Rev Environ Sci Biotechnol

DOI 10.1007/s11157-014-9359-x

REVIEWS

Advanced biodiesel production technologies:

novel developments
Gonçalo Lourinho • Paulo Brito

Ó Springer Science+Business Media Dordrecht 2014

Abstract Biodiesel, i.e. a mixture of monoalkyl establishment of these technologies, calling for the
esters of long chain fatty acids derived from renewable development of novel methods to intensify the process.
biological sources such as vegetable oils has in recent These process intensification technologies include
years emerged as an alternative fuel for transportation ultrasound irradiation, microwave heating, use of co-
sector. The conventional method of producing biodie- solvents, and membrane reactors. The main focus of
sel is through homogeneous catalytic transesterifica- this review is to discuss recent advances as regards to
tion; however, increased production costs associated biodiesel production technologies, devoting a special
with downstream purification steps have led to the attention to the use of novel catalysts, diversified
development of more cost-effective and environmental feedstocks, besides an analysis of main operational
friendly technologies. These advanced production parameters of transesterification processes.
technologies involve heterogeneous or enzymatic
catalysts to produce biodiesel, as well as no catalysts Keywords Biodiesel Transesterification
in supercritical conditions. Heterogeneous catalytic Heterogeneous catalysis Enzymatic catalysis
systems can ease the separation of biodiesel from the Supercritical transesterification Process
reaction mixture along with the possibility of catalyst intensification technologies
recovery, potentially leading to lower production
costs; enzymatic catalysts give the same advantages,
but transesterification can be carried out in milder
conditions and with a wider range of feedstocks. 1 Introduction
Biodiesel synthesis in supercritical conditions com-
poses another alternative to conventional methods due During the past decades environmental problems due
to higher reaction rates, shorter reaction times, and to the widespread use of fossil fuels have increased the
simpler biodiesel separation steps. Nevertheless, mass awareness for cleaner and alternative production
transfer limitations caused by diffusion problems technologies in the industrialized world. Currently,
between phases represent an hindrance for future transportation sector in the European Union (EU)
accounts for more than 30 % of the total energy
consumption and mainly depends on the use of these
G. Lourinho (&) P. Brito fuels (particularly petroleum) which are known to be
C3i (Interdisciplinary Coordination for Research and
sources of pollutant emissions and are thought to be
Innovation), Polytechnic Institute of Portalegre, Lugar da
Abadessa, Apartado 148, 7301-901 Portalegre, Portugal unsustainable due to their dwindling reserves (Euro-
e-mail: [email protected] pean Commission and Eurostat 2013). Therefore, the

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need for developing a clean and renewable diesel fuel 2012); it contains virtually no sulphur; it has a lower
substitute is present and has drawn extensive attention overall emission profile, a superior flash point, and
and interest within the scientific community. Liquid higher combustion efficiency. In addition, it is safe,
biofuels are believed to be a sustainable (renewable) renewable and can be used without modifying existing
and economically promising option to at least com- engines (Helwani et al. 2009; Banković-Ilić et al.
plement petroleum diesel. 2012; Abbaszaadeh et al. 2012; Aransiola et al. 2014).
Policy drivers have supported the use of biofuels At present, the main obstacle in widespread
such as biodiesel in European countries by approving production and commercialization of biodiesel is its
several target-oriented regulations and instruments. In production cost (Abbaszaadeh et al. 2012). As a
2009, a major EU policy package known as the 2020 consequence, extensive research has been carried out
strategy (European Parliament 2009) was adopted and on the use of different methods and technologies for
established a mandatory target of at least 10 % of the biodiesel production. There are four primary methods
energy consumed in the transportation sector to come of biodiesel application: direct use of vegetable oil,
from renewable sources in 2020. As a result, biofuels microemulsion, thermal cracking, and transesterifica-
consumption growth was firm in the European Union tion (Ma and Hanna 1999; Helwani et al. 2009;
since 2009 increasing by almost 19 % to reach 14.4 Abbaszaadeh et al. 2012; Aransiola et al. 2014). From
Mtoe by the end of 2012 (EurObserv’ER 2013). those mentioned, the most common process used to
Biodiesel alone made up to about 79 % of total increase the quality of the fuel in biofuel industry is
biofuels capacity in that year, most of it produced from transesterification. Transesterification is the process of
rapeseed oil followed by soybean and palm oil. The using an alcohol (e.g. methanol, ethanol) to chemi-
total share of biofuels in fuel consumption of EU cally break the molecule of the renewable lipid
transportation sector amounted to approximately 4.7 % feedstock into methyl or ethyl esters (biodiesel) with
in 2012, with member states like Germany, France, glycerol as the only by-product (Demirbaş 2003)
Spain, Italy, Poland, and the United Kingdom repre- (Fig. 1a). The reaction mechanism is shown in Fig. 1b
senting more than 70 % of the market (EurObserv’ER and consists of a number of consecutive and reversible
2013). As of today, the role of Portugal in the European reactions where 1 mol of acylglycerols reacts with
biofuel scenario is still somewhat limited; however, 1 mol of alcohol and 1 mol of ester is formed at every
boosted by the aforementioned European policies the step. Catalysts are usually used to improve transeste-
country has recently seen a sustained growth in its rification rate and product yield as they are able to
consumption and production capacity. Total consump- solve the two-phase nature problems between triglyc-
tion reached 3.3 Mtoe in 2010, but biodiesel sales fell erides and alcohol, but reaction can still occur in the
in 2011 and 2012 as a consequence of the uncertain absence of a catalyst (usually in supercritical condi-
political and economical context the country was going tions) (Abbaszaadeh et al. 2012). Thus, transesterifi-
trough (EurObserv’ER 2013). In fact, uncertainties cation reaction can either be non-catalyzed or
surrounding political and economical stability pose a catalyzed by homogeneous, heterogeneous or enzy-
challenge not only to Portugal but to the whole biofuel matic catalysts (Banković-Ilić et al. 2012). A com-
production and distribution chain within the EU, as parison between the different types of catalysts for
European policy makers try to revitalize the biofuel biodiesel production is presented in Table 1.
market while maintaining specific sustainability As of today, homogeneous catalysts show great
requirements in response to criticisms related to their performance in obtaining biodiesel (both kinetically
environmental impact and food chain competition. and economically) and are universally used in the
Biodiesel can be defined as a mixture of monoalkyl industry despite having some important disadvan-
esters of long chain fatty acids (FAME) derived from tages. The typical problems associated with the
renewable biological sources such as vegetable oils, homogeneous catalysts are high consumption of
animal fats, waste cooking oil, and algae oil (Demirbas energy, saponification by reaction of FFAs, expensive
2002; Banković-Ilić et al. 2012; Yan et al. 2014). As a separation of the catalyst from the reaction mixture
fuel, biodiesel has many benefits over petroleum and generation of large amounts of wastewater during
diesel: it is biodegradable up to four times faster than purification of biodiesel (Vyas et al. 2010). In Fig. 2 a
his petroleum counterpart and non-toxic (Tariq et al. general process flowsheet of homogeneous catalytic

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Fig. 1 a General equation

of transesterification.
b Basic reaction mechanism
for transesterification of
vegetable oils
(triglycerides); R, R1: alkyl
groups with generic
complexity

Table 1 Comparison between homogeneous, heterogeneous and enzymatic catalysts to produce biodiesel (Helwani et al. 2009; Juan
et al. 2011)
Variable Homogeneous catalyst Heterogeneous catalyst Enzymatic catalyst

Reaction rate and Ester yield Fast and high conversion Moderate conversion Slow but higher conversion
Purification process Difficult Easy Easy
Methodology Limited used of continuous Continuous operation Continuous operation
methodology possible possible
Presence of high FFA and Sensitive Not sensitive No influence
water
Catalyst reusability Not possible Possible Possible
Cost Cheap (but comparatively costly) Potentially cheaper Relatively expensive

transesterification is presented (West et al. 2008). In Since transesterification is an equilibrium reaction, it

fact, biodiesel purification steps and other by-products is difficult to drive the reaction to complete conversion
processing compose one of the main challenges faced of triglycerides and some downstream processing to
by conventional biodiesel production technologies. remove impurities such as residual glycerol, water,

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Fig. 2 General process flowsheet of alkali homogeneous catalytic transesterification (West et al. 2008; Ravindra et al. 2012)

soap, excess catalyst, and unreacted oil from the final instead of the conventional homogenous transesterifi-
product prior to any commercial use is inevitable. For cation which typically uses NaOH and KOH as
that matter, there is a growing research effort going on catalysts. In addition, a special attention will be given
around the world to develop more competitive tech- to other process intensification methods that have
nologies for biodiesel production that will not give rise shown high potential in solving some phase miscibil-
to challenging environmental problems and costly and ity problems associated with these technologies such
time consuming purification steps. On the other hand, as ultrasonic technology, microwave irradiation, co-
improved overall biodiesel processing can also be solvent, and membrane reactor.
achieved by enhancing biodiesel and glycerol separa-
tion procedures. Gravitational settling is often used as
the first pre-treatment step to separate biodiesel/ 2 Heterogeneous catalytic transesterification
glycerol mixture given the density difference between
the two phases; however, long decantation times are Heterogeneous catalysts are widely known as a prom-
generally required which lead to losses as regards to ising and attractive solution for the transesterification of
process profitability. Recently, some novel strategies vegetable oils to produce biodiesel (Zabeti et al. 2009;
for economizing biodiesel production costs by accel- Semwal et al. 2011; Santacesaria et al. 2012). Unlike
erating biodiesel/glycerol separation have been sug- their homogeneous counterparts, heterogeneous cata-
gested with promising results. Shirazi et al. (2013), for lysts act in a different phase from the reaction mixture
example, introduced NaCl-assisted gravitational set- and have the advantage of easy separation of the
tling as a beneficial strategy to accelerate the biodie- biodiesel and recovery and reuse of the catalyst,
sel–glycerol separation (Shirazi et al. 2013; Noureddin potentially leading to higher efficiencies and lower
et al. 2014). Based on the results obtained in this study, production costs (Vyas et al. 2010; Abbaszaadeh et al.
1 g NaCl/100 mL glycerol–biodiesel mixture was 2012). A biodiesel synthesis by using solid catalysts is
found as the most efficient quantity of salt to be added therefore environmentally friendly and does not imply
decreasing decantation times by 100 %. the consumption of large amounts of water during
The main focus of this paper will be devoted to the purification of biodiesel (Banković-Ilić et al. 2012).
technologies believed to be the future technologies of However, a major drawback of using heterogeneous
choice in biodiesel industry due to its potential higher catalysts to produce biodiesel must be pointed out: the
efficiency and profitability such as heterogeneous, slower transesterification rate caused by diffusion
enzymatic, and supercritical transesterification, problems. This limitation is commonly associated with

