechanical pre-treatment is
brings to lignin degradation. NaOH pre-treated lignocellulosic purposed to degrade the biomass crystallinity, thus enhancing the
biomass results higher porosity that leads to better glucose yield rest of the bioethanol production processes [33]. Conventionally,
after enzymatic hydrolysis by attacking the ester bonds [69]. Em- physical size reduction can be done by wet disk milling, ball mil-
ploying dilute NaOH is wiser than employing concentrated NaOH ling [79], vibratory ball milling, compression milling [35], hammer
for the environmental and economic benefits. Lime gives a better milling [80] and roll milling [81]. A comparison study was per-
access for the enzyme in the next hydrolysis stage to strike the formed and it showed that smaller size of corn stover (about 53–
cellulose, by removing uronic acid substitutions and acetyl com- 75 mm) produced greater outcome by 1.5-fold than the larger size
pounds [55]. A study of lignocellulosic biomass pre-treatment re- substrate [82]. This proves mechanical comminution can afford 5–
ported lime pre-treatment was performed on poplar wood at 25% improvement of hydrolysis product and boosts 23–59% rate of
temperature of 423 K for 6 h, corn stover at 373 K for 13 h, hydrolysis, depending on the milling techniques [83]. The most
switchgrass for 2 h at 373 K, and wheat straw for 3 h at 385 K [27]. well-known challenge for mechanical pre-treatment is its vast
In order to improve the digestibility exposure on the heavy-lignin power consumption. It has been reported that physical reduction
feedstock, an oxidising agent is necessary to be mixed with the approach by mechanical pre-treatment uses one-third of the total
alkali [32]. Addition of hydrogen peroxide (H2O2) as the oxidising energy consumption of entire bioethanol production [84]. A study
agent in the alkaline pre-treatment of tobacco waste resulted revealed energy consumption of hammer milling pre-treatment of
347.2% of sugar improvement than the untreated waste [70]. The wheat straw, which consumes 51.6 and 11.4 kWh/tonne of feed-
improvement is due to the ability of hydrogen peroxide to oxidise stock to produce sizes of 0.8 and 3.2 mm respectively [80]. Power
the degrading-resistant reducing ends of ligocellulosic's carbohy- consumption for mechanical comminution can be controlled by
drate in alkaline environment [71]. An organic acid, peracetic acid adjusting the sizes of the initial input and desired final substrate.
(C2H4O3), is known for its effectiveness as an oxidising agent by In addition, the material's woody characteristics and moisture
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content also influence the power input for this pre-treatment [90]. This method is strong on fibrous biomass, for instance su-
[33,80]. It is desirable to have fine form of biomass from me- garcane bagasse, than on the lignin-rich substrates, such as forestry
chanical pre-treatment, but when the subsequent process involves residues [31]. Inhibitors formation is negligible in AFEX pre-treat-
liquid, using extremely fine size of biomass may form lump [35]. ment, as reported that AFEX pre-treatment produces 100–1000-fold
Extrusion is a more advanced method of mechanical commi- of lesser carboxylic acids than NaOH alkaline pre-treatment and 36-
nution. Biomass pre-treatment by extrusion widens the access for fold of lesser furans than dilute acid pre-treatment [95].
enzyme to strike the better exposed carbohydrates. It involves Also utilising ammonia as the same pre-treatment agent, am-
shearing and mixing of the feedstock to go through the extruder at monia recycled percolation (ARP) flows recoverable aqueous am-
certain high temperature, causing deformation of biomass physi- monia through the biomass reactor. ARP is strong in lignin removal
cally, and even chemically [85]. Factors, such as speed of the screw, with high quality, without any containment of sodium and sulphur
temperature and compression ratio, should be controlled to unlike any other conventional pre-treatment methods, and hence
achieve the efficiency of extrusion pre-treatment [86]. In a study it leads to high quality pre-treatment product [96]. In contrary to
by Lee et al. [87], Douglas fir was extruded prior to hydrolysis, and AFEX pre-treatment, ARP is more suitable for hardwood and lig-
it resulted 62.4% conversion of the feedstock into glucose. Also nin-rich biomass, including oak wood waste and paper pulp sludge
reported by the same researchers, due to its ability to run con- [97,98]. One primary challenge of this pre-treatment method is the
tinuously with zero effluent waste, extrusion method is recognised unfavourableness in the total energy consumption cost.
as one feasible pre-treatment method for industry-scale applica- In wet oxidation pre-treatment, the biomass is subjected to
tion without causing any environmental problem. high pressure and temperature (about 500–2000 kPa and 170–
Microwave irradiation practices electromagnetic field applica- 200 °C respectively) for around 10–15 min. This approach degrades
tion to cause internal heating of an object. In bioethanol produc- lignocellulosic material with less inhibitors, removes lignin, and
tion, this approach is executable in the purpose of structural dis- lowers cellulose crystalline, hence it provides better condition for
ruption of the pre-treated biomass. In lignocellulosic material, the subsequent processes (enzymatic hydrolysis and fermenta-
microwave attacks the polar bonds by vibrating the structure until tion) to work on the pre-treated product. However, this method
the material is internally heated. As the result, complex lig- has the common challenge in energy efficiency and capital cost
nocellulosic structure is fractured, widening the practicable area since this pre-treatment method involves high temperature and
for the subsequent enzymatic attack [88]. Microwave treatment is pressure [99,100].
reckoned as an improvement effort through assisting other treat- The practice of supercritical fluid technology contributes to the
ment methods. In one of the recent studies, microwave was as- variance of possible pre-treatment methods for bioethanol pro-
signed to assist hydrothermal hydrolysis of sago pith waste [89]. duction. Carbon dioxide (CO2) as the supercritical fluid is commonly
This study claimed that the microwave assisted hydrothermal employed for coffee decaffeination process. However, the benefits of
hydrolysis consumed only 33 kJ and 69 kJ per every gram pro- both gas (in mass transfer) and liquid (in solvating) properties ex-
duction of glucose and ethanol respectively, which graded as en- isted in supercritical fluid, low inhibitory products, efficient in lignin
ergy efficient. removal at mild environment (low temperature, non-acidic and
non-corrosive), make this method as a favourable pre-treatment
2.1.4. Physicochemical pre-treatment method in bioethanol production compared to ammonia and steam
Steam explosion pre-treatment applies combination of hydro- explosion methods. Additionally, CO2 as the supercritical fluid
thermal and sudden pressure change in treating the biomass. In- pierces the crystalline easier without degrading the desired sugar
itially the biomass is exposed to a high temperature and pressure monomers because of its mild environment [101].
for few seconds to minutes, then the process ends after de-
pressurisation takes place on the biomass which when the steam 2.2. Hydrolysis
explodes the biomass's fibres. This method is categorized under
physicochemical pre-treatment for its fused mechanical- and Hydrolysis process separates long chain of carbohydrate (from
chemical-driven characteristics. Mechanical-wise, the steam cellulose or starch) with addition of water molecule and is usually
strikes the biomass causing fibres separation, physically shortens catalysed by enzyme or acid. This stage is critical in bioethanol
the fibres. While chemical-wise, auto-hydrolysis of acetyl groups production since the quality of hydrolysate will affect the sub-
that exists in hemicellulose takes place under high temperature, sequent fermentation process, which interconnected to the etha-
forming acetic acid; and acidic environment can be initiated when nol's quality as the end product. Hydrolysis process is needed since
the water is treated at high temperature [90]. For this nature, microorganisms (that are employed in the later process of fer-
steam explosion would be more beneficial on hemicellulose-rich mentation) are only able to digest simpler sugar form derived from
biomass. Having benefits of high xylose recovery production the complex carbohydrate of biomass. Enzymatic hydrolysis is
(around 45–65%), lesser energy usage and environmentally known for its economical challenge from high cost of enzymes and
friendly, steam explosion is favourable economically for bioethanol considered impractical for commercial purposes. However, in
production [91–93]. On the other hand, inhibitors formation as the comparison with acid hydrolysis, enzymes works at a mild en-
by-product of steam explosion method is one major challenge that vironment, hence less equipment maintenance cost will be nee-
may disturb the microbial activity on the subsequent production ded. Moreover, disposal system for acid hydrolysis is essential to
stage (fermentation) [94]. consider and it requires additional cost to take into account. An-
Ammonia fibre explosion (AFEX) has quite similar principle with other major problem is acid's ability to gradually degrade the su-
steam explosion, only with ammonia as the explosion agent. AFEX gar monomers once they are formed in a hostile acidic environ-
process depends on the immediate high pressure launch on the ment with high temperature [102,103].
biomass, forcing the recoverable and recyclable ammonia to burst the
biomass's structure and leaves some ammonia traces on the biomass 2.2.1. Enzymatic hydrolysis of lignocellulosic biomass
that is advantageous as the microbe's nitrogen source [57,90]. Like- Lignocellulosic, which majorly composed of cellulose, hemi-
wise steam explosion, AFEX brings both mechanical and chemical cellulose and lignin, is degradable enzymatically with respect to the
pre-treatment characteristics, which are bulk density lessening, major constituents. Cellulose is set by glucose chains that are con-
widens accessible area (mechanical-wise); and crystallisation re- nected by β-1,4 linkages. In nature, cellulose has certain degree of
duction, lignin breakage, hemicellulose degradation (chemical-wise) crystallinity that is formed by the hydrogen bonding along the
 H.B. Aditiya et al. / Renewable and Sustainable Energy Reviews 66 (2016) 631–653 637

