Energy 78 (2014) 72e83

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Biodiesel production from algae by using heterogeneous catalysts:

A critical review
Ahmad Galadima a, Oki Muraza a, b, *
a
Center of Research Excellence in Nanotechnology, King Fahd University of Petroleum & Minerals, Dhahran, Saudi Arabia
b
Chemical Engineering Department, King Fahd University of Petroleum & Minerals, Dhahran, Saudi Arabia

a r t i c l e i n f o a b s t r a c t

Article history: The numerous challenges associated with declining fossil fuel reserves as energy sources, have accounted
Received 6 November 2013 for a shift to biofuels as alternatives. However, transesterification of animal fats and edible vegetable oils
Received in revised form using homogeneous acids and bases for biodiesel production is recently considered unsustainable by
3 June 2014
industries, particularly due to food versus fuel competition, and economic and environmental challenges
Accepted 6 June 2014
Available online 17 July 2014
associated with the feedstocks and catalyst systems, respectively. The paper therefore presents a critical
review on the prospects of non-edible oil (i.e. algae oil) for biodiesel production via heterogeneous
catalysis. It covers the advantages of algae oil exploitation over edible oil feedstocks, progress made in
Keywords:
Biodiesel production
the oil extraction, available heterogeneous catalyst systems and reaction mechanisms, optimum trans-
Edible oils esterification conditions and the way forward. As the economic feasibility of biodiesel production from
Algae oils algae is supported by the valorization of glycerol as by-product, we have also highlighted key available
Heterogeneous catalysts heterogeneous catalysts to upgrade glycerol into more useful industrial products.
Glycerol © 2014 Elsevier Ltd. All rights reserved.

1. Introduction specifications by ASTM (American Society of Testing and Materials)

Since its early commercialization as a substitute for petroleum-
diesel for nearly a decade now, biodiesel have remained a good
global fuel for running automobile engines. Many interesting fac-
tors have been attributed to this success. Among others, biodiesel is
chemically non-toxic in nature, biodegradable and can simply be
prepared via transesterification under mild conditions [1]. In
addition to insignificant contribution to CO2 and other particulate
matter emissions, it could be employed directly in conventional
petroleum-diesel engines given optimal performance, particularly
due to very low sulfur and aromatic contents and compatible flash,
cloud and pour points [1e3]. However, although the global demand
for biodiesel has been projected to either doubled or tripled in
many regions by 2020 and beyond and relevant researches fully
intensified, a number of factors have not been critically addressed.
Conversion of the triglyceride esters in oils to the mono-alkyl esters
(biodiesel) requires a reaction of the former with monohydric
alcohol. Many researchers have recommended lower monohydric-
alcohols (i.e. methanol to propanol), with no clear justification of
which provides the best viscosity requirements in line with
* Corresponding author. Chemical Engineering Department, King Fahd University
of Petroleum & Minerals, Dhahran, Saudi Arabia.
E-mail addresses: omuraza@kfupm.edu.sa, o.muraza@gmail.com (O. Muraza).
or related international agencies [4,5]. The predicted sudden rise in
the prices of edible vegetable oils coupled with hunger threats as
well as soil degradation associated with large scale biodiesel pro-
duction have on the other hand forced many agencies, particularly
food and agricultural organizations and economic modelers to
consider the option as unviable [6,7]. So far emphasis was given to
canola, soybean, rapeseed and sunflower oils and in some instances
processed or used animals fat. The choice of most appropriate
catalyst and reaction conditions is similarly a great challenge to
industries. Initially hydroxides and alkoxides (methoxides and
ethoxides) of group IA and IIA like NaOH, KOH, NaOCH3, KOCH3,
Ca(OH)2, Mg(OH)2, LiOH, NaOCH2CH3, KOCH2CH3 etc were the main
transesterification catalysts [4,8e10]. These homogeneous mate-
rials are however, associated with great problems militating against
their continuous application. Although faster biodiesel production
could be attained in basically moderate reaction time, the catalyst
cannot be recovered at the end of the transesterification process.
Therefore must be carefully neutralized leading to production of
large quantity of wastes. Catalysts are commercially expensive and
are generally affected by fatty acid concentrations even in trace
quantities. The homogeneous acids like H2SO4, HCl, H3PO4 and
organic sulfuric acids of the type RSO3H (R ¼ alkyl or aryl) have also
been classified as unreliable due to much slower reaction rates,
difficult temperature requirements, high reactants (oil to alcohol)

http://dx.doi.org/10.1016/j.energy.2014.06.018
0360-5442/© 2014 Elsevier Ltd. All rights reserved.
 A. Galadima, O. Muraza / Energy 78 (2014) 72e83 73

ratios, concentrations of catalysts, and severe corrosion problems

[8,10].
The numerous problems identified have stimulated researchers
at university and industry to explore better options, with great
emphasis on the flexibility of feedstock, greener catalyst systems
and conversion of the waste glycerol into more useful industrial
products. Recently, many groups promoted a shift to algae as bio-
diesel feedstock and a wide range of heterogeneous materials
[11e16] as green catalyst. We have therefore documented herein a
critical survey of the relevant literature on the progress made in
this regard. The paper also discusses issues of interest associated
with heterogeneous upgrading of the glycerol produced as
byproduct from transesterification process.

Fig. 1. Yield of biodiesel per acre for some crops compared to algae.
2. Prospects of algae as biodiesel feedstock

