Reactor Technology For Biodiesel Product

Progress in Energy and Combustion Science 74 (2019) 239–303
Contents lists available at ScienceDirect
Progress in Energy and Combustion Science

journal homepage: www.elsevier.com/locate/pecs
Reactor technologies for biodiesel production and processing: A review

Meisam Tabatabaei a,b,c,∗, Mortaza Aghbashlo d,∗, Mona Dehhaghi c,e,f,
Hamed Kazemi Shariat Panahi c,e, Arash Mollahosseini g, Mehdi Hosseini c,
Mohamad Mojarab Soufiyan c,d
a
Faculty of Plantation and Agrotechnology, University Technology MARA (UiTM), 40450 Shah Alam, Selangor, Malaysia
b
Department of Microbial Biotechnology, Agricultural Biotechnology Research Institute of Iran (ABRII), Agricultural Research, Education, and Extension
Organization (AREEO), Karaj, Iran
c
Biofuel Research Team (BRTeam), Karaj, Iran
d
Department of Mechanical Engineering of Agricultural Machinery, Faculty of Agricultural Engineering and Technology, College of Agriculture and Natural
Resources, University of Tehran, Karaj, Iran
e
Department of Microbial Biotechnology, School of Biology and Centre of Excellence in Phylogeny of Living Organisms, College of Science, University of
Tehran, Tehran, Iran
f
Faculty of Medicine and Health Sciences, Macquarie University, NSW, Australia
g
Department of Chemical and Biological Engineering, University of Saskatchewan, 57 Campus Drive, Saskatoon, Saskatchewan S7N 5A9, Canada
a r t i c l e i n f o a b s t r a c t
Article history: Diesel engines are preferred over spark ignition counterparts for heavy-duty applications and power gen-
Received 24 January 2019 eration plants because of their higher efficiency, durability, and productivity. Currently, the research inter-
Accepted 19 June 2019
ests have been propelled towards renewable and sustainable diesel fuels such as biodiesel in order to ad-
dress the environmental and energy security challenges associated with these energy systems. However,
Keywords: the most challenging issue concerning large-scale production of biodiesel is its relatively high cost over
Biodiesel fossil-based diesel owing to high feedstock and manufacturing costs. Therefore, cost-effective and eco-
Transesterification friendly biodiesel production technologies should be necessarily developed and continuously improved in
Intensification order to make this biofuel more competitive vs. its petroleum counterpart. Accordingly, this paper com-
Reactor technology
prehensively reviews biodiesel manufacturing techniques from natural oils and fats using conventional
Sustainability
and advanced technologies with an in-depth state-of-the-art focus on the utmost important unit, i.e.,
Economic impacts and policies
transesterification reactor. The effects of the main influential parameters on the transesterification process
are first discussed in detail in order to better understand the mechanisms behind each reactor technol-
ogy. Different transesterification reactors; e.g., tubular/plug-flow reactors, rotating reactors, simultaneous
reaction-separation reactors, cavitational reactors, and microwave reactors are then scrutinized from the
scientific and practical viewpoints. Merits and limitations of each reactor technology for biodiesel produc-
tion are highlighted to guide future R&D on this topic. At the end of the paper, the sustainability aspects
of biodiesel production are comprehensively discussed by emphasizing on the biorefinery concept utiliz-
ing waste-oriented oils.
© 2019 Elsevier Ltd. All rights reserved.
Abbreviations: ACC, Annular centrifugal contactor; ASTM, American society for testing and materials; BSTR, Batch stirred tank reactor; [BMIm][BF4 ], 1-butyl-3-
methylimidazolium tetrafluoroborate; [BMIm][PF6 ], 1-butyl-3-methylimidazolium hexafluorophosphate; CFCTM , Controlled flow cavitation; CSTR, Continuously stirred tank
reactors; CTMAB, Cetyltrimethylammonium bromide; ECT, Electrical capacitance tomography; FAEE, Fatty acid ethyl ester; FAME, Fatty acid methyl ester; FBR, Fluidized bed
reactor; FCI, Fixed capital investment; FFA, Free fatty acid; GHG, Greenhouse gas; JSR, Jet-stirred reactor; L/dp , Length/diameter of particle; L/D, Length to diameter; LCA, Life
cycle assessment; LLPTC, Liquid-liquid ptc; LUC, Land-use change; OFR, Oscillatory flow reactors; OBR, Oscillatory baffled reactor; PBR, Packed bed reactor; PFR, Plug flow re-
actor; PTC, Phase-transfer catalyst; RTD, Residence time distribution; RTR, Rotating tube reactor; RED, Renewable energy directive; RPBR, Rotating packed bed reactor; RSSDR,
Rotor-stator spinning disc reactor; SCCD, Supercritical carbon dioxide; SCM, Supercritical methanol; SDR, Spinning disc reactor; SMCR® , Stacked multichannel reactors; SPR,
Shockwave power reactor; STT, Spinning tube-in-tube; TBR, Trickle bed reactor; WAF, Waste animal fat; WCO, Waste cooking oil.
