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(B) Patel2017. Microalgae Rev PDF
(B) Patel2017. Microalgae Rev PDF
A R T I C L E I N F O A BS T RAC T
Keywords: Uncontrolled anthropogenic activities and technological revolution increase fossil fuel consumption at higher
Aquaculture rate that prompted researchers looking for alternative energy source to cover the current need and future
Biodiesel demand of energy. Biomass of terrestrial crops has been studied as a promising source of renewable energy in
Biofuel last few decades however large scale production is still questionable because of lower productivity, indirect use
CO2 Sequestration
of fossil fuel, lack of land availability and food vs. fuel conflict. These limitations of land based system fetch
High value products
opportunity to look into untapped potential use of microalgae with high biomass productivity from saline and
Microalgae
waste water stream. This unconventional way of feedstock generation can additionally produce value added
products apart from clean energy. This review presents current scenario of microalgae applications in biofuel
production and micro algae based high value bio-product industries leveraging environmental protection and
waste utilization benefits. Microalgae cultivation, harvesting and biomass conversion technologies for biodiesel
production have been reviewed based on adapting ancient learning to understand critical factors affecting
overall productivity and economic viability. Dedicated efforts from technical experts are still required for
economic viability of large scale biodiesel production in spite of positive finding at small scale. Several high
value bio-products from microalgae amplified magnetism of trades for investment in this field. Microalgae
cultivation intersects two key concern areas of global warming and water pollution control/water recycling by
CO2 sequestration and waste water utilization respectively. Integration of suitable upstream and downstream
processing technologies with multiple product portfolio would make the microalgae bio-refinery economical
viable.
1. Introduction other air contaminants including NOx, SOx, COs, particulate matter
and volatile compounds [5]. It is expected that the global energy
Increasing population and uncontrolled anthropogenic activity consumption would increase and resulting into more environmental
created major problem for energy requirement [1]. World's oil produc- damage [6]. GHG emissions do not only increase the global warming
tion is expected to decline in between one and tenth decades based on but also have major impacts on environment and human life. Some
current consumption scenario leaving burden on researchers to search amount dissolved in oceans would gradually increase turning of water
for alternative sources of energy [2]. The International Energy Agency pH to more acidity affecting to the marine ecosystem biodiversity and
(IEA) has reported that global energy need is expected to increase by also to life on earth [7].
55% from 2005 to 2030 at annual rate of 1.8% per year [3], with Renewable and green energy source are the only alternate to
Petroleum, natural gas, coal, hydro and nuclear are the basic sources of address this energy crisis and pollution control. To find clean and
this energy [4]. This exponentially increasing demand of energy and renewable energy sources is one of the most challenging problems for
gradually depleting conventional energy sources would lead to global mankind. Several countries and regions around the world are targeting
energy crisis for present and for future if unsolved. Beside this energy for CO2 reduction in order to meet the sustainability goals. Many
crisis, the environmental impact of conventional energy sources has options are being studied with different degree of success and different
become a major issue and created threat for mankind. phases of implementations. For example solar energy, either thermal or
Transportation and energy producing sectors have significant role photo-voltaic, geothermal, wind, hydroelectric and bio-fuels [8]. Each
in overall greenhouse gas (GHG) emissions. Petroleum diesel combus- has its pros and corns depending on the area of application but one
tion is also a major source of GHG as well as other major source of important goal is the reduction of emission by replacing fossil fuels
⁎
Corresponding author.
E-mail addresses: beena.patel@abelloncleanenergy.com (B. Patel).
http://dx.doi.org/10.1016/j.rser.2016.12.081
Received 21 October 2015; Received in revised form 17 November 2016; Accepted 12 December 2016
1364-0321/ © 2016 Elsevier Ltd. All rights reserved.
Please cite this article as: Patel, A., Renewable and Sustainable Energy Reviews (2016), http://dx.doi.org/10.1016/j.rser.2016.12.081
A. Patel et al. Renewable and Sustainable Energy Reviews (xxxx) xxxx–xxxx
with renewable energy sources. Bio-diesel and bio-ethanol can replace applications of microalgae. The former one includes the stages of
diesel and gasoline, respectively with little or no modifications required microalgae to biodiesel production process reviewed based on learning
for vehicle engines. Bio-diesel is a potential substitute for conventional from historical research to understand important factors affecting
diesel fuel [9] which can be produced from oil via trans esterification overall productivity and economic viability along with technological
[10]. According to the US standard specification for bio-diesel developments we have brought out in design and development of algae
(American Society for Testing and Materials (ASTM 6751), bio-diesel reactor. The second one describes the high value microalgae products,
is defined as a fuel comprised of mono alkyl esters of long chain fatty CO2 sequestration and waste utilization potential through combined
acids from vegetable oils or animal fats [11]. Bio-diesel is the main resource utilization to reduce environmental pollution. Thus this
alternative of diesel fuel in European countries which is representing review deals with current scenario of technological developments in
more than three fourths part of overall bio-fuels production and it's still microalgae to biofuel with economic and environmental aspects to
in growing phase in Europe, Brazil, and United States [12]. Cost identify major gaps and opportunities in this field that can be
effective biodiesel production without competing with vegetable oils addressed in near future.