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the three-phase system (oil-alcohol-catalyst) of the based compounds such as Ca-glyceroxide and Ca-
reaction mixture and can be minimized using technol- glycerolate. The reaction was carried out with a 12:1
ogies described later in this review, like microwave and molar ratio in the presence of 2.0 % (w/w) Ca-
ultrasound systems (Leung et al. 2010; Banković-Ilić glyceroxide and an ester yield of 83.4 % was reported
et al. 2012). Moreover, a complex catalyst preparation, a after 2.0 h of transesterification. Nevertheless, for
high molar ratio of alcohol to oil, a large amount of identical experimental conditions, using Ca-glycero-
catalyst, as well as high temperature and pressure are late as catalyst resulted in a ester yield of just 29.9 %
also typically required when obtaining biodiesel by confirming that Ca-glycerolate exhibits less basic
using heterogeneous catalysts (Zabeti et al. 2009). strength, basicity and specific surface area than Ca-
Figure 3 presents a general process flowsheet of heter- glyceroxide (Reyero et al. 2014). Both novel catalysts,
ogeneous catalytic transesterification (West et al. 2008). however, showed inferior performance when com-
The catalytic activity of a heterogeneous catalyst mainly pared with pure CaO. Apart from that, application of
depends on its nature, specific surface area, pore size, CaO supported on several materials such as zeolites
and volume and active site concentration (Banković-Ilić have also appeared. Wu et al. (2013), for example,
et al. 2012). Heterogeneous catalysts comprehend a reported that NaY zeolite loaded with CaO showed
great variety of materials including both acidic and high catalytic activity for the transesterification of
alkaline solids such as earth metal oxides (MgO, CaO) soybean oil with methanol. The supported CaO
and other single metal oxides (SnO2, ZnO, CeO2), catalyst was prepared by microwave radiation fol-
mixed metal oxides, zeolites, Al–Mg hydrotalcites, lowed by calcination at a high temperature in air in an
zirconium oxides, tin oxides, etc. (Romero et al. 2011; attempt to increase the catalytic activity of pure CaO
Tariq et al. 2012). for the transesterification reaction. Under the optimal
Among base heterogeneous catalysts, calcium- conditions, a biodiesel yield of 95.0 % was achieved
based ones have been the most studied for biodiesel after 3 h, with a catalyst amount of 3.0 % (w/w), a 9:1
production because they are cheap, can be reused molar ratio, and a reaction temperature of 65 °C (Wu
several times, have higher activity, and require only et al. 2013). In general, these supported CaO catalysts
mild reaction conditions (Helwani et al. 2009). In this show a superior catalytic performance compared with
respect, novel calcium compounds have provoked a unsupported ones, a result attributed to the positive
considerable interest in recent times. Reyero et al. effect of the chemical and textural properties of the
(2014), for example, have investigated transesterifi- supports on the dispersion of CaO nanoparticles
cation of sunflower oil over a series of novel calcium- (Reyero et al. 2014).

Fig. 3 General process flowsheet of acid heterogeneous catalytic transesterification (West et al. 2008)

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On the other hand, some zirconia supported solid conventional homogeneous catalysts. All metal oxides
acid catalysts have also been proposed for the except MgO and ZnO have good catalytic perfor-
transesterification of vegetable oils due its strong mances and achieve high biodiesel yields at moderate
surface acidity. reaction temperature (between 60 and 70 °C with
In this regard, Zhang et al. (2013) recently evalu- CaO–CeO mixed oxide requiring 110 °C). In com-
ated the catalytic performance of chlorosulfonic acid parison, solid acid catalysts generally require higher
modified zirconia (HClSO3–ZrO2) in simultaneous temperatures to give biodiesel yields in the same
esterification and transesterification of crude rice bran percentage range but can convert very low grade
oil [refined oil with 40 % (w/w) FFA] for biodiesel (inexpensive) feedstocks into biodiesel. Furthermore,
production with interesting results. The catalytic it can also be observed that hydrotalcites and zeolite
stability, FFA and water tolerance of modified zirconia supported catalysts showed high catalytic perfor-
catalyst were also investigated. The authors found that mances establishing two other optimistic routes to
HClSO3–ZrO2 is a robust and durable catalyst and find an ideal heterogeneous catalyst to replace homo-
maintains high activity even in the presence of FFA geneous ones for biodiesel production. Therefore,
and water with conversion yields above 92.0 % for at these novel heterogeneous catalysts, especially if
least three cycles under mild conditions [12:1 molar derived from natural materials instead of chemical
ratio, 6.0 % (w/w) catalyst, 120 °C and 12 h] (Zhang sources, should be fully explored on behalf of the
et al. 2013). The results indicate that enhancing the development of new biodiesel production solutions
acidity property of ZrO2 with acidic solutions can give that take into account all the necessary economic and
promising results in terms of catalytic stability and environmental considerations.
catalytic activity for a wide range of feedstocks,
including low-grade ones.
Despite the weak basic strength and inferior cata- 3 Enzymatic catalytic transesterification
lytic performance of MgO in transesterification reac-
tion at moderate conditions (Lam et al. 2010), mixed The search for novel approaches for biodiesel produc-
magnesium–aluminium layered double hydroxides tion is not limited to conventional chemical catalytic
(LDHs), or hydrotalcites, have represented another routes. Recently, biocatalysts have also raised an
extensively researched route for biodiesel production. intensified research effort for potentially being capable
In recent times, these materials have been modified by of outperform chemical catalysts in transesterification
introducing some dopant elements to improve its of vegetable oils (Al-Zuhair et al. 2011; Abbaszaadeh
catalytic properties. On this matter, an interesting study et al. 2012). Biocatalysts are a group of enzymes called
on catalytic performance of cerium doped Mg–Al lipases which have the ability to mediate the transe-
hydrotalcites obtained by thermal activation was sterification reactions essential to biodiesel production.
recently reported by Soares Dias et al. (2012). In the In general, when compared with chemical catalysts,
tested conditions, i.e. a 9:1 molar ratio of methanol to lipases perform their catalytic activity in milder
oil, a catalyst amount of 3.0 % (w/w), and 67 °C, conditions and with a wide range of lipid sources,
transesterification of soybean oil resulted in a biodiesel including feedstocks with high levels of FFA. Further-
yield higher than 90.0 % with authors concluding that more, biodiesel separation is much easier and the
the catalyst showed excellent performance during catalysts can be reused, therefore resulting in a more
biodiesel synthesis (Soares Dias et al. 2012). environmentally friendly process (Leung et al. 2010).
In Table 2 a summary of the latest developments There are two major classifications of lipases: extra-
concerning the use of heterogeneous catalysts in cellular lipases and intracellular lipases (Abbaszaadeh
transesterification of vegetable oils is presented et al. 2012; Aransiola et al. 2014). Extracellular lipases
emphasizing the operating conditions in which the are usually recovered from the live-producing micro-
experimental works were performed, namely alcohol/ organism broth and then purified, while intracellular
oil ratio, catalyst amount, reaction conditions and ester lipases are employed in whole-cell form maintaining
yield. According to the table, it can be noted that all the enzyme immobilized (Abbaszaadeh et al. 2012;
solid catalysts need a longer reaction time to give high Aransiola et al. 2014). Extracellular lipases can be
concentrations of biodiesel when compared with immobilized on several materials so that they can be

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Table 2 Heterogeneous catalysts for transesterification of vegetable oils

Catalyst Oil Catalyst Alcohol Molar Reaction Ester yield References
amount ratio conditions (%)

CaO Sunflower 2.0 % (w/w) Methanol 12:1 60 °C, 2 h 99.6 Reyero et al. (2014)
Ca-glyceroxide 83.4
Ca-glycerolate 29.9
CaO–CeO2 Pistacia 9.0 % (w/w) Methanol 30:1 110 °C, 6 h 91.0 Yu et al. (2011)
chinensis
Sr/MgO Soybean 5.0 % (w/w) Methanol 12:1 65 °C, 30 min 93.0 Tantirungrotechai et al.
(2013)
CaO Jatropha 4.0 % (w/w) Methanol 15:1 65 °C, 6 h 85.0 Taufiq-Yap et al. (2011)
MgO 10.0
Zno 0.00
CaMgO 83.0
CaZnO 81.0
CaO–SnO2 Soybean 8.0 % (w/w) Methanol 12:1 70 °C, 6 h 89.3 Xie and Zhao (2013)
FA/Na–X zeolite Sunflower 3.0 % (w/w) Methanol 6:1 65 °C, 8 h 83.5 Babajide et al. (2012)
CaO/NaY zeolite Soybean 3.0 % (w/w) Methanol 9:1 65 °C, 3 h 95.0 Wu et al. (2013)
Na2O/NaX zeolite Sunflower 10 % (w/w) Methanol 6:1 60 °C, 6 h 99.3 Martı́nez et al. (2014)
Ce–Mg–Al Soybean 5.0 % (w/w) Methanol 9:1 67 °C, 3 h [90 Soares Dias et al.
hydrotalcite (2012)
Mg–Al Soybean 5.0 % (w/w) Methanol 12:1 65 °C, 6 h 92.5 Gomes et al. (2011)
hydrotalcite
KOH– ZrO2 S. marianum 6.0 % (w/w) Methanol 15:1 60 °C, 2 h 90.8 Takase et al. (2014b)
HClSO3–ZrO2 Rice bran 6.0 % (w/w) Methanol 12:1 120 °C, 12 h [92 Zhang et al. (2013)
SO42-–ZrO2 Rapeseed 3.0 % (w/w) Methanol 20:1 1708, 1 h 86.0 Rattanaphra et al.
(2012)
ZnO–TiO2– Soybean – Methanol 9:1 2108, 69 min 95.1 Kim et al. (2012)
Nd2O3/ZrO2
ZnO–Yb2O3– 93.0
SiO2/ZrO2