Among SCO (Single Cell Organisms), algae are as promising as
yeast and bacteria. A number of interesting factors have been
attributed to this fact. They are widely available and can be grown
anywhere with practical consistencies, thereby limiting any
competition with edible vegetable oils. Unlike many energy crops,
algae can have up to 100 times more oil content. Theoretically,
depending on the strength, algae species can produce up to a yield
of 20,000 gallons of feedstock per acre of land [17]. Table 1 presents
a short time projection of fuels from algae. By 2014, lower than 3%
of the global conventional fuels production will be substituted by
biofuels of traditional origin. This percentage represents a market
size of over $120 billions. Biofuels from algae feedstock will
potentially replace a higher percentage of fossil fuels used as
automobile fuels than the other sources. The estimated market size
for algae is $425 billions, which is more than twice the expected
market size for other traditional biofuels. Thus, the algae options
stand a market worthing hundreds of billions of dollars. Similarly,
there are possibilities that these prospects would even escalate in
the long term. For example, Fig. 1 shows a comparable biodiesel
yield per acre of farmland for different crops, with algae as the most
promising feedstock. While the yields of most common vegetable
oils is below 1000 gallons per acre, the yield from algae feedstock
reaches 5000 gallons per acre, indicating tremendously a much
higher prospect. Low land mass is required to produce huge
amount of oil for industrial biodiesel production. For example, a
recent study projected the algae biodiesel to be capable of meeting
the US diesel demand with only 2e5% of the cropland exploited for
this purpose [18]. This has strong tendency to eliminate the prob-
lems of food shortage and related price hike that are usually
associated with large scale exploitation of agricultural land for
biofuels production.
While biodiesel is considered the main obtainable fuel-
produced from algae, other important fuels can similarly be pro-
duced, thus enhancing their exploitation potentials. Fuels such as
Table 1
Short term projection of biofuels from algae.
Short term potentials, 2014 Billion gallons
Assumed 1 gallon
of oil ¼ $3.0
methane, hydrogen, ethanol and biogasoline can be generated from
algae. The biomass-residues are applicable as sustainable feedstock
for combustion. Other important areas of applications for algae
include environmental management and production of other
products. Algae derivatives have excellent bioremediation proper-
ties and therefore suitable for treating waste and sewage water
through the removal of toxins and nutrients. Pigments, nutra-
ceuticals and even fertilizers can successfully be produced from
algae.
It could be seen that, producing oil from algae and subsequently
biodiesel as well as other products is considered highly efficient by
many authors [19e21]. The processes of cultivation, oil extraction
and final conversion into biodiesel are basically comparable to
those of other edible crops such as soy, sunflower and palm. These
facts could be attributed to important factors leading to the esca-
lated growth-rates for the algae species around many places in the
world [22e25]. It is particularly important to note that, unlike other
crops, algae can be cultivated even in harsh conditions, including
salty and sewage receiving areas. During their growth, the algae
species require considerable amount of atmospheric carbon diox-
ide [26e28]. This factor implies that, they can be used for cheaper
mode of CO2 sequestration from stationary sources like oil and gas
facilities and related industrial power plants [22,27]. In fact, algae
cultivation can be considered multi-beneficial [24,29]. However,
there are certain difficulties hindering algae exploitation compared
to other crops. These include situation awareness (i.e. lack of full
knowledge of their prospects, especially in the developing world
where research is limited), poor knowledge of the most cost-
feasible cultivation method and difficulty in identifying the most
affordable algae strain with higher oil content, having fastest
growth rate with no harvesting challenges. Other challenges are;
algae production requires huge land mass and water and cold flow
problems with the net biodiesel. Some macro blueegreen algae
species are also hazardous to human beings, especially when
exposed through recreational activities or drinking contaminated
water. If these issues are fully addressed, algae market would
simply be at the forefront.
3. Heterogeneous transesterification catalysts

Total oil consumption
Total projected supply of traditional biofuels
Total ethanol production
Total biodiesel production
Share of traditional biofuels in total oil consumption
Projected market size for traditional biofuels
Share from algae
Estimated market size for algae
Source:[17]. Authors' modified.
1500 To mitigate the various challenges encountered with the use of
41 homogeneous bases and liquid acids as alcoholysis catalysts,
26
numerous studies were reported to explore the activities of a wide
15
2.73% range of heterogeneous materials [30e43]. Table 2 presents a list of
$123 billions numerous solid acids and bases documented as catalyst for the
9.2% biodiesel production. The solid acids comprised mainly of zeolite
$425 billions materials, heteropoly acids, pure or modified oxides of transition
metals like zirconium and molybdenum, silica and alumina
74 A. Galadima, O. Muraza / Energy 78 (2014) 72e83

Table 2
A summary of heterogeneous transesterification catalysts reported in the literature
[14e43].

Solid acids Solid bases

 Zeolitic materials such as HeY, H-  Oxides of group IIA elements:

Beta, ZSM-5, H-MOR, ETS-10, and CaO, MgO, SrO, BaO.
ETS-4.  Carbonates of group IIA ele-
 Sulfated zirconia (SO2 4 eZrO2) ments: CaCO3, MgCO3, SrCO3,
supported with Al2O3 or some BaCO3
times SiO2.  Carbonates of group IA elements:
 Sulfated zirconia mixed with K2CO3.
other transitional metal oxides.  Free and mixed transitional metal Scheme 1. Chemical equation illustrating biodiesel production.
e.g. SO2 2
4 eZrO2/WO3, SO4 eZrO2/ oxides. e.g. ZnO, CuO, CaLaO3,
MO3. CaCeO3, CaZrO3, CaMnO3, CaTiO3,
 Free sulfated tin oxide or sup- etc. would generally be low and the reaction can shift backward,
ported usually over alumina or  Basic zeolites.
creating further negative effect on the total biodiesel yield. How-
silica (SO2
4 eSnO2/Al2O3, SO4
2
 Cs-exchanged sepiolite.
eSnO2/SiO2).  Hydrotalcites (MgeAl) ever, at higher ratios, removal of excess alcohol may pose a great
 Acetates of zinc or copper sup-  Quanidine anchored cellulose or challenge. Factors such as reaction temperature and degree of
ported over silica other polymers. stirring are also very critical. Adequate stirring is required to ensure
 Heteropoly acids and their de-  Aluminates of Zinc. sufficient interaction between catalyst particles and the reactants
rivatives. e.g. H3PW12O40,  Metal generated salts of primary
[10e15]. The temperature must be close to the boiling point of the
H4SiW12O40 amino acids.
 Supported organosulphonic  Li-promoted oxides of group IIA monohydric alcohol. Lower temperatures favor slow reaction,
acids. The support is mostly elements. whereas much higher temperatures create handling difficulties.
mesoporous silica and some time
alumina.
 Nafion 3.1. Transesterification with solid bases

