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Energy xxx (2014) 1e12

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Energy
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Biodiesel production from algae by using heterogeneous catalysts:


A critical review
Ahmad Galadima a, Oki Muraza a, b, *
a
b

Center of Research Excellence in Nanotechnology, King Fahd University of Petroleum & Minerals, Dhahran, Saudi Arabia
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:
Received 6 November 2013
Received in revised form
3 June 2014
Accepted 6 June 2014
Available online xxx

The numerous challenges associated with declining fossil fuel reserves as energy sources, have accounted
for a shift to biofuels as alternatives. However, transesterication of animal fats and edible vegetable oils
using homogeneous acids and bases for biodiesel production is recently considered unsustainable by
industries, particularly due to food versus fuel competition, and economic and environmental challenges
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
the oil extraction, available heterogeneous catalyst systems and reaction mechanisms, optimum transesterication conditions and the way forward. As the economic feasibility of biodiesel production from
algae is supported by the valorization of glycerol as by-product, we have also highlighted key available
heterogeneous catalysts to upgrade glycerol into more useful industrial products.
2014 Elsevier Ltd. All rights reserved.

Keywords:
Biodiesel production
Edible oils
Algae oils
Heterogeneous catalysts
Glycerol

1. Introduction
Since its early commercialization as a substitute for petroleumdiesel for nearly a decade now, biodiesel have remained a good
global fuel for running automobile engines. Many interesting factors have been attributed to this success. Among others, biodiesel is
chemically non-toxic in nature, biodegradable and can simply be
prepared via transesterication under mild conditions [1]. In
addition to insignicant 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 ash,
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
intensied, 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 monohydricalcohols (i.e. methanol to propanol), with no clear justication 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).

specications by ASTM (American Society of Testing and Materials)


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 production 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 sunower 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
transesterication catalysts [4,8e10]. These homogeneous materials 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 transesterication 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 alkyl or aryl) have also
been classied as unreliable due to much slower reaction rates,
difcult 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.

Please cite this article in press as: Galadima A, Muraza O, Biodiesel production from algae by using heterogeneous catalysts: A critical review,
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A. Galadima, O. Muraza / Energy xxx (2014) 1e12

ratios, concentrations of catalysts, and severe corrosion problems


[8,10].
The numerous problems identied have stimulated researchers
at university and industry to explore better options, with great
emphasis on the exibility 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 biodiesel 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 transesterication 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 problems 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 fuelproduced from algae, other important fuels can similarly be produced, thus enhancing their exploitation potentials. Fuels such as

Table 1
Short term projection of biofuels from algae.
Short term potentials, 2014

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' modied.

Billion gallons
Assumed 1 gallon
of oil $3.0
1500
41
26
15
2.73%
$123 billions
9.2%
$425 billions

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 properties and therefore suitable for treating waste and sewage water
through the removal of toxins and nutrients. Pigments, nutraceuticals 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 efcient by
many authors [19e21]. The processes of cultivation, oil extraction
and nal conversion into biodiesel are basically comparable to
those of other edible crops such as soy, sunower and palm. These
facts could be attributed to important factors leading to the escalated 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 dioxide [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-benecial [24,29]. However,
there are certain difculties 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 costfeasible cultivation method and difculty 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 ow
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 transesterication catalysts
To mitigate the various challenges encountered with the use of
homogeneous bases and liquid acids as alcoholysis catalysts,
numerous studies were reported to explore the activities of a wide
range of heterogeneous materials [30e43]. Table 2 presents a list of
numerous solid acids and bases documented as catalyst for the
biodiesel production. The solid acids comprised mainly of zeolite
materials, heteropoly acids, pure or modied oxides of transition
metals like zirconium and molybdenum, silica and alumina

Please cite this article in press as: Galadima A, Muraza O, Biodiesel production from algae by using heterogeneous catalysts: A critical review,
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A. Galadima, O. Muraza / Energy xxx (2014) 1e12