∗
Corresponding authors.
E-mail addresses: [email protected], [email protected] (M. Tabatabaei), [email protected] (M. Aghbashlo).
https://doi.org/10.1016/j.pecs.2019.06.001
0360-1285/© 2019 Elsevier Ltd. All rights reserved.
240 M. Tabatabaei, M. Aghbashlo and M. Dehhaghi et al. / Progress in Energy and Combustion Science 74 (2019) 239–303
Contents
1. Biodiesel production. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240

1.1. Physical approaches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
1.2. Chemical approaches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
1.3. Aim and scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
2. Main parameters affecting transesterification reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
2.1. Catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
2.1.1. Type of catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
2.1.2. Effect of catalysts concentration on transesterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
2.1.3. Effect of catalyst shape and size on transesterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 248
2.2. Methanol-to-oil molar ratio . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
2.3. Mass-transfer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
2.3.1. Mixing system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
2.3.2. Temperature (heating system) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
2.3.3. Mass transfer intensification systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 251
2.4. Residence time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 252
2.5. Composition of oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
3. Reactor technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
3.1. Biodiesel production process modes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
3.2. Types of chemical reactors for biodiesel production. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
3.2.1. Tubular/plug-flow reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 254
3.2.2. Rotating reactors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
3.2.3. Simultaneous reaction-separation reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 269
3.2.4. Cavitational reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 275
3.2.5. Microwave reactors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 280
4. Environmental sustainability, economic viability, and policy-making aspects of biodiesel. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
4.1. Economic aspects and impacts of biodiesel production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281
4.2. Biodiesel policies and mandates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
4.3. Biodiesel tradeoffs and feedstock sustainability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 283
4.3.1. Edible and non-edible oil crops . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 283
4.3.2. Biodiesel production under biorefinery concept. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287
4.4. Social acceptance of biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 289
5. Concluding remarks and future prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 291
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 292
1. Biodiesel production 1.1. Physical approaches
Biodiesel (the most attractive biofuel types) as a biodegradable, In physical methods, specific proportions of diesel fuel and
sustainable, clean-burning, and nontoxic transportation fuel has other additives are employed to improve viscosity and volatility of
gained a lot of interest in recent years [1–3]. In fact, this green fuel natural oils. Since the chemical characteristics of natural oils re-
has gradually become more economical and widely used in many mains unchanged, inherent problems of straight natural oil persist
regions of the world due to the implementation of subsidiaries and as discussed in the subsequent section.
tax exemptions. In order to further boost the economic benefits Direct use and blending. The combustion of vegetable oils as
of biodiesel industry, glycerol as the main by-product of biodiesel diesel fuel was coined in 1893 when Rudolph Diesel, the German
production plants, which amounts to approx. 10 wt.% of the pro- inventor of diesel engine, examined peanut oil in his compres-
duction volume, can be valorized into combustion improvers for sion engine [15]. Although the application of vegetable oils was
diesel/biodiesel, such as solketal, solketalacetin, and acetins [4–6]. completely boycotted due to higher availability and lower cost of
In spite of these efforts, the production cost of biodiesel has still petrol-diesel in 1920, researchers again suggested the possibilities
remained a challenge toward its commercialization and industrial- of fueling diesel engines with natural oils in 1980. Brazilian re-
ization phases as well as competition with fossil fuels [7]. Biodiesel searchers successfully powered pre-combustion chamber diesel en-
highly resembles diesel fuel in terms of cetane number, density, gines with no adjustments using a diesel blend containing 10%
and viscosity [7–9]. Chemically, biodiesel is an alkyl ester (mostly sunflower oil. The application of up to 50% vegetable oil in diesel
fatty acid methyl ester abbreviated as FAME) of long chain fatty was tested by different scientists as well. In 1982, the first inter-
acids (C14–C24) synthesized from various renewable lipid feed- national conference on plant and vegetable oils as fuels was held
stocks such as vegetable oils and animal fats [10–12]. It is notewor- to consider various aspects of using vegetable oil directly in diesel.
thy that natural oils and fats can be used either in modified diesel These included oil production (oilseed processing and oil extrac-
engines in their neat form (direct use and blending as well as mi- tion) and fuel preparation methods to determine fuel cost, spec-
croemulsion; also known as physical approaches) or in existing ifications, and impact on engine performance and durability. Ad-
diesel engines in chemically modified form (pyrolysis and trans- ditionally, waste cooking oil (WCO) was filtered and mixed with
esterification; also known as chemical approaches) [13,14]. Table 1 5% diesel fuel to run a diesel fleet [16–18]. Although this cheap
compares these techniques with respect to their advantages and diesel fuel contained high thermal efficiency and no carbon build-
disadvantages. up issue (coking), the blend required pre-heating for liquefaction
M. Tabatabaei, M. Aghbashlo and M. Dehhaghi et al. / Progress in Energy and Combustion Science 74 (2019) 239–303 241
Table 1
Advantages and disadvantages of the four main biodiesel production processes.
