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INTERNATIONAL JOURNAL OF ENERGY RESEARCH

Int. J. Energy Res. (2010)


Published online in Wiley InterScience (www.interscience.wiley.com). DOI: 10.1002/er.1695

REVIEW

A review on microalgae, a versatile source for sustainable


energy and materials
K. G. Satyanarayana1, A. B. Mariano2 and J. V. C. Vargas2,,y
1
PIPE & Department of Chemistry, Federal University of Paraná, Centro Politécnico, CP 19081, Jardim das Américas, CEP:81531-980,
Curitiba, Paraná, Brazil
2
Núcleo de Pesquisa e Desenvolvimento de Energia Auto-Sustentável-DEMEC-UFPR, Centro Politécnico, CP 19011, Jardim das
Américas, CEP:81531-980, Curitiba, Paraná, Brazil

SUMMARY
Increasing energy demands, predicted fossil fuels shortage in the near future, and environmental concerns due to
the production of greenhouse gas carbon dioxide on their combustion have motivated the search for alternative
‘clean’ energy sources. Among many resources for this, microalgae have been found to be most promising due to
their high production capacity of vegetable oils. They possess a high growth rate, need abundantly available solar
light and CO2, and thus are more photosynthetically efficient than oil crops. Also, they tolerate high concentration
of salts allowing the use of any type of water for the agriculture and the possibility of production using innovative
compact photobioreactors. In addition, microalgae are a potential source of biomass, which may have great
biodiversity and consequent variability in their biochemical composition. This paper presents an overview on
microalgae with particular emphasis as a source for energy (biofuel/electricity) and new materials. Critical
issues involved in production of microalgae and their use, future R & D to overcome these, including the work
initiated by the authors at Federal University of Paraná, UFPR, in Brazil are discussed. Copyright r 2010 John
Wiley & Sons, Ltd.

KEY WORDS
biodiesel; biogas; biomass; microalgae; photobioreactor; biodigester; sustainable energy

Correspondence
*
J. V. C. Vargas, Núcleo de Pesquisa e Desenvolvimento de Energia Auto-Sustentável-DEMEC-UFPR, Centro Politécnico, CP 19011,
Jardim das Américas, CEP:81531-980, Curitiba, Paraná, Brazil.
y
E-mail: jvargas@demec.ufpr.br

Contract/grant sponsor: CNPq; contract/grant number: 552867/2007-1,574759/2008-5


Contract/grant sponsor: Araucaria Foundation of Paraná; contract/grant number: 13470

Received 16 August 2009; Revised 8 January 2010; Accepted 11 January 2010

1. INTRODUCTION sources derived from biologically based fuels such as


biomass and biofuels (biocombustible, methane and
Continuously growing population has led to increasing ethane) [3], which have attracted increased attention as
energy demands all over the world. The reported evident from the growing literature [2–70]. Biofuels have
current consumption of petroleum is at 105 times faster become increasingly necessary for the global fuel market
than nature can create [1]. These facts, along with the [29] with the reported annual estimated world raw
limited resources of oil reserves (stocks of fossil fuels) biomass energy potential in 2050 to be 150–450 EJ
and its use contributing to the increase of atmospheric (E 5 1018) leading to higher net farm incomes [19]. Also,
CO2 resulting in global warming [2] are currently biomass energy meets the increasing demands in various
recognized as great threats to mankind. Hence, both countries with Brazil between 23 and 30%, Finland
the demanding energy requirement and the ecological 20.4% and Sweden 17.5% [19]. Such a fuel should also
considerations have led to finding substitutes for the be biodegradable and non-toxic [16]. Biofuel is a fossil
fossil fuels by other resources including renewable fuel replacement that is produced from vegetable oils,

Copyright r 2010 John Wiley & Sons, Ltd.


K. G. Satyanarayana, A. B. Mariano and J. V. C. Vargas A review on microalgae

recycled cooking fats or waste oils, animal fats, or faster growth rate over energy crops [15,16,29] are
microalgal lipids [29] and is known to mankind even observed. Additionally, high production of biomass
from ancient days [37]. Table I lists some of the and some metabolites are achieved by their hetero-
renewable sources of biodiesel including microalgae. trophic growth [42–44]. Microalgae (Dunaliella tertio-
Those oils are renewable since plants and microalgae lecta), which was grown under highly saline conditions
produce oils from sunlight and air, and can do so year produced about 36% oil [17]. Further, depending on its
after year on cropland [29]. Substitution of the diesel capability of higher photosynthetic efficiency and other
used in the transport sector by the biodiesel produced characteristics mentioned above, microalgae would
starting from cultivated plants would need the use of have cost advantage. One reason for this could be that
massive lands that are presently used to produce food the oil content of several microalgae species might
[27]. A plant with the largest oil production for culti- reach up to 80% of its dry weight and their pro-
vated area is the Palm [2,38]. Even with the use of palm ductivity can be enhanced by genetic manipulations
oil to produce sufficient amount of biodiesel just to making microalgal biodiesel economically competitive
meet the half of the demand of fuel for transport in the with petrodiesel through large-scale production of ge-
United States would require about 24% cultivable area netic microalgal biomass [29].
in that country [2]. Currently, the fiscal incentives of- The utilization of microalgae as a renewable source
fered by several governments all over the world for the for obtaining fuel was an old concept proposed in fif-
production of biofuels from renewable resources are ties with follow up in sixties and seventies particularly
contributing for the decrease of the land for the pro- for producing biogas [32] and later reported for liquid
duction of food, which result in higher land costs. fuel in eighties and nineties [2,3], but received increased
Also, biodiesel derived from oil crops (e.g. soybean, attention in recent times due to the reasons mentioned
palm) cannot realistically meet existing costs of higher earlier (increasing petroleum and ecological con-
fraction of the raw materials and competitive demand siderations) [12] Also, this seems to be the ideal solu-
of the soil for their growth [29]. This is due to the cost tion for total substitution of the diesel used in the
of raw material accounting 50–85% for the total transport [2].
production cost in the current technique of the Considering the above facts, this paper gives an
preparation of biodiesel from these sources [9]. overview on microalgae with particular emphasis as a
Therefore, the cost of material is the dominant factor source for energy (electricity) and new materials. Pro-
in fixing the price of biodiesel. Hence, there are nu- duction of microalgae, their characteristics and appli-
merous criticisms for such promotion of lands for re- cations in various areas are presented. Perspectives for
newable source of energy [23] and also arguments for microalgae including the work initiated by the authors
and against the biofuels from microalgae and plant at Federal University of Paraná (UFPR) are also given.
resources [2,3,30,40,41]. Therefore, in order to complete this review study, the
One possibility to overcome the problem is the cul- application of the ideas collected in the literature review
tivation of microalgae, which is biological fuel source is also included with a brief description and status of an
[3] and seems to be a promising source for the pro- ongoing project by the authors. The main objective is to
duction of biofuels since they use carbon dioxide for provide the reader with an assessment of the feasibility
their energy in addition to sun light and carbon supply. of innovative microalgae biomass-based projects.
Also, they have higher photosynthetic efficiency than
terrestrial plants and are efficient carbon dioxide fixers
[3]. Therefore, higher biomass productions along with
2. MICROALGAE

Table I. Oil yield of sources of biodiesel (adapted from The microalgae (Figure 1) [71], one of the oldest living
Chisti [2]). organisms, are the unicellular algae that exist indivi-
dually, or in chains or groups [29] that form the base of
Source Yield of oil (L ha1) Required land area (Mha) the alimentary chain in the seas and rivers and they are
Corn 172 1540 known as ‘plankton’. There are more than 105 types of
Soyabean 446 594 microalgae used to produce biodiesel only. Further,
Canola 1190 223 they are known as essential components of coral reefs.
Jatropha 1892 140 It is reported [32] that in addition to being exception-
Coconut 2689 99 ally diverse, they represent highly specialized group of
Oil palm 5950 45 organisms, which can adapt to various ecological
Microalgaey 70 405 7.6 habits. The current market for microalgae is in the
Microalgaez 35 202 15.2 cosmetics, food industries and also in aquaculture [45].
To meet 50% of all transport fuel needs of U.S.A. In the cosmetic industry, the algae are marketed in
y
40% oil (% dry wt) in biomass. frozen condition and they supply the matter, which is
z
20% oil (% dry wt) in biomass. necessary for the preparation of anti-wrinkle cream

Int. J. Energy Res. (2010) r 2010 John Wiley & Sons, Ltd.
DOI: 10.1002/er
A review on microalgae K. G. Satyanarayana, A. B. Mariano and J. V. C. Vargas

Table II. Oil content in some microalgae.