can be possible using non-edible oils like used oils, soap stocks, greases
and animal fats. However, the quantities of waste and animal origin oil 2. Microalgae as bio-fuel feedstock
are not enough to address the current biodiesel demand. Land
availability is major challenge to grow feedstock without conflicting 2.1. What are micro algae?
with food and fodder demand. Micro algae are getting more interest
among the all possibilities at pilot scale and even at industrial scale as The earth was originated 4.5 billion years ago in solar system.
feedstock for biodiesel without direct interfering to human consump- Amino acid and nucleic acid were originated after sequential events of
tion [13]. Microalgae are also cultivated for proteins, sugars, essential chemical modification and evolution in the earth's atmosphere as
fatty acids, carotenoids or vitamins for human health, food additives protobiont in abiogenesis phase and started protobiology phase
and cosmetics as well as diet supplements for aquaculture and animal between 3.5 and 4.0 billion years ago. Tree of life has established by
feed besides biodiesel production [14]. Fig. 1 shows product value three domains: Ecobacteria, Cyanobacteria and Eukaryotes. The cya-
chain of microalgae. The inputs are constant while out puts are variable nobacteria, recently known as blue-green algae was first photosynthetic
in terms of numerous products. Algae take CO2, water and sunlight as autotrophs initiated oxygenic age of the earth during glycobacterial
input however use of various processing technology leads to diverse revolution between 2.8 and 2.9 billion years ago later prochlorophytes,
product portfolio (Fig. 1). glaucophytes and other lineages of algae were originated. The algae,
Biodiesel production from microalgae feedstock is the process of especially chlorophytes initiated overall evolution and development of
extracting oil from algae cells and trans-esterified the lipids into methyl higher organism of the planet [25].
esters. Many of the researchers described this process at more or less Microalgae are microscopic, unicellular or simple multicellular
depth [15–18]. Some researchers also explained different techniques prokaryotic or eukaryotic photosynthetic organism that can produce
for cultivation, harvesting, extraction and processing of microalgae to biomass and oxygen by using sunlight as energy source, CO2 as carbon
biodiesel production [19–21] and key factors affecting at each stage source and inorganic salt. Some species can grow autotrophically and
[13]. Direct conversion of microalgae feedstock to biodiesel had been produce organic molecules while others are heterotrophic in nature,
described by Huang and his team [22]. Baliga and Powers also growing in dark on complex organic material for energy and carbon
discussed the designing parameters of cultivation system for biodiesel sources. Cynobacteria from Cynophyceae are example of prokaryotic
production from microalgae in cold climates [23]. Frac and his team microalgae and in similar way green algae from Chlorophyta and
reported the biodiesel production stages with estimation of possibility diatoms from Bacillariophyta are example of eukaryotic microalgae
and profitability of use of biodiesel [24]. [26,27].
This review article is structured into two major portions; (1) Microalgae can grow in almost all type of ecosystems like terrestrial,
microalgae as biofuel feedstock and (2) environmental and economic aquatic marine or fresh water. Applied phycology originated with first
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microalgae culture establishment of Chlorella by Beijerinck in 1890 experiments touch the preliminary stages [13]. In summary of almost
[28]. Many microalgae species were collected from variety of habitats 20 year research, they concluded that commercialization of fuel
and analyzed by different countries. Different microalgae collection production from algae was too expensive and require long term
center have been established with highly diversified culture collection. intensive research work because of low yield, uneconomic harvesting
For example university of Coimbra from Portugal have more than 4000 processes and difficulties in maintaining potential species in the culture
strains of fresh water microalgae, university of Texas having Algae system [41].
Culture Collection of 2300 strains of fresh water microalgae and many In recent time of unpredictable crude oil price paradox and
sea water green and red microalgae, the National Institute for expected future demand with the urge of reduce GHG and non GHG
Environmental Studies Collection in Asia and Japan having richness emissions, researchers have been inspired towards production of
of 2150 strains and 700 different species of algae [13]. biodiesel from microalgae in consortium, public and private sector's
investment in research and developments to progress potential and
2.2. Benefits of selecting microalgae for biodiesel production cost effective technology for large scale oil production. Many enter-
prises are currently working on algae for fuel with few have already
• Microalgae are prokaryotic or eukaryotic organisms having simple entered in market for selling processing units for high tech algae
structure with high photosynthetic efficiency [13]. Researchers cultivation systems like photo bio-reactors with optimized control
studied more than 30,000 microalgae species in past decades from system [13].
