Journal of Environmental Chemical Engineering 1 (2013) 113–121

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Journal of Environmental Chemical Engineering

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Review

Solid acid-catalyzed biodiesel production from microalgal oil—The dual

advantage
Yahaya Muhammad Sani a,b, Wan Mohd Ashri Wan Daud a,*, A.R. Abdul Aziz a
a
Chemical Engineering Department, Faculty of Engineering, University Malaya, 50603 Kuala Lumpur, Malaysia
b
Department of Chemical Engineering, Ahmadu Bello University, Zaria 870001, Nigeria

A R T I C L E I N F O A B S T R A C T

Article history: The major challenges facing the commercialization of biodiesel are: readily available and profitable
Received 1 February 2013 feedstock and cost-effective production process. Although conventional oilseed feedstocks provided
Accepted 15 April 2013 biodiesel yields of more than 98%, sufficient land for cultivating such feedstocks is a major challenge.
Moreover, the use of refined feedstocks is uneconomical because of refining costs and priority as food.
Keywords: Algae (including macro- and microalgae) are the focus of many current research interests because they
Microalgal oil have the potential to provide sufficient fuel for global consumption. Beside their high lipid contents and
Solid acid catalysts
fast growth rate, microalgae have the potential to mitigate the competition for land-use and food-for-
Transesterification
Biodiesel
fuel conflicts. They are also able to reduce the greenhouse effects via CO2 sequestration. Critical survey of
Prospects the literature suggests that microalgal oil has the potential to produce higher biodiesel yields with about
Challenges. 25% reduction in production costs. However, the oil from microalgae contains high free fatty acids which
require pretreatment if conventional homogeneous catalysts are employed. Heterogeneous base
catalysts are also not suitable due to soap formation and post-production processes, hence the need for
solid acid catalysts. Therefore, this article provides a review on solid-acid catalysts used in processing
microalgal oil for biodiesel production. Also discussed in details are the challenges and prospects of the
production process. With more advances in technology and long-term commitment to investments,
heterogeneous acid-catalyzed microalgal-biodiesel can become the ideal process for the future.
ß 2013 Elsevier Ltd. All rights reserved.

Contents

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113

Biodiesel from algae as an alternative fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
Present and future status of microalgal biodiesel production . . . . . . . . . . . . . . .......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 114
Issues surrounding conventional transesterification processes. . . . . . . . . . . . . . .......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
Solid acid catalysts used in microalgal oil biodiesel production . . . . . . . . . . . . . . . . . . .......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
Biodiesel yields from heterogeneous acid-catalyzed microalgal oil . . . . . . . . . . .......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
The dual advantage: potentials of heterogeneous acid-catalyzed microalgal biodiesel production. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
Issues surrounding solid acid catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
Future prospects and challenges . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
Conflict of interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .......... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119

Introduction

Industrialization and transportation are two indicators used in

reflecting the global civilization status [1,2]. Human civilization
* Corresponding author. Tel.: +60 3 79675297; fax: +60 3 79675319. transformed from using animal forces (which relied on biomass
E-mail address: ashri@um.edu.my (Daud). from plants) to external combustion engines (which relied on solid