Oil content
Species (% dry wt) Reference

Botryococcus braunii 25–75 [2,36]


Chlorella sp. 28–32 [2]
Chlorella emersonii 63 [34]
Chlorella minutissima 57 [34]
Chlorella protothecoides 23 [34]
Chlorella sorokiniana 22 [34]
Chlorella vulgaris 40, 56.6 [34]
Cylindrotheca 16–37 [36]
Crypthecodinium cohnii 20 [36]
Dunaliella primolecta 23 [2]
Isochrysis sp. 25–33 [2]
M. Subterraneus 39.3 [34]
Monallanthus salina 420 [2]
Figure 1. Scanning electron micrograph of a microalgae N. laevis 69.1 [34]
(Chlorella) (Zhang et al. [[71] Reproduced with the kind Nannochloris sp. 20–35 [2]
permission of the Springer Publishers]). Nitzchia sp. 45–47 [2,36]
P.incisa 62 [34]
Phaeodactylum tricornutum 20–30 [2]
due to its great concentration in long chain fatty acids Schizochytrium sp. 50–77 [2,36]
with great regenerative capacities of the skin. That Tetraselmis sueica 15–23 [2]
differentiated composition of long chain fatty acids,
mainly the unsaturated ones such as Omega-3 and
Omega-6, besides the high concentration of proteins
agriculture and use of N2 and P as nutrients from
and carbohydrates makes the microalgae as ideal
different kinds of waste water sources.
sources of nutrients for the preparation of functional
foods, food additive or even in nutraceuticals [46].
2.1. Market and cost for microalgae and
Microalgae, which are the microscopic organisms,
different products produced by it
present possibility for higher oil production capacity
reaching up to 77% of their dry weight [2]. Table II Estimated annual world production of biomass is
lists oil content of some of the microalgae. about 5000–7500 t [24,48] generating annual turnover
Besides, microalgae possess a high growth rate with of about US$ 1.25 billion. Meanwhile the market for
duplicating the number of cells several times in a single microalgae to produce the biomass to be used mostly
day [32,47]. The microalgae have advantages over the in health food, animal feed and aquaculture is fast
cultivated plants such as faster growth, yield of high growing with an estimated retail value of US$
amount of oils and possibility of the use of any kind of 3000–4000 million [49]. With an assumption of free
water for their culture. They can also generate biomass availability of CO2, estimated cost [2] for producing
in suitable reactors [32,47] many more times per unit microalgae by two different methods (raceway ponds
area of land than growing agricultural crops that and photobioreactors with identical production capa-
double in size over several days or weeks, or trees that cities of 100 000 kg) are US$ 3.80 and US$ 2.95 per kg,
grow on a timescale of years throughout the year. The respectively. These costs could be reduced by increas-
microalgae present a very simple cellular structure in ing the production to 10 000 t. Based on this, cost of 1 l
relation to the oil crops that have been supplying of biofuel produced by the photobioreactor produced
transport systems. Depending on the species, their sizes biomass is estimated to be US$ 2.8 assuming 30% oil
can range from a few micrometers (ı̀m) to a few hun- content in the biomass, which is higher than that
dreds of micrometers [29]. The accumulated chemical produced by vegetable oil such as palm oil (US$ 0.66),
energy after the photosynthesis process is not diverted which in turn is 35% higher than the petrodiesel (US$
for the construction of complex structures allowing 0.49), both of which are free of tax and transportation
this way, the best use for the production of new cells. charges and prices as existed in 2006 in USA. Other
In addition, they are also potential source of biomass cost comparisons of 1 l of petrodiesel and biodiesel-
or specific products (e.g. lipids, pigments, antioxidants) based waste cooking oil reported are US$ 0.35 and
[18]. Other advantages of microalgae for their becom- US$ 0.50, respectively [7]. The world sale of one of the
ing as feedstock for biofuels and materials include [32]: algae (Chlorella) used in human food, animal feed and
ability to synthesize and accumulate about 20–50% as food additive was higher than US$ 38 billion per
dry cell weight of neutral lipids/oil; use of waste land annum, while annual estimated market for docosahex-
(desert, arid and semi arid), which is unsuitable for aenoic acid, another nutritional supplement or used in

Int. J. Energy Res. (2010) r 2010 John Wiley & Sons, Ltd.
DOI: 10.1002/er
K. G. Satyanarayana, A. B. Mariano and J. V. C. Vargas A review on microalgae

aquaculture, produced by microalgae (Crypthecodi- closed type photobioreactors have been proposed,
nium or Schizochytrium) is about US$ 10 billion [48]. which not only possess higher photosynthetic efficiency,
Similarly, cost per kg of pigment carotenoids derived but also temperature control of the culture medium,
from a microalgae (D. salina) used for human food and since temperature normally increases with the exposure
animal feeds is reported to be US$ 300–3000 while that to the sunlight [52], and allow for the use of external
of another pigment, Astaxanthin (used in aquaculture) contamination control. A schematic view of this type of
is US$ 2500 with an estimated world market of US$ reactor is shown in Figure 2(B). Further, despite several
200 million [18,24], which was expected to increase research efforts for the design and operation of many
to US$ 257 million in 2008 [50]. The market for photobioreactors, devising and developing suitable
b-carotene was expected to reach US$ 253 million in apparatus, cultivation procedures and algal strains
2008, while market for lutein, which is the most susceptible of undergoing substantial increases in
important carotenoid used in human foods and serum efficiency for the use of solar energy and carbon
was expected to reach US$187 million by the same time dioxide is major challenge for the industrial microalgal
[50]. Comparison of market and cost of various types culturing. Accordingly, there is no ‘best reactor system’
of high molecules derived from microalgae and their to achieve maximum productivity with minimum
producers are available [48]. Cost of biomass also operation costs, irrespective of the available biological
depends on the type and region where it is produced and chemical systems [14]. Accordingly, choice of the
[19]. For example, in USA, the cost of plant biomass is most suitable system is situation-dependent, dictated by
US$ 5–15 per barrel of oil energy equivalent compared both the available species of algae and the final
with US$ 11–39 for solid industrial residues and energy intended purpose. The need of accurate control impairs
crops (e.g. soybean, rapeseed), respectively. the use of open-system configurations, so focus has
shifted mostly on closed systems.
2.2. Production of microalgae and photo- Design and operation of the microalgal biomass
bioreactor design production systems have been discussed extensively
[2–4,7,14,15,18,28,43,44,47,51–55,58] with a recent re-
Microalgae exist in different atmospheres and a lot of
view comprehensively presenting several types of
species tolerate high concentration of salts allowing the
closed bioreactors for the production of microalgae
use of any type of water for the cultivation medium
based on transport phenomena and process engineer-
[17]. A traditional cultivation of microalgae generating
ing methodological approaches [14].
the biomass for human consumption and aquaculture is
Photobioreactors are closed systems that allow the
the use of tanks or ponds [51]. This type of reactors
cultivation of single-species culture of microalgae [2].
called ‘Raceway ponds’ are normally open shallow
The photobioreactors have minimum contamination
ponds or channel type systems [52]. A schematic view of
while having the advantage of using the solar light and
this type of reactor is shown in Figure 2(A). Also,
higher amount of CO2 [2,35,58]. It should be noted that
production through ponds requires large areas despite
the objective of the photobioreactor photosynthetic
being cheap since it uses very low amount of CO2 of the
production process of microalgal biomass is to obtain
air and thus contaminates other organisms such as
simultaneously the reduction of input energy and the
mushrooms, bacteria and protozoa. They also show
achievement of high photosynthetic production [52].
low photosynthetic efficiency [52], due to low CO2 and
Also, these closed photobioreactors may be located
sunlight available only at the pond surface. Hence,
indoors or outdoors, although outdoor location is more
common due to the ease of using free sunlight. Compa-
rison of performance of bioreactors can be done for
fixed time [3] by their volumetric productivity (biomass/
volume) or areal productivity (biomass/occupied area)
or productivity/unit illuminated (biomass) surface.
These productivities vary with type of the system.
For example, the productivity (mg L1 d1) values of
370, 400–700 and 900 have been recorded for tubular,
shallow and coiled outdoor tubular ponds, respectively,
compared with 510 mg L1 d1 obtained for the indoor
reactor. Table III compares some of the variables/
parameters of two types of bioreactors [2,50]. More
details on these can be seen in the references given in
Table III.
Although microalgae production efficiency is often
mentioned in the literature [2–72], no consensus was
Figure 2. Diagram of raceway ponds (A) and tubular photo- observed on how to calculate it. Therefore, a definition
bioreactors (B). for microalgae production efficiency based on the