different countries [28]. They can easily be adopted in different Researcher's interest has concentrated toward metabolic engineer-
environment conditions so that one can select species of choice ing and genetic studies on microalgae for development of organisms
which is best suited to local environment or growth conditions as with optimized yield and lipid productivities with high efficiency. In
biodiesel feedstock. spite of simple and non-differentiable cell system of microalgae genetic
• Microalgae are the best producers of neutral lipids/oil at 20–50% engineering in microalgae is not yet successful. Transgenic algae can
dry cell weight with 1–3 doubling/day [29], much higher than create a considerable threat to the natural ecosystem to grow in open
conventional forestry and other aquatic plants requiring less land environment with restriction [42]. However, risks for genetically
area up to 49–132 times when compared to rapeseed or soybean engineered algae research needs to be evaluated and supported with
crops [30]. Thus they provide feedstock for verities of renewable its user's guidelines creating standards and certification supported by
fuels like biodiesel, ethanol, methane, hydrogen etc. at reduced level local policies to promote its use in defined applications.
of particulate matter, CO, hydrocarbon and SOx emissions [31]. Presently it is hard to compete with conventional diesel economic-
• Different compounds may also be extracted from microalgae like ally without any incentive support; however researchers from academic
large range of fine chemicals, Poly-unsaturated Fatty Acids (PFAs), and industry are trying to make it commercially feasible. It would be
oil, natural dyes, pigments, sugars, antioxidants, bio-active com- economic and feasible once crude would be deficit in time to come with
pounds with high industrial value in cosmetics, food and nutrition, integration and exploration of various algae trains and varied waste
pharmaceuticals and pollution prevention sectors [26,32,33]. water stream to cultivate algae for fuel [13].
• Algae takes up CO2 from industrial flue gases for its growth as
breathe in metabolic process also known as bio-fixation of CO2[34] 2.4. Lipid profiles and productivities of microalgae
resulting into GHG emissions reduction of an industry while
producing algal biomass [35]. Algae takes up essential nutrients Lipid content in microalgae varies between 1–70% but under
like ammonium, nitrates and phosphate ions from industrial waste specific growth conditions some species accumulate lipid up to 90%
water effluents for its growth and removes from waste water stream, of dry weight [26,27,30,43]. Lipids from microalgae are generally
a process known as bio-remediation process [34]. Therefore algae is neutral, polar, non-polar, sterols, wax ester, prenyl derivative and
a right choice to cultivate for industries emitting CO2 and having pyrrole derivatives. The storage lipids are in the form of
large volume of spent effluent water to meet pollution control Triacylglyceride (TAG) which includes saturated and unsaturated fatty
obligations of local authorities with market potential from algae acids [44]. Photon from light source stimulates synthesis of TAGs
biomass and its products. which are stored in cytosolic lipid bodies and re-neutralize in the dark
• Moreover, de-oiled cake of algal biomass can be processed for for polar lipid synthesis [45].
production of livestock feed and organic fertilizer having high As shown in Table 1, Chlorella emersonii, Chlorella vulgaris,
Nitrogen: Phosphorus ratio [34]. Dunaliella sp., Nannochloris sp. and Phaeodactylum tricornutum
• Microalgae perhaps leverage significant social and environment can reach up to more than 50% lipid content with different productiv-
benefits because they neither compete for arable land with food ity. On the other hand Dunaliella salina and Nannochloropsis oculata
crops for human consumption nor interfere with food security have comparatively higher lipid productivity. Most of the microalgae
concern [36]. They can grow in different environments like fresh species have lipid content between 20–50% with variable productivity.
and brackish or marine water [37,38,23,39] and also tolerate Chorella and Dunaliella can be good option for oil production. Fatty
marginal lands like arid, semi-arid and desert which are not suitable acid profile of species has direct influence on bio-diesel production.
for other agriculture crops [29]. Fatty acid profile of lipid is species specific for example Cynophyceae
class contained C16:0,C18:0,C16:1 and C18:1 whereas
2.3. Historical exploration and evolution in microalgae production Nannochloropsis shows major part of C16:0, C16:1, C18:0 and C20:0
system and Spirulina platensis contained highest amount of palmitic acid
C16:0 (66.05%) [46].
Use of algae for food, feed and fuel was started before 1950s with Lipid content can be influenced by growth parameters like nutrient
methane gas and shifted to a pick interest at 1970s energy crisis, when availability, environmental factors, cultivation type, growth conditions
research diverted to produce energy from gases like hydrogen and [47]. It has also been observed that nutrient specific stress can induce
methane [40]. With an objective to study the feasibility of low cost lipid production. Nitrogen starvation gives better lipid production
biodiesel production from microalgae, the US department of Energy response at commercial stages among other induction conditions.
(DOE) by National Renewable Energy Laboratory (NREL) launched a Changes in other growth factors like temperature, pH, heavy metal
relatively small budget (about $25 million) program called ASP stress and salinity can also influence the stimulation of lipid in
(Aquatic Species Program) in 1978. Unfortunately the program was microalgae cell but all these parameter may not be regulated at large
closed in 1996 due to reduction in budget from DOE before the scale system [48].
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Table 1
Microalgae lipid content and lipid productivity [13].