chains. The presence of cellulose crystallinity is believed to affect specially served for xylan by aiming at both main and outer chains.
hydrolysis process, as such slower hydrolysis rate and lower enzyme To degrade xylan's main chain, endo-β-1,4-xylanase (EC 3.2.1.8) and
adsorption are taking place when crystallinity is high [104]. Rather β-xylosidase (EC 3.2.1.37) are employed. Endo-β-1,4-xylanase de-
than the rigid crystalline area, amorphous zone in cellulose is easier grades xylan long chains into shorter chains (xylan oligosaccharide,
to be degraded. However, in order to reduce the crystallinity of the Fig. 4) [112]. The sequential process to reduce the oligosaccharide is
biomass, mechanical pre-treatment method suits the purpose. Cel- by employing β-xylosidase to yield xyropyranose, a pyranose form of
lulase is the specific enzyme to degrade cellulose compound. Ac- xylose (Fig. 5) [113]. On the other hand, enzymes specifically to
cording to cellulases enzymatic activity, the classification is branched degrade the outer chains are so-called accessory xylanolytic en-
according to the specific task: endoglucanase (EC 3.2.1.4), exogluca- zymes, including feruloyl esterase (EC 3.1.1.73), α-L-arabinofur-
nase (EC 3.2.1.91) and β-glucosidase (EC 3.2.1.21). anosidase (EC 3.2.1.55), α-glucuronidase (EC 3.2.1.139), and acet-
The formation of 1,4-β-D-glucanohydrolase in endoglucanase ylxylan esterase (EC 3.1.1.72) [114].
targets the region with low crystallinity (amorphous zones) in the Although lignin establishes strong bonds of the cellulosic fi-
cellulose. Endoglucanase initiates the hydrolysis by linking β-1,4 bres, it is recognised as to lessen the approachability of cellulose
bond of the cellulose with water molecule. Shorter, free-chain ends to the cellulases [115]. It was reported that in aqueous solution
(reducing and non-reducing ends) are formed afterwards (Fig. 1) lignin adsorbs protein and tends to bond and precipitate with
[105]. 1,4-β-D glucan cellobiohydrolase in exoglucanase works in protein [116,117]. In fact, lignin is believed to resist cellulases
degrading the (shorter) cellulose structure, by altering both ends enzymatic activities, causing lower hydrolysis quality [118]. The
(reducing and non-reducing) chains to form two-unit glucoses presence of lignin in hydrolysis is unfavourable, hence lignin
(cellobioses, Fig. 2) [106]. Since the simplest monomer is expected removal process should be performed to maximise the effec-
for the subsequent fermentation process, cellobioses are further tiveness of hydrolysis by cellulase. In lignin removal fibrils of
treated by β-glucosidase. β-glucosidase strikes the cellobioses and microcellulose are openly exposed and neatly separated, as such
produce glucoses as the sugar monomers (Fig. 3) [107–110]. that providing better access for the cellulases [116,119]. There are
Enzymes for hemicellulose structure are complex yet more spe- many studies performed in the effort of delignification of the
cified in their purposes. Unlike cellulose, hemicellulose is typically materials to yield better fermentable sugars. A study on effect of
easier to hydrolyse due to its more amorphous property. Xylan, as milling pre-treatment in cotton stalks reported that pre-treated
one of the components in hemicellulose, is a polysaccharide with cotton stalks produces lower lignin (0.6%) and higher cellulose
xylose as the singular unit. In softwoods, xylan accounts for 10–15% (92%) compared to the one without milling pre-treatment (26.4%
of the hemicelluloses, and 10–35% in hardwoods [111]. Xylanase is of lignin and 44% of cellulose) [120].

Fig. 1. Reaction in cellulose hydrolysis catalysed by endoglucanase (1,4-β-D-glucanohydrolase), resulting shorter chain of cellulose (cellodextrin) [105].

Fig. 2. Reaction of cellodextrin catalysed by exoglucanase (1,4-β-D glucan cellobiohydrolase), producing cellobiose [106].
638 H.B. Aditiya et al. / Renewable and Sustainable Energy Reviews 66 (2016) 631–653

Fig. 3. Reaction of cellobiose with water molecule resulting 2 glucose units, as the reaction catalysed by β-glucosidase [110].

Fig. 4. Reaction of xylan hydrolysis catalysed by endo-β-1,4-xylanase, resulting shorter chain of xylan (xylan oligosaccharide) [112].

Fig. 5. Reaction of xylan oligosaccharide hydrolysis catalysed by β-xylosidase, producing xylopyranose [113].

The ability of hemicellulases to degrade hemicellulose struc- 2.2.2. Enzymatic hydrolysis of starchy biomass
ture into sugar monomers, apparently, is not so favourable for Likewise lignocellulosic material, starch is also one source of
cellulose hydrolysis. Products of hemicellulose hydrolysis, includ- carbohydrate, only with different chemical structures and char-
ing xylose, xylooligosaccharides, galactose, mannose, act as strong acteristics. Glucose molecular structure in starch is linked with α-
inhibitors to cellulase and β -glucosidase [121,122]. This indicates glucosidic bonds, in contrast with the glucose structure in cellulose
the focus on cellulases employability should be aimed only for the that is linked by β –glucosidic bonds. Therefore starch is composed
cellulose-rich materials, so that it would be economically wise to by linear α-1,4-linked glucans—amylose; and the same linear linkage
emphasise only on cellulose degrading type of enzymes. Similarly, branching with α-1,6 linkages—amylopectin (Fig. 6) [123]. Physically,
the usage of hemicellulolytic enzymes is advised only for the amylose is a linear glucose polymer with glucose unit up to 6000
hemicellulose-rich material, since the mentioned literatures in- units, while amylopectin is much shorter of 10–60 glucose units
dicate that sugars from hemicellulose could slower the cellulase where the α-1,6 linkage branch contains 15–45 glucose units [124].
activity. With this principle the overall production cost needed can Amylolytic enzymes, or called amylases, are the groups of enzymes
be estimated according to the nature of the materials. Additionally, specifically to degrade glucose linkages in starch. The groups are
focusing on the material's nature helps in the selection of the divided into four according to the functionality: endoamylases,
suitable microorganism to act as fermentation agent in the sub- exoamylases, debranching enzymes and tranferases [125].
sequent fermentation process, for the reason that specific micro- The inner zone in amylose and amylopectin, which where α-1,4
organism is needed to digest the specific sugar accordingly. glycosidic bonds are existed, is hydrolysed by endoamylase. The
 H.B. Aditiya et al. / Renewable and Sustainable Energy Reviews 66 (2016) 631–653 639

Fig. 6. Types of amylases according to the working zones (hollow ring depicts reducing ends) [123].