used several times to reduce cost and improve stability. Pseudomonas fluorescens, Pseudomonas cepacia,
Methods for lipase immobilization mainly include Burkholderia cepacia, Rhizomucor miehei, Rhizopus
adsorption processes, but also covalent bonding, oryzae, Candida rugosa, Thermomyces lanuginosus,
entrapment, encapsulation, and cross-linking (Tan and Candida Antarctica (Vasudevan and Briggs 2008;
et al. 2010b; Abbaszaadeh et al. 2012; Yan et al. Szcze˛sna Antczak et al. 2009; Abbaszaadeh et al.
2014). Despite all the merits, disadvantages such as 2012; Aransiola et al. 2014). Among these, Aspergil-
slow reaction rate and enzyme cost and deactivation lus orizae, Rhizopus oryzae, Candida Antarctica, and
still are a constraint, especially when scaling up the use Pseudomonas cepacia have been most widely used.
of biocatalysts beyond laboratory scale (Wang et al. The vast majority of investigations have focused on
2008; Bajaj et al. 2010). Figure 4 provides a general studying immobilization techniques, as well as the
process flowsheet of enzymatic transesterification. effects of reaction parameters, alcohol addition meth-
Lipases can be isolated from a number of sources ods, and water requirements for different lipases.
(animals, plants and microorganisms), particularly Athalye et al. (2013) investigated the impact of
from some bacteria and fungi species such as immobilization of R. oryzae cells on novel rigid

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Fig. 4 General process flowsheet of enzymatic catalytic transesterification (Ravindra et al. 2012)

polyethylene biomass supports for use in biodiesel and lead to a decrease in transesterification yields. In
production. The reaction was carried out at 35 °C for this study, the highest yield (97.2 %) was found with a
36 h with a 3:1 molar ratio and the highest biodiesel water content of 4–6 % after 33 h, 40 °C, 4.3 pieces of
conversion was 27.9 %. This result was attributed to lipase-immobilized membrane, and 4:1 substrate
the higher retention of lipase in the immobilized molar ratio. Moreover, results also demonstrated that
biomass due to the presence of oil, suggesting that lipase stability was high enough to permit reuse (after
future studies should focus on the improvement of the five times yields still remained at about 90.0 %)
contact between phases by either using a continuous showing that lipase immobilized on PVDF membrane
system or increasing the amount of immobilized has the potential to be effectively applied in biodiesel
biomass (Athalye et al. 2013). The effect of the production (Kuo et al. 2013).
addition of water to the reaction system should also be Most studies reviewed have been proposed in
investigated, since a minimum amount of water has solvent-free systems. In such systems, the alcohol
been suggested to be required to activate the enzyme usually has poor solubility in oil feedstocks and too
and improve catalytic activity (Vyas et al. 2010). On much alcohol in the system is believed to have some
this matter, Kuo et al. (2013) employed a C. rugosa negative effect on lipase activity. To overcome the
lipase immobilized onto PVDF membrane as a issue, the stepwise addition of the alcohol has been
catalyst for the transesterification of soybean oil with suggested instead of addition in the beginning of the
methanol in the presence of n-hexane. The main process. Since the solubility of the alcohol in the
objectives of the study were to better understand the alkyl esters is greater than in the oil, this procedure
impact of reaction parameters on biodiesel yield, limits enzyme deactivation (Vyas et al. 2010). Adachi
including added water content. Investigations found et al. (2013), for example, investigated methanol
out that in an organic solvent, a small amount of water addition pattern on methanolysis of palm oil and
is essential to maintaining the specific three-dimen- found out that the stepwise addition of methanol is
sional structure of the enzyme. However, excess water effective for maintaining the lipase activity of whole-
may also stimulate competing hydrolysis reactions cell biocatalysts (Hama et al. 2009; Adachi et al.

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2013). Specifically, the authors developed a process As shown in the summary presented in Table 3, the
for biodiesel production using a A. oryzae whole-cell efficiency of lipases in biodiesel production varies
biocatalyst expressing a thermostable lipase from greatly between different enzyme sources and reaction
Geobacillus thermocatenulatus (BTL2). The methyl conditions. In general, lipase-mediated transesterifi-
ester content reached nearly 100 % after 96 h at cation is performed under mild conditions (lower
elevated temperature (40–50 °C) and either 1.0 M temperatures and lower alcohol to oil molar ratios),
equivalent methanol was added at 0, 24, 48, and 72 h, but in much longer reaction times when compared to
or 2.0 M equivalents of methanol were added at 0 and other approaches. Among the lipases used in the
24 h. It was also found that immobilized A. oryzae reviewed research, very high conversion values
was highly tolerant to 30 % (v/v) organic solvents, ([90 %) were obtained with A. oryzae, B. Cepacia,
demonstrating that the developed whole-cell biocat- R. oryzae, C. rugosa, T. Lanuginosus, and C. antarc-
alyst shows great promise for a broad range of tica B, but different reaction conditions do not allow
applications, including biodiesel production (Adachi for direct comparisons between studies. Even so, it is
et al. 2013). Ko et al. (2012) also studied the impact clear that lipase immobilization led to higher yields as
of methanol adding strategy on transesterification compared to what was achieved with free enzymes
efficiency for jatropha oil using C. antarctica lipase B confirming that immobilization enhance some enzyme
immobilized on macroporous acrylic resin (Nov- features like stability, activity and selectivity. In this
ozym-435). In this case, gradient (continuous) addi- respect, Kalantari et al. (2013) used a lipase from P.
tion of methanol clearly offered advantage over cepacia immobilized on magnetic silica nanocompos-
stepwise addition by significantly improving conver- ite particles with various silica structures and then
sions. In optimal reaction conditions, temperature used it as a recyclable biocatalyst in a transesterifica-
was 40 °C and 64.0 % conversion was achieved in tion reaction to produce biodiesel from soybean oil.
24 h for a molar ratio of 3:1 by gradient addition of Free lipase was also used and results compared. As
methanol and 10 % (w/w) enzyme loading (Ko et al. expected, higher yields were obtained with the
2012). immobilized lipases after 24 h (54.0 % against
Organic solvents are also used in enzymatic 34.0 %) with reaction conditions of 40 °C, 5.0 mg
biodiesel synthesis in order to increase transesterifi- lipase amount, and 4:1 molar ratio (two-step addition;
cation rate through improved mutual solubility of Kalantari et al. 2013). Currently, the establishment of
hydrophobic TAGs and hydrophilic alcohols, but the biocatalyzed transesterification in the commercial
process is known to be less environmentally friendly. market is mostly dependent of lipase production costs
Among organic solvents used for enzymatic biodiesel and its limited regeneration and reuse. Despite
production the most suitable were found to be increasing research efforts, more studies focused on
hydrophobic ones such as isooctane, n-heptane, addressing these issues will be needed in order to make
petroleum ether, n-hexane, cyclohexane, and tert- the enzymatic process more competitive when com-
butanol (Szcze˛sna Antczak et al. 2009). Rodrigues pared with the chemical route.
et al. (2010), for example, used a lipase from T.
Lanuginosus immobilized on octylsepharose beads for
the enzymatic transesterification of soybean oil with 4 Non-catalytic supercritical transesterification
ethanol. The reaction was carried out either in a
solvent-free system or in the presence of n-hexane While catalytic routes for biodiesel production are
because this solvent accelerates the acyl migration, commonly used in the industry, an alternative tech-
positively affecting enzyme activity. When performed nology becoming more and more relevant recently is
in the presence of the organic solvent, reaction was transesterification of vegetable oils under supercritical
able to achieve full conversion in 8 h, but in the conditions. As is known, when a fluid or gas is
solvent free system maximum conversion reached subjected to temperatures and pressures superior to its
approximately 75.0 % after 6.0 h. The results indicate critical point, a number of unusual properties arise
that the effect that non-polar solvents exert on the rates (Leung et al. 2010). Regarding the alcohol used in
of acyl migration and on enzyme features significantly transesterification reactions, thermophysical proper-
benefit biodiesel yields (Rodrigues et al. 2010). ties such as the dielectric constant change in

123
Table 3 Biocatalysts for transesterification of vegetable oils
Carrier/Free Enzyme Lipase Oil Alcohol Molar Solvent Reaction Ester Remarks References
enzyme amount ratio conditions yield

123
(%)

Reticulated A.oryzae – Palm Methanol 4:1 Solvent 40–50 °C, [99.0 Stepwise addition of Adachi et al. (2013)
polyurethane free 96 h methanol; addition of
foam biomass 5.0 % (w/w) of water
support particles
Free enzyme P. cepacia 5.0 mg Soybean Methanol 4:1 Solvent 40 °C, 34.0 Two-step addition of Kalantari et al. (2013)
Magnetic silica free 24 h 54.0 methanol; addition of
nanocomposite 1.5 ml of water
Hybrid matrix of B. cepacia 53 % Jatropha Ethanol 10:1 Solvent 35 °C, 100 Methanol addition method Abdulla and Ravindra
alginate and j- (w/w) free 24 h not mentioned; Addition (2013)
carrageenan of 1.0 g of water
Modified B. cepacia 10 % Jatropha Methanol 6.6:1 Solvent 35 °C, 94.0 Methanol added at 3 h You et al. (2013)
attapulgite (w/w) free 24 h intervals; addition of
7.0 % (w/w) of water
Hydrophobic Burkholderia – Olive Methanol 4:1 Solvent 30 °C, 70.0 Stepwise addition of Liu et al. (2012)
magnetic sp. C20 free 12 h methanol unnecessary;
particles addiction of 10 % (w/w)
of water
Free enzyme R. miehei – Soybean Methanol 5:1 Solvent 37 °C, 39.3 Stepwise addition of De Vasconcellos et al.
Ni–P/200-ENZ free 72 h 56.2 methanol; no water added (2012)
zeolite
Free enzyme R. miehei 0.08 mg Soybean Ethanol 6:1 Solvent 37 °C, 20.0 Stepwise addition of Bergamasco et al. (2013)
Polyvinyl alcohol 4.0 % free 72 h 66.3 ethanol; no water added
microspheres (w/w)
Reticulated R. oryzae – Polanga Methanol 12:1 Solvent 35 °C, 92.0 Stepwise addition of Arumugam and Ponnusami
polyurethane free 72 h methanol; addition of (2014)
foam 15 % (v/v) of water
Rigid polyethylene R. oryzae – Cottonseed Methanol 3:1 Solvent 35 °C, 27.9 Methanol added in three Athalye et al. (2013)
biomass supports free 36 h steps; water addition not
mentioned
Free enzyme C. rugosa – Soybean Methanol 3:1 Solvent 20 °C, 61.5 Stepwise methanol Chang et al. (2014)
free 22 h addition at 6/8 h
intervals; addition of
30 % (w/w) of water
Polyvinylidene C. rugosa – Soybean Methanol 4:1 Hexane 40 °C, 97.2 One step methanol Kuo et al. (2013)
fluorid membrane 33 h addition; addition of
5.0 % (w/w) of water
Rev Environ Sci Biotechnol
Table 3 continued
Carrier/Free Enzyme Lipase Oil Alcohol Molar Solvent Reaction Ester Remarks References
enzyme amount ratio conditions yield
(%)