Table 2
Comparison of microalgae with other biodiesel feed stocks [13].
Source Seed oil content (%per weight biomass) Oil yield (Liter oil/ha year) Biodiesel productivity (Kg biodiesel/ha year)
Source: Mata TM, Martins A a., Caetano NS. Microalgae for biodiesel production and other applications: A review. 2010.
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followed by recycling of nutrient media and drying of biomass. The 2.5.2.5. Electrolytic and ultrasonic aggregation. Electric field is
main advantage is that one can easily observe and control over pH, applied to take out algae cell particles from solution. Hydrogen ions
temperature, light, CO2 and other parameters of cultivation system resulted from electrolysis of water adheres to microbial flock and
without water evaporation and other biological or chemical moves them to surface. This method has several benefits including
contaminants. It allows higher cell concentrations with volumetric effectiveness, no other chemicals require, safety and environmental
productivities [13]. PBR also has few limitations like overheating, compatibility [72]. Ultrasonic aggregation is also used for high
oxygen transfer, bio-fouling, high building and operational cost, shear separation efficiency with approximately 20 times more dynamic
stress by agitation and in scaling up. The PBRs and open raceway pond concentration [73].
cannot be compared stand alone. Where to use what depends on type of
algae, cultural conditions and end product quality to be looked at.
Table 3 describes basic parameters for both cultivation systems. One 2.5.3. Extraction
should choose the method on the basis of species and expected end Lipid extraction is one of the crucial steps for bio-fuel production
product's quality and economic value. system that adds into overall process economics. Extraction efficiency
depends on type of biomass (microalgae species), desired end product,
and method of extraction (physical, chemical or combination of
2.5.2. Harvesting different methods). The extraction process should be effective, fast,
Harvesting process represents biomass recovery from culture energy efficient, innocent to the lipid structure and easily expandable to
media. The cost effective method for harvesting is essential for large scale [69]. Overall process includes removal of water from wet
commercial production of biodiesel as it contributes around 20–30% biomass, extraction of lipids from cell and recovery or concentration of
of total production cost. This may include physical-chemical and the extracted lipids. Generally dry biomass is processed for lipid
biological approaches for liquid-solid separation. The selection of extraction as water molecules do not allow intracellular oil to extract
method is based on cell density, cell size and market value of end out easily [73]. Sun drying, spray drying, drum drying and freeze
product etc [13,19]. Commonly used microalgae harvesting techniques drying are method of choice for algal biomass drying [28] however,
include filtration, gravity sedimentation, flocculation and floatation, selection of drying dependent on end product nature. For example,
centrifugation, electrolytic and ultrasonic aggregation etc. microalgae biomass with high moisture content, sun drying is not
efficient and spray drying is too expensive for low value product.
2.5.2.1. Filtration. Filtration is most common method of choice for
solid-liquid separation being effective in larger size micro algae like S. 2.5.3.1. Mechanical. There are several different ways for cell
platensis but inadequate for small cell sized like Chlorella and disruption to release intracellular lipid molecule like cell
Dunaliella [71]. Rotary filters and micro strainers are primary homogenizers, bed mills, autoclave and ultrasound are generally used
filtration methods in microalgae harvesting wherein micro strainers to break cell wall. Selection of method depends on type of cell wall and
with fine mesh screen offers easy access and cost effective filtration nature of product to be extracted. Ultrasound and microwave assisted
[71]. Membrane filtration and ultra-filtration can also be useful as cell disruption and extraction shows higher yield than conventional
secondary filtrations optional to add on primary filters with more method in case of extraction of oil from vegetable sources as it saves
economic burden on harvesting process. time of extraction with no toxicity to end product [74].
2.5.2.2. Gravity sedimentation. This method is low cost and energy 2.5.3.2. Chemical. Chemical method for extraction of lipid is widely
efficient process, normally used for separation of larger sized adopted because of its simplicity with no need of expansive
organisms in sedimentation tank [36]. Gravity sedimentation is instruments [36]. The most popular method is Bligh and Dyer
suitable for low economic product. In some cases, this method method and Soxhlet method [4,36]. Solvents selected for extraction
influences economics of final product at downstream stages. should be inexpensive, volatile, non-polar, nontoxic and poor extractor
of non-desired cell components. Several solvents like hexane, ethanol,
combination of hexane and ethanol, methanol and chloroform can be
2.5.2.3. Flocculation. Flocculation is applied to aggregate the used on the basis of biomass type and end product purity need [28].
dispersed particles to form large particles which enhance the Ethanol is used to extract few sugars, salts, amino acids, proteins and
sedimentation by gravitational or other centrifugal forces. There are pigments however, it is not desirable for lipid extraction. Piasecka and
two type of flocculation processes in which auto flocculation by his team reported that 9.34% lipid yield obtained from wet biomass of
carbonate salts with algae cell and chemical flocculation resulted chlorella protothecoides by Bligh and Dyer extraction method [75].
from neutralization of surface charge by adding some chemicals like Mixture of dichloromethane and methanol were also used for high lipid
extraction in few species [76].