most favoured endoamylase that is able to cut down the α-1,4 suitable. Thus, it is wise to be highly selective in employing the
glycosidic bonds is α-amylase (EC 3.2.1.1). This enzyme reduces the type of enzymes, especially from the standpoint of suitability as
long chain of the sugar polymer and leaves shorter, varied lengths well as economical. It is acknowledged that enzymatic hydrolysis
products (α-configured oligosaccharides and α-limit dextrins) requires more cost, but with the proper planning analysis (e.g.
[124,126]. Besides, α-amylase works in random manner and re- employing combinations of hydrolysis methods, decision on plant
leases few glucose and maltose as well (Fig. 7) [127]. scale, raw material selection and collection methods, etc.) can be
The second group of amylases, exoamylases, aim the external resulted to the most viable approach. Also, coupled with thorough
zone (exo-) of both amylose and amylopectin. Glucoamylase (or also techno-economic studies, it will contribute to the routes formation
called amyloglucosidase; EC 3.2.1.3) and α-glucosidase (EC 3.2.1.20) of the most effective second generation ethanol production plant.
are exoamylases that are capable to degrade α-1,4 as well as α-1,6
bonds (Figs. 8 and 9) [128–131]. Another example of exoamylases, β- 2.3. Fermentation
amylases (EC 3.2.1.2), is limited to only degrade α-1,4 glucosidic
bonds. In catalysing the hydrolysis process, glucoamylase gives bet- Fermentation is one critical process in bioethanol production,
ter performance on long polysaccharides, while α-glucosidase pre- where the ethanol is directly produced from the metabolic activity
fers to work on maltooligosaccharides. The hydrolysis products by of the fermentation agent. Hydrolysate, in this process, is in-
exoamylases are maltose and glucose, as low molecular structure troduced to a specific fermentation agent (yeast or bacteria) best
residues [125,132]. according to the suitability to digest the respective sugar com-
Debranching enzymes work on α-1,6 glycosidic bonds on dif- pounds. A type of glucose-fermenting bacteria, for instance, Zy-
ferent parts of polysaccharide depending on employed debranch- momonas mobilis prefers glucose-rich hydrolysate as their ‘food’
ing enzymes. Isoamylase (EC 3.2.1.68), as one example of deb- and leaving ethanol compound as the product. It is rather hard to
ranching enzymes, degrades only α-1,6 linkages in amylopectin. expect the hydrolysate to be entirely uniform in terms of the sugar
Another type of debranching enzymes, pullulanase type I (EC monomer, it would be fractions of different monomers and several
3.2.1.41), is able to degrade α-1,6 linkages in both amylopectin and other oligosaccharides with probable inhibitors or indigestible
pullulan. Pullulanase type II is another group of the debranching substances. Theoretically, each kg of glucose and xylose can pro-
enzymes that is able to degrade α-1,4 as well as α-1,6 glycosidic duce 0.49 kg carbon dioxide with 0.51 kg of ethanol [92].
bonds, leaving maltotriose and maltose as the products [124]. Fermentation in particular requires the supporting conditions
As the last group of amylases, transferases form a new glycosidic for the microbes to sustain, namely temperature and pH range
bond by transferring molecules from the donor to the acceptor. The [133]. As mesophilic organisms, most of fermentation agents are
formation of new α-1,4 glycosidic bonds are catalysed by amylo- comfortable within 303–311 K temperature [134]. For bacteria type
maltase (EC 2.4.1.25) and cyclodextrin glycosyltransferase (EC of fermentation microbes, pH of 6.5–7.5 are typically essential to
2.4.1.19), where the later enzyme also forms cyclodextrin rings sustain the bacteria's growth [135]. Meanwhile, fungi are capable
consisted 6–8 glucose units that are linked by the α-1,4 bonds [124]. to resist more acidic environment of pH 3.5–5.0 [55]. Moreover,
A careful and well-analysed hydrolysis method is essential in additional factors that play important role in the fermentation
bioethanol production since the hydrolysate compositions de- process are the microbes' growth rate and genetic stability; tol-
termine which fermentation agent fits the best to fulfil the ethanol erance of inhibitors, osmosis and alcohol; productivity and the
production objective. The wild type of Saccharomyces cerevisiae, yield of ethanol [133].
for instance, is only be able to convert glucose as one of the sim- There are numbers of discovered bacteria suitable as fermenta-
plest sugar forms [32]. This indicates that this specific type of tion microorganisms. The most well-known fermentation bacteria,
fermentation agent is only prime to the glucose-producing mate- Zymomonas mobilis converts glucose, sucrose and fructose to etha-
rials, which cellulose and amylose are dominant. Whereas for nol. A study was performed in bioethanol production using Zymo-
xylose-producing materials, which is hemicellulose-dominant monas mobilis as the fermentation agent, and it yielded theoretical
materials, the employment of wild Saccharomyces cerevisiae is not ethanol of 97% with experimental ethanol concentration of 12%
640 H.B. Aditiya et al. / Renewable and Sustainable Energy Reviews 66 (2016) 631–653

Fig. 7. Reaction of long chained amylose hydrolysis catalysed by α-amylase (EC 3.2.1.1) in random manner, producing shorter polysaccharide, maltose and glucose [127].

(w/v) [136]. Likewise Zymomonas mobilis, Saccharomyces cerevisiae is those sugars into ethanol without any separation process in be-
one microbe (yeast type) that naturally consumes hexose sugars (e.g. tween. This way also prevents the reduction of the monomers
glucose, fructose). Although known as the most commonly em- formed after hydrolysis process. Additionally, SSF is claimed to
ployed microorganisms, both Z. mobilis and S. cerevisiae are incap- result higher ethanol yield since the hydrolysis inhibitions are
able to ferment pentose sugars. Candida shehatae, Pichia stipitis, and solved by fermentation process, which makes this approach is
Pachysolen tannophilus are recognised in their ability to convert desirable [30,152,153]. A study by Sun and Cheng [33] revealed
pentose sugars (xylose). However, these bacteria only result low other benefits from SSF method, including lesser employment of
efficiency with high-caring handling; they are vulnerable to acid enzymes; faster production period; and less number and volume
environment, inhibitors and ethanol with high concentration [137]. of reactors needed, hence lower cost required since both sugars
The limitations of the natural type bacteria and yeasts drive many releasing and sugars fermenting processes are commenced si-
researches to modify the behaviour and function genetically. multaneously. Srimachai et al. [154] extracted ethanol from oil
Through microorganisms engineering, besides improvement of the palm frond by SSF method, and the experiment resulted 0.32 g-
end product's quality, additional fermenting capability that is other ethanol/g-glucose, or about 62.75% of the theoretical ethanol yield.
than the native function can be achieved, i.e. ability to ferment more The researchers also analysed the total energy required to run the
than one type of sugars. From their research, Buaban et al. [138] overall production, which was calculated as 745 kWh/tonne of oil
reported that by using engineered Pichia stipitis BCC15191 as the palm frond. However, it is a challenge to control the solution en-
fermentation agent it resulted 8.4 g/L of ethanol concentration after vironment since enzymes and microorganisms are employable
24 h of fermentation of hydrolysed sugarcane bagasse. The study only within the preference temperature and pH. Most enzymes
was also reported that the employed engineered Pichia stipitis can still be comfortable with mild acid environment (pH o5) and
BCC15191 was able to ferment both xylose and glucose, whereas the resistant to more than 313 K of temperature, although those con-
wild type of Pichia stipitis is only capable in fermenting xylose sugar. ditions threaten the microorganisms' sustainability [155].
The more of engineered microorganisms employed in the effort to Mixing different fermenting microorganisms is seen to be one
enhance ethanol yield is listed in Table 4 [138 –151]. additional contribution to the alternative methods in ethanol
From the fundamental of the production conduct, there are production, which also comes with the term simultaneous sac-
alternatives in ethanol production including separate hydrolysis charification and co-fermentation (SSCF). This approach allows the
and fermentation (SHF); and simultaneous saccharification and mixed-culture microbes to commence the continuous process
fermentation (SSF). In a review paper written by Balat et al. [55], without sugars separation, to use various materials as the sub-
SHF method separates hydrolysis and fermentation process with strate, and no involvement of sterilisation [156]. SSCF has been
the focus in taking full advantage of each of the process. The hy- proven effective in ethanol production from corn stover [157],
drolysate is entered into the first reactor to get the glucose com- municipal solid wastes [158] and sugarcane bagasse [159].
ponent fermented. The ethanol is distilled afterwards, then the Another alternative is by consolidated bioprocessing (CBP). In
remaining of the hydrolysate is flowed into the second reactor to ethanol production from cellulosic materials, this approach per-
get the xylose components fermented. Similarly, the ethanol is forms self-cellulase production, hydrolysis of the substrates and
removed through distillation process afterwards. The main draw- fermentation of hexose as well as pentose sugars within the same
back from this process is the inhibition formation after hydrolysis, reactor by utilising the ability of certain microorganisms to per-
which reduces the hydrolysis rate and hence gives a lower and form these tasks [160]. In comparison to SHF method, CBP method
slower ethanol production. offers better benefits including lower production cost due to lesser
In contrary with SHF, SSF method allows the enzymes to per- steps required and no additional purchase of enzymes; better ef-
form hydrolysis to release the sugars and immediately ferment ficiency of conversion; and lesser energy required to run the
 H.B. Aditiya et al. / Renewable and Sustainable Energy Reviews 66 (2016) 631–653 641