Activated carbon C. rugosa 1.0 % Palm Methanol 15:1 Solvent 37 °C, 1 h 70.0 Alcohol addition method Moreno-Pirajàn and
matrix (w/w) Ethanol 15:1 free 35 °C, 1 h 80.0 not mentioned; Addition Giraldo (2011)
of 1.0 g of water
Butanol 10:1 35 °C, 1 h 85.0
Rev Environ Sci Biotechnol

Free enzyme T. lanuginosus 20 mg Sunflower Ethanol 3.4:1 Solvent 20 °C, 1 h 70.0 Ethanol addition method Verdugo et al. (2011)
free not mentioned; addition
of 14 % (w/w) of water
Octylsepharose T. lanuginosus 15 % Soybean Ethanol 8:1 Solvent 30 °C, 6 h 75.0 Single step ethanol Rodrigues et al. (2010)
beads (w/w) free addition; addition of
Hexane 30 °C, 8 h [99.0 4.0 % (w/w) of water
Free enzyme C. antarctica B 5.0 % Soybean Ethanol 5:1 Solvent 32 °C, 87.0 Ethanol addition method Rosset et al. (2011)
(w/w) free 24 h not mentioned; addition
of 1.0 % (w/w) of water
Macroporous C. antarctica B 10 % Jatropha Methanol 3:1 Solvent 40 °C, 64.0 Gradient methanol Ko et al. (2012)
acrylic resin (w/w) free 24 h addition; no water added
Acrylic resin C. antarctica B 7.0 % Coconut Ethanol 10:1 Solvent 60 °C, 80.5 Ethanol addition method Ribeiro et al. (2012)
(w/w) free 24 h not mentioned; no water
added
Acrylic resin C. antarctica B 1.0 % Coconut Ethanol 3:1 Solvent 50 °C, 3 h 92.0 Ultrasonic assisted; ethanol Tupufia et al. (2013)
(w/w) free addition method not
mentioned; no water
added

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Table 4 Supercritical transesterification of vegetable oils

Oil Molar Alcohol Temperature and Reaction time Ester yield References
ratio pressure (min) (%)

Jatropha 40:1 Methanol 320 °C, 15 MPa 10 84.6 Samniang et al. (2014)
Polanga 260 °C, 16Mpa 5 90.4
WVO 34:1 Methanol 271 °C, 23 MPa 20 95.3 Ghoreishi and Moein (2013)
Rapeseed – Methanol 350 °C, 30 MPa 20 96.3 Kim et al. (2013)
Canola 2:1 Methanol 270 °C, 10 MPa 45 102* Lee et al. (2012)
Jatropha 50:1 Methanol 400 °C, – 32 71.9 Niza et al. (2011)
Rapeseed 50:1 Methanol 330 °C, 21 MPa 16 93.6 Shin et al. (2012)
Macauba 30:1 Methanol 375 °C, 15 MPa – 78.5 Navarro-Dı́az et al. (2013)
Ethanol 69.6
Rapeseed 42:1 Methanol 350 °C, 12 MPa 15 93.0 Kiss et al. (2014)
Ethanol 30 93.2
Palm 40:1 Methanol 372 °C, 15–25 MPa 16 81.5 Tan et al. (2010a)
33:1 Ethanol 349 °C, 15–25 MPa 29 79.2
Castor 40:1 Ethanol 350 °C, 15 MPa 10 56.2 Rodrı́guez-Guerrero et al.
(2013)
Soybean 5:1 Methyl 350 °C, 20 MPa 45 44.0 Doná et al. (2013)
Macauba acetate 325 °C, 20 MPa 83.0
Rapeseed 42:1 Methyl 350 °C, 20 MPa 45 96.7 Goembira and Saka (2013)
acetate
Rapeseed 42:1 Methyl 350 °C, 18 MPa 45 97.7 Goembira et al. (2012)
acetate
WVO (waste vegetable oil)
* By-product glycerol reacted with methanol generating methyl ethers of glycerol

Fig. 5 General process flowsheet of non-catalytic supercritical transesterification (West et al. 2008)

supercritical state, thus overcoming solubility and reaction is completed in very favourable conditions,
diffusion problems associated with the two-phase usually in a very short time (Han et al. 2005; Leung
nature of the reaction mixture; as a consequence, the et al. 2010). Other advantages include the absence of

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Table 5 Comparison between main biodiesel production technologies (West et al. 2008; Lam et al. 2010; Leung et al. 2010;
Marchetti 2012; Abbaszaadeh et al. 2012)
Technology Feedstock Main features Environmental impact

Homogeneous (i) Base: requires raw materials with (iii) Difficult catalyst removal (vi) Waste water generated in
catalytic low content of FFA and water (neutralization step required) purification steps
transesterification (ii) Acid: Insensitive to feedstock (iv) Difficult biodiesel and glycerol (catalyst and glycerol
FFA and water content purification process (liquid– removal)
liquid extraction–water (vii) Surplus methanol can be
washing) recycled back to the
(v) High amount of equipment process
Heterogeneous (i) Base: feedstocks must have low (iii) Simple catalyst removal process (vi) Minimal waste generation
catalytic FFA content (gravity settling—no need for despite catalyst being
transesterification (ii) Acid: feedstocks with high FFA neutralization step) discarded as waste
and water contents can be used (iv) Simple biodiesel and glycerol product; possible
for biodiesel production purification step (gravity reusability
separation—high purity) (vii) Excess methanol can be
(v) Low amount of equipment recovered
Enzymatic (i) Wide range of lipid sources can (ii) No need for neutralization (vi) Mild reaction conditions
catalytic be used as feedstock, including process (normal temperature and
transesterification feedstocks with high levels of (iii) No need to surplus methanol pressure)
FFA and water recovery (vii) Enzyme reusability and
(iv) Simple biodiesel and glycerol regeneration possible
purification steps which lessens catalyst
disposal issues
(v) Very low amount of equipment
Non-catalytic (i) Feedstocks with very high (ii) No catalyst removal or (v) System operates at very high
supercritical contents of FFAs and water can neutralization step required pressure and temperature—
transesterification be tolerated since no catalyst is used energy intensive
(iii) Simple purification steps (vi) Excess methanol can be
(gravity separation to remove recycled
glycerol)
(iv) Low amount of equipment (but
expensive)

catalyst (which makes separation steps unnecessary), Biodiesel production by this approach is thus still in its
high conversion rates, and tolerance to the presence of infancy, but its potential as a future competitor
water and FFAs, hence allowing a variety of resources technology is undeniable (Aransiola et al. 2014).
to be used as feedstocks. The main disadvantages of Presently, most research has focused on methanol as
the supercritical technologies are the high pressures supercritical alcohol, but ethanol and carboxylate
and temperatures, and the high methanol to oil ratios esters have also been tested as supercritical fluids. The
required, which translate to higher production costs main objectives of these studies are to investigate the
(Balat and Balat 2008; Helwani et al. 2009; Marchetti effects of reaction variables on biodiesel yield, and to
2012; Abbaszaadeh et al. 2012). In Fig. 5 a general obtain optimal conditions for biodiesel production. As
process flowsheet of supercritical transesterification an example, Samniang et al. (2014) have recently
can be observed (West et al. 2008). Despite many investigated two types of non-edible oils (Jatropha oil
studies carried out on biodiesel production using and Polanga oil) with different amounts of FFA for
supercritical fluids, much remains unknown about biodiesel production via supercritical methanol transe-
non-catalytic transesterification routes. The mecha- sterification. The experimental reaction was carried
nism and detailed kinetics, for instance, have not yet out at 320 °C and 15 MPa for Jatropha oil and 260 °C
been well understood (Abbaszaadeh et al. 2012). and 16 MPa for Polanga oil, using a molar ratio of