Alum (Al2 (SO4)3), ferric ions etc. Cationic polymers and alkali
substances are also used for flocculation which fluctuates pH [69].
However, removal of chemical flocculants from harvested biomass may
increase the cost to further downstream stages in case of costly and 2.5.3.3. Super Critical Fluid (SCF). Super critical fluid extraction can
quality conscious products. displace traditional solvent extraction practice as it displays low
toxicity, favorable mass transfer equilibrium and production of
solvent free extract. Moreover residues remains after extraction can
2.5.2.4. Flotation. Floatation is the process in which solid particles be used as animal feed and subjected to anaerobic digestion [4].
adhere to the air or gas bubble and carry them to the liquid surface. It
can be applied for the cell size less than 500 µm. It works on a
mechanism of interaction between negatively charged hydrophilic 2.5.4. Processing
surfaces of microalgae cells [69]. Ozonation dispersed flotation Currently three main methods are used for conversion of micro-
increases lipid extraction by cell lysis and releasing bio-polymers algae biomass to bio-oil (liquid fuel): Trans-esterification, thermal
which are good coagulating agents for separation process. Expensive liquefaction and pyrolysis. However, trans-esterification can only
process makes it unfavorable. produce biodiesel directly from extracted microalgae lipids.
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2.5.4.1. Trans-esterification. Biodiesel is chemically fatty acid esters issue of carbon storage and supply along with GHG emission reduction
synthesized by trans-esterification (exchange of ester) between [85]. However, flue gases contain different compounds such as sulfur
triglycerides present in oil of vegetable or animal origin and alcohol. oxides (SOx), nitrogen oxides (NOx), unburned residues, halogen acids,
Overall trans-esterification reaction has three reversible steps; CO, heavy metals and PM besides CO2 and very few species can tolerate
conversion of tri-glycerides to diglycerides; di-glycerides to mono- these compounds at high concentration. Some reports have shown
glycerides and finally monoglycerides to esters (called biodiesel) and a positive effects of flue gas compounds other than CO2 in microalgae
by-product glycerol. Methanol is used as catalyst. Fig. 5 shows biomass productivity. Researchers of Seambiotic Ltd. from Israel tried
complete overall trans-esterification reaction [13]. Generally acid flue gas instead of pure CO2 and got 50% increase in productivity
(Sulfuric, sulfonic and hydrochloric acid) or alkyl (NaOH and KOH) possibly due to the existence of heavy metals, sulfates and nitrates act
catalysts are used for trans-esterification reaction while in few cases, as nutrients for algae [86].
super critical fluids are also used to initiate the conversion [77,78]. Different microalgae species display different abilities of CO2
Trans-esterification is more efficient, simplest and eco-friendly method sequestration. Some species show different degree of tolerance to high
among other production methods [79]. CO2 concentrations like Chlorococcum littorale a marine alga, can
grow easily at 40% CO2 concentrations [87] and Chlorella isolated from
hot springs can tolerate 40% CO2 concentration of industrial flue gases
2.5.4.2. Thermal liquefaction. Thermal liquefaction directly converts up to 42 °C temperature [88]. Other microalgae species reported for
wet algae biomass to liquid fuel. Conversion takes place at low CO2 fixation include Scendesmus sp.[89], and Dunaliella tertiolecta
temperature (300–350 °C and high pressure 5–20 MPa) with [90]. Table 4 shows summary of studies on CO2 sequestration by some
hydrogen as catalyst. Liquefaction results in production of 30–60% microalgae species.
dry weight of oil, however, the reactor and instruments for liquefaction Table 4 shows that, Haematococcus pluvialis can tolerate 34% CO2
are too expensive. Dunaniella tertiolecta and Spirullina platensis have concentration with CO2 fixation rate of 0.14 gL−1d−1. Other microalgae
shown yield of 42 and 30–80% dry weight basis of oil using thermal species like Chlorella sp., Scenedesmus sp., Dunaliella sp. and
liquefaction respectively [36]. Spirullina sp. can also tolerate high CO2 concentration at different
fixation rate and can be used to utilize CO2 from coal-fired power plants
and other carbon emitting industrial processes. Scenedesmus incras-
2.5.4.3. Pyrolysis. Pyrolysis is a process where in thermal conversion satulus and Scenedesmus dimorphus shows higher fixation rate
takes place in absence of oxygen. Pyrolysis chemically reduces tri- compare to others.
glycerides to fatty acid alkyl esters at high temperature [80,81]. This Because of relatively low solubility of CO2 in water, mass transfer of
process requires additional equipment for separation of fraction. CO2 is one of the rate limiting factors in microalgae cultivation.
Moreover, the product obtain after pyrolysis is similar to gasoline Common method for feeding CO2 is direct purging of pure CO2 or
containing sulfur which is less eco-friendly [82].
Table 4
Potential microalgae species for CO2 sequestration.