Reaction involving heterogeneous bases proceeds by reaction of

catalysts [14e43]. These materials are characterized by having both either the Lewis or the Brønsted basic sites of the catalyst with a
Brønsted and Lewis acid sites, that determines their activities monohydric alcohol (usually ethanol or methanol). The generated
during transesterification reactions. Activities of zeolites and het- alkoxide mixture interacts with triglyceride ester in the oil to yield
eropoly acids may also be affected by shape selectivities. Materials biodiesel and glycerol in the subsequent steps (Scheme 2). The
having multi-dimensional pore structure should be more favorable mechanism is EleyeRideal type, but the strength of the basicity
for the formation of alkyl esters without cracking. Solid bases on significantly influences how fast the reaction can proceed. The basic
the other hand, comprised of basic zeolites, carbonates and com- sites preferentially interacts with alcohol and remove Hþ, forming
mon oxides. The basic sites formed the main reaction centers for an alkoxide group (RO), which is the main active component that
these materials during biodiesel synthesis. attacks the triglyceride ester at the intermediate stages. The
In the heterogeneous catalysis a good number of factors must stronger the basic sites the more favorable the formation of the
be appropriately considered depending on whether the catalyst is alkoxide species. Similarly, strong basicity favors subsequent
a solid acid or base. The factors include transesterification tem- cleavage and glycerol formation, and consequently the overall re-
perature, the amount of catalyst, on stream reaction time, degree action rate would be enhanced.
of mixing or stirring, alcohol/oil content and purity index of the Solid basic catalysts such as zeolites, oxides of first row transi-
feedstock. Anderson et al. [14] reported the dispersion of the active tion metals like ZnO, CuO, basic polymers and compounds of group
material over the support considerably influences the alcoholysis IIA elements (Table 2), especially the oxides and carbonates such as
activity of a BaO/Al2O3, with higher dispersions being more active. CaO, MgO, SrO, BaO, CaCO3, MgCO3, SrCO3 and BaCO3, have
The selected temperature should be close to the monohydric-
alcohol boiling point to avoid handling difficulties. Adequate re-
action time should be provided (e.g. 1e3 h) in order to ensure
complete conversion. The extent by which the catalyst interacts
with the reactants is very important and thus moderate mixing
would be very important. At low mixing rate the reaction would be
very slow, whereas high degree of mixing causes side reactions
and difficulty in handling the reaction system. The key impurities
in most oils are free fatty acids; therefore those with very low
percentage of free fatty acids (e.g. algae oils < 1%) would be
desirable.
Transesterification is an equilibrium derived process, via which
triglyceride ester and monohydric-alcohol reacts in the ratio of 1:3
to produce an equivalent amount of mono-alkyl esters (biodiesel)
and a mole of glycerol (glycerine) as byproduct (Scheme 1). The
reaction is believed to proceed in three consecutive steps, each
involving the formation of mono-alkyl ester and introducing alco-
holic eOH group into the triglyceride ester chain. Therefore, glyc-
erol would be finally produced at the last step of the reaction.
Accelerating the reaction to produce more biodiesel in shorter time
requires the monohydric-alcohol/oil content in between 4:1 and
12:1 [10e15]. At values below this ratio, the yield of biodiesel Scheme 2. Mechanism of base catalyzed transesterification.
 A. Galadima, O. Muraza / Energy 78 (2014) 72e83
attracted attention as heterogeneous transesterification catalysts.
The latter being the most prominent. Their basicity is associated
with metal-oxygen ion pairs (i.e. M2þeO2) and varies in the order
Ba > Sr > Ca > Mg for the oxides. These materials are easily pre-
parable, less expensive, and showed low corrosion properties. The
severity of calcination step is a very important factor that de-
termines the transesterification activity of these heterogeneous
base catalysts. At high calcination temperatures, the conversion
gets low due to decrease in active catalyst surface. For instance, a
sample of MgO calcined at 600  C yields only 18% conversion after
8 h reaction time. Whereas high conversion up to 92% was obtained
at optimum conditions; lower calcination temperatures, the
methanol/oil content being 12:1 and 5.0 wt.% catalyst [15]. Similar
trend was observed over CaO. However, the latter catalyst caused
reusability problems after repeated cycles of applications. The
supported carbonates of group IIA are also good alcoholysis mate-
rials but these materials will be partially dissolved in the presence
of water and fatty acid impurities. The carbonates are not very
stable under very high calcination temperatures (Table 3).
Mixed oxides of Ca and transition elements like Fe, Ce, Zr and La
have also been evaluated in transesterification. Up to 95% biodiesel
yield had been recorded. However, high methanol to oil ratio of
about 6:1 may be required in order to sufficiently shift the equi-
librium position forward. Adequate transesterification time (may
be up to 10 h) is also needed with these materials. For example, a
CaTiO3 yields 79% of biodiesel in 10 h reaction time, whereas
CaCeO3 and CaZrO3 yields between 70 and 95% of biodiesel in 10 h