Method Advantage Disadvantage
Direct use and blending - Low capital and production costs - Solidification of blend at cold temperatures
- Simple production - Impractical and inappropriate for direct use in diesel
engines
- High viscosity
- Gum formation
- Lubricating oil thickening
- Incomplete fuel combustion
- Oil deterioration
- High free fatty acid (FFA)
- Low volatility
- Unsaturated hydrocarbon chains reactivity
- Injector nozzles plugging
- Poor atomization
- Engine durability reduction,
- Higher air pollution emission
- Higher engine maintenance costs
- Higher engine wear
Microemulsion - Biodiesel formation with lower viscosity and higher liquidity - Heavy deposition of carbon residue
- Lower nitrogen oxide emissions - Inadequate combustion
- No by-product or waste formation - Lubricating oil thickening
- Clear, single phase, and thermodynamically stable colloidal equilibrium - Random injector needle sticking
dispersion of biodiesel fluid
Pyrolysis - Suitable for areas with well-established hydro-processing industry - High production cost
- Generation of value-added by-products like syngas - Complex equipment requirement
- Biofuel with satisfactory physical and chemical properties - Biofuel has no oxygenated value
- Producing short chain molecules with more similarities to
gasoline than diesel fuel
Transesterification - The most common method for production of biodiesel - Dry alcohol and oil must be used to increase biodiesel yield
- Unreacted feedstock can be recycled by avoiding saponification
- The by-product (i.e., glycerol) can be converted into value-added products - Glycerol must be efficiently separated to avoid generation
of hazardous gases (i.e., acetaldehyde, formaldehyde)
- Expertise requirement
- Complex equipment requirement
at cold temperatures and also contaminated lubricating oil. The microemulsions to produce a peanut oil/diesel mixture that met
viscosity of lubricating oil was increased to the point of replace- the biodiesel fuel standards. Najjar and Heidari [22] formulated a
ment after every 6440–7240 km because of the polymerization of nine-month stable, low viscosity microemulsions containing wa-
polyunsaturated vegetable oils. Finally, it was concluded that some ter droplets of 4.6 nm by blending 1-butanol as co-surfactant
properties of vegetable oils including gum formation, high density, with diesel/colza oil (4:1 w/w), water, and Span 80 surfactant
high FFA content, high viscosity, low volatility, lubricating oil thick- (47:44:5:4 wt.%). The addition of diethylene glycol ethyl ether and
ening, and unsaturated hydrocarbon chains reactivity make direct ethyl acetate improved the fuel properties while considerably low-
application of pure vegetable in diesel engines inappropriate and ered the emissions of CO and NOx of microemulsion biofuels made
impractical [19]. If engine remains unmodified, these drawbacks from diesel/palm oil (1:1 v/v), ethanol, as well as some surfac-
lead to inappropriate fuel combustion, injector nozzles plugging, tants and co-surfactants [23]. An ecofriendly microemulsion biofuel
poor atomization, engine durability reduction, higher air pollu- with comparable fuel properties with biodiesel was generated by
tion emission, higher engine maintenance costs, and higher engine blending sorbitan monooleate (a sugar-based surfactant) and oc-
wear. tanol (1:8 molar ratio) with palm oil [24]. A number of studies
Microemulsion. The viscosity of vegetable oil and its low liq- produced bio-oil via thermochemical liquefaction (250–350 °C, 5–
uidity as well as high nitrogen oxide (NOx ) emissions of biodiesel 10 MPa) of sludges and subsequently mixed it with various solvents
can be improved through microemulsification without formation of (such as biodiesel, diesel, ethanol, methanol) and surfactants (such
by-product and waste. This method is classified into two groups, as rhamnolipid) to produce diesel fuel microemulsion, represent-
i.e., water in oil and Winsor Type II and involves mixing mi- ing better cold flow properties, improved stability and solubility,
croemulsions, solvents, or surfactants with animal fats and veg- reduced activation energy, satisfactory viscosity, and shorter igni-
etable oils to produce a clear, single phase, and thermodynamically tion delay [25,26]. However, microemulsification of oils must be
stable colloidal equilibrium dispersion of optically isotropic fluid further improved to address heavy deposition of carbon residue,
with micro-structures (1–150 nm in size) and droplet diameter of inadequate combustion, increased viscosity of lubricating oils, and
10–100 nm [18]. Different solvents including 1-butanol, 2-octanol, random injector needle sticking.
butanol, ethanol, hexanol, and methanol can be applied in prepara-
tion of microemulsions, with or without diesel fuel. A microemul- 1.2. Chemical approaches
sion comprising of soybean oil, 2-octanol, methanol, and cetane
improver (52.7:33.3:13.3:1.0) has been already approved by 200 h These methods modify the chemical nature of natural oils and
Engine Manufacturers Association test [20]. Moreover, when short- fats itself for its better exploitation in fuel industry.
