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Biofuel production
from algal biomass
Jonah Teo Teck Chye, Lau Yien Jun, Lau Sie Yon,
Sharadwata Pan, and Michael K. Danquah
Contents
3.1 Introduction.............................................................................................. 88
3.2 Biofuel production from microalgae..................................................... 90
3.3 Microalgal cultivation technologies...................................................... 91
3.3.1 Open-air systems......................................................................... 92
3.3.2 Closed photobioreactor systems................................................ 92
3.3.3 Two-stage hybrid system............................................................ 93
3.3.4 Lipid induction technique.......................................................... 94
3.4 Microalgal harvesting technologies...................................................... 94
3.5 Technologies for biomass to biofuel conversion technologies.......... 95
3.5.1 Thermochemical conversion...................................................... 96
3.5.2 Gasification................................................................................... 96
3.5.3 Pyrolysis........................................................................................ 97
3.5.4 Liquefaction.................................................................................. 98
3.5.5 Biochemical conversion............................................................... 99
3.5.6 Anaerobic digestion..................................................................... 99
3.5.7 Fermentation............................................................................... 100
3.5.8 Transesterification...................................................................... 101
3.5.9 Direct combustion..................................................................... 102
3.5.10 Ultrasonication to aid biofuel yields....................................... 102
3.6 Biochemical characterization of different algal species................... 102
3.7 Biodiesel from algal biomass............................................................... 103
3.8 Bioethanol from algal biomass............................................................ 106
3.9 Biogas and biohydrogen from algal biomass..................................... 107
3.10 Integrated algal biomass production.................................................. 108
3.11 Future outlook and commercial prospects of algal biofuels............110
3.12 Conclusion...............................................................................................111
References..........................................................................................................111
87
88 Bioenergy and biofuels
3.1 Introduction
Today, approximately 88% of worldwide energy consumption is a conse-
quence of the combustion of fossil fuels. This may be because of its domi-
nant exploitation in the transportation sector, which makes up for 58% of
the total fossil fuel usage (Brennan and Owende, 2010; Gaurav et al., 2017).
Nevertheless, exhaustive consumption of fossil fuels leads to adverse
impacts on human health and triggers environmental concerns. In par-
ticular, there is an imminent threat of global warming due to extraordi-
nary emission of greenhouse gases (GHGs), environmental pollutants, and
devastation of flora and fauna habitats due to oil resources exploration and
subsequent utilization. During past decades, biofuels have been widely
used as a viable alternative to fossil fuel resources, thanks to the crisis of
gradual oil resources depletion, as well as due to an increase in worldwide
fuel demand and consumption. The term “biofuel” refers to a fuel that
is formed directly or indirectly from the biomass feedstock. Biomass is
defined as biological materials that are either energy crops, wastes and by-
products from agricultural and forestry, manure or municipal solid wastes,
or any other material containing microbial biomass. Charcoal, fuelwood,
bioethanol, biomethane, biohydrogen, and biodiesel are some examples
of biofuels that are found in continuous production (Saladini et al., 2016).
Figure 3.1 illustrates the feedstock sources and products of biofuels.
The first generation of biofuels, such as bioethanol, biobutanol, and
biodiesels, is usually produced using edible, conventional crops (Ullah
et al., 2015). They may be produced either by utilizing feedstock via starch
fermentation of crops such as wheat, barley, potato, corn, sugar beet, and
sugarcane (mostly used), or chemically by using rapeseed, sunflower,
soybeans, palm, coconut, and animal fats as feedstocks (Lee and Lavoie,
Biofuels
Algal broth,
Harvest nutrient medium Harvest
CO2
Exhaust
Degassing
column North
Paddle wheel Fish
medium
Direction of flow Cooling
water
South
Air Solar array
CO2 CO2
Pump
Figure 3.2 Open raceway pond system (left) and tubular photobioreactor sys-
tem (right). (From Chisti, Y. 2008. Trends in Biotechnology 26: 126–131; Jorquera,
O., A. Kiperstok, E A. Sales, M. Embirucu, and M. L. Ghirardi. 2010. Bioresource
Technology 101: 1406–1413.)