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40:1 and being completed very fast (5 min). The opposite findings (Madras et al. 2004; Biktashev et al.
highest yields obtained under the specified conditions 2011). Even though the application of supercritical
were 84.6 and 90.4 % for both feedstocks, respec- technology to biodiesel production has been exten-
tively (Samniang et al. 2014). On another study, sively investigated in recent times, it is believed that
Rodrı́guez-Guerrero et al. (2013) reported experimen- great potential has yet to be earned through further
tal data on the production of biodiesel from castor oil studies on its kinetics, production process, and scale-
in a batch reactor using ethanol in supercritical state up experiments. From a research point of view,
instead of methanol. A maximum yield of 56.2 % was investigators should be focused on the development
achieved in a reaction time of 10 min when the of innovative techniques able to reduce the extreme
operational conditions were temperature 350 °C, operating parameters of the supercritical method.
pressure 14.5 MPa, and molar ratio 40:1. The results
obtained were considered quite low when compared to
similar studies in literature, but authors suggested the 5 Other technologies
low pressure attained during the study had a probable
inhibition effect on biodiesel yield (Rodrı́guez-Guer- As stated earlier, advanced technologies like heter-
rero et al. 2013). ogeneous and enzymatic catalytic transesterification
On the other hand, supercritical carboxylate esters have great potential to overcome the main problems
can also convert triglycerides into biodiesel. Goem- posed by conventional biodiesel production routes
bira et al. (2012), for example, studied biodiesel via homogeneous catalysts. However, limited mass
production from rapeseed oil by various supercritical transfer efficiency caused by diffusion problems
carboxylate esters without using any catalysts. This between phases represent an obstacle for further
non-catalytic method converted triglycerides into improvement of these technologies, especially when
FAME and triacetin, instead of glycerol. Investiga- scaling up experiments to industrial or pre-industrial
tors found out that at reaction temperature of stages, as the conversion rate of oils into esters is
350 °C, pressure up to 17.8 MPa, and molar ratio rather slow (Lam et al. 2010; Leung et al. 2010).
of 42:1, supercritical methyl acetate showed the Table 5 summarizes the main practical aspects of
highest product yield (97.7 %) after 45 min (Goem- the biodiesel production technologies discussed until
bira et al. 2012). These promising results, combined this point. In the following section, a review of some
with the prevention of glycerol by-production, have new methods which can assist heterogeneous and
composed supercritical carboxylate esters, particu- enzymatic systems in order to surmount mass
larly methyl acetate, as another viable alternative in transfer limitations and thus obtaining higher transe-
biodiesel production from vegetable oils. sterification efficiencies is presented. These process
Table 4 provides a summary of the reviewed intensification technologies, whose concepts and
investigations, pointing out key reaction parameters main technical principles are discussed in Table 6,
such as temperature, pressure, molar ratio, and ester include ultrasound irradiation, microwave heating,
yield. The reviewed studies have looked mainly at use of co-solvents, and membrane reactors.
process optimization and operating parameters effects
at a laboratory scale. From the table, it is clear that the 5.1 Ultrasound assisted transesterification
usage of very high temperature, high pressure, and
large amount of alcohol are the major drawbacks of Ultrasonic technology has been recognized as a new
supercritical technologies when compared to other and effective tool to assist and improve many reaction
approaches. Alcohol of choice seems to have some systems, including biodiesel synthesis. Ultrasounds
influence on conversion rates with supercritical meth- are defined as sound waves with a frequency greater
anolysis having higher optimum yields in shorter than the upper limit of the human hearing ability, i.e.
times than ethanolysis, but no definitive conclusion usually above 20 kHz. Like any other sound wave,
can be drawn because this observation can be ultrasound compresses and stretches the molecular
misleading due to the type of oils and the process spacing of the carrier medium through which it travels,
conditions used in the experiments. For instance, continuously vibrating molecules and causing cavita-
Madras et al. (2004) and Biktashev et al. (2011) report tion (formation, growth, and implosive collapse of

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Table 6 Technical aspects of novel biodiesel production technologies

Technology Concept Principle References

Ultrasound Use of ultrasound irradiation to Emulsification of the immiscible Vyas et al. (2010), Veljković et al.
irradiation improve miscibility between liquid reactants by microturbulence (2012) and Badday et al. (2012)
phases (cavitation)
Microwave Use of microwave irradiation to Improved temperature at the catalytic Azcan and Yilmaz (2012), Manco et al.
heating improve heat transfer between surface caused by heat generated (2012) and Motasemi and Ani ( 2012)
phases due to molecular friction
Co-solvent Use of a secondary solvent to Increased solubility of alcohol in oil Lam et al. (2010) and Banković-Ilić
enhance miscibility between phase by adding a co-solvent soluble et al. (2012)
reactants overcoming initial in both reactants
mass transfer resistance
Membrane Use of a selective barrier Improve selectivity by removing Shuit et al. (2012) and Aransiola et al.
reactor (membrane) to regulate the glycerol from product stream and (2014)
transport of substances such as retaining unreacted triglycerides
gases, vapours, and liquids, at within the membrane (reaction and
different mass transfer rates separation in a single unit)

acoustic cavitation bubbles) (Vyas et al. 2010; Veljk- an increase in reaction time and temperature was
ović et al. 2012). Then, during ultrasound assisted required (30 min and 80 °C). The maximum yields of
transesterification, cavitation bubbles are created near biodiesel obtained were 95.8 and 92.3 % for methanol
the boundary between alcohol and oil phases promot- and ethanol, respectively (Takase et al. 2014a). In
ing emulsification of the immiscible liquid reactants another work, Guo et al. (2012) reported that ultra-
by microturbulence. One of the advantages of these sound irradiation (24 kHz, 200 W) enhanced the rate
cavitation bubbles is that they cause a local increase in of transesterification reaction when compared to
temperature and the formation of micro jets. As a mechanical stirring. Specifically, authors used ultra-
result, there is no requirement for external heating and sonic waves to promote the transesterification of
intense mechanical agitation in the production process soybean oil and methanol in a batch reactor using
(Vyas et al. 2010; Koh and Mohd. Ghazi 2011; Brønsted acidic ionic liquid as catalyst and studied the
Veljković et al. 2012; Badday et al. 2012). Therefore, influences of various parameters in biodiesel yield.
ultrasound application can be implemented to increase The optimal yield of biodiesel when ultrasonication
the chemical reaction rate, mass transfer rate, and ester was used (93.2 %) was achieved after 60 min at an
yield of transesterification reactions. The method also alcohol to oil ratio of 9:1, 60 °C of reaction temper-
works better and with less energy consumption when ature, and 1.0 % (w/w) of catalyst (Guo et al. 2012). In
compared to conventional stirring processes (Vyas similar reaction conditions, the aid of mechanical
et al. 2010; Banković-Ilić et al. 2012). As an example, stirring only yielded a maximum conversion of 60.8 %
Takase et al. (2014a) comparatively studied conven- making clear that effective mass transfer in the
tional stirring (600 rpm) and ultrasound assisted ultrasonic field greatly enhanced the rate of transeste-
(40 kHz) transesterification using new potential non- rification reaction in comparison with mechanical
edible feedstock (S. Marianum seed oil) with methanol mixing.
and ethanol in the presence of KOH. Given similar Ultrasound has initially been employed in transe-
conditions, ultrasonication proved to be substantially sterification reactions catalyzed by homogeneous cat-
more efficient in the triglycerides’ conversion as alysts; however, most recent works have shifted
compared with conventional stirring. For methanol, attention towards utilization of classic and new heter-
the optimum conditions for transesterification were ogeneous and enzymatic catalysts, as well as novel
found to be molar ratio 8:1, catalyst amount 1.5 % feedstocks. Choedkiatsakul et al. (2013), for example,
w/w, reaction temperature 60 °C, and reaction time investigated the application of calcium oxide (CaO)
20 min. For ethanol, the same conditions applied, but and potassium phosphate (K3PO4) as heterogeneous

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Rev Environ Sci Biotechnol

catalysts for transesterification of refined palm oil believed to be caused by heat generated due to
using ultrasonic technology. High methyl ester yields molecular friction, since polar alcohol molecules
were achieved within 2 h of reaction time for both CaO rapidly rotate while aligning with the continuously
(90 %) and K3PO4 (80 %) at a methanol to oil molar changing magnetic field generated by electromagnetic
ratio of 6:1, a reaction temperature of 65 °C, and a irradiation. The increase in reaction rates is attributed
catalyst amount of 3.0 % (w/w) of oil. Sonication mode to an improved temperature at the catalytic surface
was continuous and provided by an ultrasonic cleaning (Azcan and Danisman 2007). Regarding transesterifi-
bath of 40 kHz with a power of 160 W (Cho- cation processes, microwave is a well-established
edkiatsakul et al. 2013). On the other hand, Gharat route for shortening reaction rates and improving
and Rathod (2013) evaluated the performance of product yields in comparison with conventional tech-
Novozym 435 lipase in the production of biodiesel niques; all at a reasonable cost and with low energy
with waste cooking oil and dimethyl carbonate in a consumption (Vyas et al. 2010; Banković-Ilić et al.
solvent free system under ultrasound irradiation. The 2012).
optimum conditions found were 200 W ultrasonic During the past decade, microwave irradiation has
irradiation, 25 kHz frequency, 6:1 dimethyl carbonate been proven to significantly accelerate transesterifica-
to oil, 10 % (w/w) enzyme, and 60 °C, leading to tion reactions with base homogeneous catalysts, both
86.6 % biodiesel yield in a relatively short reaction in batch and continuous flow systems (Hernando et al.
time (4 h) (Gharat and Rathod 2013). 2007; Azcan and Danisman 2007, 2008; Encinar et al.
Judging from the studies summarized in Table 7, 2012; Manco et al. 2012). More recently, though,
ultrasonic technology has been proven to be a valuable efforts have focused on establishing this technology for
tool for accelerating transesterification reaction. Gen- transesterification processes using heterogeneous and
erally, in transesterification processes without ultra- enzymatic catalysts; moreover, some promising new
sonication assistance, maximum biodiesel yields are feedstocks like microalgae are also increasingly being
achieved within a few hours for heterogeneous tested (Azcan and Yilmaz 2012; Cheng et al. 2013). In
catalysts to a few days in enzymatic systems; however, regard of heterogeneous catalysts, Lin et al. (2013a)
among the reviewed research one can see that developed a microwave-assisted transesterification
maximum biodiesel conversion was achieved in much approach for improving methyl ester conversion while
shorter times for both cases. Despite this large using ionic liquid 4-allyl-4-methylmorpholin-4-ium
potential, application of ultrasonic radiation in heter- bromine (IL; [Mor- MeA][Br]) as a catalyst. Experi-
ogeneous and enzymatic transesterification systems mental results indicated that microwave irradiation had
has been under explored (especially in the latter), and better performance when compared with a conven-
should require more attention from researchers in the tional heating system, offering a more energy-efficient
future. Specifically, further studies are needed on the and cost-effective route for biodiesel synthesis. A
effects of key process parameters (optimization) with 99.4 % maximum biodiesel yield was achieved with
different types of alcohols and catalysts, on the IL1NaOH0.75 catalyst (1 % (w/w) [MorMeA][Br] and
development of kinetic models, and on design of 0.75 % (w/w) NaOH) at a methanol-to-oil molar ratio
novel types of ultrasonic reactors (Veljković et al. of 9:1, a reaction time of 6 min, and a microwave
2012; Badday et al. 2013). temperature of 70 °C (1,500 W power) (Lin et al.
2013a). Another example of the effectiveness of
5.2 Microwave assisted transesterification microwave-assisted transesterification of vegetable
oils while using heterogeneous catalysts was reported
Electromagnetic energy has also emerged as a useful by Long et al. (2014). In this work, investigators
tool for preparative chemistry, including assisting evaluated calcined sodium silicate (Na2O3Si) on
transesterification of vegetable oils. Microwave irra- transesterification of rapeseed and jatropha oils to
diation is an electromagnetic irradiation in the range of biodiesel under microwave irradiation. The optimiza-
wavelengths from 0.01 to 1 m and corresponding tion study obtained maximum biodiesel yields of
frequency range of 0.3–300 GHz (Motasemi and Ani 95.8 % from rapeseed oil and 92.8 % from jatropha oil
2012; Gude et al. 2013; Teixeira et al. 2014). The in 5 min using microwave power of 400 W, methanol/
effects of microwaves on chemical reactions are oil molar ratio of 11:1, catalyst amount of 4 % (w/w),