2213-3437/$ – see front matter ß 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.jece.2013.04.006
114 Y.M. Sani et al. / Journal of Environmental Chemical Engineering 1 (2013) 113–121
Fig. 1. Total renewable energy supply (Mtoe) in year 2008.
coal). After steam engines, transportation was revolutionized to
internal combustion engines (ICE) which relied on liquid diesel and
gasoline [3]. Currently, jet planes, trains, ships and vehicles are
propelled with the help of ICE and liquid fuels such as jet fuel,
diesel and gasoline. However, the lower price advantage that made
these fuels popular [4] is becoming history. The current scenario is
an inverse relationship with petroleum becoming depleted and
more expensive [5,6]. Concomitantly, it is estimated that the world
would require 50% more energy in 2030 than it does today [7,8].
Besides, environmental degradation due to the emissions of CO2 is
becoming increasingly worrisome. In 2007 and 2008, the
transportation sector alone accounted for 22% and 23% of the
total CO2 emissions respectively. About 50% of this greenhouse gas
(GHG) emission comes from road transport [4,9]. The panacea to
these challenges confronting the world today is the provision of
alternative renewable fuels. These fuels will ensure a global energy
security with reduced environmental impacts as well as compete
favorably with petroleum diesel [10].
Concerns for the environment and biodiversity have made
biofuels the most attractive sources of alternative energy [11,12].
Other factors that contributed to their acceptability against other
sources are sustainability, seasonal changes and geographical
locations [7]. Combustible renewables and wastes have the highest
potentials to supply the global energy requirements. They accounted
for more than three quarters of the global energy supply in 2007 and
2008 (Fig. 1) [6]. From the several energy alternatives identified,
biodiesel is the most promising due to its similar properties to
petrochemical diesel. Producing biodiesel in large quantities will no
doubt help to meet the increasing global energy demands.
A promising source for the mass production of biodiesel is
microalgae. However, about 70% of the total lipids of microalgal oil is
free fatty acids (FFAs). Therefore, to produce biodiesel from
microalgal oil, the issue of the high FFAs needs to be considered.
This is where the advantages of solid acid catalysts come in handy.
Unlike heterogeneous and homogeneous base, solid acid catalysts
can effectively carry out the simultaneous esterification and
transesterification of high FFA-containing feedstocks. While some
comprehensive reviews regarding the general potentials of solid
acid-catalyzed biodiesel production and that of the prospects of
microalgal oil as source of energy are available in the literature [13–
27], instances discussing the link between the two are sparse. This is
because the efforts to produce biodiesel via solid acid transester-
ification are recent [28]. Therefore, by highlighting the prospects of
solid acid-catalyzed biodiesel production from microalgal oil, this
review aims to motivate the design and development of novel solid
acid catalysts which will ensure higher biodiesel yields.
Biodiesel from algae as an alternative fuel
Concerns over diminishing oil reserves, increasing crude oil
prices, increase in GHG emissions and associated environmental
impacts have made biodiesel to emerge as the fastest growing
industry worldwide. It is the second most abundant combustible
renewable fuel [5,29]. However, to remain sustainable, biodiesel
needs to be produced from non-food crops which require minimal
cultivation. The cultivation should be carried out without
competing with the available arable land or cause deforestation.
Though Jatropha curcas and used cooking oils are good sources in
this regards [30–33], a more reliable and efficient source is still
needed.
Advancements of biofuels as energy sources for industrial and
transport sectors encountered some criticisms from some of the
scientific communities and policy makers. These issues raised the
questions of food availability and prices, land-use, environmental
degradation and related socio-economic implications [29]. Fortu-
nately, the preliminary data obtained from biofuels produced from
biomass and wastes proffered solutions to most of these questions.
The results indicated reduced environmental degradation, espe-
cially on GHG emissions and deforestation [34,35]. The economic
standard of the personnel involved in the cultivation of the
feedstocks and biodiesel production is enhanced especially in the
developing countries.
A cheap and readily available source of feedstock which does
not compete as food or with other oilseed crops for arable land is
microalgae. Microalgae thrive in freshwater, saltwater, sludge and
contaminated water. In fact, they thrive well in habitats not
suitable for energy oil crops such as the ponds, lakes, sea, and on
wastelands. Microalgal oil also contains high percentages of
monounsaturated and saturated FAs which are important from the
standpoint of diesel fuel quality. This is because the problems
encountered with polyunsaturated fatty-acid-derived fuel could
be avoided as the monounsaturated and saturated FAs could
significantly reduce polymerization of fuel during combustion
[24,33,36]. Nannochloropsis, members of the marine green algae
are considered the most suitable candidates for biodiesel produc-
tion. These strains have shown high lipid contents and biomass
productivity. Accordingly, many researchers are exploring these
and other advantages (Table 1) to ensure a sustainable biodiesel
production from microalgae over higher plants.
Present and future status of microalgal biodiesel production
The year 2012 witnessed the weakest global growth rate from
fossil fuels. The growth was below the average of 0.6 million
barrels per day (b/d). Also witnessed was the fifth decrease in the
past six years; reaching the lowest level since 1995. Petroleum oil
is expected to continue being the slowest-growing source of
energy 20 years from now. This will be due to the increasing prices
and gradual reduction of subsidies [42]. On the other hand, the
projected global supply of biofuels is expected to be around 30% by
2030. Seemingly, the only renewable feedstock that has the
potential to replace petroleum diesel completely without adverse-
ly affecting food supply chain and other crop products is microalgal
oil [41,43,44]. Most of the productive oil crops, such as oil palm and
rapeseed do not come close to microalgae in potentially providing
the global energy security needed. More than 88% dry weight of oil
yields have been reported from comparably an order of magnitude
in land-area used [45,46]. Besides, the properties of biodiesel
produced from microalgal oil meet the standard specifications
(Table 2).
The effort to produce biodiesel from microalgal oil is not a new
one [41]. In the 1970s and 1980s; Department of Energy in the U.S.
explored the feasibility of providing fuel from algae through its
Aquatic Species Program [47]. Also, recent research efforts such as
Mcgyan process1 which have incorporated new approaches have
started yielding encouraging results [38]. Moreover, it was
postulated that the oil content in microalgae (e.g. Neochloris
 Y.M. Sani et al. / Journal of Environmental Chemical Engineering 1 (2013) 113–121 115

Table 1
Advantages and disadvantages of algae oil as feedstock for biodiesel production.

