Renewable Energy Focus  Volume 28, Number 00  March 2019 www.renewableenergyfocus.

com

RESEARCH REVIEW
Promising evolution of biofuel
generations. Subject review
Hayder A. Alalwana,*, Alaa H. Alminshidb and Haydar A.S. Aljaafaric,d
a
Mechanical Technical Department, Kut Technical Institute, Middle Technical University, Baghdad, Iraq
b
Chemistry Department, Wasit University, Kut, Wasit, Iraq
c
Department of Chemical and Biochemical Engineering, University of Iowa, Iowa City, IA 52242, United States
d
Chemical Engineering Department, University of Technology, Baghdad, Iraq

Biofuels have attracted a lot of attention due to the increasing demand on energy resources as well as
elevated concerns about greenhouse gas emissions. In contrast to other green energy resources, biofuels
can provide liquid fuels which are essential for transportation. This review reports recent advances in
liquid biofuels, focusing on their generations and types. Generally, biofuels are classified into four
generations based on the type of the feedstock that is used. First generation biofuels utilize edible
biomass which sparked controversy because it competes with global food needs. Second generation
biofuels use non-edible biomass but there are still some limitations related to the cost-effectiveness
involved in scaling the production to a commercial level. Third generation biofuels use microorganisms
as feedstock, while fourth generation biofuel focuses on modifying these microorganisms genetically to
achieve a preferable hydrogen to carbon (HC) yield along with creating an artificial carbon sink to
eliminate or minimize carbon emissions. These last two generations of biofuel are still in early
development stages. This article reviews and summarizes 124 papers, 77% of which were published
within the last three years. The aim of this work is to provide an overview of the four liquid biofuel
generations as well as the latest development efforts in this field. This review concludes that the current
production methods of biofuel in the first and second generations will soon fail to satisfy the increasing
demand on biofuel. Therefore, development efforts should be focused on third and fourth generations,
specifically the genetic engineering of algae.

Introduction suppress the rapid increase in the environmental CO2 concentration

In the twentieth century, change in the global climate was identified resulting from fossil fuel combustion. Also, the high demands on
as one of the most serious issues that the world faces. The main fossil fuels leads to another problem which is a severe depletion of
reason for this problem is high consumption of fossil fuels which this important source of energy.
represent about 80% of the global energy usage [1]. The combustion Although there are several ways to create clean energy from the
of fossil fuels results in the emission of greenhouse gases, especially wind, sun, and water, the use of biomass is very important because
CO2. There are several techniques that are used to capture CO2 such unlike the other energy sources it provides liquid fuels for trans-
as adsorbing by chemicals like amines, carbonates, and ammonia or portation. The United States (USA) is at the forefront of the biofuel
by pre-combustion techniques such as chemical looping combus- market with a target of substituting 20% of transportation fossil
tion processes [2,3]. However, these techniques are insufficient to fuels with biofuel by 2022 [4]. Based on feedstocks and method of
production, biofuels are classified in different groups named as
*Corresponding author. Alalwan, H.A. (hayderabdulkhaleq-alalwan@uiowa.edu) first, second, third, and fourth generation biofuels [4].

1755-0084/ã 2019 Elsevier Ltd. All rights reserved. https://doi.org/10.1016/j.ref.2018.12.006

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Nomenclature objectives of this work are (a) to summarize and systematize the
ETBE Ethyl tertiary butyl ether peer-reviewed data; (b) to provide details illustration about the
GHG Greenhouse gas production arts of biofuels and their evolution; and (c) to illustrate
DDGS Distillers’ dried grains and soluble the advantages and drawbacks of each biofuel’s generation and
CGM Corn gluten meal production method. Thus, this manuscript is written as a broad
CGF Corn gluten feed review covering all biofuel production aspects which is lack in the
TAEE Ter-amyl ethyl ether recent review articles in this field.
ASTM American Society for Testing and Materials
CoA Coenzyme A Generations of biofuels
First generation
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FAME Fatty acid methyl ester