Fig. 8. Reaction of maltooligosaccharide hydrolysis catalysed by α-glucosidase (EC 3.2.1.20) producing shorter maltooligosaccharide and glucose [128–131].

production [161]. The differences between fermentation methods sojae, Aspergillus niger, Aspergillus oryzae and Aspergillus terreus),
are also schematically displayed in Fig. 10 by ref [162]. Fusarium oxysporum, and Rhizopus spp. (Rhizopus koji, Rhizopus or-
It is uncommon for wild type of microorganisms to work on yzae and Rhizopus stolonifera). In contrary to category I, CBP strains
CBP method, but several studies have reported the employment of modification of category II emphasises on the genes modification of
specific microorganism in CBP method. Trichoderma reesei is naturally ethanologen microbes to equip cellulolytic property. Ca-
known as a cellulotyic type of fungi that is native in secreting tegory II modification path aims at the ability of the engineered
enzymes to degrade lignocellulosic material [163]. In addition, microbes to produce different essential exo- and endo-glucanases, to
several fungi, namely Fusarium oxysporum, Neurospora crassa and ferment all saccharides degraded from the substrates, and to be able
Paecilomyces sp are said to be practicable for CBP, as well as bac- grow sustainably by depending only from the substrates as the
terium Clostridium thermocellum [35]. However, the development carbon resource. Various bacteria, namely Escherichia coli, Klebsiella
of CBP method is encouraged due to the weaknesses it brings, oxytoca, and Zymomonas mobilis are reported to have been modified
including low rate of ethanol conversion process and considerably through modification CBP category II; as well as various yeasts, in-
low ethanol yield [163]. cluding Candida shehatae, Pachysolen tannophilus, Saccharomyces
For the auspicious advantage of low total cost production, there cerevisiae, and Pichia stipitis [165,166].
have been many efforts in the attempt to improve the feasibility of
CBP method in ethanol production, which mainly focused on the 2.4. Distillation
modification of employed microorganisms genetically. The paths of
modification are exclusively classified into two terms: CBP category I The ethanol solution resulted from fermentation process needs
and CBP category II. In CBP strains modification category I centres at to be further processed to remove the water content, giving dry
the effort to modify the cellulolytic (cellulase producer) microbes so with high quality ethanol product, or also called anhydrous etha-
that are able to produce ethanol as well (ethanologen). Although nol. In general, removal of water content can be done by the
category I is classified to be at the preliminary development stage, a principle of distillation, which is done by utilising the difference of
study by Amore and Faraco [164] described the potential of several boiling points of the mixtures in a solution. When the mixture is
fungi towards the strains modification, which ascribed to category I. heated to the ethanol boiling point (78.2 °C), ethanol in the mix-
They include Trichoderma reesei, Aspergillus spp. (mostly Aspergillus ture will be vaporised and separated from the other component
642 H.B. Aditiya et al. / Renewable and Sustainable Energy Reviews 66 (2016) 631–653

Fig. 9. Reaction of maltose, amylopectin and amylose hydrolysis catalysed by glucoamylase (EC 3.2.1.3), producing glucose [128–131].

(water). Anhydrous ethanol holds minimum of 99.5% of ethanol by low cost and environmental friendly, organic (derived from plants,
volume, with the water content is strictly cannot be more than such as cornmeal, sawdust, straw, cellulose) absorbents are incapable
0.5% by volume [167]. Besides anhydrous ethanol is widely to be regenerative [167]. However, the involvement of organic ma-
exploited for industries of pharmaceutical, cosmetics, etc., it also terials as absorbent is still favourable. Benson and George [168]
has been exploited its potential for fossil petrol substitution. This conducted a research of the usage of different lignocellulosic mate-
leads to many researches in developing techniques in producing rials as the absorbent to produce anhydrous ethanol. The research
anhydrous ethanol. A study done by Kumar et al. [167] reviewed resulted 90, 97 and 95 wt% of ethanol after absorption distillation
the existing several distillation techniques to produce anhydrous using bleached wood pulp, kenaf core and oak sawdust respectively.
ethanol. The anhydrous ethanol can be produced from any of the Regenerating the sieves is one focus in adsorption distillation
following techniques: (i) adsorption process, (ii) azeotropic dis- method. To remove or desorb the adsorbed water molecules
tillation, (iii) chemical dehydration, (iv) diffusion distillation, conventionally is by exposing the sieves to high temperature and
(v) extractive distillation, (vi) membrane process, and (vii) vacuum allowing stream of gas to expel the adsorbate (trapped water
distillation. molecules). Since it is important to maintain the high temperature
(around 288 °C) over long time (2–4 h) only for the sieves re-
2.4.1. Adsorption distillation generating process, high energy requirement from this process is
In their review, Kumar et al. [167] stated that distillation also projected into the overall energy input in the bioethanol
through adsorption method utilises the difference in molecular production. Organic absorbents are also inefficient when the ad-
sizes of the ethanol-water mixture to entrap the excess water sorption process is higher than the ambient temperature [167].
content. Adsorption distillation uses molecular sieve that is able to
separate the ethanol from the mixture according to the size of the 2.4.2. Azeotropic distillation
sieve's apertures. Ethanol's molecules of 4 Å in diameter are se- The conduct of azeotropic distillation is can only be done by
parated from water molecules by the sieve with 3 Å in diameter, (i) adding third chemical substance in the binary azeotropic mix-
since water molecules are typically size 2.5 Å in diameter. ture; (ii) and where the binary mixture disobeys Raoult's law
In typical adsorption distillation process, minimum two beds of [167]. Addition of entrainer (the third additional chemical sub-
molecular sieve in bulk are required. In the column where ethanol- stance) amends the azeotropes relative volatilities and is re-
water vapour is fed and introduced to the first bed, water vapour covered through decantation, distillation or other recovery meth-
molecules fill the voids of the molecular sieve and are adsorbed. As ods suitable to have it reusable in continuous manner [169]. The
the mixture vapour stream keeps flowing, the water molecules ab- same author also illustrated the distillation scheme for azeotropic
sorption occurs uninterruptedly until the maximum amount of the distillation to remove the water content from ethanol-water
water molecules can be absorbed by the bed, separating the ethanol mixture in Fig. 11 [169]. The mixture is flowed into the azeotropic
dehydrated and anhydrous. Once the bed is full with water mole- distillation column and the entrainer is introduced from the above
cules, swap of the fresh bed replacing the hydrated bed is then feed inlet, while the bottom of the column is where anhydrous
performed with the help from automation system or control valve. ethanol is gathered and collected. The feeding of the mixture with
The bed is regenerative, making it able to be reused for numerous entrainer results ternary azeotrope, which is then streamed to a
multiple times of absorption process. Zeolite is one instance of ab- decanter to get it recycled before it gets back to feed the mixture in
sorbent material that makes the reusable property possible. Although the azeotropic distillation column.
Table 4
List of engineered microorganisms employed in the improvement of ethanol production.