Advantages Disadvantages

(1) Manufacture and store large amounts of neutral oil and lipids
(20–50% DCW) in photo-bioreactors. Theoretically, oil yield per acre
is 100 times greater than energy oil crops and 7–31 times greater
than palm oil (the next best crop) [13,33,36–38].
(2) High growth rates (e.g. 1–3 doublings per day), daily harvesting
of certain species of algae [13,33,36,39].
(3) No competition with conventional agriculture for land resources
because they thrive in coastal seawater/brackish water/saline, or
wastewater, marginal/degraded lands (e.g. arid- and semi-arid lands
and desert) for which there are few competing demands [39].
(4) Even though it thrives in aqueous habitat, it utilizes less water
than energy oil crops [14,38,40].
(5) Wastewater sources (e.g. industrial and municipal wastewaters,
concentrated animal feed operations and agricultural run-off) provide
growth nutrients such as phosphorus and nitrogen. This helps in
wastewater bioremediation [13,40].
(6) Microalgae require 1.8 kg of CO2 per 1 kg of dry biomass production;
this can be coupled with the sequestering of CO2 from flue gases
emitted from fossil fuel-fired power plants and other sources, thereby
reducing emissions of a major greenhouse gas [42,43].
(7) Reduction in N2O emissions and fertilizer use by utilizing
waste water and recycling of biomass [13].
(8) Value-added co-products are produced (e.g. H2, ethanol,
biopolymers, pharmaceutical, proteins, cosmetic products,
polysaccharides, fertilizer, pigments and animal feed) [33,36].
(9) Microalgae reproduce themselves using photosynthesis to
convert solar energy into chemical energy, completing an entire
growth cycle every few days [40].
(10) Algae biofuel is non-toxic, contains no sulfur, environmentally
sustainable, highly biodegradable. It reduces emissions of CO,
particulate matter, hydrocarbons and SOx [13].
(11) Reduced pollution, fertilizer use, and nutrient consumption because
of greater light capture and conversion efficiencies [40].
(13) Reduced production cost since cultivation does not require
herbicides or pesticides [39,40].
(14) Completion of carbon cycle every few days via the conversion
of solar energy to chemical energy [40].
(15) Provides the highest net energy, because producing biodiesel
from algae oil requires lesser energy than other methods for
conversion to other fuels [40].
(1) Poor biodiesel performance compared to its mainstream alternative because
of the presence of many polyunsaturates [13,37,38]. Partial catalytic
hydrogenation is used to reduce the number of double bonds [32,35,39].
(2) Relatively new technology [33,36].
(3) Identifying an algal strain with fast growth rate, high lipid content
which is easy to harvest and a cost-effective cultivation system is
difficult [40].
(4) Low acceptability for biodiesel production due to susceptibility to
oxidation during storage.
(5) It is more expensive to cultivate microalgae than oil crops due to
solvent usage, CO2 availability and delivery strategies and high cost
of bioreactors [40].
(6) It is difficult to maintain selected species in outdoors culture systems and
water evaporates easily from the production ponds [40]. To solve this,
extremophiles that can tolerate extreme conditions are grown in open ponds
or photobioreactors that can keep invasive strains out of the reactor are used.
(7) Unwanted algae and other microorganisms easily contaminate cultivation
in large scale microalgae culture systems [40].
(8) Cost implication of harvesting of biomass from microalgae. High energy is
required for the extraction, purification and conversion [40].
(9) Limitations in real systems exposed to sunlight decrease the efficiency to
values of 2–3% of incoming sunlight [13].
(10) Scale-up problems due to temperature sensitivity toward biomass growth,
low light to biomass conversion rate and low lipid content high water
contents [40].

oleoabundans: 54%, Nannochloropsis sp.: 68%, Schizochytrium sp.:
77%, and Botryococcus braunii: 86%) contributed to the present day
crude oil deposits formed millions of years ago [20,48]. Approxi-
mately, 640 billion barrels of crude oil energy equivalent is
released by microorganisms on a yearly basis [49]. Therefore,
considering microalgae as a promising sustainable source of
energy for the future is reasonable. In fact, recent reports have
given inspiring indications toward reduction in the cost of
producing biodiesel from cheap sources such as microalgae by
25% [50]. For comprehensive analyses that combined economic,

Table 2
Comparison of properties of biodiesel from diesel fuel and microalgae oil to ASTM biodiesel’s Standard (D6751-02) [40,41].