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

Solid bases

 Zeolitic materials such as HeY, HBeta, ZSM-5, H-MOR, ETS-10, and


ETS-4.
 Sulfated zirconia (SO2
4 eZrO2)
supported with Al2O3 or some
times SiO2.
 Sulfated zirconia mixed with
other transitional metal oxides.
2
e.g. SO2
4 eZrO2/WO3, SO4 eZrO2/
MO3.
 Free sulfated tin oxide or supported usually over alumina or
2
silica (SO2
4 eSnO2/Al2O3, SO4
eSnO2/SiO2).
 Acetates of zinc or copper supported over silica
 Heteropoly acids and their derivatives. e.g. H3PW12O40,
H4SiW12O40
 Supported
organosulphonic
acids. The support is mostly
mesoporous silica and some time
alumina.
 Naon

 Oxides of group IIA elements:


CaO, MgO, SrO, BaO.
 Carbonates of group IIA elements: CaCO3, MgCO3, SrCO3,
BaCO3
 Carbonates of group IA elements:
K2CO3.
 Free and mixed transitional metal
oxides. e.g. ZnO, CuO, CaLaO3,
CaCeO3, CaZrO3, CaMnO3, CaTiO3,
etc.
 Basic zeolites.
 Cs-exchanged sepiolite.
 Hydrotalcites (MgeAl)
 Quanidine anchored cellulose or
other polymers.
 Aluminates of Zinc.
 Metal generated salts of primary
amino acids.
 Li-promoted oxides of group IIA
elements.

catalysts [14e43]. These materials are characterized by having both


Brnsted and Lewis acid sites, that determines their activities
during transesterication reactions. Activities of zeolites and heteropoly acids may also be affected by shape selectivities. Materials
having multi-dimensional pore structure should be more favorable
for the formation of alkyl esters without cracking. Solid bases on
the other hand, comprised of basic zeolites, carbonates and common oxides. The basic sites formed the main reaction centers for
these materials during biodiesel synthesis.
In the heterogeneous catalysis a good number of factors must
be appropriately considered depending on whether the catalyst is
a solid acid or base. The factors include transesterication temperature, the amount of catalyst, on stream reaction time, degree
of mixing or stirring, alcohol/oil content and purity index of the
feedstock. Anderson et al. [14] reported the dispersion of the active
material over the support considerably inuences the alcoholysis
activity of a BaO/Al2O3, with higher dispersions being more active.
The selected temperature should be close to the monohydricalcohol boiling point to avoid handling difculties. Adequate reaction 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 difculty 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.
Transesterication 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 alcoholic eOH group into the triglyceride ester chain. Therefore, glycerol would be nally 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 1. Chemical equation illustrating biodiesel production.

would generally be low and the reaction can shift backward,


creating further negative effect on the total biodiesel yield. However, at higher ratios, removal of excess alcohol may pose a great
challenge. Factors such as reaction temperature and degree of
stirring are also very critical. Adequate stirring is required to ensure
sufcient interaction between catalyst particles and the reactants
[10e15]. The temperature must be close to the boiling point of the
monohydric alcohol. Lower temperatures favor slow reaction,
whereas much higher temperatures create handling difculties.

3.1. Transesterication with solid bases


Reaction involving heterogeneous bases proceeds by reaction of
either the Lewis or the Brnsted basic sites of the catalyst with a
monohydric alcohol (usually ethanol or methanol). The generated
alkoxide mixture interacts with triglyceride ester in the oil to yield
biodiesel and glycerol in the subsequent steps (Scheme 2). The
mechanism is EleyeRideal type, but the strength of the basicity
signicantly inuences how fast the reaction can proceed. The basic
sites preferentially interacts with alcohol and remove H, forming
an alkoxide group (RO), which is the main active component that
attacks the triglyceride ester at the intermediate stages. The
stronger the basic sites the more favorable the formation of the
alkoxide species. Similarly, strong basicity favors subsequent
cleavage and glycerol formation, and consequently the overall reaction rate would be enhanced.
Solid basic catalysts such as zeolites, oxides of rst row transition metals like ZnO, CuO, basic polymers and compounds of group
IIA elements (Table 2), especially the oxides and carbonates such as
CaO, MgO, SrO, BaO, CaCO3, MgCO3, SrCO3 and BaCO3, have

Scheme 2. Mechanism of base catalyzed transesterication.

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attracted attention as heterogeneous transesterication catalysts.