Int. J. Energy Res. (2010) r 2010 John Wiley & Sons, Ltd.
DOI: 10.1002/er
A review on microalgae K. G. Satyanarayana, A. B. Mariano and J. V. C. Vargas

Table III. Comparison of some parameters of two types of bioreactors (adapted from Chisti [2] and Del Campo et al. [50]).

Open system Closed system


Parameter raceway pond photobioreactor Reference
2
Area needed (m ) 7828 5681 [2]
Annual biomass production(kg) 100 000 100 000 [2]
Volumetric Productivity (kg m3 d1) 0.117 1.535 [2]
Oil Yield (m3 ha1) 56.8 78.2 [2]
Contamination control Difficult Easy [50]
Operation regime Batch or Continuous [50]
semi-continuous
Area/volume ratio Low High [50]
Light utilization efficiency Poor Excellent [50]
Process control Difficult Easy [50]
Scale up Difficult Easy [50]
Based on 40 % dry wt oil in biomass.

products/conversion efficiency definition for fluidized


catalytic cracking reactors in the oil refining industry
[73,74] is suggested as follows:
m_ db;out
Yi ¼ ð1Þ
m_ T;in

where subscript i accounts for the microalgae growth


process type (control volume) through which the mi-
croalgae biomass was produced (e.g. open pond,
photobioreactor); m_ db;out is the microalgae dry biomass
output mass flow rate [kg d1], and m_ T;in is the total
mass flow rate of all substances that enter the defined
control volume (process), including CO2, feedback
water, nutrients and others [kg d1].
Generally, in any photobioreactor design, the system Figure 3. Microalgae specific growth rate as a function of
productivity in continuous operating mode is obtained sunlight intensity [[2] Reproduced with the kind permission of
by multiplying the steady-state biomass concentration the Elsevier Publishers].
by the dilution rate used. These are related to the
average irradiance inside the photobioreactor, which in
turn is a function of the irradiance on the reactor examine the possibilities for the combinations of the
surface, operational variables such as fluid-dynamics microalgae used for practically higher photosynthetic
and dilution rate along with the pigment content production of microalgal biomass, with less operating
[32,47,53,57,58]. energy consumption throughout the year at various
Of several geometries of photobioreactors (helical, sites. A large difference in photosynthetic productivity
vertical and horizontal), the most efficient one is re- was caused by the difference in ambient temperature in
ported [2] to be tubular type, which should maximize each site, if temperature control of the culture medium
the use of solar light, to avoid large areas of shade and was not maintained. This helped to get practically
facilitate the diffusion of CO2 along with the control of higher photosynthetic production with less operating
temperature. The microalgae are maintained in circu- energy consumption throughout the year, using a
lation with turbulent flow to avoid the sedimentation combination of various strains that had different
and to reduce deposit in the walls of the tubes [2]. characteristics relative to temperature. Figure 3 shows
Further, time-dependent changes in the culture the effect of high sunlight intensity on specific growth
medium temperature in every season have been pre- rate of microalgae [2].
dicted [52] using a heat balance model of the conical Studies have also been carried out to find the influ-
helical tubular photobioreactor previously established ence of various reactor operating conditions such as
[4]. Using these results, the energy required to maintain temperature, solar irradiance and air flow rate on the
the temperature of culture medium within an appro- yield of the culture. In one such study, biomass pro-
priate range and the maximum and minimum culture ductivities up to 1.5 g L1 per day are reported with
medium temperatures have been predicted for several photosynthetic efficiency up to 14% by maintaining
sites with different climate characteristics. This helps to the cultures below 30.81C, dissolved oxygen levels less

Int. J. Energy Res. (2010) r 2010 John Wiley & Sons, Ltd.
DOI: 10.1002/er
K. G. Satyanarayana, A. B. Mariano and J. V. C. Vargas A review on microalgae

than 400% saturation (with respect to air saturated the nutrient-rich algal biomass is collected, which may
culture) while controlling the cell density. This has led be used for different purposes such as health food for
to achieve an average irradiance within the culture less human consumption, as animal feed or in aquaculture.
than 250 mE m2 s1 [58]. When the nutrient level goes below the limit for such
Production of microalgal biomass may be improved applications, the algal biomass may contain large
by specific cultivated conditions such as mixotrophic amounts of valuable biomolecules, which may be of
and heterotrophic cultivation [58,69]. It is also de- small percent of the biomass. They can be extracted for
monstrated that [22,33,56,59] variations in the cultiva- pharmaceutical or industrial retail. The remaining
tion conditions such as temperature, concentration of biomass will still contain good amount of the fixed
salts, nitrogen and CO2, for instance, interfere directly CO2. Hence, the residual algal biomass from different
in the biochemical composition of the microalgae. process stages can be used as a fertilizer for agriculture,
A modular concept of photobioreactors is expected to wherein retention of fixed carbon for some years is
allow verification of these different parameters to ob- possible. Otherwise, the fixed CO2 may be stored by
tain high amount of lipid and biomass production. industrial applications like production of plastics.
For using the microalgal fuel to produce electricity There is a possibility either to extract biodiesel from
(using stationary diesel engines), microalgae of lipid the residual biomass (energy carrier) or its direct con-
content should be grown in large quantities with high version into other energy carriers using biological or
productivity (1.5 g L1 d1) [2]. There are a large num- thermo-chemical methods.
ber of systems available for the mass cultivation of algae
[42,43] with outdoor systems (open ponds and raceway
2.3. Biodiesel production
types) [3] and closed bioreactors consisting of thin pa-
nels or tubes laid horizontally [3]. Growth rate of mi- The biodiesel consists of a biodegradable fuel pro-
croalgae depends on type of pumps used to circulate the duced from renewable sources. The synthesis of this
culture. For example, centrifugal and rolling pumps fuel can be accomplished by methodologies such as
damaged the algae, while a diaphragm pump showed cracking, esterification or transesterification using
very little effect on the growth rate of S. platentis [3]. animal fat or vegetable oils. Table IV shows a
Advantages of a closed system particularly with he- comparison of characteristics of biofuels and petro-
lical type are (i) increase in incidence of light energy per diesel along with ASTM biodiesel standard [15,29].
unit volume and reduction of self shading due to the The methodology mostly used for biodiesel pro-
large surface area to volume of the bioreactor, (ii) easy duction is based on the transesterification reaction, as
control of temperature and contaminants and (iii) ex- follows:
tensive pathways for CO2 absorption leading to better
CO2 transfer from gaseous stage to liquid stage [58].
Further, in recent times, based on increasing focus on
biotechnological potential of microalgae due mainly to
the identification of several substances synthesized by
these organisms, commercial scale production of mi- (2)
croalgae has been drawing the attention of the scientific The transesterification reaction, as stated by
community [38]. In fact, the great biodiversity and Equation (2), takes place in the presence of either
consequent variability in the biochemical composition homogeneous or heterogeneous catalysts (traditional
of the biomass obtained from various microalgal cul- method). Those alternatives can be compared in search
tures, which can be subjected to genetic improvement for the most efficient method of biodiesel production
and for massive production possibilities have allowed from microalgae lipids.
various species to be commercially cultivated. Thus, the
biomass production not only for use in the food ela-
2.4. Chemical composition of microalgae
boration but also for obtaining natural compounds
with high value in the world market have aimed at As the microalgae do not possess specialized structures,
developing microalgae cultivations on large scale [38]. except for the presence of the pigments and photo-
Figure 4 illustrates an innovative integrated multi- synthetizers, their composition basically consists of
disciplinary process. The first step consists of CO2 carbohydrates, proteins and lipids. They are also
capturing by the photobioreactors followed by algae sources for almost all types of essential vitamins
growth in the presence of sunlight, biomass production (e.g. A, B1, B2, B6, C, E) although environmental
and possibilities to produce various useful products, factors, harvesting treatment and cell drying method
including CO2 fixation by microalgae and production determine their quantity [49]. Table V lists the chemical
of biohydrogen [24]. composition of some microalgae, which are used to
The microalgae are then transferred to a separate produce food, cosmetics, big molecules and biofuels.
photobioreactor to produce H2 using energy by a While Table V(A) compares the composition of some
biophotolytic process without the use of sulfur. Then, microalgae with those of other food sources, Table V(B)