using 1:6 (oil to methanol) ratio at 60 C. Among the support ma-
terials Al2O3 shows higher activity, specifically due to sufficient
stability and dispersion properties. It also allows enhanced surface
reactants interaction [13e15,24].
Basic zeolites and hydrotalcites are increasingly gaining atten-
tion. Materials such as oxides containing zeolites, ETS-10 and fau-
jasites possess basic cations that could be generated via thermal
decomposition of their supported salts. Ion exchange with highly
electropositive cations is also very critical to the enhanced trans-
esterification activity. The hydrotalcites (MgeAl) possess good ba-
sicity but dissolution problems require that the materials are
carefully prepared. Preparation by co-precipitation method has so
far shown reliable stability.
3.2. Transesterification with solid acids
Catalysts in this category are more environmentally benign and
sustainable than their homogeneous counterparts and have so far
shown very limited corrosion and recycling problems. However, high
porosity systems are required to obtain better performance. The
porosity allows appropriate adsorption-desorption and diffusion of
the reactants and products. Thus, acidic zeolites (see Table 2) would be
preferable here than the metal oxides or carbonates. Their structural
and acidity properties can always be modified to address diffusional
limitations and thus enhance the production of larger biodiesel yields
[44e47]. However, a challenging issue with zeolites is selecting the
most appropriate silicaealumina ratio as well as the modifier
Table 3
Role of calcination temperature on the activity of WO3 modified ZrO2 [49].
Sample Calcination Conversion (%), Conversion (%),
code temperature [ C] 5 wt.% WO3/ZrO2 15 wt.% WO3/ZrO2
A 400 93 78
B 500 95 81
C 600 10 20
D 700 5 25
E 900 5 17
75
concentration. With oxides, high loading causes a blockage to the pore
systems whereas free metals like Pd or Pt causes hydrogenolysis and
subsequent dehydrogenation, thus limiting biodiesel yield.
The numerous separation and environmental challenges asso-
ciated with sulfuric acid have triggered the evaluation of sulfated
zirconias and organosulphonic acids as transesterification catalysts.
With unsupported systems, the SO2 4 may easily be lost in the re-
action medium and thus the catalyst deactivation by acidity decay.
Therefore the incorporation of porous silica or alumina as support
material is necessary to solve this problem. Zirconia normally exists
as monoclinic, tetragonal and cubic phases. It has been established
that, the tetragonal phase exerts much higher transesterification
activity than the other phases, especially when doped with
appropriate quantity of amorphous WO3. In some cases, sulfated
zirconia can be replaced with sulfated tin oxide or tungstated-
zirconia supported over alumina to obtain comparable activity
[49]. In addition to the phase properties, the loading of WO3 and
calcinations temperature influence the activity of ZrO2 (Table 3).
Calcination at 500  C ensures optimum ester yields, especially with
the lower loadings. Higher calcination temperatures sintered the
catalyst, with significant resistance associated with higher WO3
loadings [49].
Heteropoly acids and their derivative salts are also good mate-
rials for alcoholysis. Especially due to their water tolerance poten-
tials, which significantly limit deactivation by hindering the
conversion of Lewis to Brønsted acid sites. Their super acidity
properties coupled with structural networks promote their degree
of transesterification, compared with homogeneous hydroxides
and acids. They can easily be recycled and reused, thus reducing
production cost and environmental inconsistencies. However, their
specific mechanism of action has not yet been established [48e53].
Recently, Alsalme et al. [52] heterogeneously esterified hexanoic
acid and transesterified the corresponding ester as a model study
with a range of heteropoly acids (H3PW12O40, Cs2.5H0.5PW12O40,
H4SiW12O40, H3PW12O40/Nb2O5, H3PW12O40/ZrO2, and H3PW12O40/
TiO2) and high methanol concentration (1:20) at 60  C and atmo-
spheric pressure. The results when compared with some homo-
geneous and solid acid catalysts such as sulfuric acid, Amberlyst-15,
HeY and H-Beta zeolites indicated the heteropoly acids to be better
materials due to higher yield and catalyst stability. Kinetic
modeling by Talebian-Kiakalaieh et al. [51] has also shown these
materials to offer significant resistance to fatty acid interference
during the conversion of used cooking oil. Good activity of 88.6%
conversion was achieved under optimal parameters; at 65  C,
methanol/oil content of 70:1 and 10 wt.% catalyst. This implies the
materials to have considerable prospects for the transesterification
of macro-algae (i.e. those with high fatty acid concentrations).
In acid catalysis, both the homogeneous and heterogeneous
methods proceed via basically a similar reaction mechanism, with
the Brønsted option being preferential. The acidity should be of the
Brønsted type, production of water and glycerol during the trans-
esterification process have previously been reported to significantly
deactivate the Lewis acid sites. Initially, a carbonyl group is pro-
tonated in order to enhance its electrophilicity thereby making it
more ready for nucleophilic attack (Scheme 3). The rate of attack
between free alcohol and the Brønsted sites adsorbed carboxylic
acid is usually the rate determining step with most solid acids.
Thus, the mechanism is of the EleyeRideal type. However, where
Lewis sites participate, their strength determines the slowest step.
4. Heterogeneous transesterification of algae oil
Oil extraction is basically the initial and critical step in biodiesel
production from plants after harvesting (Fig 2). An attractive pro-
cedure is one that ensures reduced extraction cost but high oil yield
76 A. Galadima, O. Muraza / Energy 78 (2014) 72e83

Table 4
Data for biodiesel production over solid catalysts (including zeolites) from algae and
some common oils.

Feedstock Catalysts Biodiesel yield/

Conversion (%)