The latter being the most prominent. Their basicity is associated
with metal-oxygen ion pairs (i.e. M2eO2) and varies in the order
Ba > Sr > Ca > Mg for the oxides. These materials are easily preparable, less expensive, and showed low corrosion properties. The
severity of calcination step is a very important factor that determines the transesterication 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 materials 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 transesterication. Up to 95% biodiesel
yield had been recorded. However, high methanol to oil ratio of
about 6:1 may be required in order to sufciently shift the equilibrium position forward. Adequate transesterication 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 materials Al2O3 shows higher activity, specically due to sufcient
stability and dispersion properties. It also allows enhanced surface
reactants interaction [13e15,24].
Basic zeolites and hydrotalcites are increasingly gaining attention. Materials such as oxides containing zeolites, ETS-10 and faujasites 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 transesterication activity. The hydrotalcites (MgeAl) possess good basicity but dissolution problems require that the materials are
carefully prepared. Preparation by co-precipitation method has so
far shown reliable stability.
3.2. Transesterication 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 modied 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 modier

Table 3
Role of calcination temperature on the activity of WO3 modied ZrO2 [49].
Sample
code

Calcination
temperature [ C]

Conversion (%),
5 wt.% WO3/ZrO2

Conversion (%),
15 wt.% WO3/ZrO2

A
B
C
D
E

400
500
600
700
900

93
95
10
5
5

78
81
20
25
17

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 associated with sulfuric acid have triggered the evaluation of sulfated
zirconias and organosulphonic acids as transesterication catalysts.
With unsupported systems, the SO2
4 may easily be lost in the reaction 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 transesterication
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 tungstatedzirconia supported over alumina to obtain comparable activity
[49]. In addition to the phase properties, the loading of WO3 and
calcinations temperature inuence 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 signicant resistance associated with higher WO3
loadings [49].
Heteropoly acids and their derivative salts are also good materials for alcoholysis. Especially due to their water tolerance potentials, which signicantly limit deactivation by hindering the
conversion of Lewis to Brnsted acid sites. Their super acidity
properties coupled with structural networks promote their degree
of transesterication, compared with homogeneous hydroxides
and acids. They can easily be recycled and reused, thus reducing
production cost and environmental inconsistencies. However, their
specic mechanism of action has not yet been established [48e53].
Recently, Alsalme et al. [52] heterogeneously esteried hexanoic
acid and transesteried 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 atmospheric pressure. The results when compared with some homogeneous 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 signicant 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 transesterication
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 Brnsted option being preferential. The acidity should be of the
Brnsted type, production of water and glycerol during the transesterication process have previously been reported to signicantly
deactivate the Lewis acid sites. Initially, a carbonyl group is protonated 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 Brnsted 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 transesterication of algae oil
Oil extraction is basically the initial and critical step in biodiesel
production from plants after harvesting (Fig 2). An attractive procedure is one that ensures reduced extraction cost but high oil yield

Please cite this article in press as: Galadima A, Muraza O, Biodiesel production from algae by using heterogeneous catalysts: A critical review,
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Table 4
Data for biodiesel production over solid catalysts (including zeolites) from algae and
some common oils.
Feedstock

Catalysts

Soybean
Corn oil
Algae oil
Algae oil

Zirconia, titania [73]


Zirconia, titania [73]
Zirconia, titania [73]
4% NiO, 18% MoO3/
alumina [79]
0.75% Pt-SAPO-11 [79]
4% NiO, 18% MoO3/HZSM-5 [79]
Microporous titania
[79]
(HY-340) niobium
oxide [79]
Hierarchical H-Beta
zeolites [79]
Amberlyst-15 [78]
Modied alumina [71]
Modied titania [15]
Porous titania
microsphere [15]
BaO/Al2O3 [14]
BaO/Al2O3 [14]

Algae oil
Algae oil
Algae oil
Algae oil
Algae oil
Scheme 3. Mechanism of transesterication via acid catalysis.

[18,46]. The two fundamental methods available for algae today are
the mechanical and chemical methods. The mechanical method is
mainly expeller press or ultrasound-assisted whereas hexane solvent, soxhlet and supercritical uid extractions are the available
chemical methods. The mechanical method requires algae drying,
thus making it energy intensive whereas health and safety issues
are critical for the chemical option [18,46]. Adopting supercritical
extraction process involved the used of expensive high pressure
equipment that is also energy intensive. Industrially, a single step
process by OriginOil Company is used in wide application. The
method involved sequential steps of harvesting, concentration, and
extraction oil from algae. It separate oil, biomass and water in a
single step (mostly in less than 1 h). No chemicals or heavy
equipment is needed and the process requires no initial dewatering
of the fresh algae. Another novel method is that of Cavitation
Technologies Inc. The company's Nano-based reactor is employed
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
method, which is under research and development stage, would be
of great interest to the Nano-technologists. Specially developed
mesoporous nanoparticles would be employed to preferentially
extract and sequester specic fuel-based compounds in the algal

Fig. 2. Flowsheet representation of biodiesel production from algae.