Int. J. Energy Res. (2010) r 2010 John Wiley & Sons, Ltd.
DOI: 10.1002/er
A review on microalgae K. G. Satyanarayana, A. B. Mariano and J. V. C. Vargas

Figure 4. Schematics of an innovative integrated multidisciplinary process [[24] Reproduced with the kind permission of the Elsevier
Publishers].

Table IV. Comparison of properties of biodiesel from microalgal oil, biodiesel fuel and ASTM biodiesel standard (adapted from Miao
and Wu [15]).

Biodiesel from ASTM biodiesel


Properties microalgal oil Biodiesel fuel standard

Density (kg L1) 0.864 0.838 0.86–0.9


Viscosity (mm2 s1, cSt at 401C) 5.2 1.9–4.1 3.5–5.0
Flash point (1C) 115 75 Min 100
Solidifying point (1C) 12 50 to 10 —
Cold filter plugging point (1C) 11 3.0 (Max 6.7) Summer max 0;
winter maxp15
Acid value (mg KOH g1) 0.374 Max 0.5 Max 0.5
Heating value (MJ kg1) 41 40–45 —
H/C ratio 1.81 1.81 —

lists some microalgae products used in cosmetics. in food varies between 1 and 35% while that for biofuels
Table V(C) summarizes the composition of some lies between 20 and 80% [29,49] compared with 15–30%
microalgae that are of interest for biofuel production. in vegetable oils, all on dry weight basis.
Therefore, Table V shows that most of the microalgae In order to use microalgae as a fuel, the algae should
have high protein content, particularly those ones that be of high calorific value and must be capable of
are used as food sources. Also, carbohydrates are found growing in large volumes. Main contribution to the
mainly as starch, glucose and other polysaccharides calorific value of cells is from their carbohydrate,
whose digestibility being high, can be used in dry form protein and lipid content [3]. Microalgae grown under
without any limitation [49]. Further, lipid content for use normal conditions possess calorific values in the range

Int. J. Energy Res. (2010) r 2010 John Wiley & Sons, Ltd.
DOI: 10.1002/er
K. G. Satyanarayana, A. B. Mariano and J. V. C. Vargas A review on microalgae

Table V. (A) Chemical composition of some food source microalgae compared with other human food sources (% of dry matter)
(adapted from Miao and Wu [15]), (B) Some of microalgae products with applications in cosmetics (adapted from Derner et al. [38])
and (C) Chemical composition of biofuel source microalgae.

Source Carbohydrates (%) Proteins (%) Lipids (%)

(A)
Anabaena cylindrica 25–30 43–56 4–7
Chalmydomonas rheinhardii 17 48 21
Chlorella vulgaris 12–17 51–58 14–22
Dunaliella salina 32 57 6
Porphyidium Cruentum 40–57 28–39 9–14
Spirulina maxima 13–16 60–71 6–7
Baker’s yeast 38 39 1
Meat 1 43 34
Milk 38 26 28
Rice 77 8 2
Soya bean 30 37 20

(B)
Products

b-carotene
Vitamin C and E
Arachidonic acid—ARA
Eicosapentaenoic acid—EPA
Starch
Poly-b-hydroxylbutyric acid—PHB
Peptides

(C)
Microalgae species Carbohydrates (%) Proteins (%) Lipids (%) Reference

Chaetoceros muelleri 11–19 44–65 22–44 [33]


[59]
Chaetoceros calcitrans 10% 58% 30 [59]
Isochrysis galbana 7–25 30–45 23–30 [61]
[62]
Chlorella sp. 38–40 12–18 28–32 [2]
Chlorella protothecoides 10.62–15.43 10.28–52.64 14.57–55.20 [19]
Nannochloropsis sp. n.a. n.d. 31–68 [2]
Neochloris oleoabundans n.a. n.d. 35–54 [2]
Schizochytrium sp. n.a. n.d. 50–77 [2]
Scenedesmus– obliquus 10–17 50–56 12–14 [y]
Quadricauda de Scenedesmus — 47 1.9 [y]

n.a.—not available.
Values are for two types of reactors used and not the range.
y
Homero E Bañados. Biodiesel de microalgas: part 1. (2007—Unpublished).

of 18–21 kJ g1, while the value for petrodiesel is in both algae, which increased their calorific value; the
42 kJ g1. Some microalgae such as Chlorella vulgaris highest calorific value of 28 kJ g1 was obtained with C.
and C. emersonii have been shown to grow in a 230 L vulgaris with the biomass productivity of 24 mg dry
pumped tubular photobioreactor in Watanabe’s med- wt L1 d1 which was lower than that obtained with
ium and a low nitrogen medium. While Chlorella species Watanabe’s medium (40 mg dry wt L1 d1).
can accumulate up to 58% lipid under low nitrogen
conditions [3], the Chlorella emersonii accumulates 63%
lipids in small (2 L) stirred-tank bioreactors, which re- 3. CHARACTERISTICS OF
sulted in 29 kJ g1 of calorific value [4] although the MICROALGAE
growth, productivity and lipid accumulation are yet to
be determined at a larger scale. It is found [3] that this In this section, some characteristics of the microalgae
low nitrogen medium induces higher lipid accumulation that have made them to be most promising source

Int. J. Energy Res. (2010) r 2010 John Wiley & Sons, Ltd.
DOI: 10.1002/er
A review on microalgae K. G. Satyanarayana, A. B. Mariano and J. V. C. Vargas