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Table 7 Ultrasound assisted transesterification of vegetable oils
Oil Molar Alcohol Catalyst Ultrasound conditions Catalyst Reaction Ester Transesterification/Experimental References
ratio amount conditions yield apparatus/Typical oil sample
(%)

WCO 12:1 Methyl CH3KO 22 kHz, 750 W, 1.0 % 40 °C, 30 min 90.0 Homogenous/100 mL three-neck Maddikeri et al.
acetate continuous mode (w/w) batch reactor equipped with a (2013)
condenser, an ultrasonic
transducer, and a temperature
Rev Environ Sci Biotechnol

sensor/–
Castor 6:1 Methanol KOH 45 kHz, 1920 W, 0.7 % 35 °C, 92.2 Homogeneous/500 mL spherical Encinar et al.
continuous mode (w/w) 60 min glass reactor provided with a (2012b)
thermostat, sampling outlet and
condensation system, within a
ultrasonic cleaner/–
Babassu 9:1 Ethanol KOH 20 kHz, 1.0 % 30 °C, 96.7 Homogeneous/125 mL Paiva et al.
600 W, continuous mode (w/w) 10 min Erlenmeyer flask equipped with (2013)
a reflux condenser within an
ultrasonic bath/22 g
S.Marianum 8:1 Methanol KOH 40 kHz, 1.5 % 60 °C, 20 min 95.8 Homogeneous/250 mL three- Takase et al.
Ethanol 250 W, continuous mode (w/w) 80 °C, 30 min 92.3 neck reaction flask equipped (2014a)
with a condenser and an
ultrasound processor/30 g
WCO 9:1 Methanol NaOH 20 kHz, 500 W 0.5 % 60 °C,1–2 min 90.0 Homogeneous/50 mL glass batch Gude and Grant
(w/w) reactor (beaker) equipped with (2013)
an ultrasonic transducer and a
digital temperature probe/
10 mL
Palm 9:1 Methanol SrO 20 kHz, 140 W, pulse mode 2.5 % 65 °C, 50 min 90.0 Heterogeneous/Three-neck glass Salamatinia
Corn (varying between 1-9 s) (w/w) 97.3 batch reactor equipped with an et al. (2013)
ultrasonic transducer and probe,
Canola 97.5
a condenser, a stirrer and a
Sunflower 87.7 thermocouple thermometer/–
Palm 9:1 Methanol SrO 20 kHz, 200 W, pulse mode 2.0 % 65 °C, 45 min 94.0 Heterogeneous/Three-neck glass Salamatinia
(9 s on, 3 s off) (w/w) batch reactor equipped with an et al. (2012)
ultrasonic transducer and probe,
a condenser, a stirrer, and a
thermocouple thermometer/–

123
Table 7 continued
Oil Molar Alcohol Catalyst Ultrasound conditions Catalyst Reaction Ester Transesterification/Experimental References
ratio amount conditions yield apparatus/Typical oil sample

123
(%)

Palm 6:1 Methanol CaO 40 kHz, 3.0 % 65 °C, 90.0 Heterogeneous/125 mL three- Choedkiatsakul
K3PO4 160 W, continuous mode (w/w) 120 min 80.0 neck round bottom flask et al. (2013)
equipped with a condenser, a
thermometer and a sampling
valve, immersed into an
ultrasonic cleaning bath/2 mL
Soybean 9:1 Methanol Brønsted 24 kHz, 200 W 1.0 % 60 °C, 93.2 Heterogeneous/Ultrasonic Guo et al.
acidic ionic (w/w) 60 min processor in a reactor equipped (2012)
liquid with a jacket. The transducer
was submerged 2 cm in a
reactive mixture of about
50 mL/–
Jatropha 19:1 Methanol TPA25–Al 20 kHz, 4.4 % 65 °C, 50 min 83.6 Heterogeneous/Three-neck glass Badday et al.
240 W, (w/w) reactor partially submerged in a (2013)
water bath and equipped with a
pulse mode (3 s on and 3 s
condenser. Ultrasonic energy
off)
was supplied using an ultrasonic
processor/–
Jatropha 4:1 Methanol E. aerogenes 24 kHz, 200 W, continuous 5.0 % 20–30 °C, 84.5 Enzymatic/25 mL Erlenmeyer Kumar et al.
mode (w/w) 30 min type flask with an ultrasonic (2011)
processor equipped with a
transducer/–
Soybean 3:1 Ethanol Novozyme 37 kHz, 13 % 57 °C, 4 h 57.5 Enzymatic/Ultrasonic water bath Batistella et al.
435 100 W, continuous mode (w/w) 63 °C, 4 h 86.5 in which a round bottom flask of (2012)
Lipozyme 27 % 250 mL coupled with a total
RM IM (w/w) reflux condenser was immersed/
1g
WCO 6:1 Dimethyl Novozyme 25 kHz, 10 % 60 °C, 4 h 86.6 Enzymatic/Ultrasonic water bath Gharat and
carbonate 435 200 W, continuous mode in a (w/w) equipped with a transducer in Rathod (2013)
15 min cycle which a glass reactor of 50 ml,
provided with a six-bladed
turbine impeller was immersed/
2g
WCO waste cooking oil, TPA25 tungstophosphoric acid with 25 % (w/w) catalyst loading
Rev Environ Sci Biotechnol
Rev Environ Sci Biotechnol

and a recycle number of three times (biodiesel yield Experimental results have shown that ether-related
reduced to 83.6 % at the fourth cycle) (Long et al. solvents such as Tetrahydrofuran (THF), dimethyl
2014). ether (DME), diethyl ether (DEE), and tert-butyl
Microwave irradiation has also been applied in the methyl ether (TBME) can greatly accelerate biodiesel
enzymatic synthesis of biodiesel. In this regard, Da production in homogeneous systems (Guan et al.
Rós et al. (2014) studied the application of high- 2007; Yang and Xie 2007; Guan et al. 2009a, c; Lam
frequency electromagnetic fields (microwaves) to the et al. 2010; Banković-Ilić et al. 2012; Khang et al.
enzymatic synthesis of biodiesel from babassu oil and 2014). Guan et al. (2009c), for example, have inves-
ethanol in a solvent-free medium, using B. cepacia tigated biodiesel production from sunflower oil by
lipase immobilized on SiO2. Under optimal condi- using a KOH catalyst in the presence of various readily
tions, nearly 100 % conversion was attained at a available co-solvents, namely THF, DME, DEE, and
reaction time of 10 h, molar ratio of 12:1, and reaction TBME. They discovered that addition of a co-solvent
temperature of 50 °C. Under conventional heating, the significantly enhanced the transesterification rate as
same results were achieved only after 48 h, confirming sunflower oil was almost completely converted into
the effectiveness of microwave irradiation to conduct biodiesel after 20 min, while only approximately
enzymatic transesterification reactions (Da Rós et al. 78.0 % conversion was reached in the absence of a
2014). co-solvent (Guan et al. 2009c). However, when the
Table 8 lists some reviewed studies pointing out same authors used THF or DME in heterogeneous
the main operating conditions in which they were transesterification of waste cooking oil results showed
performed. From the table, it is clear that microwave a drop in biodiesel yield (Guan et al. 2009b). Based on
technology has been found to be an efficient method to these findings, it was suggested that mass transfer is
accelerate and enhance the transesterification reaction not significantly enhanced in a heterogeneous catalytic
in heterogeneous and enzymatic systems. However, system even in the presence of a co-solvent.
much remains unknown about this technology and Hexane is another co-solvent proved to ease the
further research is needed with diversified catalysts formation of a single phase reaction mixture, facili-
and feedstocks; microwave-assisted enzymatic transe- tating mass transfer in transesterification (Peña et al.
sterification, for instance, has been specially under 2008; Li et al. 2010b; Lian et al. 2012). It can play a
explored despite the encouraging results already role of both co-solvent and co-extractant attracting
achieved. Further, it should be noted that the great attention from an engineering perspective by enabling
majority of the reviewed studies were carried out at a the integration of extraction and transesterification of
laboratory scale, and thus future efforts in microwave oil to produce biodiesel (Lian et al. 2012). On this
application for biodiesel synthesis should be focused matter, (Lian et al. 2012) reported that the production
in guaranteeing that the scaling-up of the process to of biodiesel with heterogeneous KF/c-Al2O3 catalyst
large scale is technically (process engineering, safety was successfully realized in the presence of hexane as
and operational logistics) and economically feasible co-solvent by using an integrated apparatus. Under
(Gude et al. 2013). optimal conditions, temperature 75 °C, 60 mL meth-
anol–hexane mixed solvent (8:1, v/v), reaction time of
5.3 Co-solvent for transesterification 4.0 h, experimental results showed that the yield of
FAME reached the maximum (80.2 %) when the ratio
Another approach to overcome miscibility problems of catalyst to raw material was 10 wt% (Lian et al.
in biodiesel synthesis is to use a secondary solvent 2012).
which is soluble in both reactants, i.e. alcohol and Despite all the advantages, the possible hazard and
vegetable oil. By adding a co-solvent to the reaction toxicity of conventional co-solvents and the higher
mixture phase miscibility is facilitated and transeste- production costs due to the extra processing steps
rification rate is enhanced by allowing the system to required for removing them have caused recent
overcome some initial mass transfer resistance. By advances to focus on developing inexpensive and
definition, an appropriate co-solvent should be inert environmentally benign solvents for homogeneous
and cannot either react with reactants or deactivate the catalysis, especially for heterogeneous and enzymatic
catalyst (Banković-Ilić et al. 2012). catalytic systems. In Table 9, the most recent