DME Dimethyl ether First-generation biofuels produced from edible biomass such as
MTBE Methyl teritiary-butyl ether starch (from potato, wheat, barley, and corn) or sugars (from sugar-
DEE Diethyl ether cane and sugar beet), initially showed a promising capability in
TAME Ter-amyl methyl ether minimizing the fossil fuels combustion and lowering atmospheric
VOC Volatile organic compound levels of CO2 which is consumed by crops as they grow [13].
FA Fatty acids However, concerns arose about using edible crops as feedstocks
and the impacts on croplands, biodiversity, and food supply.
First-generation biofuels, which are produced commercially today
at around 50 billion liters per year, include biodiesel (bio-esters), and
First-generation biofuels use edible biomass such as starch and bioethanol, as well as bio-gas. Unlike the other two types of biofuels,
sugar [5] which increases the cost of production and causes ineffi- bio-gas, which is derived from anaerobic processing of manure and
cient utilization of resources and energy spent in cultivating crops. other biomass sources, has limited utilizing the transportation sector
Specifically, using edible biomass competes with food crops, requires [14]. The fuels are evaluated either by their abilities to be blended
significant amounts of fertilizer and water, and large areas of crop- with petroleum-based fuel for use in internal combustion engines or
land [6]. The second generation of biofuels are based on more by their utility in alternative vehicle technology such as natural gas
efficient renewable alternatives by utilizing inedible lignocellulosic vehicles or flexible fuel vehicles [14]. Several points must be consid-
biomass such as switch grass, sawdust, low-priced woods, crop ered in the evaluation of edible biomass to produce biofuel. These are
wastes, and municipal wastes [7]. While this generation overcomes (a) the biomass chemical composition, (b) energy balance, (c) avail-
the drawbacks of the first generation, more steps are required to ability of croplands and the contribution to biodiversity and crop-
produce adequate biofuels at a competitive cost [6]. The last few years land value losses, (d) competition with food needs, (e) cultivation
have seen several studies aiming to achieve this goal by using practices, (f) emission of pollutant gases, (g) impact of mineral
thermal, biological, enzymatic or chemical processes. Obstacles absorption on water resources and soil, (h) use of pesticides, (i) cost
have been encountered with all these conversion techniques. How- of the biomass and its transport and storage, (j), soil erosion, (k)
ever, chemical processes are identified as the most flexible [8]. economic evaluation considering both the coproducts and feed-
Combinations of multiple processes have also been investigated stocks, (l) creation or maintenance of employment, and (m) resource
such as the production of sugar solution from biomass using a availability such as water [15].
chemical method followed by an enzymatic or biological step [8].
Aquatic feedstock such as alga biomass is used in third-generation First generation bioethanol
biofuels [9]. Algae, which are photosynthetic plants such as seaweed, Bioethanol fuel is liquid ethyl alcohol (C2H5OH or EtOH) produced
capture high quantities of CO2 and generate O2 as well as oil [6]. from feedstocks such as wheat, sugar beet, and corn through fermen-
However, this kind of biomass has some disadvantages such as its tation. Its primary application is in motor vehicles. It can be used as a
high cost and the fact that biofuel produced from algae is less stable transportation fuel in its pure form or by blending it with gasoline in
than that produced from other sources. The main reason for this is traditional combustion engines especially in flex-fuel vehicles. It is
that the oil generated by algae is highly unsaturated, which means it most commonly blended with gasoline at a low percent (10% bioetha-
is more volatile especially at high temperatures, and therefore more nol) which known as E10. It can be also used as a feedstock to produce
likely to degrade [10]. Fourth-generation biofuels, which are still in ethyl tertiary butyl ether (ETBE) which is blended with gasoline to
an early developmental stage, use bioengineered microorganisms increase its oxygen content for pollution control [16].
such as bioengineered algae or crops that are genetically altered to Historically, bioethanol was utilized industrially in Germany
consume more CO2 from the environment than they emit when and France as early as 1894 [17]. In 1925 Brazil started to use it as a
they are consumed (burning). Biofuels are used to produce different transportation fuel. Its use as fuel was common in Europe and the
fuels including ethanol, butanol, hydrogen, methane, vegetable oil, United States until the early 1900s. However, due to its high
biodiesel, isoprene, gasoline, and jet fuel [11,12]. production cost, it was ignored especially after World War II until
This article provides a comprehensive review of the four gen- the oil crisis of the 1970s [18]. In the last three decades, the use of
erations of biofuels including their advantages, limitations, tech- bioethanol has gotten more attention as an alternative transpor-
nologies, and evaluations. This work summarizes the most recent tation fuel. Several countries such as Brazil and the USA have long
contributions, criticisms, and evaluations that have done in this promoted domestic production of bioethanol.
field. Particularly, this article reviews and summarizes 124 papers, Shifting to the use of bioethanol as a green energy source could
77% of which were published between 2015 and 2018. The main decrease CO2 concentrations in the atmosphere in two ways. First

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it reduces dependence on fossil fuels, and second it consumed CO2 Biodiesel fuel depends mainly on oil crops and 75% of its
in the atmosphere to grow the feedstock crops. Global bioethanol production cost is due to the feedstock production cost [28]. More
production reached about 93 billion liters in 2014 which is approx- than 350 oil-bearing crops, both edible and non-edible, have been
imately four times more than its production a decade earlier [19]. A suggested as promising feedstock for biodiesel manufacturing [29].
recent investigation showed that most bioethanol production is The most common food crop sources are rapeseed, soybean, palm,
based on sugarcane and maize followed by wheat, sugar-beet, and sunflower, peanut, safflower, corn, rice bran, coconut, olive, cas-
sorghum. These crops could have fed 200 million people [5], thus tor, milkweed seed, and linseed. Jatropha curcas, Pongamia glabra,
concerns arose about competition of fuel with food needs. Madhuca indica, Salvadora oleoides, cotton seed oil, Tobacco, Calo-
In term of edible biomass, sugarcane is the highest crop used in phyllum Eruca Sativa Gars, inophyllum, terebinth, rubber seed,
bioethanol production and requires less water than maize and desert date, Jojoba, neem oil, leather pre-fleshings, apricot seed,