3. Environmental and economic application of microalgae S. No Microalgae CO2 concentration CO2 fixation References
tolerance (%) rate (g
L-1d−1)
3.1. Environmental applications
1. Scenedesmus 0.03 1.50 [91]
3.1.1. CO2 sequestration incrassatulus
Carbon dioxide is one of the principle greenhouse gases responsible 2. Scenedesmus 0.03 1.27 [91]
dimorphus
for global warming. Till now, many technologies were used to capture
3. Spirulina platensis 15 0.92 [92]
CO2 including chemical and physical absorption, membrane separation 4. Chlorella sp. 5 0.7 [93]
and cryogenic distillation [83]. The CO2 captured needs to transport 5. Scenedesmus sp. 15 0.61 [94]
and us in a way that is environment friendly and energy saving. 6. Scenedesmus 10 0.55 [95]
Nowadays, biological fixation of CO2 has drawn much attention obliquus
7. Chlorella vulgaris 2 0.43 [96]
worldwide as the green algae Chlorophyta showed CO2 fixation ability 8. Dunaliella sp. 3 0.31 [97]
by using solar energy with an efficiency of 10–50 times greater than 9. Dunaliella 10 0.27 [98]
terrestrial plants [34]. Carbon is the main structural element for tertiolecta
microalgae as it is a key source for microalgae biomass production. 10. Chlorella vulgaris 10 0.25 [98]
11. Chlorella kessleri 18 0.16 [99]
The supply of atmospheric CO2 to microalgae culture through diffusion
12. Haematococcus 34 0.14 [100]
is insufficient for rapid growth at large scale cultivation system [84]. pluvialis
Therefore microalgae cultivation by utilizing flue gas can address the
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from flue gases which has major limitation of absorption of CO2 in engineering for better efficiency. Rishiram and their team also studied
liquid leads to loss in atmosphere and low carbon utilization efficiency the effect of calcite formation linked with CO2 fixation in microalgae
because of lower solubility of CO2 in water [101]. CO2 fixation and Chlorella sp. and Spirulina platensis and found that growth rate of
biomass production efficiency can be improved by high aeration rate algae and efficiency of CO2 fixation were significantly higher when
and proper mixing which also increases CO2 mass transfer and excess coupled with calcite deposition in mini-raceway pond [111].
oxygen removal rate. However, it increases overall operational cost and CO2 bio-fixation maximization efficiency requires optimization of
physical stress to the microalgae cell [102]. process parameters and efforts to develop potential microalgae strains
Closed PBRs can reduce the CO2 losses compared to open-culture are still needed.
systems as they could prolong CO2 retention time and improve mass Algal industries like Algae Floating Systems, Inc. from San
transfer efficiency. A novel gas sparger of bubble tank was adopted in a Francisco, Algae. Tec from Australia [86] and Seambiotic Ltd. From
PBR by Chai and his group to increase CO2 mass transfer rate as well as Israel [86] are developing carbon capture and sequestration system
alleviate dissolved oxygen (DO) accumulation with 94% CO2 removal from power plants and converting them to renewable fuel and other
efficiency [103]. A membrane-sparged helical tubular PBR was also valuable products. Abellon Clean Energy, India has developed 660 L
designed by Fan et al. [104] for carbon dioxide biofixation by C. tubular glass reactors with Programmable Logic Controller (PLC)
vulgaris. This kind of studies show that CO2 fixation with closed PBRs system which purges CO2 automatically as pH of the medium increases
is a better option compare to open system [105]. and monitors online CO2, O2, pH, TDS and other growth parameters2
Ketheesan and Nirmalakhandan [106] reported highest CO2 con- (Fig. 6). The reactor has been design for simulation trials for various
sumption in microalgae cultivation by airlift –driven raceway reactor. algae species growth and subsequent characterization of algal biomass
Similarly Fulke et al. [107] also found that Chlorella sp. could for its industrial applications.
efficiently fix the CO2 gas up to 15% concentration with air lift
photo-bioreactor.
3.1.2. Removal of NOx and SOx by microalgae
Another method to improve the utilization efficiency is to introduce
Besides the CO2 removal from flue gas, microalgae can also remove
CO2 to the culture in soluble form. For this, some absorption liquids are
NOx, SOx and some heavy metals from flue gas and thus help in
used to stabilize CO2 in form of carbonate and then supplied to algae.
reduction of overall GHG emissions to the environment. Nagase et al.