compared with other resources of biofuels are hereby as well as natural dyes. In fact, interest in the
recalled: (i) high production capacity of oils; (ii) high development of active biomolecules from microalgae
growth rate and (iii) requirement of abundantly is rapidly growing [55]. Microalgae have been used to
available solar light and CO2, that make them more fix CO2, and hence its growth can be linked to the
photosynthetically efficient than oil crops. They are removal of carbon dioxide from industrial waste gases
tolerant to high concentration of salts allowing the use (stack and exhaust gasses) [4], for wastewater treat-
of any type of water (fresh, brackish, highly saline and ments, as animal food as human food or to produce
marine) for the agriculture and possibility to produce numerous high-value bioactives [57,58].
them by photobioreactors [2–4,18,24,35,52,53,55,56,58]. The photosynthetic product (microalgal biomass)
In addition microalgae are a potential source of can be used as livestock fodder and as forage crops
biomass, which may have great biodiversity and substitute [4], while attempts have been made to
consequent variability in their biochemical composition develop composite materials using a microalgae
[38]. Their size (mean diameter in mm) such as of (Chlorella vulgaris) as filler in various polymers such as
Chlorella is about 5–10 mm, similar to that of powdered polypropylene, PVC, polystyrene and polyethylene
coal and cellulose to a few hundreds of micrpmetre. [2,3,71,72,77–79]. As these microalgae may putrefy and
Quantity of the oil produced by these depends mainly decompose, resulting in the release of CO2 to the en-
on their lipid content. Higher lipid content gives higher vironment, they have been used by incorporating them
calorific value of the fuel produced by the microalgae in polymer matrices up to 50 wt.% and the resulting
[4]. Some microalgae such as cyanobacteria (also called composites exhibited interesting tensile properties. For
‘blue algae’) may be cultivated without nutrients from example, PVC-Chlorella composite prepared by hot
N2 or C and hence cost-effective as well as manageable. molding process exhibited tensile strength (TS) be-
In view of microalgae having a greater capacity for tween 30 and 41 MPa and % elongation of 1.86 for
photosynthesis than plants they are capable of syn- average particle sizes of 5–110 mm. With microalgae
thesizing a number of valuable substances (e.g. health content waso20 wt.%, while it was 415 MPa when its
foods, food supplement, food color, food for livestock, content waso50 wt.%. These values were lower than
feeds for bivalves) [15,52]. that of PVC matrix (TS: 50.4 and % elongation: 180).
Similarly, its composite with polyethylene showed
good thermal plasticity whereby it could be shaped
into plates and dishes [79].
4. APPLICATIONS OF MICROALGAE Figure 5 shows scanning electron micrographs of
two polymer composites containing Chlorella micro-
Since the first use of microalgae in China about 2000 algae [71,72]. Figure 5(A) is the surface of the PVC
years back and the first concept of microalgae for use composite revealing the reinforcements lying in the
in the production of biogas in fifties, and later proposal matrix surrounded by air gaps, but without any
as a source of different types of fuel, namely liquid fuel changes in their shape due to the processing while
(from Botyrycoccus sp.) [4], and ethanol and methanol Figure 5(B) is the fractograph of this composite
after degradation of the algae [26], also converting into showing fracture of microalgae. One can see the
a gaseous fuel (methane) [28] as well as to produce bonding between the matrix and the reinforcement
hydrogen [75], a number of application areas have been does not exist and hence no increase in the tensile
identified [2–4,24,37,38,48–50,54,57–61,71,72,76–79]. properties was observed. However, about 22% in-
They include human and animal nutrition, cosmetics, crease in volume of the composite over the matrix was
high-value molecules such as fatty acids and pigments observed suggesting the microalgae could be good filler

Figure 5. Scanning electron micrographs PVC–Chlorella composite: (A) Surface; (B) Fracture surface; and (C) Fracture of PE–Chlorella
composite [[71,72] Reproduced with the kind permission of the Springer and American Chemical Society Publishers].

Int. J. Energy Res. (2010) r 2010 John Wiley & Sons, Ltd.
DOI: 10.1002/er
K. G. Satyanarayana, A. B. Mariano and J. V. C. Vargas A review on microalgae

for polymers. On the other hand, composite of PE with These include bulk biological chemicals and rapidly
the same reinforcement showed improved TS and growing biofuel industries. There are also limited
modulus when the matrix was modified. reviews in recent years on the perspectives on different
Figure 5(C) is the fractograph of maleic anhydride aspects of microalgae including critical issues and
modified polyethylene composite containing 40 wt.% of possible remedies [2,24,29,32,34,36,50,65–67]. Some of
the same reinforcement. Here also good bonding (che- these are summarized below:
mical bonds formed between Chlorella grains and the Isolation, culturing and characterization of microalgae:
PE matrix) between the matrix and the reinforcement is While isolation and characterization from any unique
evident from the fracture of the reinforcement itself and environment have been ongoing processes, culturing
also non-existence of any gap between the matrix and still remains a niche area needing continued R&D
the reinforcement, which exhibited TS twice that of a efforts towards cost-effective technologies [2,32].
composite with unmodified PE. Some of these proper- Research efforts towards additional organisms which
ties suggest these composites can be used as substitutes may possess unique mechanism for efficient production
for rigid and plasticized PVC and similar products. of lipid/oil should continue, while innovative develop-
Table VI summarizes the products and applications ment of large-scale culture systems through proper se-
of microalgae as reported by Rozas and Belli [46] lection of algal strains that lead to high and sustained
(Table VI(A)), and effective applications of microalgae growth rates of oil-rich biomass should be looked into
studied by Usui and Ikenouchi [24] (Table VI(B)). [32]. Production of higher biomass yield through the use
of genetic engineering to increase the photosynthetic
efficiency or to produce higher yields of oil, stability of
5. CRITICAL ISSUES INVOLVED IN such strains, identification of new strains capable of
THE PRODUCTION AND USE OF faster growth at high cell densities, increasing the
MICROALGAE AND FUTURE R & D growth rate of biomass and its oil content, reduction of
photooxidation susceptibility which damages cells,
Owing to increasing applications of microalgae parti- identification of factors including biochemical triggers
cularly for meeting the energy demands, despite its cost and environmental that enhances the oil content are
disadvantage, there is a growing interest to develop some of the issues needing greater attention [2,32,50].
cost-effective processes and to enlarge their application Design Aspects of Photobioreactors: This aspect is
areas based on various advantages mentioned earlier. an important issue to achieve cost-effective

Table VI. (A) Various products from microalgae with their applications [38] and (B) Microalgae applications considered effective
[Adopted from [55]].

Product Application

(A)
Biomass Biomass Natural ‘health food’, Functional food, Food
Additives, Aquaculture
Carotenes and antioxidants Xantophils, lutein, b-carotene, vitamin C and E, Food additives, cosmetics
arachidonic acid, eicosapentaenoic acid
Fatty acids Docosahexaenoic acid, g-linolenic acid, L dismutase Food additives
superoxide linolenic acid
Enzymes Phosphoglycerate quinase, lucipherase and lucipherin, Natural food, research and medicine
restrictive enzymes, polysaccharides
Polymers Starch, polyhydroxybutyrate (PHB), peptides, toxins Natural food, cosmetics and medicine
Special products Istotopes, aminoacids, steroids Research and medicine
(B)

Item Method and application

Fuel Extraction of carbohydrate


Direct liquefaction using coal liquefaction technology
Manure Compost
Animal feed Fodder or feed for domestic animals or fish cultivation
Building materials Plastic filler
Concrete additives for high efficiency concrete
Biodegradable plastic Plastic forming processes, biodegradable polymer
products including biodegradable composites
Physiologically active material Reformation of carbohydrates

Int. J. Energy Res. (2010) r 2010 John Wiley & Sons, Ltd.
DOI: 10.1002/er
A review on microalgae K. G. Satyanarayana, A. B. Mariano and J. V. C. Vargas