term performance is considered, ionic and non-ionic microemul- Pyrolysis. This is a thermochemical process applying heat (300–
sions prepared by mixing ethanol with soybean oil have qualities 700 °C or higher) to convert various feedstocks into value-added
close to No. 2 diesel fuel. chemical species (such as energy carriers) under anoxic condition
Nguyen et al. [21] extracted peanut oil (95% efficiency, at atmospheric pressure [27]. More specifically, this technique al-
10 min, room temperature) using diesel-based reverse-micellar lows the degradation of animal fat, methyl esters of fatty acids, or
vegetable oil into a fuel resembling diesel fuels under a predefined it economically unfeasible and hinder its commercial application
process duration with or without catalyst. Pyrolysis of oils is par- [18,39,40].
ticularly suitable for areas with well-established hydro-processing The elementary reaction of a triglyceride with methanol is
industry due to its similarity to conventional petroleum refining a three-step successive reversible reaction. First, methanol reacts
method [28,29]. A second generation biofuel was synthesized from with triglyceride producing a diglyceride, followed by the reaction
pyrolysis-treated WCO (800 °C, 15 °C/min) to yield 80 wt.% bio-oil of diglyceride with methanol producing a monoglyceride, and fi-
with a high heating value of 8843 kg/kcal. The by-products of this nally monoglyceride is reacted with methanol yielding glycerol. A
process, i.e., syngas and biochar could also be conveniently con- mole of FAME is produced in each of the above-mentioned steps
sumed as energy source for the pyrolysis reactor and iron-rich fer- [41,42]. Thus, the overall reaction can be summarized as follows
tilizer, respectively [30]. [43]:
Abdelfattah et al. [31] synthesized castor-based diesel fuel via
catalyst
pyrolysis of crude castor oil in presence of 1% v/v NaOH and ZMS- TG + 3 MeOH −−−−→ Glycerol + 3 FAME (1)
5 as catalysts. The resultant diesel fuel showed satisfactory phys-
ical and chemical properties and was suitable as 5–10% blend in These reactions proceed with different reaction rate constants
diesel to run single cylinder four stroke direct injection compres- (km ) in both forward and reverse directions and can all be con-
sion ignition engine. In another study, a high energy (42–49 MJ/kg), sidered second order or pseudo-second order reactions [41]. The
low nitrogen and oxygen, sulfur-free liquid oil with C13–C24 hy- first reaction occurs at a slower rate compared with the second
drocarbons was obtained through microwave co-pyrolysis of WCO and the third reactions owing to the formation of diglyceride and
and waste polyolefins under vacuum (20–25 °C/min, 62 wt.% yield) mass transfer limitations imposed by the immiscibility of the oil-
[32]. Despite the high versatility of pyrolysis technique, it is not methanol combination [44–46]. The second reaction, however, is
highly appreciated due to high production cost as well as complex the fastest step of all because the produced methyl esters con-
equipment requirement. Moreover, the generated biofuel has no tribute to the development of a homogeneous phase by acting
oxygenated value and harsh reaction conditions lead to production as a solvent or co-solvent in the reaction [47]. Unlike the first
of short chain molecules with more similarities to gasoline than two steps, the third reaction tends to reverse because of the low
diesel fuel. amount of reactants remained [48].