Algae oil
Microalgal's lipid
Fresh water microalgae oil
Fresh water microalgae lipids
Groundnut oil
Cotton seed oil
(fatty acid 4.34%)
Sunower oil
Yellow horn
Waste cooking oil
Palm oil
Jatropha curcas oil
Soybean oil
Chinese tallow seed oil
Croton megalocarpus oil
Waste cooking oil
Waste cooking oil
Waste cooking oil
Mutton fat
Sunower oil

ZrO2/La2O3 [16]
Cs2.5H0.5PW12O40 [16]
MgO/TiO2 [16]
CaO/Al2O3 [16]
CaO/Fe3O4 [30]
Li/MgO [30]
KF/CaO [30]
sulfated SnO2eZrO2
[30]
Zeolite Y (Y756) [31]
H3PW12O40.6H2O [31]
K3PO4 [31]
MgO/KOH [35]
NaeX zeolite [45]

Biodiesel yield/
Conversion (%)
88.10
88.30
90.20
99.00
83.00
98.00
94.70
94.27
99.50
>98
97.5
>95
>95
80
80
84.9
96.22
91.6
98.64
95
93.9
96.8
95
85
87
97.3
98
83.53

lipid feed. The free fatty acids and triglycerides rich balanced algal
oil would be transesteried into biodiesel using the T300 catalyst
developed by the company. A key important issue here is that, the
technology is potentially very efcient and involved heterogeneous
catalyst, thereby ensuring environmental sustainability, cost
reduction, catalyst reusability and high purity biodiesel and glycerol [54]. Other methods of oil extraction that are under investigation include enzymatic extraction and osmotic shock, with the
former being considered much more expensive than the hexane
extraction method. The process utilizes specic molecules of enzymes 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 gure 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 sunower 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, docosahexanoic and ecosapentanoic acids. These compounds could be isolated and employed for other industrial applications, consequently
favoring economic exploitability [59,60].
After the successful oil extraction, the next step is the transesterication of the oil into biodiesel. Algae oils are basically

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A. Galadima, O. Muraza / Energy xxx (2014) 1e12

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 temperature 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 materials. 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 purication). 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 biodiesel 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-ETS10, H-ETS-4 with moderate acidity properties and sufcient
porosity allow faster transesterication with limited side reactions
interference for the vegetable oils under controlled conditions
[44e47]. This is another great opportunity for the algae oils. Materials 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. Heterogeneous bases are also prospecting materials (see Table 4). Oxides
of Ca, Sr and Mg, mixed oxides with transition metals, and supported over silica or alumina were extensively studied for other oils
with their properties fully evaluated. These materials could similarly be fully exploited for the algae oils, with the hope that, challenges 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 transesterication [25,69,71e77]. Umdu et al. [71] studied the properties 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 transesterication temperature. Similarly, no unwanted products that
require purication 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 xed-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

feedstocks (algae, corn, tall and soybean oils). The catalysts proved
very efcient, 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 reusability 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 preesterication of the algae oil before the base-catalyzed transesterication. 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
transesterication 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, PtSAPO-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 production from algae or comparable non-edible feedstock via heterogeneous catalysis would be the best method for the future.
However, research should be intensied to identify what the
technical and economical feasibility by integrating economic aspects 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 hydrocarbons [99e102], animal feeds and ne 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 hydrodeoxygenation [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, sulphides of NiMo and CoMo and their silica-alumina supports are
good candidates for hydrotreating of bio-oils even at low temperatures, 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 xed bed reactor. The liquid bio-oil
produced was found to be rich in gasoline and diesel range hydrocarbons, especially at the optimal temperature of 500  C. Benzene, phenols, methylphenols and heterocyclic amines like pyrrole,
indole, pyridine and substituted pyrazines were similarly detected
to signicant concentrations. Similar observations were reported
by other authors using different species [63,106e112].