Employed microorganism Microorganism type Features Substrate used Ethanol yield Ref.

H.B. Aditiya et al. / Renewable and Sustainable Energy Reviews 66 (2016) 631–653
Candida shehatae NCL-3501 Yeast Co-ferment xylose and glucose Rice straw
0.45 g/g of sugar by autohydrolysis [139]

0.5 g/g of sugar by immobilized cells
Clostridium thermocellum DSM1313 Bacterium Improved ethanol yield Not specified
0.8 g/L at 0.5 g/L cellobiose [151]
Clostridium thermocellum YD01 Bacterium Improved ethanol yield Not specified (cellobiose)
1.33 mol-ethanol/mole-glucose equivalent (three [141]
times than resulted from the wild type)
Clostridium thermocellum YD02 Bacterium Improved ethanol yield Not specified (cellobiose)
1.28 mol-ethanol/mole-glucose equivalent (three [141]
times than resulted from the wild type)
Escherichia coli KO11 Bacterium Ferment both xylose and glucose Sugarcane bagasse
31.5 g/L or theoretically 91.5% after 48 h [149]
fermentation
Escherichia coli FBR5 Bacterium Ferment xylose Xylose
0.5 g/g of xylose [147]
Escherichia coli FBR5 Bacterium Ferment xylose and arabinose, the process was Rice hull
2.25% (w/v) [145]
bioabated by Coniochaeta ligniaria NRRL30616
Pichia stipitis A Bacterium Adapted at hydrolysate increased concentration Wheat straw
0.41 gp/gs [146]
Pichia stipitis NRRL Y-7124 Bacterium Adapted at hydrolysate increased concentration Wheat straw
0.35 gp/gs [146]
Pichia stipitis BCC15191 Bacterium Ferment both xylose and glucose Sugarcane bagasse
8.4 g/L after 24 h fermentation [138]
Saccharomyces cerevisiae D5a Yeast Improved ethanol yield Rice hull
0.58% (w/v) or 100% theoretical yield [145]
Saccharomyces cerevisiae 590. E1 Yeast Ferment glucose and cellobiose Whatman paper
1.09% from 2% glucose [150]

1.16% from 2% cellobiose
Saccharomyces cerevisiae 590. E1 Yeast Ferment cellulose without additional enzymatic Corn stover
63% theoretical ethanol after 96 h fermentation [150]
hydrolysis process
Saccharomyces cerevisiae RWB 217 Yeast Ferment glucose and xylose 2% glucose þ 2% xylose
0.43 g/g of sugars [143]
Saccharomyces cerevisiae RWB 218 Yeast Ferment glucose and xylose 2% glucose þ 2% xylose
0.4 g/g of sugars [143]
Zymomonas mobilis ZM4(pZB5) Bacterium Ferment both xylose and glucose Stillage (residue from starch fermentation)
11 g/L with supplementation with 10 g/L of glucose [140]

28 g/L with supplementation with 5 g/L yeast extract
and 40 g/L glucose
Zymomonas mobilis AX101 Bacterium Ferment glucose, xylose and arabinose Various agricultural wastes (dominated
3.54 g/L.h (no presence of acetic acid) [144]
with wheat straw and corn stover)
1.17 g/L.h (with presence of acetic acid)
Thermoanaerobacterium saccharolyticum Bacterium Improved ethanol yield, able to ferment glucose, Not specified
37 g/L [148]
ALK2 xylose, mannose and arabinose
Thermoanaerobacter mathranii BG1L1 Bacterium Improved ethanol yield Wheat straw
0.39–0.42 g/g sugars [142]

643
644 H.B. Aditiya et al. / Renewable and Sustainable Energy Reviews 66 (2016) 631–653

Fig. 10. Schematic diagrams of different available methods of ethanol production [162].

The most frequently used entrainers are cyclohexane and 2.4.3. Chemical dehydration
benzene, despite the nature of benzene possesses carcinogenic Dehydration through hygroscopic chemical substances is one of
property [167,169]. Other researches also have utilised other dif- the most conventional methods in producing anhydrous ethanol.
ferent chemical substances as entrainers in azeotropic distillation The hygroscopic substances are introduced to the ethanol-water
to produce anhydrous ethanol, namely acetone [170], diethyl ether mixture (in liquid or vapour phase), forcing the substances to
hydrate with the water molecules. For laboratory scale dehydra-
[171], hexane [172], isooctane [170], n-heptane [173], n-pentane
tion, calcium oxide or quicklime is the most frequently used to
[169,171] and polymers [174]. However, azeotropic distillation still
force the chemical reaction with water, forming the obvious in-
draws concerns, especially in economy-wise. This distillation
soluble calcium hydroxide as the result and leaving the ethanol at
method involves high principal cost and energy input. The ne-
the top. Dehydration by quicklime is typically done with the ratio
cessity of maintaining large stream of entrainer flow to have it water to quicklime 1:4.2, means for every 1 kg of removable water
keep continuously circulated draws more of distillation cost. The content must be at least reacted with 4.2 kg of quicklime. Dis-
usage of harmful entrainer, e.g. benzene, is also undesirable to the tillation or thorough filtration is required to completely remove
overall anhydrous ethanol production as it could damage the hu- the calcium dioxide in the mixture, and it can be recycled for the
man operator as well as the environment [167]. next batch use by reversing the calcium hydroxide reaction with
 H.B. Aditiya et al. / Renewable and Sustainable Energy Reviews 66 (2016) 631–653 645