Transesterification. The most widely employed chemical meth-
ods for converting natural oils and fats into diesel fuel is trans-
esterification [33–35], in which, stoichiometrically, three moles of 1.3. Aim and scope
light alcohols (mainly methanol) react with one mole of triglyc-
eride. This process is usually performed in the presence of a cat- Currently, the high cost of biodiesel induced by high feedstock
alyst (60–70 °C, atmospheric pressure, 90 min) and results in the and process costs is the major obstacle hampering its widespread
production of a mono-alkyl ester (mainly methyl ester) called commercialization. Therefore, this paper is aimed at reviewing
biodiesel and glycerol as a by-product [36,37]. The unreacted al- biodiesel production techniques from natural oils and fats using
cohol can be recovered to some extent at the end of the process conventional and advanced reactors with an in-depth state-of-
and glycerol can be sold to existing markets to reduce the pro- the-art focus on the transesterification process as the beating
duction costs. The separation of glycerol is extremely important to heart of biodiesel plants. The effects of the main influential pa-
enhance the quality of biodiesel and to prevent formation of haz- rameters including quantity and type of catalyst, FFA content of
ardous gases, i.e., acetaldehyde or formaldehyde during its combus- feedstock, mixing intensity, alcohol/triglyceride molar ratio, reac-
tion [38]. The application of dry alcohol and oil (with low con- tion temperature, alcohol type, water content of feedstock, type
centration of FFA) is crucial for inhibiting the saponification and of oil, and reaction time [19,39,48,49] on the transesterification
increasing biodiesel formation. The holding time is in inverse re- process are first discussed in detail. Different transesterification
lation with temperature; however, temperature must be elevated reactors; e.g., tubular/plug-flow reactors (packed bed reactors,
above 60 °C in combination with pressure due to methanol boil- fluidized bed reactors, trickle bed reactor, oscillatory flow reactors,
ing point (65 °C) as the most widely used alcohol. Alternatively, a micro-channel reactors), rotating reactors (stirred tank reactors,
higher temperature at ambient pressure can be applied when other rotating/spinning tubes reactors, spinning disc reactors), simulta-
alcohols such as butanol or ethanol is used. In contrast, lower cost neous reaction-separation reactors (membrane reactors, reactive
of methanol as well as its chemical and physical features is highly distillation reactors, annular centrifugal contactors), cavitational
preferable for transesterification though it develops a two-phase reactors (sonochemical/ultrasonic reactors, hydrodynamic cavita-
system. tion reactors, shockwave power reactors), and microwave reactors
Among different catalysts, i.e., acids, alkalis, and lipases (en- are then scientifically and practically scrutinized. Advantages and
zymes), alkaline-catalyzed process is currently regarded as the disadvantages of each reactor technology are comprehensively
most popular and commercial approach by accelerating the re- described. Some of the challenging issues impeding commercial-
action up to 40 0 0 times. Alkoxides such as sodium methoxide, ization of each reactor technology are also highlighted. In the
hydroxides such as potassium or sodium hydroxides, and potas- final part of this paper, the sustainability aspects of biodiesel
sium and sodium carbonates are some common alkalis for this obtained through transesterification of various available feedstocks
purpose. Despite the higher price, the best alkaline catalysts are have been analyzed with respect to net GHGs emission, impacts
alkaline metal alkoxides that provide up to 98% yields at low on tropical forests and biodiversity, socioeconomic impacts, and
concentrations (0.5 mol%) after 30 min reaction time. At higher food/water vs. fuel debate. The biorefinery concept utilizing waste-
molar concentration of catalyst (1–2 mol%), alkoxides can be sub- oriented oils is also elaborated as a potential strategy to further
stituted by cheaper catalysts including potassium or sodium hy- boost the economic viability and environmental sustainability of
droxides. In contrast, acidic treatment, catalyzed by hydrochloric or the biodiesel industry.
sulfuric acids, is mostly applied as a pre-treatment process (es- Overall, the present manuscript is very relevant to ongoing re-
terification) for raw materials with high FFA contents. Although search on biodiesel production and processing while the detailed
enzyme-catalyzed transesterification can be done in both aqueous information provided will be very useful for researchers (i.e., en-
and organic systems and it is chemically clean and specific reac- couraging future R&D) in the field, industrial experts and policy
tion, the high cost of enzyme and long processing time render makers.
2. Main parameters affecting transesterification reaction the production of biodiesel with 98.4% yield [55]. Su [56] tested
three homogeneous acid catalysts including hydrochloric acid, ni-
2.1. Catalyst tric acid, and sulfuric acid to convert soybean oil into biodiesel. All
these acids showed high catalytic activities; however, hydrochlo-
2.1.1. Type of catalyst ric acid was the only recoverable acid and could be reused for
2.1.1.1. Homogenous catalysts. Homogeneous catalysts have been up to five cycles. After optimization of the process, a conversion
conventionally used in transesterification reaction by the biodiesel of 98.1% was obtained at 76.6 °C and methanol-to-oil molar ratio
industry. Homogeneous basic and acidic catalysts are inexpensive of 7.9:1.
and effective, but both require excess amount of alcohol and rela-
tively high energy to complete the conversion. Moreover, their ap- 2.1.1.2. Heterogeneous catalysts. The biodiesel production cost
plication is usually limited to batch processes and a catalyst sepa- can be discounted by applying heterogeneous catalysts [57,58],
ration step is inevitable. offering several advantages such as easy recovery from the end
Homogeneous basic catalysts. Alkaline metal hydroxide and products (i.e., biodiesel and glycerol) as well as high tolerance to
methoxides such as potassium hydroxide (KOH), sodium hydrox- feedstock moisture and FFAs contents. These advantages reduce
ide (NaOH), potassium methoxide (CH3 KO), and sodium methox- saponification and contribute to the production of up to 24% more
ide (CH3 ONa) are the most commonly used homogeneous base pure biodiesel and glycerol, compared with that of homogeneous
catalysts in transesterification reaction [50]. Among them, NaOH catalysts (75% purity). Nevertheless, heterogeneous catalysts also
and KOH are extensively used by the industry in transesterifica- suffer from several disadvantages including more costly operating
tion process. Although catalysts containing sodium are preferable conditions (higher temperature and pressure), less contact with
compared with potassium-based catalysts because of their lower the reactants (lower conversion rate), and the possibility of leach-
molecular weight, potassium phosphate could be obtained after ing solid supports and consequent contamination of the produced
neutralization of KOH at the end of the process and used as fer- biodiesel as well as loss of the catalyst [49].