Soybean Zirconia, titania [73] 88.10

Corn oil Zirconia, titania [73] 88.30
Algae oil Zirconia, titania [73] 90.20
Algae oil 4% NiO, 18% MoO3/ 99.00
alumina [79]
Algae oil 0.75% Pt-SAPO-11 [79] 83.00
Algae oil 4% NiO, 18% MoO3/H- 98.00
ZSM-5 [79]
Algae oil Microporous titania 94.70
[79]
Algae oil (HY-340) niobium 94.27
oxide [79]
Algae oil Hierarchical H-Beta 99.50
zeolites [79]
Scheme 3. Mechanism of transesterification via acid catalysis.
Algae oil Amberlyst-15 [78] >98
Microalgal's lipid Modified alumina [71] 97.5
Fresh water microalgae oil Modified titania [15] >95
[18,46]. The two fundamental methods available for algae today are Fresh water microalgae lipids Porous titania >95
the mechanical and chemical methods. The mechanical method is microsphere [15]
mainly expeller press or ultrasound-assisted whereas hexane sol- Groundnut oil BaO/Al2O3 [14] 80
Cotton seed oil BaO/Al2O3 [14] 80
vent, soxhlet and supercritical fluid extractions are the available
(fatty acid ¼ 4.34%)
chemical methods. The mechanical method requires algae drying, Sunflower oil ZrO2/La2O3 [16] 84.9
thus making it energy intensive whereas health and safety issues Yellow horn Cs2.5H0.5PW12O40 [16] 96.22
are critical for the chemical option [18,46]. Adopting supercritical Waste cooking oil MgO/TiO2 [16] 91.6
extraction process involved the used of expensive high pressure Palm oil CaO/Al2O3 [16] 98.64
Jatropha curcas oil CaO/Fe3O4 [30] 95
equipment that is also energy intensive. Industrially, a single step Soybean oil Li/MgO [30] 93.9
process by OriginOil Company is used in wide application. The Chinese tallow seed oil KF/CaO [30] 96.8
method involved sequential steps of harvesting, concentration, and Croton megalocarpus oil sulfated SnO2eZrO2 95
extraction oil from algae. It separate oil, biomass and water in a [30]
Waste cooking oil Zeolite Y (Y756) [31] 85
single step (mostly in less than 1 h). No chemicals or heavy
Waste cooking oil H3PW12O40.6H2O [31] 87
equipment is needed and the process requires no initial dewatering Waste cooking oil K3PO4 [31] 97.3
of the fresh algae. Another novel method is that of Cavitation Mutton fat MgO/KOH [35] 98
Technologies Inc. The company's Nano-based reactor is employed Sunflower oil NaeX zeolite [45] 83.53
to generate cavity bubbles in the solvent [54]. Collapsing of the
bubbles close to the cell walls generates pulses that break the cell
walls to produce oils into the extraction solvent. The Catilin's lipid feed. The free fatty acids and triglycerides rich balanced algal
method, which is under research and development stage, would be oil would be transesterified into biodiesel using the T300 catalyst
of great interest to the Nano-technologists. Specially developed developed by the company. A key important issue here is that, the
mesoporous nanoparticles would be employed to preferentially technology is potentially very efficient and involved heterogeneous
extract and sequester specific fuel-based compounds in the algal catalyst, thereby ensuring environmental sustainability, cost
reduction, catalyst reusability and high purity biodiesel and glyc-
erol [54]. Other methods of oil extraction that are under investi-
gation include enzymatic extraction and osmotic shock, with the
former being considered much more expensive than the hexane
extraction method. The process utilizes specific molecules of en-
zymes to break the cell walls with a common solvent, thereby
making fractionating the oil easier.
Demirbas and Demirbas [55] recently reported an estimate of up
to 80,000 liters per acre of algae oil. This figure exceeds 30 times the
quantity obtainable from other feedstocks like palm oil. They
showed common algae species such as Botryococcus brauni and
Schizochytrium sp. to yield up to 77% oil based on dry matter. A
model by the same authors revealed 100,000 L of oil per hectare for
algae species compared to only 446 and 952 L per hectare for soy
and sunflower plants, respectively. Vazhappilly and Chen [56],
Volkman et al. [57] and Yaguchi et al. [58] have reported closer
trends. Algae oils are also known to be rich in fatty acids of the
unsaturated class. They include omega-3's, omega-6, docosahex-
anoic and ecosapentanoic acids. These compounds could be iso-
lated and employed for other industrial applications, consequently
favoring economic exploitability [59,60].
After the successful oil extraction, the next step is the trans-
Fig. 2. Flowsheet representation of biodiesel production from algae. esterification of the oil into biodiesel. Algae oils are basically
 A. Galadima, O. Muraza / Energy 78 (2014) 72e83
converted using similar methods adopted for other vegetable oils
[55,61e63]. Xu et al. [61] employed Chlorella protothecoides (an
algae specie) for biodiesel synthesis. Cells removal was achieved by
agitation coupled with distilled water-washing before drying using
a freeze dryer process. Oil was obtained through pulverization of
powdered cells using mortar followed by extraction with n-hexane.
The optimum parameters include equivalent catalyst concentration
(i.e. according to oil weight), methanol/oil ratio (56:1) at temper-
ature of 30  C, which reduces product density from 0.912 to 0.864
during 4 h on stream. There are evidences that, homogeneous
catalysts were given emphasis to the production process in the
recent time [64e70]. However, the sensitivity of these materials to
fatty acids of the algae oil feed and production of low quality
glycerol suggested the need for a shift to the heterogeneous ma-
terials. Both materials can be employed in line with Fig 2. With the
latter catalysts, limited energy is required for soap and glycerine
removal (i.e. during purification). Catalyst is also easily removed
and recycled during the separation process. The heterogeneous
method will greatly replace the currently used homogeneous
process in the near future. Heteropoly acids such as H3PW12O40,
Cs2.5H0.5PW12O40, H4SiW12O40, H3PW12O40/Nb2O5, H3PW12O40/
ZrO2, and H3PW12O40/TiO2 have shown desirable tolerance to high
free fatty acid concentrations, yielding high conversions of bio-
diesel at ordinary conditions for vegetable oils [50e53]. This novel
opportunity could be extended to algae oils with much greater
potential. Acidic zeolites such as H-Beta, H-ZSM-5, H-MOR, H-ETS-
10, H-ETS-4 with moderate acidity properties and sufficient
porosity allow faster transesterification with limited side reactions
interference for the vegetable oils under controlled conditions
[44e47]. This is another great opportunity for the algae oils. Ma-
terials based on WO3/ZrO2 should be employed at appropriate
loadings and calcinations. The 15 wt.% WO3/ZrO2 calcined at 500  C
used for oil yields 95% conversion for other oils (see Table 3). Thus,
similar preparations have potentials for much higher yields with
algae oil under comparably constant reaction conditions. Hetero-
geneous bases are also prospecting materials (see Table 4). Oxides
of Ca, Sr and Mg, mixed oxides with transition metals, and sup-
ported over silica or alumina were extensively studied for other oils
with their properties fully evaluated. These materials could simi-
larly be fully exploited for the algae oils, with the hope that, chal-
lenges such as dissolution, sintering, thermal instability and
recyclability problems encountered could be mitigated through
appropriate choice of parameters.
The choice of appropriate reaction conditions and support
materials is very important in heterogeneous algae trans-
esterification [25,69,71e77]. Umdu et al. [71] studied the proper-
ties of Al2O3 doped MgO and CaO during the conversion of a
marine microalgae, by monitoring the methanol concentration
and the amount of active materials at 323 K. They observed that
unsupported CaO and MgO showed negligible activity, whereas
CaO/Al2O3 system yields the most promising activity, due to higher
basic sites concentration and basic strengths. Dacus et al. [72]
tested pure metal and metal oxide catalysts in order to develop a
heterogeneous method using algae as feedstock. It was concluded
that like other vegetable oils, algae can be successfully converted
to biodiesel using these heterogeneous materials at low trans-
esterification temperature. Similarly, no unwanted products that
require purification were produced. The catalysts also produced
biodiesel at low temperatures for a number of edible vegetable oils
containing common impurities like free fatty acids. This implies
the materials to have strong potentials for algae oils. McNeff et al.
[73] incorporated a new fixed-bed continuous reactor system,
employing porous titania, zirconia and alumina (with their mixed
oxides) as heterogeneous alcoholysis catalysts under high pressure
(2500 psi) and temperatures of 300e450  C, with a number of
77
feedstocks (algae, corn, tall and soybean oils). The catalysts proved
very efficient, especially with the algae oil (Table 4). Percentage
biodiesel yields of 90.2, 88.3 and 88.1% were obtained from algae,
corn and soybean oils, respectively under constant conditions.
Similarly, the economics of the process indicated much more cost
effectiveness than with conventional homogeneous options.
Limited interference due to fatty acids was encountered. The
thermal stability of the catalysts is also very interesting for reus-
ability purpose. Some authors [78], have recently developed a two
steps in situ process, with potentials to reduce the fatty acids
interference encountered with some heterogeneous base catalysts
and increase biodiesel yield. The method involved a pre-
esterification of the algae oil before the base-catalyzed trans-
esterification. It can allow biodiesel recovery up to 98%, greater
than values obtainable by a single-step catalytic in situ process.
Dong et al. [78] shows that, the heterogeneous material,
Amberlyst-15, was employed without activity decay for eight
repeated times. Catalyst loading causes increased in ester yield up
to 30 wt.%, beyond which its concentration has no any effect on the
transesterification activity. On the contrary, increasing methanol
to algae oil ratio shows the negative effect on biodiesel yield, with
optimal value obtained at a yield of 20%. The technology can
potentially play a good role as more environmentally sustainable
cost-reduced method due to the optimal biodiesel yield and
catalyst reusability. Recently, Sani et al. [79] have also reported a
range of heterogeneous solid acids such as NiOeMoO3/Al2O3, Pt-
SAPO-11, NiOeMoO3/H-ZSM-5 and microporous titania to be
successfully employed for microalgae oil. The conversions were
generally between 83 and 99% (see Table 4), catalysts were very
stable, no corrosion or recycling problems encountered and the
materials showed potentials for reduced industrial production
costs in comparison to homogeneous systems. Generally, many
authors [25,46,80e98] have the great opinion that biodiesel pro-
duction from algae or comparable non-edible feedstock via het-
erogeneous catalysis would be the best method for the future.
However, research should be intensified to identify what the
technical and economical feasibility by integrating economic as-
pects with science, technology and policy issues.
Another interesting issue is that, algae oil can similarly be
employed for production of gasoline and or diesel range hydro-
carbons [99e102], animal feeds and fine chemicals [25] and even
HVO (Hydrogenated Vegetable Oil). Solid acid catalysts are the key
heterogeneous materials exploited in this respect. The general
conversion processes include cracking, hydrotreating and hydro-
deoxygenation [99,103,104]. Among the solid catalysts Al2O3, AlCl3
and oxides of Ca and Mg, SAPO-5, SAPO-11 [99], HZSM5, HBEA and
USY [99,104] have been evaluated as good materials for the cracking
reactions. Heterogeneous systems such as NieMo/g-Al2O3, sul-
phides of NiMo and CoMo and their silica-alumina supports are
good candidates for hydrotreating of bio-oils even at low temper-
atures, with limited stability challenges. They have shown good
thermal stability with resistances to catalyst poisons in the reaction
feed. Alumina, zeolites and silica supported Ni and/or noble metal
catalysts are primary deoxygenation materials and could be used to
convert fatty acids in the algae oil to liquid hydrocarbons of mostly
diesel range.
Recently, Hu et al. [105] pyrolyzed oil obtained from oil-riched
blue-green algae (microcystis species) at temperatures ranging
between 300 and 700  C in a fixed bed reactor. The liquid bio-oil
produced was found to be rich in gasoline and diesel range hy-
drocarbons, especially at the optimal temperature of 500  C. Ben-
zene, phenols, methylphenols and heterocyclic amines like pyrrole,
indole, pyridine and substituted pyrazines were similarly detected
to significant concentrations. Similar observations were reported
by other authors using different species [63,106e112].
78 A. Galadima, O. Muraza / Energy 78 (2014) 72e83