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wheat [5]. The USA is at the forefront of the bioethanol market Pistacia chinensis Bunge Seed, sal (Shorea robusta) and fish oil,
with about 47% of the global bioethanol production [20]. Moringa oleifera and croton megalocarpus are common non-edible
To produce high bioethanol equality from crops with reference oil sources.
to greenhouse gas (GHG) benefits, two important requirements Several technologies have been established to produce high
should be considered. These are the wise choice of croplands and quality biodiesel such as direct use and blending, pyrolysis of
fertilization strategies to avoid increasing the carbon concentra- vegetable oil micro-emulsions, and transesterification. The direct
tion in/on ground and minimize nitrous oxide emissions [21,22]. use of vegetable oils blended with diesel fuel is used to overcome
In addition, by-product production should be emphasized and the drawbacks of using the high viscous pure vegetable oil. These
utilized efficiently to maximize the cost effectiveness. drawbacks include coking and trumpet formation on the engine
Several carbohydrate-containing crops have been utilized as injectors after long-term use, as well as carbon deposits, thickening
feedstocks for ethanol production using a fermentation process. and gelling of the lubricant, and oil ring sticking [28]. Another
These feedstocks are classified in two major categories: (a) Sugar- common solution is decreasing the vegetable oil’s viscosity by
containing crops, such as palm juice, sugar cane, beet root, wheat, preheating it and that also improve the atomisation and mixing
fruits. (b) Starch-containing crops including grain, such as wheat, process to achieve better combustion [30].
barely, sweet sorgum, rice, and corn. The direct conversion of Micro-emulsification can be used to solve the high viscosity
starch to ethanol cannot be done using conventional fermenta- issue of vegetable oils. Micro-emulsion is defined as clear thermo-
tion technologies due to the long chain polymer structure of dynamically stable isotropic liquid mixtures of oil with dimen-
glucose [23]. Therefore, a practical approach involves breaking sions range between 1–150 nm created spontaneously from two
down the macromolecular structure first into simpler and smaller normally immiscible fluids and one or more ionic or non-ionic
glucose molecules. In order to do this, starch feedstocks are con- amphiphiles [31]. Microemulsions consists of three phases, which
verted to a mash typically containing 15–20% starch. The process are surfactant, oil, and aqueous phase. Methanol and ethanol are
involves starch grinding, mixing with water, and then cooking at the common solvents used in this process. The standard viscosity
or above its boiling point. The process also requires using two limitation for diesel engines can be achieved by all micro-emul-
enzymes. The first enzyme, amylase, breaks down starch molecules sions with butanol, hexanol and octanol [32,33]. The pyrolysis
to short chains and releases dextrin and oligosaccharides. These process is also used to enhance the quality of biodiesel by thermal
components are hydrolyzed in a process known as saccharification and catalytic means. In pyrolysis a conversion of one substance
which uses enzymes such as pullulanase and glucoamylase. This into another can be achieved by using heat or with the assistance
process converts all dextrans to glucose, maltose and isomatose. of a catalyst in the absence of oxygen. Compared with other
The next step is cooling the mash to 30  C and yeast is added for cracking processes, pyrolysis is very simple, waste-free, pollution
fermentation [24]. free, and very efficient [34].
Bioethanol production from corn can be classified into wet & dry Transesterification of oils (triglycerides) with alcohol is the most
mill processes [25]. The wet mill ethanol process has usually a developed and promising method of biodiesel production which
higher production capacity than the dry process and produces produces glycerine as a by-product. Figure 1 which is adapted from
some valuable coproducts such as nutraceuticals, pharmaceuticals, Ghazali et al. shows the transesterification reaction of triglycerides
organic acids and solvent [26]. In addition to ethanol, the dry [31]. Transesterification, or alcoholysis, is replacing alcohol from
milling process produces distillers’ dried grains and soluble an ester with another alcohol in a similar way to hydrolysis, but
(DDGS) which is an excellent livestock feed because it contains using alcohol instead of water [35]. Figure 2 shows the process
protein, fats and carbohydrates. On the other hand, in addition to diagram of biodiesel produced by the transesterification reaction
ethanol the wet milling process produces corn oil, and two types of using alkali catalyst [36]. Catalysts usually speed the completion of
animal feed which are corn gluten meal (CGM) and corn gluten the transesterification reaction. Several operating variables such as
feed (CGF) [27]. reaction temperature, time, and pressure, as well as the molar
ratios of alcohol to oil, catalyst concentration and type, mixing
First generation biodiesel intensity and kind of feedstock can affect the transesterification
Diesel fuel, which has a chemical formula range between C10H20 to process [37].
C15H28 with an average molecular weight 168 (amu), is an impor- Albayati and Doyle recently reported using the incipient wet-
tant liquid petroleum fuel that is widely used in transportation. ness impregnation method to manufacture nonporous catalyst,
Several technologies have been well established to produce bio- SBA-15, from encapsulated of alkali metals and their hydroxides to
diesel (fatty acid esters) from different feedstocks. produce biodiesel from sunflower oil [38]. Specifically, they used

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FIGURE 1
Transestrification reaction of triglycerides with alcohol.
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FIGURE 2
A schematic diagram of biodiesel production according to the transesterification process.

Na, NaOH, Li, and LiOH to prepare the catalyst which showed to achieve 93% and 89% for batch and continuous reactors,
promising results with yields of fatty acid methyl ester (FAME) in respectively [41].
the range between 96 to 99% at moderate process conditions (1
atm and 65  C). The catalyst also showed high production stability First generation bioethers
and easy recovery through seven production cycles under the same Bioethers (also known as fuel ethers) are used to enhance the
conditions with better fuel properties than those of fossil fuels. octane number of fuels. They can replace petro-ethers and improve
Also, Doyle et al. reported that using zeolite Y, with a Si/Al ratio engine performance [42]. Furthermore, bioethers can greatly
3.1 for the biodiesel production from oleic acid esterification with reduce engine wear and toxic exhaust emissions [42]. They are
ethanol increased the oleic acid conversion to 85% comparing produced by the reaction of bioethanol with iso-olefins, such as iso-
with 76% using commercial catalyst of HY zeolite [39]. Later, the butylene. The usual source of bioethers are wheat and sugar beet
same research group reported that using FAU-type zeolites showed [43]. However, their main drawback is low energy density. There
similar oleic acid conversion to that reported for commercial HY are six ether additives that are commonly used to enhance trans-
zeolite [40], while addition of Co-Ni-Pt to the FAU-type zeolites portation fuel quality: dimethyl ether (DME), methyl teritiary-
enhanced its efficiency in biodiesel production in the same process butyl ether (MTBE), diethyl ether(DEE), ter-amyl methyl ether

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(TAME), ethyl ter-butyl ether (ETBE), and ter-amyl ethyl ether fermentation, and (4) product separation/ distillation [56]. The
(TAEE) [44]. Ethers have been used in Europe since the 1970s to hydrolysis step increases the complexity of the fermentation of
replace highly toxic compounds such as lead especially MTBE and sugar which is released from the cellulosic part of the biomass, and
ETBE. However, bioethers are no longer used in the USA as fuel fermentation converts these sugars to bioethanol. To promote the
additives [45]. hydrolysis step, a pretreatment step is required that softens the
biomass and breaks down its cell structures. An efficient pretreat-
Second generation ment must meet the following standards: (1) enhance the forma-
In this generation, a more sustainable protocol is used to produce tion of sugars by hydrolysis, (2) avoid the degradation or loss of
biofuels. The net carbon (emitted–consumed) from combusting carbohydrate; (3) avoid the formation of undesired by-products
second-generation biofuels is neutral or even negative. The feed- that reduce the hydrolysis and fermentation process efficiencies,