Potassium carbonate is one of the cheap absorption liquid which can
reported the potential of NOx removal from flue gas by Dunaliella
reduce the energy requirement for purging of pure CO2[108].
tertiolecta with 65% NO removal efficiency. He also observed that NO
Microalgae CO2 fixation at larger scale is influenced by various
removal efficiency is closely associated with strain of microalgae and
factors like algae species and physico-chemical condition of cultivation
level of dissolved oxygen [112–114]. Kao et al. also found the faster
system.
growth rate and higher cell concentration in Chlorella sp. with higher
Moreover, genetic engineering is also an option to control the
concentration of NOx in flue gas (i.e. flue gas from coke oven) [115].
regulation of biosynthetic genes and its expression in microalgae cell
Santiago et al. [116] found positive results by using counter-flow type
under different stress conditions for CO2 sequestration. Researchers
airlift reactor to overcome the problem of low NO dissolution in the
from Taiwan genetically modified the cyanobacterium, Synechococcus
aqueous phase. He also reported that addition of Fe (II)-EDTA to the
elongatus PCC 7942, through transformation by genomic homologous
culture of microalga Scenedesmus sp. enhances the NO fixation to a
recombination with plasmid DNA vectors and found positive effects in
greater degree than seen with bacterial denitrification systems. These
CO2 bio-mitigation and biomass production in a photo bioreactor
findings suggest that the NOx concentrations at sub inhibitory levels
[109]. Significant genetic modifications in RuBisCO (Ribulose-1,5-
bisphosphate carboxylase) gene and its functions should be investi-
gated more to increase the photosynthetic efficiency of microalgae 2
“Design and Development of Dual Operating pilot Scale Bio Reactor System for
[110]. Another protein called carbonic anhydrase enzyme plays an Comparative Simulations studies On Algal Cultivation” (October 2011 – September
important role in CO2 fixation [111] which can be targeted for genetic 2012) accessed from http://mnre.gov.in/file-manager/UserFiles/bio-fuel/R_D_biofuel-
Design- & -Devlopement….cultivation.pdf on 10th October 2015.
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could enhance the microbial growth. The study of DeNOx process on Table 5
Chlorella sp. C2 suggested that the adverse effect of nitrite on cell Bio-active compounds from microalgae and their applications [14].
growth could be ignored when 17.65–88.25 mM nitrite was utilized as
Species Product Applications
the nitrogen source [117].
Sulfur oxides (SOx) are also important components present in flue Dunaliella salina Carotenoid, β Health food, food
gas, which directly contribute to degradation of the ozone layer and carotene supplement, feed
Haematococcus Carotenoids, Health food,
acid rain formation. Matsumoto et al. [118] studied the negative
pluvialis astaxanthin pharmaceuticals, additives
impact of pH fluctuation by presence of SOx on microalgae growth. Odontella aurita Fatty acid Pharmaceuticals, cosmetics,
Kao had also reported that SOx in the flue gas served as a sulfur source baby food
that support the growth of algae [115]. Studies show that NOx and SOx Porphyridium Polysaccharides Pharmaceuticals, cosmetics,
might be used by microalgae as nutrients only when pH is stably Cruentum nutrition
Phaedactylum Lipids, Fatty acids Nutrition
regulated [119]. Moreover, microalgae strains have their own tolerance
Tricornutum
limits for SOx and NOx exposure [113]. Lyngbya mujuscule Immune modulators Pharmaceuticals, nutrition
3.1.3. Nutrient recycling from waste water Source: Priyadarshani I, Rath B. Commercial and industrial applications of micro
Effluent treatment plants (ETPs) are installed in manufacturing algae – A review. Journal of Algal Biomass Utilization 2012; 3:89–100.
9
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Moreover, carotenoids found in Spirulina and Dunaliella sp. are more development of economically viable cultivation system with higher
effective anti-cancer agents than β-carotene [141,143]. yield, energy efficient processing and conversion system for large scale
Vitamins like biotin and α-tocopherol can be synthesized by sustainable bio-fuel production from microalgae. Fully optimized
cultivating Euglena gracilis and ascorbic acid by Prototheca morifor- culture system with controlled environment and utilization of cheap
mis [27]. Microalgae like Ochromonas sp., Prymnesium parvum and carbon dioxide sources like flue gases from power plant with water
other blue green algae produce toxic compounds which may have wide remediation can make large scale biofuel production from microalgae
pharmaceutical and therapeutic application [144,145]. Various strains economically and environmentally sustainable. Moreover, the optimi-
of blue green algae are reported to produce intracellular as well as zation of nutrient level, light and growth conditions as well as
extracellular metabolites with different biological activities like anti- development of highly efficient microalgae strains are key concerns to
bacterial, antiviral, antifungal as well as antialgal. Large scale produc- complete the milestones in this direction. Large scale biodiesel
tion of these bioactive compounds depends on various factors like production from microalgae biomass requires process optimization at
temperature, pH, media components, light intensity and duration of oil extraction and purification phases.
culture growth [146]. Astaxanthin produced by H. pluvialis protects Although, solvent extraction methods provide highest lipid recovery
membrane phospholipids against peroxidation. H. pluvialis is ap- and lipid denaturation at higher temperature with environmental risk
proved by U.S. FDA for marketing as dietary supplements and also of solvents released Solvent-free methods appear to be effective at
approved in few European countries for human consumption. Health laboratory scale where more research is needed for commercial scale.