Table 5
A summary of key industrial derivatives from glycerol [110e125].

Product Uses Production process

1,3-Propanediol Formulation of solvents, co-polyesters, powder, Clostridium butyricum method.

UV-cured coatings etc.
1,2-Propanediol Industrial commodity/raw-material. Raney Nickel method, Pt on NaeY zeolite.
Dihydroxyacetone In cosmetic industry as a tanning agent. Catalytic oxidation of aqueous glycerol using Pt
catalysts.
Succinic Acid Manufacture of synthetic resins, biodegradable Fermentation process.
polymers etc.
Hydrogen Next generation renewable fuel, hydrogenation Heterogeneously catalytic steam reforming at
reactions etc. moderate temperatures, aqueous reforming
over tin promoted Raney nickel catalysts.
Polyglycerols Anti-fogging, lubricants, antistatic additives, Selective etherification of glycerol.
plasticizers etc.
Polyesters Polymer applications. The reaction of glycerol with adipic acid using
Sn based catalysts, catalytic reaction of citric
acid with glycerol at different mole ratios.
Liquid hydrocarbons e.g. diesel, light naptha Fuels applications. Low temperature catalytic synthesis followed
by FischereTropsch synthesis.
Polyhydroxyalkanoates Polymer applications. Fermentation process.
Syngas, methane Fuel for energy. Catalytic supercritical water gasification
(CSCWG) method.
Oleifins Polymer feedstock, fuel additives. Catalytic conversion using zeolites like ZSM-5,
zeolite Beta, and zeolite Y.
Others e.g. allyl alcohol, methanol, and formaldehyde Industrial raw-materials, solvents, etc. Catalytic supercritical water gasification
(CSCWG) method.