25% of the biomass produced during the day is consumed to sustain the
cell culture until the next day. Variation in the algal growth is a conse-
quence of the light levels during daytime, growth temperature, culture
pH, dissolved oxygen levels in the medium, and the night temperature
(Chisti, 2008). Because photosynthesis will be inhibited at 400% of the
air saturation value of the dissolved oxygen in the medium, degassing
column is necessary for o xygen removal (Molina et al., 2001). According
to Jorquera et al. (2010), PBRs have higher volumetric productivity com-
pared to the open-air ponds because they are more efficient in capturing
solar energy and require less area. Besides, the PBR system permits con-
trolled cultivation conditions, and the system protects the microalgae
from probable contamination. Nonetheless, they are more expensive in
terms of capital and operational costs owing to elevated levels of energy
consumption and suffer from limited sunlight penetration due to algal
attachment. Zhou et al. (2012) established a multilayered PBR structure
that can reduce the occupying space, as well as mitigate the sunlight
penetration issue.
Hydrogen
Photobiological H2 production gas
Biochemical Bioethanol, acetone,
conversion Fermentation
butanol
Anaerobic digestion Methane, hydrogen
Gasification Syngas
Thermochemical
conversion Pyrolysis Bio-oil, charcoal, syngas
Microalgal
biomass Liquefaction Bio-oil
Chemical
reaction Transesterification Biodiesel
Figure 3.3 Microalgal biomass conversion processes. (Adapted from Dragone, G.,
B. D. Fernandes, A. Vicente, and J. A. Teixeira. 2010. Current Research, Technology
and Education Topics in Applied Microbiology and Microbial Biotechnology, ed.
A. Mendez-Vilas, 1355–1366. FORMATEX; and Zinnai, A., C. Sanmartin, I. Taglieri,
G. Andrich, and F. Venturi. 2016. Journal of Supercritical Fluids 116: 126–131.)
3.5.2 Gasification
Gasification is achieved by the reaction of microalgal biomass in a gas-
ifier in the absence of any form of combustion under partial oxidation
of air, oxygen, or steam. The conventional gasification process is usually
accompanied by other downstream processes such as drying, pyrolysis,
combustion, and reduction, and produces hydrogen, methane, and car-
bon monoxide (collectively known as syngas), alongside certain unde-
sired tar, ash, and solid by-products (Raheem et al., 2015). Gasification
may encompass two broad domains: conventional gasification and super-
critical water gasification (SCWG). Conventional gasification is achieved
at high temperatures of 800–1000°C either in a fluidized or fixed bed.
SCWG has an operational temperature range of 375–550°C at 22.1–36 MPa
Chapter three: Biofuel production from algal biomass 97
3.5.3 Pyrolysis
Microalgae are thermally decomposed by heating in the absence of oxy-
gen or air. Operating conditions normally proceed at atmospheric pres-
sure, with a temperature range of 400–600°C for conventional pyrolysis,
up to 800°C for microwave pyrolysis and a minimum of 300°C for cata-
lytic pyrolysis (Chen et al., 2015). Fast or flash pyrolysis is known to have
highly intensive heating rates and a short residence time, and maximizes
98 Bioenergy and biofuels
3.5.4 Liquefaction
In HTL of algae, the physical and chemical conversion is performed at
high temperatures of approximately 250–500°C under high autothermal
water pressures of 5–20 bar with or without catalysts, with the microal-
gae making up to 5%–50% mass fraction of the slurry feed (Chen et al.,
2015; Raheem et al., 2015). The products of liquefaction include bio-oil
and additional gaseous coproducts of methane. The pressure is kept
high to maintain the water in liquid phase, and the residence time is
approximately 5–60 min. Chen et al. (2015) reported production of differ-
ent strains of microalgae based on diverse operating conditions as well
as the bio-oil yield and efficacy in terms of higher heating values (HHVs).
Similar to SCWG, this process does not require drying of the wet algal
biomass, making it an energy-efficient and more economically viable
process. The advantage of HTL over SCWG is that it is suitable for wet
biomass with high moisture contents. The physical properties of water
Chapter three: Biofuel production from algal biomass 99
3.5.7 Fermentation
In the fermentation process, the constituent carbohydrates such as sugar,
starch, or cellulose are converted to bioethanol. Microalgae with high
starch contents are traditionally suitable for fermentation. This enzymatic
process involves the hydrolysis of starch to simple sugars, followed by
yeast fermentation, producing bioethanol (Milano et al., 2016). Similar to
anaerobic digestion, fermentation requires pretreatment to release carbo-
hydrates from the algal cell wall by either ultrasonication or hydrolytic
enzymatic conversion to allow for the biomass fermentation (Suali and
Sarbatly, 2012; Naveena et al., 2015). The pectinase enzyme group has a
high potential for excretion of fermentable sugars present in microalgae.