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stock is lignocellulosic material which include the inexpensive and and (4) be economically feasible [57].
abundant nonedible biomass available from plants [46]. The cost- Fermentation is the metabolic process in which an organic sub-
effectiveness of this generation of biofuels still needs development strate is converted due to the activities of enzymes excreted by micro-
because there are several technical barriers that need to be overcome organisms. Generally, there are two main methods of fermentation
[47]. The use of waste plant biomass has attracted researchers for a (a) aerobic and (b) anaerobic according to whether oxygen is
wide variety of uses such as feedstock to generate heat and electricity involved in the process or not [58]. Thousands of micro-organisms
by direct burning [14,48] or as a raw material for wastewater treat- in nature have been identified as fermentative agents. Some of these
ments [49]. However, utilizing it as an inexpensive source of biofuel are used to convert sugar and starch to ethanol. The use of micro-
is very attractive [50]. A wide variety of abandoned materials can be organisms for ethanol production relies on three main types which
used as biofuel feedstock such as agriculture waste, poplar trees, exist in nature and are very selective in their fermentation char-
willow and eucalyptus, miscanthus, switchgrass, reed canary grass, acteristics. These types are yeast (saccharomyces species), bacteria
and wood and they mostly consist of plant cell walls whose primary (zymomonas species), and mold (mycelium) [59]. Some of these
components is polysaccharides (75%) [50,51]. These polysacchar- micro-organisms are specific to hexoses or pentose, or mixtures of
ides have a high sugar content which is preferred for biofuel produc- both [14]. Developing ideal micro-organisms, which can convert
tion. However, agricultural by-products can provide only a limited any carbohydrate to ethanol has attracted a lot of attention [14].
proportion of the increased demand for biofuels [14].
The feedstock is also known as lignocellulosic material because it is Second generation biodiesel
derived from lignin, cellulose, and hemicellulose [52]. These three Several kinds of second-generation feedstocks can be utilized to
components are characterized by their large and complex structures produce biodiesel such as energy crops, agricultural remains, and
which consist of repeating cyclic units with different functional wood residual wastage. The most common energy crops for this
groups. Figure 3 which is adapted from Sadeck et al. [53], shows the purpose are Jatropha, Aleurites moluccana, salmon oil, Rubber tree
three component structures. Figure 3A shows the carbohydrate Madhuca longifolia, tobacco seed, sea mango, and jojoba oil. In
polymer structure of cellulose which consists of D-glucose mono- addition, waste from cooking oils, non-edible oil crops, restaurant
mers connected by b-1,40-glycosidic bonds. This rigid structure is grease, beef tallow, animal fats, and pork lard can also be utilized as
usually found in the primary cell wall of plants. Figure 3B shows that biodiesel feedstocks [60]. Animal fats are preferable over first
hemicellulose consists of a variety of carbohydrate monomers with a generation feedstocks due to properties such as higher-octane
branched random structure which varies by plant type. Finally, numbers, non-corrosiveness, lack of waste and sustainability.
Figure 3C shows the noncarbohydrate irregular polymer structure However, the main drawback of this generation of feedstocks is
of lignin which is more complex than the other two components. the lack of active technologies for the commercial exploitation of
Three essential types of monomeric subunits are found in lignin, waste generated by biodiesel production. Furthermore, most ani-
each derived from an aromatic alcohol. These are the syringyl group mal fats possess a high concentration of saturated fatty acids,
which is derived from sinapyl alcohol, the guaiacyl group derived which increases the transesterification complexity [10]. The main
from coniferyl alcohol, and the p-hydroxyphenyl group which is limitation of biodiesel is its comparatively low performance in
derived from p-coumaryl alcohol. cold temperatures which hinders their ability to fully replace
petroleum transport fuels [61]. Furthermore, bio-safety issues
Second generation bioethanol can present in cases of contaminated animal feedstocks [10].
Bioethanol can be produced from lignocellulosic biomass through
hydrolysis and subsequent fermentation. It can also be produced Second generation butanol
by thermochemical processes which include gasification followed Butanol alcohol (C4H10O) consists mainly of hydrogen and car-
by either fermentation or a catalyzed reaction [54]. However, these bon, so it can be easily blended with gasoline and other hydrocar-
processes are complicated due to (1) the difficulty of biomass bon products [62]. Butanol has more heat energy than ethanol,
breakdown, (2) the release of different types of sugars after hemi- which increases the harvestable energy gains (around 25%)
cellulose and cellulose polymers breakdown and the need to [63,64]. The gross heat value of butanol is 110,000 BTU per gallon
ferment these sugars with suitable organisms which can require which is closer to that of diesel fuel (115,000–138,700 BTU per
genetic engineering, and (3) the cost of collection and storage of gallon) [64]. Butanol is safer to handle than gasoline and ethanol
low density lignocellosic feedstocks [55]. due to its low Reid Value of 0.33 psi. The Reid Value is a measure-
There are four main operational steps in the lignocellosic con- ment indicator of a fluid’s rate of evaporation, and it has values of
version process to ethanol: (1) pretreatment, (2) hydrolysis, (3) 8–15 and 2.3 psi, for gasoline and ethanol, respectively [65].

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FIGURE 3
Chemical Structures of A- cellulose, B- hemicellulose, and C- lignin.