123
123
Table 8 Microwave assisted transesterification of vegetable oils
Oil Molar Alcohol Catalyst Microwave Catalyst amount Reaction Ester Transesterification/Experimental apparatus/ References
ratio conditions conditions yield Typical oil sample
(%)

Palm 18:1 Methanol CaO 900 W 15 % (w/w) –, 4 min 96.7 Heterogeneous/Teflon-line autoclave reactor Khemthong
placed inside a household microwave oven/ et al.
10 mL (2012)
Soybean 6:1 Methanol SrO 900 W 2.0 % (w/w) –, 97.0 Heterogeneous/50 mL round bottom flask Koberg
WCO \1 min 99.0 within a microwave oven. Microwave et al.
irradiation with a cycle mode of 21 s on and 9 (2011)
s off/15g
Soybean 14:1 Methanol C4H6O4KNa/ – 10 % (w/w) 65 8C, 94.8 Heterogeneous/Microwave digestion system Li et al.
ZrO2 30 min equipped with six 60 mL digestion reactors/ (2013)
1g
Soybean 9:1 Methanol [MorMeA][Br] 1500 W 1.0 % ? 0.8 % (w/w) 70 8C, 99.4 Heterogeneous/Microwave synthesis reactor, Lin et al.
? NaOH 6 min equipped with a mechanical stirrer, a round (2013a)
bottom flask and a condenser/–
WCO 9:1 Methanol [MorMeA][Br] 800 W 1.0 % ? 0.8 % (w/w) 70 8C, 98.1 Heterogeneous/Microwave synthesis reactor, Lin et al.
? NaOH 7 min equipped with a mechanical stirrer, a round (2013b)
bottom flask and a condenser/–
Rapeseed 11:1 Methanol Na2SiO3 400 W 4.0 % (w/w) –, 5 min 95.8 Heterogeneous/60 mL teflon reactor fitted with Long et al.
Jatropha 92.8 a thermocouple and a magnetic stirrer, and a (2014)
commercial microwave apparatus/15g
Macauba 9:1 Ethanol Novozyme 435 – 2.5 % (w/w) 15 min 45.2 Enzymatic/Microwave reactor vessel equipped Nogueira
Lipozyme IM 5.0 % (w/w) 5 min 35.8 with a gas bulb thermosensor/10g et al.
(2010)
Babassu 12:1 Ethanol B. cepacia 80–100 W – 50 8C, 100 Enzymatic/100 mL spherical glass reactor Da Rós
10 h within a microwave reactor with a cylindrical et al.
internal chamber/12g (2014)
Palm 8:1 Ethanol P. fluorescens 8–15 W 20 % (w/w) 43 8C, 97.5 Enzymatic/100 mL spherical glass reactor Da Rós
12 h within a microwave reactor with a cylindrical et al.
internal chamber/12g (2013)
WCO waste cooking oil
Rev Environ Sci Biotechnol
Rev Environ Sci Biotechnol

developments regarding the aforementioned efforts Moreover, the yields remained higher than 85 % after
are listed. 20 repeated batch cycles. These results show promise
Glymes (i.e. glycol diethers) have lately been in using lipase-displaying whole-cell biocatalyst as a
explored as alternative environmental benign co-sol- new type of biocatalyst for biodiesel production (Jin
vents for enzymatic and heterogeneous catalytic sys- et al. 2013).
tems as these solvents have some favourable properties From Table 9, it can be seen that the majority of
such as low viscosities, low toxicities, and high reviewed studies achieved high biodiesel conversions
chemical and thermal stability (Tang et al. 2013a). in very short times, bearing in mind the typical yields
Tang et al. (2013b) have investigated the role of glymes obtained without the presence of co-solvents; how-
as co-solvents in biodiesel preparation by heterogeneous ever, for heterogeneous systems not all the solvents
transesterification and concluded that its triglyceride tested had a positive effect in the transesterification
dissolving capability led to an increase in the reaction rate. Todorović et al. (2013), for example, tested the
rate and minimized saponification. A [ 98,0 % ester effects of various organic co-solvents in the transe-
yield was achieved in 4 h and 60 °C using CaO as the sterification of sunflower oil using CaO and discov-
catalyst (Tang et al. 2013b). On another study, the same ered that only n-hexane and tetrahydrofuran (THF)
authors (Tang et al. 2013a) returned to evaluate glymes slightly improved the reaction in its initial period
as co-solvents, but this time for lipase-catalyzed transe- (Todorović et al. 2013). As a result, one can conclude
sterification. Glymes were found highly compatible that benign solvents like glymes seem to afford a more
with immobilized C. antarctica lipase B (CALB), promising route for biodiesel production with solid
leading to high enzyme activities. Furthermore, CALB catalysts. For enzymatic transesterification systems,
showed a very high tolerance to high methanol concen- co-solvent mixtures containing tert-butanol have
trations (up to 60–70 % v/v). A laboratory scale-up shown great potential as reaction facilitators. Thus,
achieved a high conversion of soybean oil (95.5 %) in order to establish co-solvent addition as an effective
under mild conditions (10 mL glyme, 0.5 mL methanol, route for biodiesel preparation, future research trends
1.0 g soybean oil 10 % w/w lipase, and 50 °C for 24 h.). should continue to focus on verifying the effects of co-
These results suggest that glymes can be environmen- solvent in heterogeneous and enzymatic systems,
tally friendly and inexpensive solvents for the enzymatic while simultaneously developing and searching for
preparation of biodiesel (Tang et al. 2013a). novel environmentally benign solvents.
Biodiesel itself has been gaining momentum as co-
solvent for transesterification as it does not require 5.4 Membrane reactors for transesterification
additional separation steps, since it is the desired final
product of the reaction. Lam and Lee (2010) demon- Production systems involving the use of membrane
strated that biodiesel can be used as co-solvent in the technology to regulate the transport of substances are
transesterification of waste cooking oil catalyzed by a well-established methods in a variety of applications
solid acid catalyst (/SnO2-SiO2). It was found that (Leung et al. 2010). Despite newly applied inside the
with use of biodiesel as co-solvent, a high FAME field of biodiesel production, investigators have
yield of 88.2 % (almost 30 % higher than without already offered proofs of concepts that the transeste-
using co-solvent) can be obtained in a shorter reaction rification of vegetable oils is a classic chemical
time (1.5 h) under optimum conditions (reaction reaction with which membrane reactors can be
temperature of 150 °C, methanol to oil ratio of 15, successfully combined (Cao et al. 2007; Dubé et al.
and catalyst loading of 6 % w/w) (Lam and Lee 2007; Tremblay et al. 2008; Cao et al. 2008). A
2010). On another approach, Jin et al. (2013) studied membrane reactor is a device in which a chemical
the application of tert-butanol and isooctane as the co- reaction and a membrane-based separation process
solvent media for biodiesel production by combined occur simultaneously in a given particular physical
displayed lipases (C. antarctica lipase B and R. miehei enclosure or in close proximity (Cao et al. 2007;
lipase). Scaled-up experiments using refined vegeta- Aransiola et al. 2014). The membrane can either be
ble oils and waste oils (soybean, sunflower, waste organic in nature (i.e. polymeric) or inorganic being
frying oil, and gutter oil) were carried out in a stirred the latest more suitable for use with organic solvents
reactor, affording biodiesel yields over 90 % in 12 h. (Dubé et al. 2007).

123
Table 9 Co-solvent for transesterification of vegetable oils
Oil Molar Alcohol Catalyst Co-solvent Catalyst/Co- Reaction Ester Transesterification/Experimental apparatus/ References
ratio solvent amount conditions yield Typical oil sample

123
(%)

Canola 4.5:1 Methanol KOH Acetone 1.0 % (w/w) 25 °C, 98.3 Homogeneous/100 mL Erlenmeyer flask Thanh
WCO 25 % (w/w) 30 min 98.1 immersed in a water bath equipped with a et al.
thermostat/40 g (2013)
Jatropha 97.9
Canola 4.5:1 Methanol KOH Acetone 0.5 % (w/w) 20 °C, 99.0 Homogenous/100 mL Erlenmeyer type flask/ Maeda
IPA 25 % (w/w) 5 min 99.0 40 g et al.
(2011)
THF 90.0
DE 85.0
AN 60.0
Cottonseed 6:1 Methanol KOH DCB 0.8 % (w/w) 60 °C, [90.0 Homogeneous/250 mL batch reactor made up of Alhassan
Acetone 10 % (v/v) 10 min [90.0 three neck round bottom flask immersed in et al.
magnetic stirrer water bath with condenser (2014)
DEE \80.0
unit/–
Soybean 6:1 Methanol KOH Biodiesel 0.8 % (w/w) 70 °C, [90.0 Homogeneous/Tubular reactor with mechanical Park et al.
5.0 % (w/w) 30 min agitation/– (2009)
WCO 15:1 Methanol SO42-/SnO2–SiO2 Biodiesel 6.0 % (w/w) 150 °C, 88.2 Heterogeneous/300 mL stainless steel batch Lam and
50 % (v/v) 1.5 h reactor equipped with thermocouple and Lee
magnetic stirrer/50 mL (2010)
Sunflower 6:1 Methanol CaO THF 5.0 % (w/w) 60 °C, 98.1 Heterogeneous/500 mL three-neck round- Todorović
DEE 20 % (w/w) 4h 88.3 bottomed flask, placed in a glass chamber and et al.
equipped with a magnetic stirrer and a (2013)
Dioxane 94.8
condenser/92 g
MEK 14.7
TEA 97.9
Hexane 98.8
EA 97.1
Soybean 10:1 Methanol CaO Glymes 0.05 g 60 °C, [98.0 Heterogeneous/5 mL micro-reaction vessel Tang et al.
24 % (w/w) 4h sealed and incubated in an oil bath/0,7 g (2013b)
Soybean – Methanol CALB Glymes 10 % (w/w) 50 °C, 95.5 Enzymatic/5 mL micro-reaction vessel sealed Tang et al.
– 24 h and incubated in an oil bath/0,1 g (2013a)
Soybean 3.65:1 Methanol CALB ? RML Isooctane 19 % (w/w) 50 °C, 95.3 Enzymatic/25 mL Erlenmeyer shake flasks in a Jin et al.
Sunflower (83 %) ? 90 % (v/v) 12 h 94.3 shaking incubator/0.965 g (2013)
tert-butanol
WFO 91.2
(17 %)
GO 90.1
Rev Environ Sci Biotechnol
Rev Environ Sci Biotechnol