Property Method Limits Units Microalgal biodiesel Petroleum diesel

Flash point, closed cup D 93 130 min 8C >160 75

Water and sediment D 2709 0.050 max % volume <0.005 0.05 max vol.%
Kinematic viscosity, cSt at 40 8C D 445 1.9–6.0 mm2/s 4.519–4.624 1.9–4.1
Density – 0.86–0.9 kg/l 0.864 0.838
Sulfated ash D 874 0.020 max wt.% <0.005 0.0015 max
Total sulfur D 5453 0.05 max wt.% 0.6–5.1a –
Copper strip corrosion D 130 No. 3 max (3 h at 50 8C) 1a No. 3 max
Cetane number D 613 47 min – 48–65 40–55
Cloud point D 2500 Report to customer 8C 5.2 to 3.9 35 to 5
Carbon residue D 4530 0.050 max wt.% – 0.05 max %mass
Acid number D 664 0.80 max mg KOH/g 0.022–0.003 0.5 max
Free glycerine D 6584 0.020 wt.% 0.009–0.014b –
Total glycerine D 6584 0.240 wt.% 0.091–0.102b –
Phosphorus D 4951 0.0010 wt.% <0.1a –
Vacuum distillation end point D 1160 360 8C max, at T 90 % distilled – –
Cold filter plugging point – 0 to 15 8C 7 to 2 3 (max. 6)
Solidifying point – – 8C 12 50 to 10
Calorific (heating) value – – MJ/kg 41 40–45
H/C ratio – – – 1.81 1.81
a
ppm.
b
% (m/m).
116 Y.M. Sani et al. / Journal of Environmental Chemical Engineering 1 (2013) 113–121
Table 3
Physicochemical properties of zeolite catalysts [65].
Sample SBET(m2/g) SEXTa (m2/g) Vpore (cm3/g)
ZSM-5 431 78 0.6234
h-ZSM-5 696 456 0.8725
Beta 599 87 0.4316
h-Beta 725 287 0.6451
a
SEXT = SBET Smp, Smp and Vmp obtained by NLDFT over Ar isotherm.
b
ICP-AES.
c
From NH3-TPD measurements.
energetic and environmental aspects of the energy balance and
production costs of biodiesel from algal oil, we refer the reader to
[51,52]. For brevity however, it suffices to state that the conflicting
estimates such as 1.08 s/L [41], 1.06 s/L [53], 2.00 s/L and
4.17 s/L for open pond [54] and 1.39 s/L [41] and 7.44 s/L for
photobioreactor (PBR) systems [55] are mainly due to methodo-
logical differences used in the modeling assumptions, scope and
system boundaries [53,56,57].
Issues surrounding conventional transesterification processes
Fatty acid methyl ester (FAME) or biodiesel is mostly produced
from vegetable oils or animal fats [58]. This involves catalytic
transesterification of triglycerides (TGs) with alcohol and a
catalyst. Homogeneous alkaline catalysis received wide accept-
ability because of its fast reaction rates. However, raw material and
production costs are hindering this biodiesel production technol-
ogy. Most available feedstocks contain water and FFAs. The water
hydrolyzes the TGs into new fatty acids and diglycerides. This leads
to the formation of stable emulsions and saponification. Further-
more, the soaps dissolve into the glycerol phase during the
separation stage owing to their polarity [59]. As a result, the
solubility of the methyl esters into glycerol increases. This reduces
the biodiesel yield as it gets entrapped in the soap phase during
washing while separation and purification becomes difficult and
expensive. Likewise, feedstocks that contain high amounts of FFAs
need to be pretreated to contain as low as 0.5% FFAs prior to the
transesterification process.
These requirements restrict the range of feedstocks employed
for the homogeneous alkaline catalyzed-transesterification pro-
cesses. Cheap and readily available feedstocks such as used
cooking oil are only used after pretreatment. Furthermore, the
wastewater generated from the alkaline-catalyzed processes
causes environmental problems while loss of catalysts from the
homogeneous processes poses financial glitches. Thus, this method
is not cost-effective when compared with petroleum diesel
[20,48,49]. Other methods of transesterification include the use
of homogeneous acids, enzymes and supercritical process [5,58–
62]. However, limitations in commercializing these methods led
many researchers to explore the solid acid catalysts. Unlike
heterogeneous and homogeneous base, solid acid catalysts can
effectively carry out the simultaneous esterification and transes-
terification of high FFA-containing feedstocks. They offer economic
benefits because the saponification and post production problems
are minimized. Solid acid catalysts are also easily separated,
readily regenerated and recycled [63].
Solid acid catalysts used in microalgal oil biodiesel production
As earlier stated, in order to achieve commercial production
that will sustainably meet the global biodiesel demands, raw
materials such as microalgae and other affordable renewable
feedstocks are required [38,50,64]. The production process must be
efficient and affordable. In the same line, Carrero et al. [65] recently
produced biodiesel from oleaginous Nannochloropsis gaditana (one
Vmpa (cm3/g) Si/Alb Tmaxc (8C) Acidityc (mmol/g)
0.2031 31 357 0.4259
0.1334 32 329 0.3303
0.3039 27 321 0.4434
0.2600 28 316 0.4236
of the most suitable microalgal oil sources) using hierarchical Beta
(h-Beta) zeolites and ZSM-5 (h-ZSM-5). The authors were able to
prepare hierarchical zeolites with similar physicochemical prop-
erties to conventional zeolites (Table 3). They found out that
incorporating organosilane anchored on the zeolite seeds en-
hanced the textural properties of the catalysts. However, higher
catalytic activity was observed from h-Beta than h-ZSM-5. The
authors attributed the lower activity of h-ZSM-5 to the narrow
pore structures which hindered diffusion of the microalgal oil to
the active sites of the catalyst.
Increase in the external surface area was reported as silaniza-
tion agent was increased while seed silanization treatment
enhanced the secondary porosity in micro-mesopores range. As