Another reason why butanol is considered safer than ethanol and friendly choice [64]. There are four isomers of butanol with similar
gasoline is its low production of volatile organic compound energy and which are identical in blending with gasoline and in
(VOC), which is also due to its low evaporation rate. In addition, combustion. These are normal-butanol CH3CH2CH2CH2OH (n-buta-
the corrosiveness of butanol is less than that of ethanol which nol), secondary-butanol CH3CH2CHOHCH3 (2-butanol), iso-butanol
helps with shipping and distribution it through existing pipelines (CH3)2CH2CHOH (i-butanol) and ter-butanol (CH3)3COH (t-buta-
and filling stations [65]. nol). However, their manufacturing processes are very different
The relatively high oxygen content of butanol, 21.6%, makes it a [66]. t-Butanol is limited to petrochemical manufacturing and there
great fuel extender that is cleaner than ethanol [65]. It has also been is still no biological technique to produce it [67]. n-Butanol, which is a
reported that burning butanol in an internal combustion engine toxic alcohol, was manufactured using a fermentation process with
releases only CO2 and H2O, which makes it more the environmentally sugar or starch even before the rise of the petroleum industry. This

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complicated fermentation process involves the anaerobic conversion from California in the USA were the first researchers who investi-
of carbohydrates into acetone, butanol and ethanol (known as ABE gated microalgae anaerobic digestion. They used different micro-
process) with a product ratio of 3:6:1, respectively [68]. algal biomass types such as high rate ponds and harvested the
The production of iso-butanol, which is less toxic than n-butanol biomass for biogas production. [10].
[69], has attracted several organizations’ attention such as, The oil content of microalgae biomass varies widely. In some types
DuPont, BP, GEVO [64]. Wine manufacturing yeast cultures gen- oil composes more than 80% of the dry weight of algal biomass while
erate small amounts of iso-butanol. However, to produce high in other types it is about 15–40% [10]. In comparison with crops, the
quality wine, careful distillation is needed to remove i-butanol and oil content of palm kernel, copra, and sunflower is between 50 to
methanol. The manufacturing of 2-Butanol involves, first, a bac- 60%. In general, microalgae are considered the best oil provider
terial fermentation that help to convert glucose (from starch or among various plants. The production capacity of oil from micro-

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cellulose) and all kinds of sugars resulting from hemicellulose to a algae is up to 100,000 l/hectare/year, whereas the capacity of palm,
nontoxic intermediate product. Then this intermediate product is coconut, castor and sunflower is between 1000 and 6000 l/hectare/
converted to 2-butanol through a chemical conversion step. The year [79]. Microalgae can be used in the production of several
overall conversion rate of the raw materials to 2-butanol is higher biofuels including bioethanol and biodiesel as well as CH4 and H2
than that with other butanol isomers [64]. using different processes. Biofuels produced from microalgae are
compatible with presenting fuel engines which eliminate the need
Third generation for further modification [80]. Microalgae-based biodiesel fuels have
Several kinds of microorganisms are used as feedstocks in the third similar properties to petroleum-based biofuels such as density,
generation of biofuels [70]. Promising microalgae are the most viscosity, flash point, heating value, cold filter plugging point,
common type for biodiesel production. There are two main clas- and solidifying point. Thus, they are compatible with the standards
sifications for algae based on their size and morphology: macro- of both the American Society for Testing and Materials (ASTM) and
algae and micro-algae. One of the most commonly used marine the International Biodiesel Standard for Vehicles [81]. In addition,
macro-algae is kelp which has multiple cells, resembling the roots, microalgae-based biodiesel fuel produces less pollutant gases such as
stem and leaves of higher plants. In contrast, microalgae which are CO and SOx than petroleum-based fuel.
classified as autotrophic, heterotrophic, and mixotrophic micro- Microalgae-based bio-oil has a high heating value, low density and
scopic organisms, exist in both fresh and marine water [71]. low viscosity compared with fossil-based oil produced by fast pyrol-
Microalgae organisms have excellent potential to produce spe- ysis of wood [82]. It is also preferable to lignocellulose-based oil due
cial chemicals and nutritional products due to their photosyn- to its better quality. Figure 4 presents a schematic diagram of third
thetic ability [72]. Autotrophic and heterotrophic microalgae dif- generation biofuel production. Table 1 comparing the results of bio-
fer in the source of the carbon they consume, where autotrophs oil produced by algal pyrolysis technique that reported by different
use inorganic carbon while heterotrophs use organic carbon researchers. Microalgae have advantages such as the ability to elimi-
sources [73]. Mixotrophic algae can simultaneously drive autop- nate inorganic nutrients from wastewater and to generate higher
hototrophy and heterotrophy to use both inorganic and organic quantities of green biomass due to their tendency to uptake nitrogen
carbon substrates, which increase the productivity and enhance and phosphorous [10]. Therefore, a promising strategy to enhance
the capability of microalgae to grow in wastewaters [74]. This kind the economic and production efficiency of microalgal-based bio-
of algae could overcome issues associated with the growth of fuels is by coupling microalgal cultivation with wastewater treat-
autotrophic algae regarding light limitation at high cell densities ment [83,84]. This strategy has several advantages over other feed-
and dark colored wastewaters [75]. The mixotrophic growth of stocks such as (a) lower cost due to simple solar energy requirements,
Chlorella protothecoides can provide 69% higher lipid than that (b) the ability to effectively reduce CO2 concentrations, (c) the
of heterotrophic yield on glucose with a reduction CO2 releasing absence of required extra organic carbon sources unlike for biologi-
by 61.5% [74]. Despite the high biomass and lipid productivities, cal nitrification and denitrification, (d) fewer sludge handling issues,
the cost of glucose represents around 80% of the total fee penalty and (e) a tendency to increase the dissolved oxygen level (i.e. O2
of growth medium which making mixotrophic algae cultivation concentration) in water bodies [85]. On the other hand, this kind of
unattractive economically [75]. However, utilizing inexpensive biomass has some limitations such as its high cost and the fact that
carbon sources offers excellent promise for the cultivation of biofuel produced from algae is less stable than that produced from
mixotrophic algae. Example sources of carbon are sugars from other sources. This is because the oil generated by algae is highly
industrial and agricultural waste, crude glycerol from biodiesel unsaturated, which means it is more volatile, especially at high
industry, cellulosic materials and cane molasses [74]. temperatures, and therefore more likely to degrade [10].
Microalgae have several important properties such as requiring In addition, microalgae have great potential to achieve high
less space to grow, high oil content, the ability to grow in both lipid content due to their high photosynthetic ability. Specifically,
artificial and natural environments, and being ecofriendly [76]. the lipid production capacity per unit dry is between 15 to 300
They also possess a unique advantage which is the capability for times that of conventional crops [10]. Anaerobic digestion of
both oxygenic photosynthesis and hydrogen production [10]. In organic biomass, which is known as methanogenesis, is used to
addition, their growth requirements are simple and limited to produce biogas fuel. The main requirements for this process are
light, carbon dioxide and other inorganic nutrients [77]. Micro- cellulosic and hemicellulosic sources. Thus, microalgae are prom-
algae also assist to decrease the CO2 level in the environment ising source of biofuels.
because the production of 1 kg of algal biomass consumes around Production of biofuel from biomass using microorganisms can
1.8 kg of CO2 [78]. Historically, in the 1950s Oswald and Golueke be done through biochemical or thermochemical processes.