tilizer in agriculture [51]. Alkaline-catalyzed biodiesel production Heterogeneous basic catalysts. Various types of heterogeneous
follows a simple mechanism through which a tetrahedral interme- basic catalysts including hydrotalcites, metal oxides, mixed metal
diate is initially formed as a result of the interactions between the oxides, supported hydroxides and oxides, and zeolites have been
negative species of the incorporated alcohol (such as CH3 O− ) and used in transesterification reaction. Among the alkaline metal ox-
the carbonyl groups of the oily feedstock. Afterwards, new O–H ides, calcium oxide (CaO) has been known as a non-corrosive and
bonds are formed by the departure of R1 COOCH3 . Reformation of ecofriendly alkaline catalyst with a high catalytic activity. Mixed
carbonyl groups will continue for two more identical cycles so that metal oxides have also been introduced as promising heteroge-
a methyl ester is formed (Fig. 1). neous basic catalysts. These catalysts consist of two or more met-
A study conducted by Dias et al. [52] revealed that sodium- als and the characteristics of the catalyst depend on the type and
based catalysts like NaOH and CH3 ONa have higher activities in the amount of each of these metals. The efficacy of various un-
comparison with KOH for conversion of sunflower oil, WCO, and supported mixed metal oxides including CaMnOx , BaMnOx , CaFeOx ,
soybean oil. Notably, some investigations have documented that BaFeOx , CaZrOx , and CaCeOx in conversion of animal fats into
alkali methoxides are more desirable in the industry than alkali biodiesel have been studied by Dias, Alvim Ferraz [59]. Although
hydroxides because they do not generate water in reaction sys- all the mixed metal oxides presented great basicity, the only un-
tem. Application of homogeneous alkali catalysts in the industry supported mixed metal oxides that showed catalytic activity was
has advantages such as high catalytic activity, low cost, wide avail- CaMnOx with a biodiesel yield of 98% (4 wt.%, 60 °C, 9 h).
ability, and short reaction time. However, it is accompanied with Taufiq et al. [60] synthesized CaO–La2 O3 metal oxide as cata-
some unfavorable issues as well. For example, homogeneous ba- lyst for transformation of jatropha oil into methyl ester. The cata-
sic catalysis is limited to batch process, which needs high amount lyst was synthesized through co-precipitation procedure with vari-
of energy and high product cost. Moreover, water production, and ous Ca:La atomic ratios. A yield corresponding to 87% was resulted
subsequently saponification could lower the final yield of methyl when the reaction was carried out with 4% catalyst at 60 °C and
esters. Importantly, alkali catalysts are sensitive to high content of methanol-to-oil molar ratio of 24:1. The catalyst was regenerated
FFA in feedstock. Therefore, substrate containing more than 3 wt.% through washing with methanol and calcination at 900 °C, but it
of FFA must be pre-treated using acid catalysts to decrease the acid lost its activity after three cycles and the conversion of oil into
value before alkali catalyzed-transesterification [53]. biodiesel reduced to 18%. Sahani et al. [61] examined the strontium
Homogeneous acid catalysts. Acid catalysts are used less com- lanthanum mixed metal oxide as catalyst for converting Schleichera
monly than their basic counterparts in transesterification reaction Oleosa oil into biodiesel. A FAME conversion of 76% was obtained in
mainly due to their slow reaction rate and corrosive nature. the presence of 1.5% of catalyst loading with methanol-to-oil molar
In addition, higher alcohol requirement, compared with that of ratio of 14:1 at 60 °C for 40 min.
the homogeneous basic catalysts is another major shortcoming Zeolites are another effective heterogeneous catalyst used in
associated with the application of acidic catalysts [54]. In contrast transesterification process. Zeolites are constructed by SiO4 and
to alkali catalysts, acid catalysts can be used for conversion of AlO4 -tetrahedral structures, which constitute a crystalline alumi-
low cost feedstocks into biodiesel due to their insensitivity to nosilicate with high surface area. This microporous structure and
the high amount of FFA in oils. Moreover, saponification never high capability in adsorption mark zeolites as efficient catalysts in
occurs during acidic catalysis. The most common acid catalysts biodiesel production. These compounds are categorized in cation-
applied in esterification reaction are sulfuric acid, phosphoric acid, exchange materials, which can generate various types of structures
hydrochloric acid, and sulfonic acid. During the acid-catalyzed with different chemical and physical characteristics by substitution
biodiesel production process, tetrahedral species are resulted from of cations during ion exchange process. Zeolites Beta, X, A, Mor-
the interaction of positively-charged hydrogen ions and carbonyl denite, USY and ZSM-5 are the most common zeolites. Babajide
groups by the nucleophilic attraction of alcohol. In the next step, et al. [62] investigated the catalyst activity of zeolite FA/NaX for
H+ is mobilized and the process is carried out for two more cycles conversion of sunflower oil into methyl ester. FA/NaX was synthe-
so that a methyl ester is formed (Fig. 2). sized from coal fly ash, a by-product of coal combustion, and ion
Trifluoroacetic acid (0.2 M) was used for acid catalysis of soy- exchanging with K+ . Conversion of oil was conducted in methanol-
bean oil at 80 °C using methanol-to-oil molar ratio of 20:1 for to-oil molar ratio 6:1 at 65 °C with 3 wt.% of catalyst concentration.