benefits of astaxanthin include immuno-modulating functions, antic- Eco-friendly and cost effective mechanical lipid extraction methods
ancer activity, photo protection, anti-inflammatory, cardiovascular have poor recovery with significant degradation of lipids. Sonication
health, reduce risk for neurodegenerative diseases, eye retina protec- and super critical fluid extraction are advanced techniques that
tion from oxidative damage and positive effects in age related macular replaces traditional solvent extraction and mechanical practices with
disease [135]. added economical factor of higher energy consumption. Thus selection
of oil extraction method is one of the rate limiting step for biodiesel
3.2.2. Aquaculture and animal feed production from microalgae feedstock. The combinative methods can
Increasing needs for protein and price volatility in fish meal market be an effective and promising way for oil extraction from microalgae
in recent years led to search for new alternative sources. One such like partial cell disruption by mechanical or enzymatic cell degradation
highly nutritional and cost effective food component that can address followed by solvent extraction. This will be energy efficient and
the questions raised in aquaculture is microalgae. environment friendly. Moreover, mathematical models can be devel-
Microalgae can be used in aquaculture as live feed for bivalve oped for using solvent ratio to optimize lipid extraction.
molluscs, for juvenile stages of abalone, some fish species and High cost of technology in oil extraction can be overlooked if algae
crustaceans and for zooplanktons [147]. Microalgae species like cultivation process coexists with waste water generating and CO2
Isochrysis galbana and Tetraselmis suecica are used as best food for emitting industry which pays lots towards environmental penalty.
larval bivalves. Scenedesmus and Chlorella can also be used as Artemia CO2 emission charges called Carbon price or carbon tax is the amount
food and rotifer Brachionus plicatilis cultivation respectively [50]. that must be paid for the right to emit a tone of CO2. Industries
Use of microalgae as an aquaculture feed should devoid of toxicity, emitting such CO2 with high carbon tax could opt for algae cultivation
easy to ingestion to make nutrients available, correct cell size and shape diverting CO2 into cultivation process as a source of carbon and thereby
and have sufficient biochemical and nutrient content [148]. Fish health offset at downstream high cost technological barriers. Further indus-
depends on amount of essential fatty acids present in microalgae as trial waste water treatment plants also add to the cost of water
food. Nutritional value of microalgae varies species to species and may purification. Instead, utilization of such waste water with suitable algae
influenced by different culture conditions [142,149]. C. calcitrans, S. cultivation system may further reduce economics on cost of cultivation
costatum, Isochrysis sp., P. lutheri, T. suecica, C. muelleri, and which may later be diverted to high cost efficient oil extraction process.
Thalassiosira pseudonana have good nutritional properties as mono- Establishing such waste utilizing projects need encouragement through
species or with mix diet [142,150]. Combination more than one carbon finance.
microalgae species instead of monospecies provides better and ba- Waste water utilization and CO2 sequestration from flue gas would
lanced nutrition [43]. reduce production cost influencing GHG emissions reduction mandates
Predation by various protozoans like zooflagellates, ciliates, and and effective waste utilization. Integration of all downstream proces-
rhizopods and blooming of undesirable toxic species of blue-green of sing technologies with multiple end products can make microalgae
red tide are major problems with culturing of marine microalgae. Few cultivation an economic and environmentally sustainable process.
algae species like chlorococcalean (green algae), such as Synechocystis Considerable effort in technological development and technical exper-
(freshwater algae) and Phaeodactylum (seawater algae) are detrimen- tise are still needed to make algal biodiesel technically and economic-
tal for growth of bivalve molluscuss [50]. Monoculture cultivation of ally viable. Integration of innovative policy supports and financing
microalgae for aquaculture feed is pathogen free and nutritionally well schemes are also required to push market demand of microalgae
balanced. cultivation for bio-energy and bio-products in progressive direction.
Recently, being a good producer of astaxanthin content, H.
pluvialis is popular in market for salmon and trout diet and for other Acknowledgment
aquatic life like shrimp, prawns, and chickens [141]. Production of H.
pluvialis is carried out in large scale PBRs in completely controlled Mr. Akash Patel is registered Ph.D. scholar (Registration No.
conditions to stimulate synthesis of astaxanthin and finally harvested 001945) working for his studies on “microalgae isolation, identification
by gravitational sedimentation and centrifugation [151]. and characterization for industrial applications”, at Department of
Biotechnology, Hemchandracharya North Gujarat University (HNGU),
4. Conclusion Patan, India in association with Abellon Clean Energy Ltd to develop
environmental and economic feasibility of algal biofuel. This review is
Microalgae are getting more attention from academic and industrial part of the Ph.D. studies. Mr. Akash Patel is recipient of Prime
research as renewable energy feedstock coupled with higher sustain- Minister's Fellowship Scheme for Doctoral Research jointly promoted
ability index. Many researchers and industries are showing positive by Science & Engineering Research Board (SERB) and Govt. of India
finding towards technological development in microalgae to bio-fuel (DST). Authors are thankful to HNGU and Abellon Clean Energy Ltd.
and other high value products. However, research is still needed for for their critical inputs and infrastructural support to accomplish the
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