component to be extracted at the first column while the other is

taken out at the second column, is dependent on the selection of
the added solvent. In general, the used solvent must possess sev-
eral important properties, including ability to easily recovered,
non-toxic substance, holds boiling point higher than the mixture,
and thermally stable [185]. In a research by Yuan et al. [181], ad-
ditional selection criteria of solvent in extractive distillation was
planned and performed in their study to distillate various binary
azeotropic mixtures, which by comparing the dielectric constant
and boiling point of the mixture's components with the potential
solvents. Here, dielectric constant acts as the polarity property in
which the solvent's polarity should be close to the heavy compo-
nent to let the interaction occurs. Consequently, heavy component
should have close dielectric constant with the solvent; both are
then as the bottom product in the first column beforehand flowed
to the second column. In a binary azeotropic mixture, assignation
of heavy and light component is determined by the boiling point.
Light component that is taken out in the first column is due to its
Fig. 11. Azeotropic distillation scheme [169].
lower boiling point, or higher volatility. On the other hand, heavy
component is drawn with the solvent to the second column due to
water to produce calcium oxide. Quicklime dehydration method its higher resistance to vaporise compared to the other component
apparently consumes a quite large energy amount due to the need in the binary mixture. The desired product to be extracted from
of high temperature during the process, although this method the binary mixture can be from either light or heavy component.
produces high quality of anhydrous ethanol for above 97%. Fur- For example in ethyl acetate-ethanol binary mixture, the desired
thermore, this method seems impractical for continuous, large fine ethanol extraction is drawn from the second column. In this
scale ethanol dehydration process since the removal of the in- combination, ethyl acetate and ethanol have insignificant differ-
soluble calcium hydroxide is performed per batch, unless con- ence in their boiling points, which are 77 and 78.3 °C respectively.
tinuous distillation plant is installed which practically adds up the However, by adding solvent with higher dielectric constant than
total production cost of the ethanol production [167]. ethanol in the mixture, for instance N,N-dimethylformamide,
N-methyl-2-pyrrolidone, dimethyl sulfoxide with dielectric con-
2.4.4. Diffusion distillation stant of 36.71, 32 and 48.9 respectively, makes ethanol acts as the
This distillation method was initially studied by Fullarton and heavy component due to the closer dielectric constant value with
Schlunder [175], who proposed separation by diffusion through ethanol (dielectric constant: 25.7) than that of ethyl acetate (di-
the voids of intern gas then condensed. The mixture is vaporised electric constant: 6.02). Table 6 lists typical substances used as the
at before the boiling temperature and the diffusion affects the mixtures and solvents in extractive distillation [186,187].
volatility of the mixture and inert gas's diffusivity. In their re- The energy requirement for extractive distillation with liquid
search, different several pre-distillation mixtures of alcohol and solvent apparently does not support the overall cost efficiency de-
water were tested, namely isopropanol-methanol-water and bin- spite the fine outcome it produces. To run the distillation, average
ary isopropanol-water, and the tests were run with variance of ratio of mixture feed to solvent is 1:5, which also makes the solvent
condensation, evaporation temperatures, inert gasses and wetted- recovery process drains a large sum of energy [188]. The hazard of
wall column's annular widths. The authors claimed that their re- the solvent is also one of the shortcomings in the technique. Ethy-
search was in alignment with Stefan-Maxwell and vapour-liquid lene glycol, as the typical solvent in anhydrous ethanol production, is
equilibrium equations through experimental modelling analysis extremely toxic to human's health that may cause kidney failure,
from perspective of a single point behaviour. Other researchers cardio-pulmonary failure and central nervous depression [189].
also have reported their studies of diffusion distillation process Extractive distillation using soluble salt to replace liquid sol-
(Table 5) [175–180]. vent is an alternative to achieve the same objective with lesser
drawbacks. The soluble salt serves as the separating agent and
2.4.5. Extractive distillation intervenes the azeotropic system in the mixture. It uplifts the
In the chemical and pharmaceutical industries extractive dis- volatility of the component with the higher volatility than the
tillation is a popular method to produce higher purity of a liquid other, and therefore eases the components separation. Salt effect,
component by separating the component from the mixture by ad- the name of the phenomenon, occurs due to the salt's ions ten-
dition of a non-volatile solvent. In fact in the Second World War this dency of solvation with the less volatile component in the mixture.
technique was used for production of butadiene and toluene with The extracted component, which changes its phase from liquid to
fine purity [181]. The solvent addition is purposed to separate the vapour, due to its higher volatility is salted out [167]. The ami-
components. The component with higher volatility (light compo- abilities of using salt as the separating agent include low toxicity,
nent) presents at the column's top while the added solvent presents much lesser energy consumption since evaporation-condensation
at the column's bottom along with the component with lower vo- system cycle is trivial (comparison of energy consumption is listed
latility (heavy component). As the result from this separation based in Table 7 by refs [171,190,191]), salts recyclability, lesser dimen-
on the volatility, the light component is extracted out from the first sion needed in the column design, corrosion resistive and better in
column, while the heavy component is run into the second dis- material handling (transporting) [190,192]. The usage procedure of
tillation column along with the added solvent which to be separated salt in extractive distillation is likewise as that of liquid solvent.
here (Fig. 12) [182,183]. The process in the second column, in addi- The soluble salt is added through the top feed and streamed down
tion, recycles the used solvent, which is able to be utilised again in to the bottom of the column. The removal of the salt is concurrent
the first column as continuous extractive distillation technique [184]. with the heavy product at the column's bottom.
The extracted component out of the columns, which by other Researchers have shown interest in utilising salt as the separ-
words the decision which component comes out as the light ating agent in extractive distillation of ethanol-water mixture.
646 H.B. Aditiya et al. / Renewable and Sustainable Energy Reviews 66 (2016) 631–653

Table 5
Researches on diffusion distillation for anhydrous ethanol production.

Researcher(s) Description of the study Ref.

Fullarton and
Diffusion distillation study by varying alcohol-water mixtures, inert gasses, condensation and evaporative temperatures, wetted-wall co- [175]
Schlunder lumn's annular widths.

Alcohol-water mixtures including: isopropanol-methanol-water and isopropanol-water.

Illustrated by Stefan-Maxwell and vapour-liquid equilibrium equations modelling.

Does not further explain the essence behind the diffusion distillation process.

Results obtained are not further process to show possible potential separation extension.
McDowell and
Improvement of Fullarton and Schlunder modelling study by computerised simulation. [178]
Davis
Reveals the important parameters and gives wider exposure of the nature of diffusion distillation through the integral column which created
by the simulation.
Taylor and
Suggests the improved method by McDowell and Davis to be practiced in anhydrous ethanol production. [180]
Krishna
Chung et al.
Performed diffusion distillation with observation on the effect of the distillation parameters, including temperature in evaporation and [176]
condensation process, annular widths and the selection of the inert gas.
Kim et al.
Modelling development of previous researches by including heat transfer of sensible heat [177]

Algorithm development to compute interfacial temperature to have better accuracy.
Singh and
Proposed a way to obtain the optimum temperature of vaporisation by a introducing new variable Saz(N2/N1), which quantified as 46 °C. [179]
Prasad
The experimental results were aligned with the theory of Stefan-Maxwell equations.

Fig. 12. Extractive distillation schematic diagram (water-ethanol binary azeotropic mixture). Extractive column is where the light component extracted, while heavy
component is extracted at the recovery column [182,183].

Soares et al. [193] conducted a study in using different salts to From the energy consumption analysis, 82% of the total energy
dehydrate ethanol from ethanol-water azeotrop, including calcium consumption, or 22.1 MW accounted for the first proposed process
chloride, potassium acetate, sodium chloride, sodium-potassium was spent only on the salt recovery process. The opposite was
acetate mixture and calcium nitrate. The study observed the found on the second proposed process, which salt recovery pro-
ethanol concentration on the top and the bottom feed of the col- cess only accounted 9.7% of the total energy consumption, or
umn, which showed enhancement by the salt addition than the 0.555 MW. The authors also claimed that the second proposed
one without. Ligero and Ravagnani [190] performed salt extractive process requires lesser dimension of the equipment, absence of
distillation by varying the salt recovery processes. The first pro- multiples recovery columns, lesser cool water and hot air for
posed process was by introducing the salt to the ethanol-water condensation and drying process, and is easy to be installed. Usage
feed in the first column. The bottom products, water and salt, were of salt as the separating agent has also reported to be suitable in
drawn to the multiple recovery columns where they were eva- salt-solvent combination for extractive distillation. In a study by
porated and dried (by spray dryer). Anhydrous ethanol produced Lei et al. [194], calcium chloride was mixed with ethylene glycol in
from this process was drawn out from the first column as the top ethanol-water mixture, and it was compared with distillation
product. In contrary, the second proposed process by the same process of plain ethanol-water and ethanol-water with only
authors was by pre-treating the feed prior introducing it to the ethylene glycol as the separating solvent. The presence of calcium
separating salt. In the first column, the feed was distilled to have chloride salt with solvent was observed enhancing than the other
better ethanol concentration and was flowed to the second col- processes tested. This however limited to the concentration of the
umn afterwards. The salt was initiated in the second column with salt mixed with solvent, which was best at 5–10%. Mixing salt with
the more concentrated ethanol in the feed. The difference lies on solvent benefits in the ways of lowering required salt to be re-
the salt recovery step, where evaporation columns were un- covered, lesser theoretical plates, and lesser equipment cost and
necessary and only spray dryer was installed to recycle the salt. energy consumption.
 H.B. Aditiya et al. / Renewable and Sustainable Energy Reviews 66 (2016) 631–653 647

Table 6
List of substances with boiling points and dielectric constant [186,187].