photobioreactors with high efficiency, keeping in mind environmental risks by its use. Hence, there is need for
that there is no such thing as ‘the best reactor system’ studies including modeling to look into toxic effects
to achieve maximum productivity with minimum caused by this fuel particularly the WSF of biofuels
operation costs. Efficiency of present day photo- although some attempts towards these have recently
bioreactors lies between 5 and 10% [65], so that de- initiated [80].
pendence of efficiency with high irradiance intensity
and reactor size is one of the major issues. Particularly
the latter with the retention of high photosynthetic 6. WORK AT UFPR
efficiency even at large sizes and at high light intensities
at longer periods should be looked into. Probably, Increasing global demand for fuels from renewable
optimization of photobioreactor for various variables energy sources, with motivation by tax exemptions of
through separation of reactor and collection system for biofuels has triggered many initiatives in the federal
light may be one way. Then, performance of micro- and private sectors aimed at producing biofuels,
algae culture should be tested. As the efficiency of particularly in Brazil, USA and Europe [23]. For
photobioreactors depends on irradiance of light, example, European production of biodiesel was
proper design for motionless mixers inside the reactors reported to have increased from about 1.9 billion liters
should be thought off to obtain better mixing between in 2004 to about 4.9 billion liters in 2006 [66], while
properly lit zone and dark zone in the reactor [2]. estimated annual production of biodiesel in Brazil is
Further, process strategy may be changed to get in- about 176 million liters, which advocates the first use
creasing yields at lower costs as reported in the efficient of diesel with 2% biodiesel in the current year and then
production of astaxanthin-rich biomass using con- of 5% by 2012–2013 [see: http://www.biodiesel.gov.br].
tinuous photo-autotrophic cultures [50]. It is also interesting to note other advantages accruing
Downstream processing: This is one of the major from this, such as increased employment avenues and
issues in microalgal biotechnology, which includes se- useful co-products obtained during the processing of
paration of biomass and concentration of microalgae this new fuel such as about 110 kg of crude glycerin
culture. Attempts should be made to develop cheaper from 1 t of biodiesel [31]. These require new develop-
and energy conserving processing methods [32,53,58] ments in technology of biofuels.
including genetic modification and engineering of algal As a first example, in a recent work, Gravalos et al.
strains from dilute cultures with optimum photosynth- [81] showed that vegetable oils are one of the alter-
esis and product formation [50,65]. Also, development natives utilized by farmers, which can be used as fuel in
of economical, quick and efficient processes for har- diesel engines either in the form of straight vegetable
vesting and de-watering of biomass depending on the oil or in the form of biodiesel. The study presented
end use is another area of interest for R&D [32,50,65]. experimental data by utilization of home and industrial
Cost: High cost to produce microalgae, which leads biodiesel as fuel in an agricultural tractor diesel engine.
to high cost of microalgal fuel (biodiesel), is another The home biodiesel production was made from dif-
issue. Some of the methods to offset that problem may ferent vegetable oils (crude rapeseed, edible sunflower
be by (i) resorting to production strategy to integrated and waste oil) with the process of one-stage-based
biorefinery, where useful products are produced using catalyzed transesterification. According to the results,
every component of biomass [2], (ii) identifying high- agricultural tractor diesel engine operating on home
value products particularly big molecules type based on biodiesel fuels had better performance characteristics
specific microalgae used [2] or broadening commer- related to industrially produced biodiesel and similar
cially viable product range such as nutraceuticals based to conventional diesel fuel.
on highly productive heterotrophic type cultures [32,65] Physical properties of biodiesel are another im-
and (iii) sale of generated excess power [2]. Also, pro- portant issue, playing an important role in the injec-
cessing of biomass for oil, wherein lipid extraction is an tion, atomization and combustion performance.
important step [32], is another issue to be looked into. A recent work investigated the spray properties of
Environmental aspects: Although biofuel is con- biodiesel [82]. In sum, the results indicated that, on the
sidered environmentally less harmful than diesel fuel, macroscopically view, the shape of biodiesel spray is
its eco-compatibility depends on method of its pro- similar to that of diesel.
duction, use and trade [80]. These in turn determine its Next, in order to complete this review study, the
economic, environmental and social aspects since not application of the ideas collected in the literature re-
much is reported on its eco-toxicological information view is illustrated in this section with a brief descrip-
of non-regulated emissions, effluents generated during tion of an ongoing project by the authors of this study
its production and on its water-soluble fractions under implementation at Federal University of Parana,
(WSF). These factors have to be considered as they are Curitiba, Brazil along with status of each of the items.
important to follow the precautionary principle pre- The main objective is to provide the reader with an
scribed by law in many countries that have plans to assessment of the feasibility of innovative microalgae
increase the production of biofuel, which may lead to biomass-based projects.

Int. J. Energy Res. (2010) r 2010 John Wiley & Sons, Ltd.
DOI: 10.1002/er
K. G. Satyanarayana, A. B. Mariano and J. V. C. Vargas A review on microalgae

Keeping in sight the current needs of technology Sometimes, smaller amounts of additions may result in
development in the area of biofuels elsewhere and va- slow growths and consequently low productivity.
lue addition to renewable resources, the Center for A new design conception for compact photo-bior-
Research and Development of Sustainable Energy eactors for the cultivation of microalgae has been de-
(NPDEAS) was created at UFPR in Curitiba, Parana, veloped. The photo-bioreactor design has the
Brazil. The main objective of this center is to demon- innovation of the maximization of the cultivation and
strate the concept of energy sustainable plants powered sun exposed area in a given volume, by utilizing cir-
by renewable fuels in a possible future scenario of cular transparent polymeric staggered tubes (crystal
distributed power generation. Specific objectives in- PVC). The geometric conception is based on the
clude: (i) design and fabrication of compact photo- compact heat exchangers technology [83].
bioreactors for microalgae cultivation; (ii) obtaining Although attempts have been made to achieve cost-
biodiesel and other co-products and possible uses of effective photo-bioreactors with high efficiency, not
byproducts particularly residues; (iii) mathematical much success has been reported and photo-bioreactor
modeling, experimental validation and thermodynamic technology is still in its early steps as discussed earlier
optimization of the components and processes, as well in the text. In that direction, Prakash et al. [84] de-
as of the entire system, and finally (iv) divulgation of veloped a transient thermal analysis and estimated the
the results of the project, improvement of the current incident solar energy for two designs of tubular photo-
technology of microalgae cultivation, evaluation of bioreactor installed outdoors arranged in one and two
system functionality and the possibility of general re- planes, respectively. The model was validated by
plication. comparing the experimental data and predicted values
of culture temperature. The performance of the two
photobioreactors for mass culture of Spirulina was also
6.1. Photobioreactor development
studied with respect to their design and culture tem-
An important step of this project is the development perature. Among several important conclusions, it is
and improvement of compact photobioreactors for interesting to note that the average biomass yield ob-
microalgae cultivation. Aiming to reach compatible tained in one-plane and two-plane photobioreactors
efficiency with the target plant needs and taking into were (dry weight) 23.7 g m2 day1 and 27.8 g
account the various parameters that affect the effi- m2 day1, respectively, giving a clear indication that
ciency of the bioreactor, the photobioreactor design superimposing planes could increase density produc-
has an innovative geometric conception. The objective tion, therefore exploring design compactness.
is to achieve high biomass productivity through the Figure 6 shows the flowchart of the proposed sus-
best use of the solar light under a fixed volume tainable energy plant with the details of the integration
constraint. The volumetric productivity (kg m3 d1) of all engineering subsystems. The main components
and surface (kg m2 d1) will be analyzed and com- are described in the next subsections.
pared with data available in the literature for tradi-
tional methods of microalgae cultivation in tubular/ 6.1.1. Gasser/degasser system. During the photosynth-
helical photobioreactors and ponds. esis process, conversion of CO2 and H2O in sugar
With a view to have freedom to vary several para- (glucose) will take place along with oxygen (O2)
meters allowing for appropriate flexibility of the sys- release. Therefore, there is no limitation for the growth
tem, the proposed photobioreactors will be built in a of the microalgae provided that CO2 is injected during
modular way. The modular construction will make it the growth process through a gasser/degasser system.
possible to study different types of microalgae in par- Injected CO2 may be originating from the atmospheric
allel, as well as comparison of different ways for their air or from external gas sources (exhaust gases from
cultivation. The possibility to alter several parameters thermal plants, motors or industrial processes) [63].
in parallel allows the determination of the best condi- The larger the concentration of CO2 in the injected air,
tions for the cultivation with the proposed specific the better will be for the microalgae. In this project,
objective of obtaining great biomass production and exhaust gases from a biodiesel powered motogenerator
high amount of fat. Considering the effect of the use of as source of CO2.
inoculum, the Integrated Group of Aquaculture and The biodiesel produced from the microalgae-ex-
Environmental Studies at UFPR will produce in- tracted oil as well as gases generated in biodigester will
oculum and supply the required amount of microalgae feed a motogenerator, a multifuel (biodiesel/biogas)
for this project taking into account the minimum time internal combustion engine. The hot exhaust gases
to get the maximum productivity in the photo- coming from the engine will be the heat source for an
bioreactor. The processes of cultivation of unicellular absorption refrigerator in order to produce cooling for
organisms usually begin with the addition of a stan- utilization by the plant processes and climatization. In
dardized amount of cells called inoculum. As it could this way, the motogenerator will have three functions,
be presumed, the quality of the growth process is di- i.e. as supplier of electrical energy, heating and cooling,
rectly dependent on the quality of the inoculums. namely a trigeneration system. Additionally, the