For instance, it has been reported that pectinase from Aspergillus aculeatus
may achieve a saccharification yield of 79% during hydrolysis of C. vulgaris
at 50°C after 3 days (Kim et al., 2014). Ethanol production via fermenta-
tion involves four principal stages. The first step is glycolysis, character-
ized by formation of two molecules of pyruvate (CHCOCOO−) and water
and hydrogen ions (H+) as by-products from glucose breakdown. During
glycolysis, coenzymes adenosine diphosphate (ADP) and nicotinamide
adenine dinucleotide (NAD+) are reduced to adenosine triphosphate
(ATP) and NADH, respectively. Following glycolysis, the second step is
the production of acetaldehyde, CO2, and H+ from pyruvate, catalyzed by
the enzyme pyruvate decarboxylase. The third step involves conversion of
acetaldehyde into ethanol anion, aided by coenzyme NADH, which is syn-
thesized during glycolysis. The last step involves the protonation of etha-
nol anion by hydrogen ions forming ethanol (Suali and Sarbatly, 2012). It
is a fact that higher yeast concentrations may improve ethanol production
Chapter three: Biofuel production from algal biomass 101
3.5.8 Transesterification
Transesterification is characterized by the conversion of microalgal bio-
mass to biodiesel and is subcategorized as chemical changeover of algal
biomass. Triglyceride or lipid reacts with a monoalcohol with the additive
of catalysts in the form of acid, alkali, or enzymes to produce fatty acid
methyl ester (FAME) and glycerol (Milano et al., 2016). The process has
garnered a lot of attention in recent times for biodiesel production, but its
economic feasibility is still limited due to the high enzyme cost. Razzak
et al. (2013) reported that alkali-catalyzed transesterification is the most
commonly used method for biodiesel production. If the raw materials
are rich in free fatty acids, they may react with the alkaline catalysts and
undergo saponification, which is undesirable. High water content may
hydrolyze the triglycerides to diglycerides, which in turn generates more
free fatty acids, demanding pretreatment to eliminate the acidic materi-
als. The transesterification process may either be conventional or in situ
(direct). While conventional transesterification demands drying, lipid
extraction before the actual process, and a subsequent purification, in situ
transesterification omits the lipid-extraction stage (Milano et al., 2016).
In situ transesterification is a simpler and cheaper form of algal biodiesel
manufacturing, compared to the conventional method. In situ studies of
transesterification of C. vulgaris by Velasquez-Orta et al. (2012) showed
that for a methanol-to-lipid molar ratio of 600:1 and catalyst-to-lipid ratio
of 0.15:1, an alkaline catalyst (NaOH) could outperform an acid catalyst
(H2SO4), attaining higher conversion into FAME (77.6 wt%) for low resi-
dence time of 75 min at room temperature. This was the case when acid
catalyst-to-lipid ratio of 0.35:1 (≈96.8 wt% conversion) was achieved for
longer reaction times up to 20 h. In a similar study, in situ transesterifica-
tion of Chlorella sp. with 20 wt% sulfuric acid showed a 96%–98% yield
of FAME within 4 h (Viegas et al., 2015). The study showed that higher
weight compositions of sulfuric acid produced higher FAME yields, but
it is economically unfeasible because sulfuric acid is expensive. Teo et al.
(2016) investigated a nanocatalyst of calcium methoxide, Ca(OCH3)2, with
3 wt% of catalyst loading, a methanol-to-lipid molar ratio of 30:1, reaction
102 Bioenergy and biofuels
3.6 Biochemical characterization
of different algal species
Scott et al. (2010) have reported the existence of nearly 300,000 species
of algae, with varied oil contents and growth rates. Microalgal biomass
is mainly constituted of lipids, carbohydrates, and proteins. Different
microalgal species have significantly different compositions, where the
average lipid oil content typically varies between 8% and 31%. This lipid
oil can be extracted and converted into biodiesel. Mendoza et al. (2015)
reported that microalgae have a high variability of lipid extractability,
Chapter three: Biofuel production from algal biomass 103
which is related to the resistance of the cell walls to physical and chemical
extraction treatments. Del Río et al. (2017) reported that Chlorococcum oleo-
faciens and Pseudokirchneriella subcapitata have daily maximal production of
110 mg fatty acids L−1 and 160 mg fatty acids L−1, respectively. It was also
reported that the strains react differently in terms of nitrate availability,
and the species P. subcapacitata has a more acceptable fatty acid profile
for biodiesel production because it has a low nitrogen stress threshold
that activates fatty acid accumulation. Quantification of lipid content in
microalgae may be carried out by gravimetric methods, which is, however,
a time-consuming process. Balduyck et al. (2015) achieved lipid staining
with Nile red followed by lipid quantification using a spectrofluoromet-
ric device. However, this method is argued to be species-dependent and
requires a species-based optimization. Table 3.3 illustrates the biochemi-
cal compositions of various types of microalgae, including their lipid,
protein, and carbohydrate contents on the dry mass basis (Alam et al.,
2012; Dragone et al., 2010).