5. Glycerol conversion reaction conditions influences the key reaction products from the
gasification process. For example, Markocic et al. [116], Long and
Glycerol (propan-1,2,3-triol) is a simple trihydric-alcohol with Fang [117] and Peterson et al. [118] reported high pressures, low
other names as alcohol glyce
rine

, glicerol, glucerite, glycerin, temperatures, upgraded feeds and acid catalyst systems to produce
glycerine, glyce
rine, vegetable glycerin etc. It both occurs naturally mainly liquid products. Whereas opposite conditions produced
and can be synthesized industrially or in the laboratories. The mainly hydrogen, syngas and other gaseous hydrocarbons. Guo
compound forms the triester backbone of triglycerides (see Scheme et al. [119] showed that, depending on reaction conditions, a
1) and phospholipids. Glycerol is colorless, odorless compound number of liquid products (including methanol and formaldehyde)
widely employed as raw-material in some key industries. The three could be generated as intermediates during the CSCWG process
hydroxyl groups account for considerable water solubility. (see Fig. 3).
Glycerol is the key waste product produced (up to 1 kg per 10 kg Zeolite systems like HeY, H-ZSM-5, H-Beta etc could similarly be
of algae oil) from biodiesel production, that has in the past been employed to convert glycerol into olefins (usually ethene, propene
considered a great challenge to industries [14e16,68e70,113]. and n-butene) under controlled conditions, the choice of which
However, there are progresses that the compound could be purified depends on the zeolite and/or desired reaction products. Liquid
and successfully converted to a number of useful industrial raw- hydrocarbons of diesel and naphtha range could similarly be ob-
materials (Table 5). Initially, homogeneous catalysis was mainly tained. Zakaria et al. [120] reported an integrated route to diesel and
employed, but series of problems similar to those of biodiesel
synthesis have accounted for a shift to the heterogeneous method.
Hirai et al. [114] has carried out gaseous phase steam reforming
of glycerol with a range of transition metals using MgO, Y2O3, Al2O3,
ZrO2, SiO2, CeO2 and LaO3 as support materials, prepared by
employing the conventional impregnation method and reactions
monitored under atmospheric conditions. Best and promising
result was obtained with 3 wt.% Ru supported on Y2O3 at 500  C,
due to significant resistance to deactivation by carbon deposition.
Tapah et al. [115] employed mixed Fe2O3 and Cr2O3 as catalyst and
glycerol concentrations of 2e30 wt.% at flow rates from [10e65 ml/
min] for a CSCWG (catalytic supercritical water gasification) con-
version of glycerol. The results showed high temperature and low
glycerol concentrations to increased the yield and selectivity to-
ward H2 production. Similarly, syngas of about 64 mol % was pro-
duced with minimum 4:1 mol ratio of H2:CO. Other volatile
hydrocarbons (methane and ethylene) were obtained to significant
yields. This promotes the optional use of the technology for turbine
operations. Nearly 100% conversion of glycerol was successful at
high temperature of 550  C. Also a maximum of 11 wt.% of meth-
anol, allyl alcohol and formaldehyde were obtained at 400  C
temperature. Catalyst stability was also studied and was found to Fig. 3. Conversion of glycerol to gaseous and intermediate liquid products via com-
reach relative stability for up to 9 h of reactions. The choice of bined gasification and pyrolysis process.
 A. Galadima, O. Muraza / Energy 78 (2014) 72e83 79

Fig. 4. Integrated routes for the conversion of glycerol, a byproduct in biodiesel plant, to fuels.

light naphtha production coupling low temperature catalytic con-
version of glycerol with WGS (wateregas shift) technology and
FischereTropsch synthesis (Fig. 4). They have also reported a
number of authors have successfully converted glycerol into olefins
using USY, ZSM-5, H-MOR, macroporous NieW system, Y-zeolite,
BETA and silica and alumina supports at temperatures between 300
and 650  C, yielding nearly 100% glycerol conversion and up to 60%
olefins production. Zakaria et al. [121] showed the activity of Ca, Cu,
Li, Mg and Ni doped ZSM-5 zeolites characterized by FTIR, XRD and
NH3 desorption, to depends on the catalyst structureeacidity
properties during oleifins and paraffins production from glycerol.
Metal loadings improved HZSM-5 acidity and glycerol conversion.
Recently, Van de Vyver et al. [122], Possato et al. [123], Serafin et al.
[124], Gonzalez et al. [125] and Kim et al. [126] showed the activity of
zeolites in glycerol conversion to diols and olefins, to be dependent
on the structural, acidity and active metal properties. Zeolites with
low porosity produced light gaseous products, acidity enhances
conversion and metals loading promotes acidity and textural
properties thereby enhancing glycerol conversion. Table 6 presents
a further detail of various literature reports on the conversion of
glycerol to different products over a range of zeolites and other solid
acid catalysts. The selectivity to the desired reaction product(s) has
shown dependence on the catalyst compositions and the conversion
method adopted. An important issue is that glycerol has clear po-
tentials as industrial raw-material for the generation of many reli-
able products and/or feedstock. However, full realization of its
numerous benefits requires improved studies [127e132], involving
economic, policy, science and engineering issues. Integrating
appropriate environmental designs (giving emphasis to catalyst and
reactor design and experimental conditions) with life cycle assess-
ment and economic implications would be a great deal in this re-
gard. Another important area of vital importance that should be
further explored is the conversion of glycerol to glycerol carbonate
and relevant alcohols like 1,3-ditert-butoxypropan-2-ol, that is a
compound with excellent properties as combustion improver for
diesel fuel [133e141]. Al-Lal et al. [133] showed the reaction of
glycerol with hydrochloric acid to produced epichlorohydrin, which
can subsequently be converted to 1,3-ditert-butoxypropan-2-ol via
reaction with tert-butanol. Catalytic conversion and selectivity were
100 and 48.9%, respectively. At constant conditions, the activity is

Table 6
A literature report of glycerol conversions into various products over zeolites and some other solid acids.