Int. J. Energy Res. (2010) r 2010 John Wiley & Sons, Ltd.
DOI: 10.1002/er
A review on microalgae K. G. Satyanarayana, A. B. Mariano and J. V. C. Vargas

Figure 6. Flowchart of the sustainable energy plant under construction at UFPR, Curitiba, Brazil.

system will supply CO2 that will be directed to the ways including waters with high concentration of
photobioreactors, acting as substrate for the micro- pollutants such as in ponds and in treated industrial
algae in the photosynthesis process. wastewater. Hence, the project predicts the use of
Another function of the gasser/degasser system different types of water.
is the removal of O2 generated by the photosynthesis. The utilization of sea and fresh water in the photo-
The excess oxygen is poisonous to the algae because bioreactors are discussed separately, as follows:
it promotes oxidative stress leading to death of cells.
On the other hand, small amount of O2 leads to in- 6.1.2.1. Sea water. The use of algae that grow in
hibition of the photosynthesis, therefore impeding seawater allows for a biodiesel production that does
the microalgae growth. The modular concept of not compete with food-oriented agriculture since it
gasser/degasser system allows the adaptation of the uses water that is not used for irrigation. The use of
photobioreactors to operate with: (a) any type of such a system is best suited for coastal areas where
microalgae, (b) appropriate growth rate and (c) avail- seawater is cheaply available and the production of a
ability of solar light during the year. Alteration of residue containing high amounts of salt does not
any one of these parameters alters the use of CO2 matter. The seawater possesses mainly sodium chloride
and consequently, the production of oxygen. To in- with an average mass concentration of approximately
crease the solubility of CO2 during microalgae growth, 35 g l1. Besides CO2 and the sunlight, these organisms
the medium will be artificially cooled. The cold need several other ions that are present in the sea. With
water used in the process will be supplied by the the objective of obtaining the best microalgae growth
absorption refrigerator powered by the tri-generation conditions, besides seawater, other low-cost additives
system. are needed such as those used in agriculture, i.e. urea
(source of nitrogen) and superphosphate (source of
6.1.2. Composition of the medium. The composition of phosphate).
the medium of culture is defined by the microalgae and
the cultivation conditions. As mentioned earlier in the 6.1.2.2. Fresh water. At places distant from the coast,
text, microalgae are capable of growing in different use of salty water becomes somewhat unfeasible for the

Int. J. Energy Res. (2010) r 2010 John Wiley & Sons, Ltd.
DOI: 10.1002/er
K. G. Satyanarayana, A. B. Mariano and J. V. C. Vargas A review on microalgae

cultivation of sea microalgae in view of the cost increase in pH of a Nannochloropsis oculata microalgae
involved for the transport of seawater or sea salt. solution, by sodium hydroxide (NaOH) addition, to
Additionally, a problem would be created with the the flocculation, making possible a simple harvesting
production of residues with high amount of salt. of the cells. The results suggest that increase of pH of
The cultivation of algae with fresh water consumes the culture broth is a suitable methodology for mi-
higher amounts of water than with seawater initially. croalgae separation from the growth solution. Similar
After the establishment of the culture, the amount of results were obtained with cultures of Phaeodactylum
water eliminated by evaporation in the gasser/degasser tricornutum.
system has to be replaced. This water can be recycled in Another work by the UFPR team [86] was con-
the system with the need for addition of the elements ducted to produce dry Nannochloropsis microalgae
consumed by the algae. The cultivation medium in biomass with a spray dryer system before oil separa-
fresh water also needs the addition of nitrogen, phos- tion and biodiesel production. With this process it was
phate and some of the ions used by the metabolism of obtained, in the end, powdered N. oculata biomass,
the microalgae. which was submitted to lipid extraction with solvent,
and thereafter to biodiesel synthesis. The experimental
results suggest that the proposed process is a suitable
6.2. Biodiesel production
and low energy consumption methodology for micro-
The project will use oil extracted from microalgae algae drying.
biomass cultivated in compact tubular photobioreac-
tors to produce biodiesel and possibly other valuable 6.2.1.2. Oil extraction and biodiesel. Separation meth-
products, as discussed earlier in the text. Next, the ods used in plant oils can be used for microalgae. The
subcomponents utilized for biodiesel production ac- techniques commonly used include: pressing, solvent
cording to the flowchart shown in Figure 6 are extraction and supercritical extraction [68]. Each one
discussed. of these processes requires energy and gives different
yield. With a view to get almost 100% yield, a
6.2.1. Unit operations. A fundamental point in the combination of two techniques can be used such as
biodiesel production from microalgae consists of pressing and solvent extraction. However, new ap-
the choice of the methodologies to be used in the proaches in the extraction of microalgae lipids are
separation and drying of the microalgae biomass and necessary so that the total cost of biodiesel production
also in the oil extraction process. Methodologies that will become commercially competitive. Accordingly, it
are high energy consuming make the biodiesel produc- is planned to have new approaches in this work for the
tion process commercially unattractive. Further, since separation of microalgae lipids. These studies will be
the project is aimed at developing sustainable electric taken up after the start of the photobioreactor
power plants, it is mandatory to minimize energy operation and consequently after the production of
consumption at every stage of the biodiesel production biomass.
process, as follows. It is proposed to synthesize the biodiesel using the
microalgae produced by the photobioreactors by em-
6.2.1.1. Separation and drying of the microalgae. Dif- ploying cracking, esterification or transesterification
ferent methodologies such as flocculation, centrifuga- normally used with animal fat and vegetable oil. Also,
tion or filtration can be used for the separation of the innovative chemical in situ transesterification process
microalgae biomass from the culture medium. will be proposed and tested in two different ways. In
After the separation, drying of the material takes the first, simultaneous extraction and transesterifica-
place through sun drying, liofilization, spray-drying or tion is being carried out with new catalysts by the
even competitive flow, since the possibility of ‘free’ UFPR team [87]. The work consists of the develop-
heating exists by burning natural gas produced in the ment of a new heterogeneous catalyst for the ester-
biodigester, as shown in Figure 6 which uses residues ification of free fatty acids and the transesterification
generated by the system. of vegetable oils. The layered compound zinc hydro-
The choice of the methodologies to be used in the xide nitrate (Zn5(OH)8(NO3)2  2H2O) was very effec-
microalgae biomass separation and drying will be tive in the alcoholysis of palm oil and the esterification
based on efficiency and cost, whichever produces the of lauric acid with m(ethanol), even when hydrated
most favorable results in operation. ethanol was used. Over the range of 100–1401C, the
The culture medium can be recycled after the re- ester yield was the highest at 1401C, while the catalyst
moval of the algae taking into account the necessary concentration had a much greater effect on ester yields
corrections for consumed nutrients and also elimina- than the molar ratio of alcohol to acid did. Total ester
tion of possible chemical or biological pollutants as it contents above 95 wt.% were obtained in both reac-
has been reported by Hu et al. [32]. tions and 93.2 wt.% glycerin streams were recovered as
A study was developed by the UFPR team [85] a result of methanolysis. Such process which has not
with the purpose of demonstrating the efficiency of the been reported till now with microalgae, although 98%