a result, the h-Beta catalyst retained most of its acid strength and
acid site population while both properties were decreased for h-
ZSM-5. In addition, h-Beta zeolite had the highest BET surface area,
while h-ZSM-5 had the highest values of external surface (with
lower acid sites population of 0.33 mmol/g). This is another reason
why the activity of h-ZSM-5 was low for biodiesel production [63].
Similarly, earlier investigation by Giannakopouloua et al. [66]
showed that the selectivity and activity of h-ZSM-5 and h-Beta
depend on the method of preparation. Consequently, their report
showed that h-ZSM-5 had better activity than the h-Beta zeolite.
Though the authors [65] alluded to how the catalyst activity
was affected by temperature and structure/surface area, the report
did not elaborate further regarding the acid site population. It is
important to mention here that the catalytic activity of any catalyst
is expressed by its turnover frequency (TOF). Whereas, reaction
conditions such as pressure, temperature, concentration of the
reacting species, catalyst structure and concentration determines
the value of TOF [67]. Therefore, the observed activity might have
been due to other parameters like the number of active sites,
possible reactions between the active sites, defects, framework
density and the Si/Al ratios of the zeolites vis-à-vis hydrophobicity
in addition to those mentioned by the authors [67]. Moreover, the
surface acidity of zeolites changes depending on the Si/Al ratio
[65,68,69]. On the other hand, though the secondary porosity
provides enhanced accessibility which improves the catalytic
activity of the hierarchical zeolites, nonetheless it has some
negative effects that need further studies. This is because it can
create discontinuity within the catalyst framework which leads to
lower shape-selectivity, confinement effects, lower acidity, hydro-
thermal stability and hydrophilic/hydrophobic property than are
obtainable from the conventional zeolites [70].
Verma et al. [71] also developed hierarchical mesoporous
catalysts with tunable properties such as zeolitic acidity, porosity
and crystallinity. Control of the various properties was achieved by
manipulating the concentration of the mesopore-template in the
synthesis gel. The researchers were successful in tailoring a single-
step process for hydroconverting TGs and FFAs from algae into
aviation biofuel. The sulfided catalysts were used in a fixed trickle
bed reactor for the reaction. A yield of 54% for jet range
hydrocarbons was obtained when ZSM-5 with higher surface area
and acidity (but lower crystallinity) was employed. The reported
high yield and selectivity were attributed to the balance between
 Y.M. Sani et al. / Journal of Environmental Chemical Engineering 1 (2013) 113–121
the cracking functionalities of the catalyst to the hydrogenation
process. Similarly, higher yield of 77% and conversion of 99% were
achieved from the microalgal oil when acidic Ni–Mo catalyst
anchored on high surface area semi-crystalline (HSASC) support
was used.
The effect that acidity and structure of a catalyst support have
on product yields and conversion were demonstrated by [71]. Solid
acid catalyst support matrix can sterically hinder the solvation of
the catalyst active sites due to the action of water. Also, the support
has the potential to minimize lower reaction rates caused by mass
transfer (diffusion) limitations because more pores (especially the
micropores) and channels are made accessible to the reacting
species [72]. The authors also observed that the yield of the jet
biofuel increases with increase in temperature while maximum
selectivity was obtained at 420 8C. This further confirmed earlier
report that the maximum temperature dependency of C12 isomer
selectivity is at 410 8C [71]. The enhanced selectivity (fine-tune
adsorption) was probably due to the modulation of the strong
electric fields created by the loosely held cations which have the
ability to preactivate the reactants within the catalyst framework
[73]. Furthermore, the catalysts were regenerated at 450 8C in
steam air and reused after resulfidation and they showed no
significant decrease in performance [71].
The potential of amorphous carbon bearing sulfonic acid groups
(a solid Brønsted acid catalyst) was also demonstrated in the
production of biodiesel from biomass [74]. The catalyst was
prepared in two ways: (a) by sulfonating incomplete carbonized
organic matter and (b) by the incomplete carbonization of
sulfopolycyclic aromatic compounds in concentrated H2SO4 [75].
The catalysts showed comparable Hammett function to concen-
trated H2SO4 with H0 = 8 to 14. This acidity value is higher than
that of conventional sulfonated polystyrene-based resins
(H0 > 3). The author theorized that the presence of three
different functional groups (SO3H, COOH and phenolic OH) and
the strong linkage between the hydrogen and SO3H groups (which
leads to mutual electron-withdrawal) in the catalyst gave rise to
the observed high acidity. This explains why the catalytic
performance of the carbon-based acid catalysts exceeded that of
conventional solid Brønsted acid catalysts, such as Amberlyst-15,
niobic acid (Nb2O5
nH2O), and Nafion NR50. The catalytic activity
of the carbon-based acid catalyst is ca. 60% that of concentrated
H2SO4 [76]. The catalyst activity was retained even after
regenerating (washing with water and drying at 103 8C) and
reusing ten times [74]. The fact that the composition of microalgal