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A. Galadima, O. Muraza / Energy xxx (2014) 1e12

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

Uses

Production process

1,3-Propanediol

Formulation of solvents, co-polyesters, powder,


UV-cured coatings etc.
Industrial commodity/raw-material.
In cosmetic industry as a tanning agent.

Clostridium butyricum method.

1,2-Propanediol
Dihydroxyacetone
Succinic Acid
Hydrogen

Polyglycerols

Manufacture of synthetic resins, biodegradable


polymers etc.
Next generation renewable fuel, hydrogenation
reactions etc.

Polyesters

Anti-fogging, lubricants, antistatic additives,


plasticizers etc.
Polymer applications.

Liquid hydrocarbons e.g. diesel, light naptha

Fuels applications.

Polyhydroxyalkanoates
Syngas, methane

Polymer applications.
Fuel for energy.

Oleins

Polymer feedstock, fuel additives.

Others e.g. allyl alcohol, methanol, and formaldehyde

Industrial raw-materials, solvents, etc.

5. Glycerol conversion
Glycerol (propan-1,2,3-triol) is a simple trihydric-alcohol with
rine
, glicerol, glucerite, glycerin,
other names as alcohol glyce
rine, vegetable glycerin etc. It both occurs naturally
glycerine, glyce
and can be synthesized industrially or in the laboratories. The
compound forms the triester backbone of triglycerides (see Scheme
1) and phospholipids. Glycerol is colorless, odorless compound
widely employed as raw-material in some key industries. The three
hydroxyl groups account for considerable water solubility.
Glycerol is the key waste product produced (up to 1 kg per 10 kg
of algae oil) from biodiesel production, that has in the past been
considered a great challenge to industries [14e16,68e70,113].
However, there are progresses that the compound could be puried
and successfully converted to a number of useful industrial rawmaterials (Table 5). Initially, homogeneous catalysis was mainly
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 signicant resistance to deactivation by carbon deposition.
Tapah et al. [115] employed mixed Fe2O3 and Cr2O3 as catalyst and
glycerol concentrations of 2e30 wt.% at ow rates from [10e65 ml/
min] for a CSCWG (catalytic supercritical water gasication) conversion of glycerol. The results showed high temperature and low
glycerol concentrations to increased the yield and selectivity toward H2 production. Similarly, syngas of about 64 mol % was produced with minimum 4:1 mol ratio of H2:CO. Other volatile
hydrocarbons (methane and ethylene) were obtained to signicant
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 methanol, allyl alcohol and formaldehyde were obtained at 400  C
temperature. Catalyst stability was also studied and was found to
reach relative stability for up to 9 h of reactions. The choice of

Raney Nickel method, Pt on NaeY zeolite.


Catalytic oxidation of aqueous glycerol using Pt
catalysts.
Fermentation process.
Heterogeneously catalytic steam reforming at
moderate temperatures, aqueous reforming
over tin promoted Raney nickel catalysts.
Selective etherication of glycerol.
The reaction of glycerol with adipic acid using
Sn based catalysts, catalytic reaction of citric
acid with glycerol at different mole ratios.
Low temperature catalytic synthesis followed
by FischereTropsch synthesis.
Fermentation process.
Catalytic supercritical water gasication
(CSCWG) method.
Catalytic conversion using zeolites like ZSM-5,
zeolite Beta, and zeolite Y.
Catalytic supercritical water gasication
(CSCWG) method.

reaction conditions inuences the key reaction products from the


gasication process. For example, Markocic et al. [116], Long and
Fang [117] and Peterson et al. [118] reported high pressures, low
temperatures, upgraded feeds and acid catalyst systems to produce
mainly liquid products. Whereas opposite conditions produced
mainly hydrogen, syngas and other gaseous hydrocarbons. Guo
et al. [119] showed that, depending on reaction conditions, a
number of liquid products (including methanol and formaldehyde)
could be generated as intermediates during the CSCWG process
(see Fig. 3).
Zeolite systems like HeY, H-ZSM-5, H-Beta etc could similarly be
employed to convert glycerol into olens (usually ethene, propene
and n-butene) under controlled conditions, the choice of which
depends on the zeolite and/or desired reaction products. Liquid
hydrocarbons of diesel and naphtha range could similarly be obtained. Zakaria et al. [120] reported an integrated route to diesel and

Fig. 3. Conversion of glycerol to gaseous and intermediate liquid products via combined gasication and pyrolysis process.