Fig. 1. Schematic steps of base-catalyzed transesterification.
The biodiesel production yield was reported as 56% after 8 h of (wt.) of KOH was loaded on different supporters including Al2 O3 ,
reaction time. To achieve higher yields, they used ion exchange Nd2 O3 , TiO2 , and ZrO2 . The best results were obtained by using
process with potassium acetate to synthesize the catalyst FA/KX. KOH/Nd2 O3 with a yield of 90%, followed by KOH/Al2 O3 with a
The substitution of catalysts increased the product yield to 83.5% biodiesel yield of 89%. Moreover, they found that KOH/Nd2 O3 could
with same reaction time. The catalyst was also reused for further be used five times without any loss in functionality.
reactions without activity loss after three cycles. Heterogeneous acidic catalysts. Heterogeneous acid catalysts
Hydrotalcites are anionic clays which are known as aluminum must meet some criteria such as having hydrophobicity, high num-
and magnesium hydroxycarbonates. Hydrotalcites can be thermally ber of active sites, and mild acid strength to be appropriate cata-
decomposed and mixed oxide elements including MgAl2 O4 and lysts for transesterification reaction [51]. Although acidic catalysts
MgO can be generated. These elements with high surface area pro- are less attractive than basic catalysts for biodiesel synthesis be-
vide suitable catalysts for biodiesel synthesis. In a study presented cause of their low activity rate, recent investigations have led to
by Navajas et al. [63], magnesium-aluminium hydrotalcites (2 wt.%) new advancements in acidic catalysis minimizing their limitations.
was used for transformation of sunflower oil into methyl ester at Development of solid acid catalysts which possess both character-
methanol-to-oil molar ratio of 48:1 and reaction temperature of istics of heterogeneous basic catalysts and mineral acids (such as
60 °C. High yield (96%) was achieved after 8 h of reaction time and cation exchange resin, hetero-polyacids, silica-alumina, sulfonated
the catalyst was successfully recovered for reutilization. Another polystyrene, and zeolites) capable of performing simultaneous es-
group of heterogeneous basic catalysts are alkaline hydroxides sup- terification and transesterification reactions while being resistant
ported on inorganic oxides. Li et al. [64] explored the effect of vari- to water content and high FFA content is among such advance-
ous oxides as supporter of KOH on catalysts activity. Thirty percent ments [65].
Fig. 2. Schematic steps of acid-catalyzed transesterification.

Table 2
Recent reports (2016 to 2018) on the application of different kinds of homogeneous and heterogeneous catalysts for converting natural oils and fats
into biodiesel.
Feedstock Alcohol Catalyst Conditions Yield Ref.
Soybean oil Methanol (1:30)1 1 wt.% Cs-Na2 ZrO3 Basic heterogeneous 65 °C, 15 min 98.8% [71]
Waste cottonseed oil Methanol (1:30) 5 wt.% Ti/SiO2 nanoflowers 65 °C, 204 min ˃98% [72]
Macaw palm oil Methanol (1:9) 2 wt.% Strontium and Nickel 65 °C, 300 min 97% [73]
Canola oil Methanol (1:24) 5 wt.% Li/TiO2 65 °C, 180 min 98% [74]
Sunflower oil Methanol (1:9) 3 wt.% CaO-based/Au nanoparticles 65 °C, 180 min 94–97% [75]
Soybean oil Methanol (1:4.6) 15 wt.% CaO-K2 O 70 °C, 240 min 99% [76]
Cooking oil Methanol (1:12) 5 wt.% Zinc-doped calcium oxide 65 °C, 132 min >98% [77]
palm oil Methanol (1:9) 5 wt.% Calcium oxide functionalized with strontium 65 °C, 30 min 98.31% [78]
WCO Methanol (1:10) 8 wt.% FeCl3 -modified resin 90 °C, 120 min 92% [69]
Castor oil Methanol (1:12) 5 wt.% Si-MMT- pH-SO3 H 60 °C, 300 min 89.8% [79]
Various oils Methanol (1:12) 2.5 wt.% Sodium silicate 65 °C, 30 min 97% [80]
Rubber seed oil Methanol (1:9) 9 wt.% Sodium metasilicate 65 °C, 40 min 97% [81]
Palm oil Methanol (1:12) 9 wt.% CaO 60 °C, 120 min 90% [82]
Scenedesmus obliquus lipid Methanol (1:12) 15 wt.% Tungstated zirconia 100 °C, 180 min 94.58% [69]
Canola oil Methanol (1:7.6) 5.3 wt.% Calcined dolomite 60 °C, 150 min 96.6% [83]
Castor oil Methanol (8:1) 11 wt.% Ni doped ZnO nanocatalyst 55 °C, 60 min 95.20% [84]