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FIGURE 4
A schematic diagram of microalga-based biofuels production.

Biochemical processes can be classified into alcoholic fermenta- and might need several days to complete. In contrast, thermo-
tion, anaerobic digestion, transesterification and photobiological chemical methods rely on heat and/or physical catalysts only and
hydrogen production. Thermochemical processes include heating require shorter time to complete [86].
and decomposition of biomass in the absence of oxygen. Cur-
rently, thermochemical processes are more favorable due to their Third generation bioethanol
better conversion efficiency, required production time, and lower Algae have attracted wide attention as an alternative renewable
production costs compared to biochemical processes. In addition, source for bioethanol production to overcome the problems
it provides a simpler production route but with using high tem- accompanying first and second generation biofuels [94]. The
peratures. Specifically, the biochemical method relies on heat, investigation of algae as biofuel feedstock started in the late
chemicals, and biocatalysts, such as enzymes and microbial cells, 1950s and then got wide attention after the oil crisis in the

TABLE 1
Comparison of the algal pyrolysis results reported by different researchers.
Feedstock Conditions Main results Ref.
Spirulina sp. Stainless steel fixed-bed reactor made of steel, The best yield of bio-oil was 46% and achieved at [87]
125 g microalgae, a450–600 ℃, b8 ℃/min, 550 ℃, While bio-char was secondary product with
nitrogen, c30 ml/min, d60 min maximum yield of 33% at 500  C
Lipid-extracted residue of T. Stainless steel fixed-bed reactor, 5 g The highest bio-oil yield was 29.82% at 450 ℃. The [88]
minus microalgae, a300–500 ℃, b10 ℃/min, nitrogen, produced bio-oil was riches with alkane/alkene and
c
50 ml/ min, d60 min nitrogenous compounds.
S. dimorphus Quartz glass fixed-bed reactor made of, 10 g The products include bio-oil (best yield 39.6%), bio- [89]
microalgae, a300–600 ℃, b40 ℃/min, nitrogen, char (best yield 36%) and bio-gas (best yield 25%)
c
100 ml/min. were obtained at 500, 300, and 600 ℃ respectively.
Four algal and lignocellulosic Fixed-bed tubular quartz reactor, 3 g Microalgae yielded more bio-oil than lignocellulosic, [90]
biomass samples microalgae, a300–900 ℃, nitrogen, c50 ml/min, and the best yield was 32.69% obtained for C. vulgaris
d
60 min microalgae at 500 ℃.
Isochrysis and defatted Isochrysis Tubular-quartz fixed-bed reactor, 2.5 g bio-oil yielded from [91]
microalgae, a475 ℃, nitrogen, c400 ml/min. lipid extracted residue of microalgae (36.86%) was
lower than that yielded from regular microalgae
(41.32%) at 475 ℃
Blue-green algae blooms Fixed bed reactor, 5 g microalgae with different The best bio-oil yield was 54.97%. and was achieved at [92]
particle size, a300–700 ℃, b40 ℃/min, 500 ℃.
nitrogen, c0–400 ml/min, d15 min
C. vulgaris and D. salina Quartz-glass fixed-bed reactor, 1 g microalgae, The best bio-oil yields of C. vulgaris and D. salina were [93]
a
300–700 ℃, nitrogen, c400 ml/min, d20 min 49.2% and 55.4% at 500 ℃, respectively. Temperature
increasing
from 300 to 700  C, increased and decreased the gas
and char yields, respectively.
a
Temperature of process.
b
Heating rate.
c
Volumetric flow of carrier gas.
d
Duration of process.