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A. Galadima, O. Muraza / Energy xxx (2014) 1e12

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

light naphtha production coupling low temperature catalytic conversion 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 olens
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%
olens 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 oleins and parafns production from glycerol.
Metal loadings improved HZSM-5 acidity and glycerol conversion.
Recently, Van de Vyver et al. [122], Possato et al. [123], Seran et al.
[124], Gonzalez et al. [125] and Kim et al. [126] showed the activity of
zeolites in glycerol conversion to diols and olens, 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 potentials as industrial raw-material for the generation of many reliable products and/or feedstock. However, full realization of its
numerous benets 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 assessment and economic implications would be a great deal in this regard. 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 olens (high olens selectivity)


Glycerol to ethane and propane (high selectivity)
Glycerol to fuel
Glycerol to propane
Glycerol to olens
Glycerol to parafns, light olens, CO, CO2 and hydrogen
(variable selectivities)
Glycerol dehydration to acrolein and acetol (high selectivity
to acrolein)
Glycerol conversion to 1,2-propanediol (higher selectivity
to 1,2-propanediol than ethanol or propanol)
Glycerol etherication with t-butanol (Higher selectivity to
glycerol monoethers, i.e. 64e100%)
Glycerol conversion to hydrogen by steam reforming
(nearly 90% selectivity to hydrogen)
Glycerol reforming in supercritical water

CuZSM-5
H-ZSM-5 (29)
H-ZSM-5 (29)
Macropore NieW
USY
Cu/ZSM-5, Cr/ZSM-5, Ni/ZSM-5, Li/ZSM-5

100 [120]
35.70e80.20 [120]
91e95 [120]
100 [120]
100 [120]
100 [120]

MFI-15, MFI-40 and Al2O3

95, 78 and 78, respectively [123]

Pt/NaY

18.1e18.4 [122]

Amberlyst-15, mordenite, Beta and ZSM-5

81, 10, 83 and 58, respectively [125]

Ru/Y2O3, Ru/Al2O3 and Ru/ZrO2

100, 80 and 100, respectively [114]

ZnSO4, WO3/TiO2 and Ru/TiO2

80, 100 and 100, respectively [116]

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A. Galadima, O. Muraza / Energy xxx (2014) 1e12

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 conversion 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
modication to inuence the acidic and catalytic properties of a low
temperature etherication 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 decomposition was noticed at temperatures exceeding 236  C. Pico et al. [143]
showed benzyl alcohol etherication 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 etherication process, group IIA oxides (e.g. CaO and modied
catalysts), zeolites like basic mesoporous MCM-41, acidic BETA, ion
exchange resins like Amberlysts and metal modied heteropoly
acids are widely considered [130,144e150]. Some recent studies
[151e160] have also shown catalysts such as tungstated zirconia, Cu/
Al2O3, La modied Ni/Al2O3, Ni/CeZrO, oxides of W and V, Ru on IrReOx/SiO2, Na, K, Li and Cs modied alumina and K-zeolites as good
systems for catalytic conversion of glycerol to polyols, polyurethanes, glycerol carbonates, oxygenated fuel additives and corich hydrogen gas. However, a major issue is that the most favorable reaction conditions for achieving higher yields and the mechanisms 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 ndings to industrial 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 environmental challenges. The methods of cultivation, oil extraction and
transesterication are basically comparable to those of regularedible 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 prospects as sustainable feedstocks. Transesterication using heterogeneous 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 transesterication 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 conversion 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
transesterication 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 actions for improved performance. Exploitation of algae for biodiesel
and other industrial raw-material production is certainly a multifunctional option. However, a number of issues must be
addressed to ensure full benets. The most cost effective algae
cultivation and oil extraction methods must be identied. Affordable algae species with high oil contents and fast-growth rates in
specic environments should be fully examined.
On the other hand, the high purity glycerol from the heterogeneous transesterication of algae oil has strong potentials to reduce
industrial dependence on non-renewable petrochemicals as rawmaterials. However, the research must be intensied 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, oleins, methane and hydrogen fuel, as well as other liquid hydrocarbons like diesel and light naphtha. Other important products are
glycerol carbonate and derived alcohols like 1,3-ditert-butoxypropan-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 10NAN1392-04 as part of the National Science, Technology and
Innovation Plan.
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