Substance Boiling point Dielectric

(°C) constant

1-butanol 117.7 17.8

1-propanol 97 20.1
1,2-dichloroethane 83.5 10.42
1,3,5-Trimethylbenzene 164.716 2.279
1,4-dioxane 101.1 2.21
2-butanol 99.5 17.26
2-butanone 79.6 18.6
2-propanol 82.4 18.3(25)
2-methylpyridine 129.4 9.46
3-methylpyridine 143.8 10.71
Acetic acid 118 6.2
Acetone 56.3 20.7
Acetonitrile 81.65 36.64 Fig. 13. Simplified version of membrane distillation process [195].
Butyl ether 142 3.06
Carbon tetrachloride 76.8 2.24
Chlorobenzene 131.7 5.69
Chloroform 61.2 4.81 experiment, the ethanol mixture used was produced in-
Cyclohexane 80.7 2.02 dependently from molasses wort undergone fermentation process
Diethylbenzene 181.102 2.369
(Lyophilised S. cerevisiae was employed in the fermentation). The
Diglyme (diethylene glycol dimethyl ether) 162 7.23
DME, glyme (1,2-dimethoxy-ethane) 84.5 7.3 selected membrane material was polypropylene microporous hy-
DMF (N,N-dimethylformamide) 153 36.71 drophobic capillary, with dimensions of 0.2 mm pore diameter,
DMSO (dimethyl sulfoxide) 189 48.9 capillaries diameter 1.8 and 2.6 mm for inside and outside re-
Ethanol 78.3 25.7 spectively (Fig. 14) [182,197]. Temperature difference of 20 °C was
Ethyl acetate 77 6.02
Ethylene glycol 195 37.7
set between the distillate and fermentation bioreactor: 15 °C at the
Glycerine 290 42.5 distillate side while 35 °C at the fermentation bioreactor. Com-
Heptane 98 1.92 pared to batch fermentation (without membrane distillation),
Hexamethylphosphoramide (HMPA) 232.5 31.3 ethanol recovery with membrane distillation was observed to be
Methanol 64.6 32.6
15.6% higher. In continuous fermentation (with membrane dis-
Methylene chloride 39.8 9.08
n-Hexane 68.7 1.89 tillation) ethanol produced was 0.45 g ethanol/g glucose, which
NMP (N-methyl-2-pyrrolidone) 204 32 visibly higher than the one produced in batch fermentation (0.38 g
Nitromethane 101.2 35.9 ethanol/g glucose). Membrane distillation also increased the
Pentane 36.1 1.84 ethanol productivity of the process from 1.4 g/L.h ethanol by batch
Pyrrole 130 8
Tetrahydrofuran (THF) 65.4 7.58
fermentation to 2.15 g/L.h.
Toluene 110.6 2.38 Although frequently mistaken with membrane distillation,
Triethyl amine 88.9 2.4 pervaporation is another type of membrane process that also can
Water 100 78.54 be exploited in producing anhydrous ethanol. To distinguish the
Xylene 144.4 2.266
two, some essential characteristic must be examined. Based on the
*Note: values of dielectric constants are taken at averagely 20–25 °C material selection, pervaporation technique uses thick polymer
membranes, while microporous, non-wetting membranes are
employed in membrane distillation [198]. The permeability force
Table 7
Energy consumption in extractive distillation by various separation agent in pervaporation is from the low vapour pressure established by
[171,190,191]. condensation of the permeate vapour. On the other hand, mem-
brane distillation forces permeability from the difference of partial
Type of agent Separation agent Consumption of energy (MJ/kg ethanol)
pressure between the membrane pores' sides. Membrane material
Liquid solvent Benzene 13.59
selection in pervaporation is dependent upon the affinity of the
Liquid solvent Ethylene glycol 34.06 feed to the membrane, while membrane distillation selects its
Liquid solvent Diethyl ether 13.59 membrane materials according to the membrane properties and
Liquid solvent Pentene 10.87 the application of the distillation process [198,199]. Regarding the
Salt Calcium chloride 5.02
membrane selection for membrane distillation, a recent study by
Salt Potassium acetate 9.27
Vacuum Vacuum 11.72 Wang and Chung [195] reported the development of membrane
fabrication, including mixed matrix membranes and other mem-
branes modifications.
2.4.6. Membrane distillation Traditionally, anhydrous ethanol can be achieved by vacuum
Distillation through membrane stimulates mass transfer of spe- distillation, which is by lowering the pressure below 11.5 kPa to
cific component from the mixture through a semipermeable mem- disrupt the azeotrope system of the ethanol-water. Once the azeo-
brane by permeability principle (Fig. 13) [195]. Surface tension of the trope is disrupted, the separation can be run conventionally, which
membrane blocks the feed, while the volatile component crosses the usually takes two columns: first column is at moderate pressure,
membrane. Typically, organic polymers are chosen as the mem- where the second column is at the low pressure [167]. Nevertheless,
brane, though some gas, liquid, metal and ceramic materials are also modification of conventional vacuum distillation to vacuum mem-
applicable. For the real application, membrane distillation is useful in brane distillation has been performed by Izquierdo-Gil and Jonsson
wastewater treatment, desalination of seawater, dairy processing [200] to gain both vacuum and membrane distillation favourable
and separating volatile components [167,195]. properties. In their research, factors affecting the ethanol distillation
In their study of membrane distillation, Lewandowicz et al. were observed, including pore sizes and materials of the membrane,
[196] ran an experiment for ethanol recovery attempt. In their temperature of the feed, native characters of the mixtures and flow
648 H.B. Aditiya et al. / Renewable and Sustainable Energy Reviews 66 (2016) 631–653

Fig. 14. Polypropylene membrane under scanning electron microscope. (A) Undergone melt-extrusion-mono-axially-stretching fabrication. (B) Undergone thermally induces
phase separation (TIPS) fabrication [182,197].

rate of the cycle. Additionally, the membranes used were poly- reported that by 2030 the cost of bioethanol production can reach
tetrafluoroethylene, polypropylene and polyvinylidene fluoride with as low as US$ 0.55–0.65/lge (litre gasoline equivalent). The fore-
variance of pore sizes. This study displayed highly reliable experi- casting also predicted the production cost by 2050 would reach a
mental results as they were agreed with the theoretical estimations slightly smaller range of US$ 0.55–0.60/lge. The forecast is noted
by Knudsen model. with the scenarios of 50% reduction of annual carbon dioxide
Membrane distillation holds several practical benefits, for in- emission by 2050, high priority in the second generation pro-
stance, works at rather lower temperature and pressure, perfect duction global development, and the expectation to drastically
theoretical separation and less mechanical properties requirement fulfil the 26% of biofuel demand for transportation sector from
[195]. In contrast to those, Lewandowicz et al. [196] claimed that year 2030–2050. In a techno-economic study in Colombia by
membrane distillation technique is impractical once it is installed Quintero et al. [203], production cost of bioethanol from empty
in a commercial scale, which namely due to the heat loss and fruit bunch as the lignocellulosic feedstock is as low as US$ 0.58/
module design problems that further expand the cost inefficiency. litre for the stand-alone production plant, and US$ 0.49/litre by the
Suitability of the selected material for membrane is another co-generation plant system. The authors also reported the analysis
challenge since the membrane fabrication spends high technolo- of bioethanol production from other lignocellulosic materials,
gical, energy and production costs [195]. which is listed in Table 8 [203]. In Malaysia, Tye et al. [204] de-
scribed the production cost of bioethanol is estimated as around
US$ 5.62/GJ, which is comparable with the petrol fuel production
3. The future of second generation bioethanol production cost of US$ 5.12/GJ (US$1 E RM4.23, as per December 2015 rate).
Even though at the moment it seems that bioethanol production
When second generation bioethanol is implemented wholly in cost is higher than petrol, the feedstock cost accounts majorly in
industry, it becomes an industrial strategy to fulfil both industries the total production cost. This means it is possible to have a fea-
demands in energy sector (especially renewable energy sector) for sible, in fact cheaper, bioethanol production cost than fossil fuel in
its biofuel product; and agricultural sector for its role in utilising the future.
the biomass as value added product. Also, unsurprisingly bioe- The sustainable future for second generation production is
thanol has gained many popularity in both developed and devel- strongly related with the development of the current technology.
oping countries since the reliance of fossil petrol has always been The advance in technology is what makes the current production
harmfully striking the global environment, air quality, as well as of 270 l/tonne biomass to as high as 400 l/tonne biomass in the
the oil reserves. At the current state, first generation production is future year 2030 as forecasted by the National Renewable Energy
well-developed in several countries to supply the bioethanol de- Laboratory (NREL) [205]. The success of second generation pro-
mand for transportation sector. However, the dependence of first duction is also impeccably reliant to the government policies. The
generation production in its edible feedstock has started to raise capital investment in this route is undeniably high and risky. But
many sceptical opinions questioning the sustainability issue of this with the support from the government by its policies will not only
approach. The edible feedstock is concerned to contribute negative help uplift the possibility of second generation production, but
impacts in the world's societies since it looks inhumane and irony also will allow the further actions of many research applications to
to ‘feed’ the vehicle than millions of malnourished world's popu- suppress the environmental harms caused by the emissions of the
lation. The prospect of second generation bioethanol production non-renewable energy products. Sims et al. [54] stated that in the
eliminates the bad image of bioethanol production since it simply establishment of policies regarding the route of second generation
utilises the non-edible feedstock (from agricultural and forestry production there are several points and objectives needed to be
biomass). covered, including (i) improvement of crop productivity along
Second generation bioethanol production is forecasted to be with the balance ecosystems, (ii) evaluation on greenhouse gas
excelled than the first generation production in approximately the emission and soil carbon content, (iii) analysis of the total pro-
next ten years due to the unfavourable characteristic of the first duction cost from collection to distribution and (iv) opportunities
generation feedstock. In fact, it is expected that second generation to allow production from different technologies to produce the
bioethanol production will overlap the dominance of the first better production efficiency. The same authors also suggested the
generation production in the biofuel global market [201]. The In- government to imply the policies through tax credits or fuel-
ternational Energy Agency (IEA) [202] has forecasted the cost of blending targets. The visible outcomes may be directly obtained by
production of bioethanol from lignocellulosic biomass. IEA setting the national fuel-blending targets, although tax credits
 H.B. Aditiya et al. / Renewable and Sustainable Energy Reviews 66 (2016) 631–653 649