produced are some of the pertinent challenges that mar biodiesel produc-
tion (Mehrabadi et al., 2016). Past studies have shown that lipid induc-
tion may be achieved by applying stressors, such as either by limiting
the nitrogen and/or phosphorus content or by removing it entirely,
which results in lipid accumulation in certain strains of microalgae. As
for diatomic microalgae, silicium is a potent stressor for lipid growth.
Other potential stressors include irradiation, low light intensity, dark
exposure, and shortened light period. Ultraviolet irradiation and com-
bined effects were also reported to induce TAG agglomeration (Chernova
and Kiseleva, 2017). Biodiesel quality is determined based on the cetane
number (CN), calorific value, melting point, and viscosity, all of which
significantly impact the fuel performance in a diesel engine. It should be
noted that the values of the aforementioned quantities are proportional to
the chain length. The higher the degree of saturation of fatty acids in the
biodiesel, the greater is its oxidation stability, viscosity, and CN (Chung
et al., 2017). Pure biodiesel and biodiesel blends have lower CN and heat-
ing values compared to petroleum-based diesel, which causes a drop in
the engine performance. Engine tests on pure biodiesel (B100) have shown
that engine power output was 6% lower than that of conventional diesel,
but with a significant drop in CO emissions (Piloto-Rodríguez et al., 2017;
Tuccar and Aydin, 2013).
Currently, the increased cost factor for biodiesel production from
algae is still an issue and widescale commercialization is yet to be
achieved. Furthermore, biodiesel manufacturing generates the by-
product glycerin, which has already reached the market saturation point,
causing depreciation of its market value and affecting the commercial-
ization potential of biodiesel (Galan et al., 2009; Patil et al., 2017). Patil
et al. (2017) have studied a glycerin-free noncatalytic transesterification
process using supercritical methyl acetate, and based on initial outcomes
have commented on its high efficiency in producing relatively stable algal
biodiesel. Chung et al. (2017) proposed multiple strategies to improve
microalgal cultures, lipid accumulation, and improvement of biodiesel
quality, which includes bioengineering of microalgal strains as well as
other molecular strategies.
106 Bioenergy and biofuels
Figure 3.4 Potential process integration options for different methods of biofuel
production.
110 Bioenergy and biofuels
3.12 Conclusion
In this chapter, the first, second, and third generations of biofuels have
been reviewed and compared, and the benefits of algae as a crucial feed-
stock for biofuel production have been detailed. A sequential review has
been done for the entire process of biofuel production, starting from cul-
tivation, harvesting, pretreatments, and the conversion processes. Algal
cultivation technologies have been discussed including their advan-
tages and disadvantages. A wide range of harvesting technologies have
been reviewed based on their respective benefits and pitfalls as an aid
for technology selection. Conversion technologies of the harvested algal
biomass have been outlined, with several optimization recommenda-
tions for each process. Characterization of algal biomass based on their
lipid, carbohydrate, and protein contents have been reviewed, and char-
acterization profiles of different species have been compiled based on
previous studies. This chapter also discusses the suitability and appli-
cability of biodiesel, bioethanol, biogas, and biohydrogen as biofuel
products, comparing their performance with fossil fuels. Furthermore,
there is a focus on the biorefinery concept whereby integration of several
industrial units or integration within a biomass production plant is pos-
sible by recycling of nutrients and CO2. Future outlooks and commercial
prospects of algal biofuel have been reviewed and a few recommenda-
tions, based on the bottlenecks of the current state of the art, have been
stated.
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