fatty acid also contains high proportions of oleic acids (58–60 wt/
total lipid) [77] indicates the potentials of solid acid catalysts such
as the amorphous carbon bearing sulfonic acids to catalyze the
transesterification of microalgal oil for biodiesel production.
Reyes et al. [78] achieved enhanced conversion of 94.27% by
using 10% niobium oxide powder (HY-340) with 90m2/g surface
area in hydroesterification (hydrolysis followed by esterification)
process. They employed Monoraphidium contortum (MORF-1)
microalgal biomass for the in situ methanol hydrolysis reaction.
The reactions were carried out with excess alcohol molar ratio
(30:1) at 200 8C, under 1 h reaction time and 500 rpm agitation.
This procedure has the potential to achieve radical innovations and
compliment the conventional transesterification process. It has
significant economic benefits since it favors the use of feedstocks
with high acidity and moisture contents and may be performed
with heterogeneous acid catalyst, which favors high conversions in
a small range of time (30 min). In addition, hydroesterification
with heterogeneous acid catalyst has the potential to produce
biodiesel directly from wet biomass, eliminating the lyophilization
and oil extraction processes. Furthermore, no glycerol was formed
during the reaction and the catalysts were recovered by filtration
[78]. Despite the promising potentials of this process, it is pertinent
117
to suggest the need for further research that will take into
cognizance the reaction mechanisms and kinetics in relation to the
catalyst TOF.
The foregoing highlights that the reaction conditions such as
time, temperature, oil to alcohol ratio and other parameters such as
microalgal oil source and acid strength of the catalyst determine
the production of the alkyl esters [80,81]. Therefore, in order to
develop the much needed suitable solid acid catalysts for
microalgal biodiesel, proper understanding of the reaction
mechanisms and kinetics for a given set of reaction conditions
is important [26,82]. According to Di Serio et al. [26] the
mechanism of heterogeneous catalysis is similar to that of acid
or base homogeneous catalysis. The surface of the solid catalyst
adsorbs the TGs in the liquid phase via protonation of the carbon
from the carbonyl group prior to the attack by the alcohol
molecules [83,84]. However, the mechanism of the solid acid
catalysis is still opened to further studies as to whether it is based
on Lewis or/and Brønsted solid acids [84]. Besides, two solid acid
catalyzed reaction mechanisms were proposed for the esterifica-
tion and transesterification reactions—the single-site or the Eley–
Rideal type and the dual-site mechanisms or the Langmuire–
Hinshelwood model. The Eley–Rideal (ER) type reaction mecha-
nism theorizes that single-active-site adsorbs and protonates the
carboxyl of the TG and hence facilitates the nucleophilic attack by
the unadsorbed alcohol in the liquid phase. Whereas the
Langmuire–Hinshelwood (LH) model hypothesizes that both the
alcohol and the TG are adsorbed by the active sites of the catalyst
where the reaction occurs [84,85].
In addition, the type of alcohol used also influences the reaction
mechanism as catalyzed by the solid acid catalysts. Generally,
biodiesel is produced from TGs and low carbon alcohols such as
methanol and ethanol which follows the ER type reaction
mechanism. Aside the availability and cheaper nature of these
reactants, another plausible explanation for their acceptability is
the ease with which they carry out the nucleophilic attack [86].
Conversely, higher carbon alcohol prefers the LH model [84]. Thus
as it was earlier mentioned, more studies are required to elucidate
more on this subject because it is possible for both mechanisms to
operate in parallel within the same reaction [87].
Biodiesel yields from heterogeneous acid-catalyzed microalgal oil
The FAME yields obtained by Carrero and co-researchers [65]
from the h-Beta zeolite-catalyzed production were not high.
Nonetheless, their findings further prove the potentials of solid
acid catalysts for biodiesel production. This is because the general
reports on the activity of zeolites used in the production of
biodiesel have been averagely lower compared to others such as
superacids and hetropolyacids catalysts [88]. Usually, higher
temperatures of >350 8C are required for heterogeneous acid
catalysts [80,89–91]. Nonetheless, the authors were able to obtain
promising results at lower reaction temperatures (115 8C) for the
solid acid catalysts [65]. This lower temperature requirement
implies lower energy consumption. In addition, their results
corroborated previous report that higher activities with zeolitic
catalysts require larger channels and pores.
High selectivity and yields which were attributed to the desired
balance between the cracking functionalities and the hydrogena-
tion of the catalyst were obtained by Verma et al. [71]. These high
yields obtained further illustrate the promising potentials of
producing microalgal biofuels by utilizing solid acid catalysts. One
excellent breakthrough in the production of biodiesel from algae
was demonstrated by the Mcgyan1 process [38,50]. The process
illustrated the role of alcohol supercritical conditions (ca. 2500 psi
and 300–450 8C) to achieve ultrafast reaction residence time of
30 s and how heterogeneous catalysis aided in the biodiesel
118 Y.M. Sani et al. / Journal of Environmental Chemical Engineering 1 (2013) 113–121