Table 8 designs (CCRD), partial factorial and full factorial [208]. As one sce-
Production cost from different lignocellulosic materials [203]. nario example, oil palm biomass can be focused as the primary
Malaysia's tropical feedstock for bioethanol production, since it is the
Biomass Production cost from stand- Production cost from co-
alone plant (US$/litre) generation plant (US$/litre) home of 5.1 million hectares of oil palm and occupies 77% of Ma-
laysia's agricultural land [209]. Because of this massive oil palm
Coffee cut stems 0.68 0.59 production in Malaysia, the potential of second generation bioe-
Empty fruit 0.58 0.49 thanol that could be produced from oil palm biomass has been re-
bunch
Rice husk 0.64 0.53
ported as about 13.5 million-tonnes in 2014 alone, which makes oil
Sugarcane 0.77 0.68 palm biomass is the wisest choice to be considered here [210]. Oil
bagasse palm biomass is high in cellulose and low in lignin, especially in
frond, empty fruit bunch (EFB) and trunk [207], hence ammonia fi-
bre explosion (AFEX) is one suitable pre-treatment method for this
bring the potential in the improvement of the production cost. biomass type [211]. Besides the advantage of having ammonia traces
Government policies should also charm the private industrial during the process and further utilised as microbes food (as nitrogen
players to contribute to the actualisation of the new route, thus source) [57,90], oil palm biomass pre-treatment via AFEX also re-
shorter development period and more positive impacts are quires no effort in inhibitors removal process, hence lesser refinery
reachable. Consequently, this interesting industry of bioethanol cost is required. Hydrolysis can be done enzymatically by cellulase.
production can also open many employment opportunities and Balat [211] stated that enzymatic hydrolysis requires lesser utility
develop rural areas of where the biomass is mostly collected from. cost, and Saini et al. [208] found that commercial enzyme technol-
This because to develop a new branch of industry it requires hu- ogy is developing very well which leads to the cost reduction of the
man resources with high educational level, of which the industry commercial enzyme. To simplify the production, enzymatic hydro-
will subsequently elevate the society's educational level to fill the lysis of oil palm biomass in Malaysia can be co-conducted with
vacancies. In other words, the new industry will not only bene- fermentation, or is called as simultaneous saccharification and fer-
ficial to satisfy the energy demand renewably but also to develop mentation (SSF) method. The obvious value to select this method is
the society to the better economy state [21]. With a solid com- the simultaneous process reduces the direct production cost, than
mitment from all industrial players and supporting policies set by having separate conventional hydrolysis and fermentation processes
the government, the benefits of second generation production are that automatically needs higher processing cost to fulfil. To refine
feasibly extractable. the fermentation product, extractive distillation method by Ligero
It is well-known that second generation bioethanol production and Ravagnani [190] can be performed afterwards, since the method
is still at its embryonic phase. However, experts have started to is claimed to require lesser energy input with the good quality of
develop the suitable approach by conducting numerous studies to distillation product. Although, it must be noted that this benefit can
carry out the concept into real-life scale. Limayem and Ricke [206] only be gained with soluble salt as the separating agent, along with
suggested to use Life Cycle Analysis (LCA) to compare the favour- other benefits of low toxicity, less space required in the column,
ability from multiple possible routes resulted from the growing easier to be logistically transported, tough against corrosion and its
technologies development. Moreover, the authors also suggested recyclability characteristic [190,192].
to optimise each of the production stage, to yield the ideal amount As one of rapidly developing countries in the Southeast Asia
of ethanol. The optimisation can be done by setting up the pre- and one nation with massive potential in green technology, Ma-
ferable constrains as the parameters, for instance amount of water laysia is one good model to be set a new standard on second
used, total energy used, total production cost, amount of waste generation bioethanol scheme, and it seen capable to afford the
produced, etc. Moreover, pre-treatment, as the beginning stage of technologies mentioned in the given scenario example. However, a
bioethanol production, can be taken into the focus in optimisation thorough study (e.g. LCA study) is still compulsory for Malaysia in
to result better fermentable sugar. Haghighi Mood et al. [25] re- order to establish the second generation bioethanol production
ported various pre-treatment methods in second generation nationally. The existence of national car manufacturers, Proton and
bioethanol production as well as their limitations. The authors Perodua, may actually help Malaysia to promote the actualisation
stated that the most suitable pre-treatment method can be applied of bioethanol fuel as the product of the national renewable energy
through the basic comprehension of the available pre-treatment sector, such as by manufacturing flexible-fuel vehicles (FFV) in the
technologies, feedstock characteristics, and the connection be- future, as long as it is paired with the adequate government po-
tween these two. licies to initiate and attract the investors into the programme
As one of South East Asia countries with enormous tropical [207]. Malaysia can look up to Brazil, which as one of the leading
biodiversity, Malaysia has the appealing tremendous potential seen bioethanol implementers, in terms of practicing the national
from the availability of raw feedstock, yet Malaysia still has not bioethanol policies. Brazil includes several important key points in
implemented the second generation bioethanol policy to its national energy policy making, which are comprised of: involving private
primary sectors, especially the transportation sector which can sector in the entire national bioethanol production development,
benefit directly from the production of bioethanol. LCA and opti- enforcing fuel tax policy that based on carbon-footprint, granting
misation of bioethanol production in Malaysia, therefore, are es- research funds for bioethanol production further development and
sential as the fundamental to start the prospect. Goh et al. [207] FFV endorsement [207,212]. A more local perspective is delivered
studied the possibility of lignocellulosic bioethanol in Malaysia. They by Poh and Kong [213] in a study of renewable energy policy
claimed that to validate the establishment of bioethanol refineries analysis in Malaysia. The authors suggested that in order to initiate
must include availability of the feedstock, domestic demand, feed- the second generation bioethanol policy, it should be started with
stock collection scheme, proper feedstock storage and transporta- a consistent awareness spreading programme on second genera-
tion. In fact, these factors can be considered in LCA study for Ma- tion bioethanol to all layers of society and industries. Also, Ma-
laysia case according to the real condition in Malaysia. Optimisation laysia's government must involve external (private) sectors in
study is equally essential in order to design the suitable bioethanol running this new renewable energy scheme and should ease and
refinery sites in Malaysia, which can be done commonly by response secure any loan relevant to second generation bioethanol scheme
surface methodology (RSM), and various optimisation analysis to attract more investors. Further, as an additional supporting
techniques including Box-Behnken, central composite rotatable study, Tye et al. [204] revealed that 10% ethanol blend in petrol
650 H.B. Aditiya et al. / Renewable and Sustainable Energy Reviews 66 (2016) 631–653

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