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1970s [95]. Bioethanol can be produced by any of the three algal TABLE 2
processes that have been discussed (mixotrophic, heterotrophic, Advantages and disadvantages of bioethanol fuel [98–100].
and autotrophic). After hydrolysis, algal starch, cellulose or other Advantages Disadvantages
accumulating carbohydrates can be converted to ethanol. [96].
 It has a high-octane number  It has a lower energy density than
The high photon conversion efficiency of algae makes them (108), high flame speeds, broader gasoline (66% of the gasoline energy)
promising candidates for renewable bioethanol applications. The flammability limits, and higher  Its corrosiveness
algae-bioethanol production process is simpler than that of lig- heats of vaporization which lead  It has low flame luminosity
nocellulosic biomass because it does not require the chemical and to better efficiency  It has lower vapor pressure which
making cold starts difficult
enzymatic pre-treatment steps that are necessary to breakdown
 miscibility with water
lignocellulosic biopolymers into fermentable sugars [97]. An  toxicity to ecosystems

RESEARCH REVIEW
example of algae-bioethanol production technologies is that  It has high emission of acetaldehyde
developed by Algenol Biofuels Inc. which utilizes sunlight trap-
ping microalgal cells as a tiny biorefinary using a specialized
bioreactor. The production rate is 6000 gallons of ethanol per CoA by acetyl CoA carboxylase (ACCase) [102]. This pathway
acre per year. This production rate is much higher than that generates between 16 to 20 types of carbon fatty acids which
produced from corn which is reported to be 400 gallons of are used in the synthesis of triacylglycerols as well as cellular
ethanol per acre per year [95]. Table 2 summarizes the advantages and organelle membranes. Triacylglycerols are accumulated in
and limitations of bioethanol alcohol. Figure 5 represents a higher percentages (30–60% of dry cell weight) by some oligea-
schematic diagram of the bioethanol produced by different gen- nous microalgae than by first-generation crops [101]. The major
erations of biofuels. triacylglycerol manufacturing pathway for lipid accumulation in
algae occurs in the chloroplast. To promote the biodiesel yield,
Third generation biodiesel yeast, oligeanous algae and bacteria have been investigated for
Microalgae are considered a very promising choice for biodie- lipid content. Some microalgal species possess a high triacylgly-
sel production and a variety of microorganisms can be used for cerol content of up to 80% of their total dry biomass [103].
this purpose. Both microalgae autotrophs and heterotrophs However, there are production difficulties which must be elimi-
can be used for biodiesel production but vary in their biodiesel nated for the commercialization of these species. These difficulties
yield [101]. Table 3 shows the oil yield of different microalgae include scaling up their culture and investing in stress control for
species [10]. lipid production [104].
Using biodiesel in diesel engines might have minor impacts on To develop the microalgal ability for high lipid accumulation,
operating performance. The gross heat value of biodiesel is stress control strategies are commonly used. These strategies
126,200 BTU per gallon which is similar to that of diesel fuel involve manipulating the nutritional or cultivation circumstances
(115,000–138,700 BTU per gallon) [64]. The production of biodie- (i.e., temperature, pH, nitrogen, phosphate concentrations, etc.)
sel involves the formation of fatty acids (FA) as precursors which in to make microalgal cells adapt to the changing environmental
turn involves the catalyzed conversion of acetyl CoA to malonyl conditions. In addition, recombinant DNA technology has been

FIGURE 5
A schematic diagram of bioethanol production based on different generations.

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TABLE 3 information. Interest in this technology began in the 1980s [105].

Oil contents of different microalgae strains [10]. Generally, eukaryotic cells are formed in the random integration
Microalgal species Oil composition (%) of exogenous genes into the nuclear genome. Several kinds of
microalgae have been successfully generated by gene transforma-
Ankistrodesmus TR-87 28–40
Botryococcusbraunii 34–75 tion into the cellular nucleus, chloroplasts and mitochondria
Chlorella sp. 50 [111]. The most investigated eukaryotic microalgae is Chlamydo-
Chlorella protothecoides (autotrophic/ heterotrophic) 40–55 monas reinhardtii. It is a very common model organism used to
Dunaliellatertiolecta 33 investigate the essential mechanisms of biological processes, such
Hantzschia DI-160 66
as oxygenic photosynthesis, circadian rhythms, and flagella bio-
Nannochloris 25
genesis [112].
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Nannochloropsis 35–47
Cenedesmus 34 The first investigation of the chloroplast DNA map of Chlamy-
Stichococcus 32–40 domonas reinhardtii was in 1978 and led to successful genetic
Tetraselmissuecica 20–35 transformation in the Chlamydomonas reinhardtii chromosome,
Phaeodactylumtricornutum 20–28
chloroplast, and mitochondrial genome by 1993 [113–115]. Chla-
mydomonas has shown great ability to produce recombinant pro-
teins. It enables the generation of various types of proteins includ-
ing complex mammalian therapeutic enzymes and monoclonal
utilized to improve biodiesel production. For example, a photo- antibodies at commercial levels with presenting production plat-
synthetic organism, C. cryptica, was used to isolate and character- forms [116].
ize an acetyl-CoA carboxylase (ACCase) gene in 1993. This gene Chlorella which is another kind of unicellular green algae
was also transformed into the diatoms C. cryptica and Navicula organism with a transformation system [117] which has attracted
saprophila. However, only a small increase in the lipid concentra- the attention of researchers lately. Several steps have been taken
tion of the microalgae was observed [105]. Biodiesel advantages since its transient expression system was first described by Jarvis
and limitations are summarized in Table 4. et al. in 1991 [118]. In recent years, marine diatoms have attracted
a lot of attention due to their wide prevalence, ability to adapt to
Fourth generation varying environments, and substantial biomass production in
In fourth-generation biofuels, genetically modified microorgan- water [119].
isms such as microalgae, yeast, fungi and cyanobacteria are utilized
as sources. The ability of microorganisms to convert CO2 to fuel Techno-economic and environmental analysis
through photosynthesis is utilized [106]. The multiple advantages A lot of effort has been made to determine the techno-economic
of microalgae such as their high growth rate and oil content and characteristics of biofuel production and to integrate them with
low structural complexity enhance their numerous commercial its environmental impact [120–122]. However, the results of
applications [86]. In addition to genetic modification, some these studies vary due to the difference in the basis of the
fourth-generation technologies involve pyrolysis (in a tempera- production process such as the availability of the feedstock
ture range between 400 to 600  C) [86], gasification, upgrading, and the production technique adapted as well as the assump-
and solar-to-fuel, pathways [107]. The general purpose of these tions made in these studies [123]. The U.S. National Renewable
modifications is to improve the HC yield and create an artificial Energy Laboratory (NREL) conducted a valuable economic and
carbon sink to eliminate or minimize carbon emission [108]. These environmental study of biodiesel production from algae. Their
technologies are still in early developmental stages [108]. study estimated the cost of biodiesel production is in the range
between $0.53 to 0.85/L, which is close to what was estimated
Cyanobacteria by Nagarajan et al. after a careful consideration of the cost of
Cyanobacteria have attracted a lot of attention in bioenergy and land and transesterification that found a range between $0.42 to
biofuel industries. Recently, the genomic revolution has greatly 0.97/L [124]. These estimated costs are close to the commercial
developed metabolic engineering for several photosynthetic value of diesel fuel which indicates the high promise of biodiesel
organisms. Synechocystis was the first photosynthetic organism choice.
for which the genome was completely sequenced [109]. Synecho- On the other hand, Kern et al. investigated the possibility of
cystis, which has the ability for both photoautotrophic and het- enhancing the cost-competitiveness of algal biofuel production
erotrophic growth, is a freshwater, non-filamentous, non-nitrogen by adding an up-front investment in anaerobic digestion to
fixing organism. The most valuable characteristic of this strain of increase the flexibility in using lipid-extracted algae as feed or
cyanobacteria as a genetic and physiological case study of photo- to recover nutrients and energy. Their investigation showed that
synthesis are the available genomic, biochemistry, and physiolog- there is no additional economic value due to discourage feed
ical information. It is also well known as a model system for the meal prices [120].
investigation of oxygenic photosynthesis in higher plants due to Recently, Olcay et al. evaluated the conversion of red maple
its small genome size compared to higher plant systems [110]. wood, cellulosic feedstock, using aqueous-phase processing (APP)
techniques with different parameters such as pretreatment meth-
Eukaryotic microalgae ods, product slates, and gas sources [121]. Their lifecycle analysis
Eukaryotic microalgae-based technology has attracted a lot of results for GHG varied, due to the different refinery configurations,
attention recently due to the availability of eukaryotic genomic from 31.6 to 104.5 gCO2 per MJ which is 64% lower and 19%