Table 4
Different heterogeneous acid catalysts used for biodiesel production of algal oils and cellulosic biomass.

Feed oil Catalysts Temperature (8C) Pressure Conversion (%) Yield (%) References

(a) Algae oil 4% NiO, 18% MoO3/Al2O3 370 5000 kPa 99 12 (C9–C15) [71]
(b) Product from (a) 0.75% Pt-SAPO-11 375 1000 kPa 83 32.8 (C9–C15) [71]
(c) Algae oil 5% NiO, 18% MoO3/H-ZSM-5 410 50 kPa 98 78.5 (C9–C15) [71]
(d) Kelp Microporous titania 360 15824.03 kPa 94.7 85.5 [38]
(e) Wild algae Microporous titania 340 15513.78 kPa 31.0 84.4 [38]
(f) Algae oil (Monoraphidium (HY-340) niobium oxide 200 20684.27 kPa 94.27 Not reported [78]
contortum)
(g) Oleic acid (fresh; 4 h) Carbon-based solid acids 95 Not reported Not reported 99.9 [74]
(h) Oleic acid (2nd run; 4 h) Carbon-based solid acids 95 Not reported Not reported 99.8 [74]
(i) Oleic acid (3rd run; 4 h) Carbon-based solid acids 95 Not reported Not reported 99.6 [74]
(j) Triolein (fresh; 5 h) Carbon-based solid acids 103 700 kPa Not reported 98.1 [74]
(k) Triolein (4th run; 5 h) Carbon-based solid acids 103 700 kPa Not reported 95.5 [74]