WCO waste cooking oil, WFO waste frying oil, GO gutter oil, CALB Candida antarctica lipase B, RML Rhizomucor miehei lı́pase, IPA isopropyl alcohol, THF tetrahydrofuran,
References There are two basic principles of operation in

(2010a)
Li et al.
biodiesel production via membrane technology (Shuit
et al. 2012); these are separation based on oil droplet size,
Enzymatic/50 mL flask stoppered with a plug/– which requires a microporous ceramic or carbon mem-
brane (Gomes et al. 2011; Atadashi et al. 2012; Xu et al.
2014); and separation based on catalytic membranes,
Transesterification/Experimental apparatus/

which involves a non-porous dense polymer membrane

such as polyvinyl alcohol (PVA) (Guerreiro et al. 2010;
Zhang et al. 2012; Casimiro et al. 2014). In membrane
separation based on oil droplet size, the membrane acts
as a selective barrier and plays an important role by
allowing the reaction to be carried out in an emulsion
Typical oil sample

where unreacted triglycerides are continuously separated

from the methyl ester product, thus eliminating side
DEE diethyl ether, AN acetonitrile, DCB dichlorobenzene, MEK methyl ethyl ketone, TEA triethanolamine, EA ethyl acetate

reactions. As a result, a high purity biodiesel is obtained

and the reaction equilibrium is shifted to the product side
(Dubé et al. 2007; Shuit et al. 2012). Membrane
separation based on the catalytic membrane is based on
96.4
Ester

the interaction between the target component and the

yield
(%)

polymer group of the membrane. In biodiesel production

via this type of catalytic membrane, glycerol and
conditions
Reaction

methanol are able to form hydrogen bonds with the

40 °C,
20 h

OH groups in the polymer membrane and are therefore

continuously removed from the mixture during the
reaction. The unreacted triglycerides and the produced
solvent amount

4.3 % (w/w)
Catalyst/Co-

biodiesel are retained within the membrane because of

their difference in chemical properties with the polymer
group of the membrane (Guerreiro et al. 2006; Shuit et al.
2012). Membrane technology also enables the integra-
–

tion of both reaction and separation steps into a single

AN (60 %)
Co-solvent

process, thereby reducing separation steps (Cao et al.

butanol
(40 %)
? tert-

2008; Saleh et al. 2010). In comparison to the conven-

tional biodiesel production processes, the main advan-
tage offered by membrane reactors is therefore the
435 ? Lipozyme

reduction of operating costs due to the elimination of

intermediate processing steps (Shuit et al. 2012).
Novozyme

Presently, the main engineering aspects of membrane

TL IM
Catalyst

technology (namely reactor design and membrane

characteristics) have not yet been fully explored;
nevertheless, some publications have started to show
Methanol

relevant advances in order to successfully develop

Alcohol

membrane reactors for biodiesel production. Most

studies have been carried out using ceramic membranes
operating as selective barriers for the separation of
Molar
Table 9 continued

6.4:1
ratio

biodiesel and reaction by-products. Atadashi et al.

(2012), for example, used a ceramic membrane to purify
crude biodiesel considering the simultaneous retention
Stillingia

of glycerol and catalyst. The effects of process operating

Oil

parameters were investigated and the optimum

123
Rev Environ Sci Biotechnol

conditions obtained were transmembrane pressure

Chong et al.
Cheng et al.
References
200 kPa, temperature 40 °C, and flow rate 150 L/min.

Xu et al.

Xu et al.

Ko et al.
Atadashi
(2012)

(2012)

(2014)

(2013)

(2012)
(2013)
et al.
The results showed that with membrane technology,
biodiesel with high qualities that meet the stringent
international standards specifications can be achieved

Heterogeneous/Lab-scale membrane reactor equipped

Heterogeneous/Lab-scale membrane reactor equipped

Enzymatic/Continuous membrane bioreactor system.

Homogeneous/Tubular membrane reactor integrated

(Atadashi et al. 2012). On another example, Xu et al.

Homogenous/1 L batch reactor with mechanical

Homogeneous/5 L batch reactor coupled with a
thermometer and a mechanical stirrer. Multi-

agitation. Ceramic tubular TiO2 membrane/–

(2014) investigated the production of biodiesel from

with a ceramic cylindrical membrane/30 g

with a ceramic cylindrical membrane/30 g

channel tubular-type Al2O3/TiO2 ceramic
soybean oil in a membrane reactor in which a ceramic

50 k (open circle) MWCO membrane/–

membrane packed with MCM-41 supported p-toluene-
Transesterification/Experimental

sulfonic acid (PTSA) was used. In this study, the main

apparatus/Typical oil sample

aim of investigators was to couple the solid acid

catalyzed transesterification with membrane separation
in a membrane reactor and then optimize the process.
with a pre-reactor/–

membrane/2.5 L

Reaction temperature, catalyst amount, and circulation

velocity were found to be the most significant param-
eters of the reaction. The highest biodiesel yield of
84.1 % was obtained at 80 °C of temperature, 0.27 g/
mL of catalyst amount, 4.15 mL/min of circulation
velocity, and transmembrane pressure of 80 kPa. In a
yield (%)

related study (Xu et al. 2013), the same authors utilized a

Ester

50.0

84.1

91.0

95.0

fixed bed membrane reactor to produce biodiesel from

–

soybean oil, but this time with a ceramic membrane

Residence

packed with KF/hydrotalcite solid catalyst. The opti-

(H)time

mized FAME yield of 91.0 % was obtained at 70 °C of

reaction temperature, 0.0531 g/cm3 of catalyst amount,
1.2

1.0

1.0

3.0

2.5

12

and 3.16 mL/min of circulation velocity, showing that

0.05 % (w/

0.1 % (w/

3.0 % (w/

the combination of solid base catalyzed transesterifica-

Catalyst

270 mg/

531 mg/
amount

1.0 %
(w/w)

cm3

cm3

tion and ceramic membrane microfiltration can effec-

w)

w)

w)

tively contribute to high quality biodiesel production

without any unreacted triglycerides (Xu et al. 2014).
4.15 mL/min

3.16 mL/min

0.40 mL/min
200 mL/min
Table 10 Membrane reactors for transesterification of vegetable oils
Circulation

0,018 m3/s
150L/min

Other experimental works are presented in

velocity

Table 10. From the review of the table, it is clear that

membrane reactors are still very much under explored
regarding biodiesel production from novel catalysts,
0,8 9 105kPa, 60 °C

but can be considered an emerging and promising

200 kPa, 40 °C
13 kPa, 65 °C

80 kPa, 80 °C

50 kPa, 70 °C

technology despite the few studies already published.

temperature
Membrane

From this perspective, one can conclude that more

pressure/

–, 50 °C

research about membrane characteristics and optimi-

zation of key process parameters (with diversified
feedstocks and catalysts) is needed to advance mem-
hydrotalcite

brane technology in biodiesel industry beyond current

Novozym
MCM-41
Catalyst

PTSA p-toluenesulfonic acid

state.
PTSA/
NaOH

NaOH

435
KOH

KF/
Methanol

Methanol

Methanol

Methanol

Methanol

Methanol
Alcohol

6 Conclusion

The hindrances faced by conventional biodiesel pro-

Soybean

Soybean

Soybean
Canola

Canola

duction processes have limited the establishment of

Palm
Oil

biodiesel as an economic and environmentally friendly

123
Rev Environ Sci Biotechnol

fuel in the commercial market. Due to its fast kinetics commercial scale is still a challenge due to issues
and good economic performance, homogeneous transe- relating not only to its reusability and regeneration, but
sterification methods are still very common and widely also to the low activity of the catalysts tested. In this
available commercially, but environmental consider- regard, some new advanced technologies have been
ations associated with the high energy consumption and introduced with good results in recent years. Technol-
the costly separation processes required for its opera- ogies such as application of ultrasonic irradiation,
tion, as well as the unfeasibility of producing biodiesel microwave heating, co-solvents, and membrane reac-
from cheaper unrefined vegetable oils have called for tors are able to complement the use of heterogeneous
the search of novel biodiesel production technologies. and enzymatic catalysts by reducing energy consump-
The use of heterogeneous and biocatalysts instead of tion and enhancing the reaction rate and ester yield.
its homogeneous counterparts are currently recognized Nevertheless, most of these process intensification
as two of the most promising technologies in biodiesel techniques are still in its infancy as regards to biodiesel
field. Heterogeneous catalytic systems can ease the synthesis and deeper development will be required from
separation of biodiesel from the reaction mixture and an engineering point of view for its complete integration
allow the recovery and reuse of the catalyst, potentially with the novel production systems. Specifically, more
leading to higher efficiencies and lower production optimization studies and mathematical models describ-
costs. The utilization of biocatalysts offers the same ing the process flow will be necessary for a better
advantages, but the reaction can be carried out in milder understanding of reaction kinetics, therefore allowing
conditions and with a wider range of lipid sources, for better reactor design, cost performance analysis and
including unrefined feedstocks with high levels of FFA. process scale-up beyond current laboratory scale. Much
Apart from that, biodiesel production in supercritical remains to be made for biodiesel to constitute a
conditions also stands out when compared to conven- sustainable and economic alternative in transportation
tional methods as the reaction rate is higher, the reaction sector but judging from the new techniques being
time is shorter, and biodiesel separation steps are developed, biodiesel production systems are well placed
simpler. However, the supercritical method requires to play a special role of in the energy paradigm of the
high pressures and temperatures which often translate to future.
higher production costs.
From this perspective, heterogeneous and biocata-
lysts seem to emerge as the future technologies of choice
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