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TABLE 4
Bio-diesel’s advantages and disadvantages [98–100].
Advantages Disadvantages
 Generates fewer pollutant emissions such as COx, SO2, PM and HC compared to diesel  Its combustion generates higher NO2 and NO than diesel
 Its production is easier and faster than diesel  It has a higher pour point and cloud point which may cause
fuel freezing and difficulty starting in cold weather
 It has shown better performance in vehicles due to its higher-octane number
 It helps to prolong engine life and minimizes the engine maintenance required
 Unlike diesel engine, it does not need additional lubricant to be used
 It has a magnificent potential for stimulating sustainable rural development and as a

RESEARCH REVIEW
solution for energy security issues
 It has a higher cost efficiency than diesel
 Unlike diesel, it does not require any drilling, transportation or refinement
 Compared with diesel fuel, it has better sulfur content, flash point, aromatic content, and
biodegradability
 It is safer to handle and less toxic than diesel fuel
 It is non-flammable, non-toxic, and it reduces tailpipe emissions, visible smoke and
noxious fumes and odors
 It does not require any engine modification
 It has high combustion efficiency, portability, availability, and renewability

higher than that reported for petroleum fuel, respectively. Their due to competition with food needs. In contrast, third and fourth
estimated cost of production was in the range between $0.26 to generation biofuels are more promising choices because they do not
1.67/L, which is 61% lower and 146% higher than that reported for involve such food-fuel competition. Another valuable parameter to
petroleum-based jet fuel price, respectively. secure the sustainability of liquid biofuels is advances in technology.
Improvements in cost effectiveness and yield conversion systems are
Policies and future needs required for widespread commercial production of biofuel. This goal
The future for biofuel production should focus on lowering the will probably be achieved by utilizing metabolic engineering tools
production cost and utilizing technological advance to increase which improve biofuel both quantitatively and qualitatively by mod-
the production of biofuel from marine biomass. Specifically, ifying existing biological pathways. This has the potential to alter
efforts should focus on developing new high active and stable feedstock or identify more useful microbes to get better conversion
catalysts, higher efficiency reactors, continuous operation biore- rates. More investigations are needed to achieve higher yields and
actor, and minimizing the required energy and GHG emissions as more cost-effective production processes. For greenhouse gas reduc-
well as waste. In addition, government support will be the key for tion, second and third generations biofuels have shown much better
shifting communities towards green energy. performance compared to first generation biofuels. More reduction in
For example, the current estimated production price of biodiesel greenhouse gas emissions is expected from fourth generation biofuels.
does not encourage its adoption over petro-diesel fuel. The absence Currently first-generation liquid biofuels are considered the most
of clear government policies is a main cause of the poor biodiesel cost-effective. However, production is limited to certain countries
industry. Thus, governments should create and expand policies to due to high land and water demand. The second and third generation
help marketing of biodiesel by direct or indirect financial support liquid biofuels still have production cost limitations due to high
such as tax credits and subsidies. On the other hand, there is still investment costs and low efficiencies of feedstock conversion to
some room for possible reduction in the cost of biodiesel produc- biofuel. Further development and perfection of production technol-
tion. Specifically, most investigations have focused on algal ogies of both second and third generation bioethanol and biodiesels
growth, but more attention should be paid to increasing lipid may enhance their cost-effectiveness. Overall, the future of liquid
content due to its potential to increase production yields of biofuel may be an integration of some or all of the four generations.
biofuels. Also, utilizing algal residue for biogas production may
improve the economic benefits of this process. Conflict of interest statement
The authors declare no financial or commercial competing interest.
Conclusions
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