production. The yields were enhanced from 14.1% (uncatalyzed) to
95% with the aid of heterogeneous catalysts such as acid modified
titania microspheres [8,50]. The presence of the catalyst is
necessary to increase transesterification reaction yield as well as
the reaction rate [92]. Conversions as high as 86% to 95% were also
obtained from high FFAs feedstocks such as algae oil, yellow grease
and acidulated soapstock. Similarly, the simultaneous esterifica-
tion and transesterification of TGs and FFAs was achieved under
residence time of 5.4 s via supercritical conditions and heteroge-
neous catalysis [50]. It is evident from these studies that a
multifaceted experimentation has higher prospects of achieving
the much needed biodiesel prominence. Different reaction
conditions, conversions and yields obtained from some selected
heterogeneously catalyzed reactions are presented in Table 4.
The dual advantage: potentials of heterogeneous acid-catalyzed
microalgal biodiesel production
We have shown from the previous section, instances discussing
some of the specific potentials of solid acid-catalyzed microalgal
oil biodiesel for production. This section elucidates further the
general advantages of these catalysts that make them attract
greater attention for the transformation of microalgal oil. These
include amongst others: (1) their high catalytic activities and
specific selectivity with higher conversions. (2) Simultaneous
esterification of fatty acids and transesterification of TGs. (3)
Insensitive to high FFAs and water contents of the oil (preference
for low-grade feedstocks). Also, the support matrix of solid acid
catalysts can sterically hinder solvation of the active sites from the
action of water. This leads to minimized deactivation of the
catalyst active sites [72,94–97]. (4) Less susceptible to leaching. (5)
Ease of separation from products. (6) Catalysts can be reused and
regenerated many times [92,93]. (7) Economic viability due to
their hydrophobic surfaces, large pores, numerous strong acid sites
and high stability [98]. Consequently, the dual advantage
distinctive of microalgae (daily mass production of oil) and those
highlighted for solid acid catalysts will no doubt enable competi-
tive biodiesel productions which will significantly reduce the
world’s dependence on fossil fuels.
For instance, the high FFAs in many microalgae [acid number
(mg KOH): Nannochloropsis oculata = 83.4012, wild al-
gae = 102.5237, Dunaliella tertiolecta = 167.2505 and Dunaliella
tertiolecta (crude) = 117.7146] limits the suitability of convention-
al catalysts [99]. Any attempts to refine the high FFA content only
increases the market price of the oil (sold at USD 5/L against USD
3.69 to USD 4.20 for diesel) [100]. Some of the heterogeneous acid
catalysts that have been investigated for biodiesel production
include ion-exchange resins and membranes [101], tungstated and
sulfated zirconia (superacid catalysts with acid strength stronger
than 100% H2SO4; H0  12) which gives more conversion rates
and still remain active in the high FFA oils [100–111], hetropo-
lyacids [102,110,111] and metal oxides [112–116].
Issues surrounding solid acid catalysis
In spite of the numerous advantages and encouraging results
obtained from solid acid-catalyzed biodiesel production, techno-
logical innovations are still required. This is because despite
efforts in the past decade, industrial esterification of fatty acids
with solid acid catalysts is yet to be fully established [50,93]. It is
therefore pertinent to underline some challenges that require the
attention of the scientific communities. Major among these
include: (a) the difficulties in calculating the number of active
sites, determination of reaction rates and TOFs. Solving these
issues will enable the reproducibility of experiments by other
researchers and hence, discerning strategies for further catalyst
development [79]. (b) Low reaction rates of most solid acid
catalysts compared to those obtainable from their homogeneous
counterparts. (c) Complex procedures involved in the develop-
ment of many solid acid catalysts. (d) Poor thermal/hydrothermal
stability and lower acid strength observed with ion exchange
resins and other mesostructured materials [69,92]. (e) Mass
transfer limitations involving bulky molecules which lead to poor
activities for biodiesel production with microporous zeolites [88].
(f) The development of catalysts that can selectively disrupt the
functional group(s) and/or break specific chemical bonds from
biomass to facilitate the transesterification process [117]. These
challenges await the ingenuity of the researchers to provide more
affordable solid acid catalysts.
Future prospects and challenges
As highlighted, the possibility of a sustainable biodiesel
production from microalgal oil is beyond speculations [48,53].
Nonetheless, ensuring microalgal biodiesel competitiveness with
petroleum diesel requires that the price of the former to be less
than s0.30/L [41,43]. This projected target of rapid energy growth
at affordable costs will only be achieved through continued policy
supports and technological advancements [46]. These include: (1)
the establishment of proficient systems for the production of vast
quantities of feedstocks at affordable costs. In this regard,
maintaining optimum growth conditions (such as light intensity,
CO2 partial pressure, concentration of nutrients, pH, temperature
and agitation) specific to each type of microorganism is critical to
maximizing biomass yield/unit area of microalgal culture [34]. For
instance, a significant percentage of the Isochrysis total lipid extract
(TLE) of the microalgal oil is formed by alkenones. These
components are not chemically affected by transesterification
and pose detrimental effects to the quality of biodiesel [13,118–
120]. (2) Design and development of novel and affordable catalysts
 Y.M. Sani et al. / Journal of Environmental Chemical Engineering 1 (2013) 113–121
with higher activities which can produce greater yields in shorter
time with lesser refining difficulties. (3) Development of innova-
tive means for separating and refining crude biodiesel. (4)
Enactment of policies that favor biodiesel production. (5)
Minimizing costs, energy and water usage by implementing the
excellent findings from the research communities [5,10,14,121].
These will definitely reduce the current estimated costs of
microalgal biomass production which are three order magnitude
(PBR: 23.08–53.85s/L) and two order magnitude (open ponds:
7.69s/L) higher compared to the conventional seed crops [41,43]
and hence, the overall biodiesel production costs.
A vital means of solving some of the aforementioned
challenges of microalgal oil supply is advances in biotechnology.
Genetic modifications of the metabolic pathways of marine
microalgae can efficiently produce high-value products while
avoiding the excessive accumulation of toxic metabolites [122–
127]. Moreover, these organisms could be genetically modified to
produce more oil from their energy storage mechanism without
ethical debates [128]. Recently, different levels of branching and
molecular weights of easily separable fatty acid-derived hydro-
carbons (HCs) which are adequate for diesel and jet fuel
applications have been produced in large scales. Also, alkanes
have been synthesized from microalgae without carbon source
except CO2 via direct phototropic technologies [129]. The
knowledge from the responses of microorganisms was success-
fully utilized to manipulate the accumulation of lipids during cell
cultures [120,130–133]. Also, cheaper, ultraclean and more
abundant biomass for producing biodiesel free of aromatics has
been reported. This methodology simplifies product purification,
reduces costs and fulfills the strict standard requirements for
diesel fuels [55–58]. It is therefore plausible to assert that a cost-
effective production of microalgal oil for industrial application is
imminent.
Conclusion
In recent years, microalgae have been attracting increasing
interests as feedstock for biodiesel production due to compelling
evidence of its significant potentials in reducing particulate
emissions and solving the energy problems. In the same respect,
the potentials of heterogeneous acid catalysts over conventional
ones have become evident. Hence, this article presented
instances discussing the advantages of solid acid-catalyzed
microalgal biodiesel to inspire radical innovations regarding
same. The following conclusions are made from the present
study:
1. Though some engines currently run on blended diesel, the cost
of producing biodiesel from energy crops is still high.
2. Oil from microalgae can sufficiently provide the feedstock to
provide the required global energy security at affordable price
and reduced environmental impacts.
3. Several efforts are currently targeted toward the reduction of
biodiesel production costs by harnessing the numerous
advantages of microalgae and solid acid catalysts. These include
microalgae genetic engineering, valorization of microalgal oil
coproducts, development of novel solid acid catalysts and
governmental policies.
4. Interestingly, about 25% reduction in cost of biodiesel produc-
tion from microalgal oil have been predicted. Solid acid-
catalyzed microalgal-biodiesel is thus on its way to becoming
the ideal process for the future.
5. In order to reap the dual advantages from the fast growth rates
and high lipid contents of microalgae and the effective
transesterification of solid acid catalysts, new advances must
be established.
119
Conflict of interest
There are no known conflicts of interest associated with this
publication.
Acknowledgement
This study was carried out with the aid of a research grant from
High Impact Research (HIR-MOHE) Grant (No: D000011-16001)
under University of Malaya.
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