Method/process Catalyst system Conversion (%)

Glycerol to olefins (high olefins selectivity) CuZSM-5 100 [120]

Glycerol to ethane and propane (high selectivity) H-ZSM-5 (29) 35.70e80.20 [120]
Glycerol to fuel H-ZSM-5 (29) 91e95 [120]
Glycerol to propane Macropore NieW 100 [120]
Glycerol to olefins USY 100 [120]
Glycerol to paraffins, light olefins, CO, CO2 and hydrogen Cu/ZSM-5, Cr/ZSM-5, Ni/ZSM-5, Li/ZSM-5 100 [120]
(variable selectivities)
Glycerol dehydration to acrolein and acetol (high selectivity MFI-15, MFI-40 and Al2O3 95, 78 and 78, respectively [123]
to acrolein)
Glycerol conversion to 1,2-propanediol (higher selectivity Pt/NaY 18.1e18.4 [122]
to 1,2-propanediol than ethanol or propanol)
Glycerol etherification with t-butanol (Higher selectivity to Amberlyst-15, mordenite, Beta and ZSM-5 81, 10, 83 and 58, respectively [125]
glycerol monoethers, i.e. 64e100%)
Glycerol conversion to hydrogen by steam reforming Ru/Y2O3, Ru/Al2O3 and Ru/ZrO2 100, 80 and 100, respectively [114]
(nearly 90% selectivity to hydrogen)
Glycerol reforming in supercritical water ZnSO4, WO3/TiO2 and Ru/TiO2 80, 100 and 100, respectively [116]
80 A. Galadima, O. Muraza / Energy 78 (2014) 72e83
catalyst dependent. For example HClO4 and BF3/Et2O both yield
conversion of 100%, but with selectivities of 25.8 and 52.6%,
respectively whereas KOH produced only 56.5 and 6.7% for con-
version and selectivity, respectively. It is particularly important that
the net CO2 emission for the feedstock combustion was found to be
very negligible. Ellis [142] on the other hand, indicated eSO3
modification to influence the acidic and catalytic properties of a low
temperature etherification carbon catalyst. Sulfonation creates
acidity up to 4 mmol/g and only mono- and d-glyceryl ethers were
produced to very high selectivities. However, catalyst decomposi-
tion was noticed at temperatures exceeding 236  C. Pico et al. [143]
showed benzyl alcohol etherification of glycerol to produced
dibenzyl ether as the most selective reaction product at temperature
close to 100  C. Mechanistically, the reaction obeys EleyeRideal
scheme. Among the heterogeneous materials gaining attention for
the etherification process, group IIA oxides (e.g. CaO and modified
catalysts), zeolites like basic mesoporous MCM-41, acidic BETA, ion
exchange resins like Amberlysts and metal modified heteropoly
acids are widely considered [130,144e150]. Some recent studies
[151e160] have also shown catalysts such as tungstated zirconia, Cu/
Al2O3, La modified Ni/Al2O3, Ni/CeZrO, oxides of W and V, Ru on Ir-
ReOx/SiO2, Na, K, Li and Cs modified alumina and K-zeolites as good
systems for catalytic conversion of glycerol to polyols, poly-
urethanes, glycerol carbonates, oxygenated fuel additives and co-
rich hydrogen gas. However, a major issue is that the most favor-
able reaction conditions for achieving higher yields and the mech-
anisms of action of most materials are still being soughted. Further
studies should therefore be carried out with the aim of identifying
the most appropriate catalysts preparation methods, favorable
temperature, pressure and space velocity. Reaction mechanisms
must be fully followed to understand the actual chemistry involved.
These are required for extending the laboratory findings to indus-
trial applications. Large quantities of glycerol are produced from
biodiesel production daily [161,162]. Therefore, understanding the
overall reaction design for glycerol conversion would be very
economical for the industry.
6. Conclusions
The numerous studies indicated the continuous exploitation of
edible oils, either from plants or animals, as biodiesel feedstock to
be seriously associated with hunger threats and food prices.
However, algae species that can produce high grade biodiesel are
widely abundant and can also be cultivated with limited environ-
mental challenges. The methods of cultivation, oil extraction and
transesterification are basically comparable to those of regular-
edible crops. Algae can be cultivated even in salty environments.
They are known for CO2 consumption during their growth period,
therefore dually suitable for environmental management. These
and many other stated factors would certainly eclipse their pros-
pects as sustainable feedstocks. Transesterification using hetero-
geneous catalysts from oxides, zeolites and their derivatives will
continue to attract industrial attention. Solid acid and solid base
catalysts are potentially cheaper and can be recovered, recycled and
reused after the transesterification process. They show very less
sensitivity to free fatty acids in the feed, if appropriately designed,
and therefore produce high purity biodiesel, with properties
meeting international standards. However, the actual reaction
mechanisms and ways of optimizing the triglyceride esters con-
version with many of these catalysts must be fully investigated.
Taking into account the nature of the support or the active phase,
well dispersed catalyst particles and moderate temperature are
potential approaches to enhance the adsorption-desorption of the
reactants and to improve product yield. Zeolite catalysts should be
tailored such that the frameworks possess desirable porosity and
acidity/basicity properties. Where doped with metals or oxides care
must be taken to avoid pore blockage that can result to competitive
transesterification versus cracking process. Heteropoly acids are
also promising, especially due to free fatty acid tolerance, however
extensive studies are required to fully establish their mode of ac-
tions for improved performance. Exploitation of algae for biodiesel
and other industrial raw-material production is certainly a multi-
functional option. However, a number of issues must be
addressed to ensure full benefits. The most cost effective algae
cultivation and oil extraction methods must be identified. Afford-
able algae species with high oil contents and fast-growth rates in
specific environments should be fully examined.
On the other hand, the high purity glycerol from the heteroge-
neous transesterification of algae oil has strong potentials to reduce
industrial dependence on non-renewable petrochemicals as raw-
materials. However, the research must be intensified to identify
the most appropriate heterogeneous catalysts, their mode of action
(s) and optimal reaction conditions. Oxides and zeolites have
indicated strong potentials in the formulation of many liquid and
gaseous products such as formaldehyde, diols, allyl alcohols, olei-
fins, methane and hydrogen fuel, as well as other liquid hydrocar-
bons like diesel and light naphtha. Other important products are
glycerol carbonate and derived alcohols like 1,3-ditert-butox-
ypropan-2-ol, that are compounds with excellent properties as
combustion improver for diesel fuel. Attention can therefore be
directed toward their improved performance.
Acknowledgments
The authors would like to acknowledge the support provided by
King Abdul-Aziz City for Science and Technology (KACST) through
the Science & Technology Unit at King Fahd University of Petroleum
& Minerals (KFUPM) for funding this work through project 10-
NAN1392-04 as part of the National Science, Technology and
Innovation Plan.
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