Int. J. Energy Res. (2010) r 2010 John Wiley & Sons, Ltd.
DOI: 10.1002/er
A review on microalgae K. G. Satyanarayana, A. B. Mariano and J. V. C. Vargas

oil yield has been reported with sulfuric acid or hy- such estimations. The simulation of microalgae bio-
drochloric acid as catalyst [21]. On the other hand, in diesel allowed a better understanding of the potential
the second, alkaline catalysis is being substituted by of this feedstock. As the ‘synthetic’ algae oil had high
enzymatic catalysis, which has yielded conversion of amounts of oleic acid and palmitic acid, their esters
98% of oil in 12 h in low temperatures with im- presented properties that were intermediary between
mobilized lipase of Candida sp. [22]. Recently, a tech- Soy/Canola and Palm oil ethyl esters, and might per-
nique to minimize the cost of production of the form very well. Microalgae cultivation also allows a
enzymatic catalyst was developed. It was demonstrated better control on the fatty acid profile, which is espe-
for the first time that it is possible to produce a lipase cially important for fuel optimization. Many fuel
in fermentation in the solid state and directly apply the properties affect directly the engine performance and
dried and fermented solid in an organic reaction to pollutant emissions, what makes the importance of
catalyze the transesterification reaction. In that way, knowing and optimizing the fuel composition clear.
necessary extraction and immobilization of the enzyme Even if many plants or microorganisms may produce
is avoided [60]. oils, not necessarily the biodiesel produced from it
In a recent development by the UFPR team [88], have the quality necessary for the operation of modern
three methods for the extraction of lipids from two engines. With the improvement in biodiesel produc-
different microalgal species were evaluated: N. oculata tion, it may be possible to produce high-quality fuel
and P. tricornutum. The methods were adaptations of that complies with international standards and helps
the Folch and the Bligh and Dyer methods [89,90], limiting the pollutant emission and has the potential to
both of which are based on the use of a monophasic replace conventional diesel.
mixture of chloroform, methanol and water
(CHCl3:CH3OH:H2O). The extraction mixture was
6.3. Biodigester
varied showing the best results with Method 1 which
consisted of CHCl3:CH3OH (2:1, v:v). During the process of biodiesel production from
An evaluation of the potential performance of mi- microalgae, biomass residues will be generated at
croalgae as a raw material for the production of bio- different stages, which may contain some commercially
diesel was conducted experimentally by Carvalho et al. valuable substances [70]. The remaining substances will
[91]. For that, organic solvent extraction of lipids from be sent to a biodigester for anaerobic decomposition to
microalgae that does not have dependency on petro- produce biogas (methane) in a modular biodigester
leum was investigated as an alternative technique. The developed by the authors [93]. The equipment for
microalgae-extracted oil had its chemical structure biogas production consists of a cylindrical and
checked via the Fourier Transform Infrared spectro- hermetic reactor where the residues will ferment
scopy method, confirming that indeed triacylglycerol producing the biogas that is captured at the top. The
was obtained. The main conclusion was that the pro- process has approximately a 40 days retention time.
duction of biodiesel through the proposed system, in The gases generated in the biodigester are meant to be
view of the high production of ethanol in Brazil, has used by the tri-generation system or other heat-
the potential to be independent of exports such as demanding processes in the plant.
solvents of fossil origin, therefore allowing for a sus- Recently, Fernández et al. [28] reported the pro-
tainable microalgae derived biodiesel production. As a duction of about 180 mL g1 of dry microalgae d1 of
sequence of this study, the in situ transesterification biogas, with 65% methane concentration, which de-
process is currently being investigated, i.e. the direct monstrates the energy potential of microalgae biomass
conversion of microalgae biomass into biodiesel, i.e. as substrate in biodigesters.
without having to convert or extract oil from biomass,
to avoid unnecessary steps in the process, therefore
6.4. Biomass and residues
increasing energetic and productivity efficiency.
Additionally, biofuels present new challenges con- Residues are produced during microalgae derived
cerning the engine adaptation and the pollutant emis- biofuel production as discussed throughout this study.
sions. In this context, Torrens et al. [92] developed a Currently, in the project, they are being analyzed to
study in an attempt to clarify the relation between fuel evaluate their characteristics such as chemical compo-
properties of microalgae biodiesel and pollutant emis- sition, morphology and thermal stability. For example,
sions, studying which properties are desirable in these the morphologies of microalgae produced by the
new fuels to guarantee engine operation without de- authors in different conditions (triglyceride extracted,
gradation of performance in comparison to conven- sun and air dried, spray dried and P. tricornutum salt
tional diesel. The methods used were accurate enough, water medium) have been observed in a scanning
for a first estimative. Viscosity estimation should be electron microscope. Figure 7(A)–(D) shows the
refined. As the method applied is very complex, the micrographs of two types of microalgae samples with
deviation may be affected by an error. Other method, different drying processes indicating the morphological
based on experimental data might perform better in details of these samples. This suggests that their

Int. J. Energy Res. (2010) r 2010 John Wiley & Sons, Ltd.
DOI: 10.1002/er
K. G. Satyanarayana, A. B. Mariano and J. V. C. Vargas A review on microalgae

Figure 7. Scanning Electron micrographs showing the morphology of two different microalgae: (A) Nannochloropsis oculata
triglyceride extracted; (B) Nannochloropsis oculata sun and air dried; (C) Nannochloropsis oculata spray dried; and (D) Phaeodactylum
tricornutum spray dried.

morphology such as shape, size, porosity, etc. depends and operating parameters for maximum system global
on the way they are obtained and dried. Further performance.
studies on their chemical composition and thermal Initial modeling attempts have been started by the
properties are being carried out. Based on this, authors in two studies [83,95]. In the first study, a
possibility for their use as fillers in polymers to develop simplified physical model was introduced [81] for one
composite materials, as fertilizers or possibly for other pipe photo-bioreactor operating in a closed circular
uses including as additives to soil after carbonizing will mode, which combines fundamental and empirical
be explored. correlations, and principles of classical thermodynamics,
biochemistry, mass and heat transfer. The model is
6.5. Software expected to be a useful tool for simulation, design and
optimization of compact photo-bioreactors. In the
A complete mathematical model of all components
second study [95] the microalgae growth was modeled
shown in Figure 6 is currently under development,
based upon a mathematical relationship with the light
with the objective of producing a software for the
intensity. The numerical solution of this computational
simulation of the entire sustainable energy plant. The
model allows for the prediction of photobioreactor
idea is to produce a low computational time-demand-
biomass concentration and production per unit volume.
ing graphical application through a thermodynamics-
based simplified mathematical model to analyze the
transient and spatial behavior of the plant using a
volume element methodology [94]. After experimental 7. CONCLUDING REMARKS
validation of the numerical results obtained with the
mathematical model, the software will be available for The main objective of this overview is to provide the
the thermodynamic optimization of design (geometric) reader with an assessment of the feasibility of

Int. J. Energy Res. (2010) r 2010 John Wiley & Sons, Ltd.
DOI: 10.1002/er
A review on microalgae K. G. Satyanarayana, A. B. Mariano and J. V. C. Vargas

innovative microalgae-based projects including the one expected to lower the cost of production. Indeed,
being initiated in authors’ University, which address economically attractive biofuel associated with new
important aspects of energy (biofuel) and materials. It materials production have the potential to turn mi-
is now known that only renewable biofuel can croalgae-based industry from a future possibility into a
potentially replace non-renewable and limited sources present reality.
of petroleum-derived liquid fuels. Although microalgae
are known to be one such alternate source for biofuel
since fifties, its technical feasibility is underlined by the
ACKNOWLEDGEMENTS
studies carried out thereafter by many including the
authors, with increased attention being given in recent The authors sincerely acknowledge the publishers
times due to increasing problems posed by the Copyright Clearance Center’s Rightslinks service,
conventional petroleum-based fuels and ecological Elsevier, Springer and American Chemical Society who
considerations. It is also clear that microalgae are the have given permission to reproduce figures and tables.
only biofuel source that could be grown without The authors thank the Brazilian funding agencies,
competing with agricultural land, due to the possibility CNPq (projects 552867/2007-1 and 574759/2008-5)
of using photobioreactors that can grow vertically and and Araucaria Foundation of Paraná (project 13470)
that can also be made compact whereby biomass for the Fellowships and funds provided to carry out
production per unit volume can be maximized. this work. They also thank Director of Advanced
Materials and Processes Research Institute (AMPRI),
Accordingly, design of suitable photobioreactors to
Bhopal (M.P. India) for permitting to use their
produce microalgae, their characteristics and applica- scanning electron microscope (SEM) and Mr TSV
tions in various areas are well documented. While Chakradhar Rao, Technical officer, who helped in
comparison of market with its fast growth and cost of obtaining the SEM photographs of our samples.
various types of high molecules derived from micro-
algae and their production are available, design and
operation of the microalgal biomass production
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