WCO Methanol (1:10) 3 wt.% Magnetic SO4 /Fe-Al-TiO2 solid acid 90 °C, 150 min 96% [70]
Waste cotton seed oil Methanol (1:40) 10 wt.% Mesoporous CeO2 /Li/SBA-15 65 °C, 240 min >98% [85]
Palm oil Methanol (1:8) 5 wt.% 30Ca/APB-700 65 °C, 150 min 93.4% [86]
WCO Methanol (1:30) 5 wt.% Tungsten supported TiO2 /SiO2 65 °C, 240 min >98% [72]
Soybean oil Methanol (1:15) 1 wt.% Calcinated form of waste tucuma peels 80 °C, 240 min 97.3% [87]
Soybean oil Methanol (1:36) 8 wt.% Magnetic LiFe5 O8 -LiFeO2 65 °C, 120 min 96.5% [88]
Oleic acid Methanol (1:9) 0.75 wt.% SO4 2− /La3+ /C 62 °C, 300 min 98.3% [89]
Soybean oil Methanol (1:36) 6 wt.% Fe3 O4 @SiO2 @CPTMS@amine 160 °C, 180 min 96% [90]
Soybean oil Methanol (1:9) 6 wt.% Calcined marble slurry and hydroxyapatite 65 °C, 180 min 94% [91]
Date seed oil Methanol (1:12) 5 wt.% Egg shell derived catalyst 65 °C, 90 min 93.5% [92]
Waste kernel oil Methanol (1:15) 3 wt.% Mn@MgO-ZrO2 90 °C, 240 min 96.4% [93]
1
Alcohol-to-oil molar ratio.
Non-edible oils or waste products of agriculture and food indus- and animals [104,105]. Although the price of enzymatic catalysts
try can be used for biodiesel production which in turn can solve, are relatively high, their industrial applications have been adapted
to some extents, the food vs. fuel debate [66–68]. If this is the by some companies around the world such as Hainabaichuan Co.
case, the application of heterogeneous acid catalysts is critical for LTD and Lvming Co. LTD (China), Piedmont Biofuel (USA), and
conversion of these low cost feedstocks. Guldhe et al. [69] tested Sunho Biodiesel Corporation (Taiwan) [106]. Enzymatic mechanism
tungstated zirconia (WO3 /ZrO2 ) as a heterogeneous acid catalyst (Fig. 3) is, however, slightly different as both positive and negative
for biodiesel synthesis from microalgal lipids. They compared the charges are available. Active sites containing acidic or basic char-
tungstated zirconia activity with homogeneous acid catalyst and acteristics initiate the reaction by donating or accepting protons in
enzymatic catalysts. Their results demonstrated that 94.6% FAME a mechanism known as Bi model. Accepting or donating behavior
conversion was achieved with WO3 /ZrO2 at 100 °C which was com- is in relation with the nature of the incorporated enzyme. Whilst
parable with that of the homogeneous catalyst but was superior vs. enzymes like lipase act as a hydroxyl (OH¯ ) group acceptor, other
the enzyme catalyst. Recently, a magnetic solid acid nano-catalyst enzymes like those bearing amine groups are expected to donate
(SO4 /Fe-Al-TiO2 ) was synthesized and used for conversion of WCO protons. Afterwards, the reaction is completed by the same steps
into biodiesel. The nano-catalyst showed high activities with 96% previously discussed in the acidic or basic mechanisms (Fig. 3).
of FAME yield under experimental conditions with remarkable sta- Table 4 tabulates a summary of the most recent research works
bility for reutilization over 10 cycles [70]. Table 2 tabulates a conducted (2016–2018) on the application of enzymatic catalysts
summary of the most recent research works conducted (2016– for converting natural oils and fats into biodiesel.
2018) on the application of different kinds of homogeneous and
heterogeneous catalysts for converting natural oils and fats into 2.1.2. Effect of catalysts concentration on transesterification
biodiesel. Catalyst loading in transesterification reaction is recognized
Table 3 tabulates some heterogeneous catalysts synthesized by as one of the critical factors to achieve the maximum biodiesel
different methods for biodiesel production. Moreover, this table yield. The lowest concentration of catalyst is normally decided
summarizes available techniques for recovering and regenerating in primary steps of process, and then it is gradually raised based
used catalysts. on the reaction conditions and products content. Amani et al.
[115] showed that FAME content increased to some point with
2.1.1.3. Enzymatic catalysts. Application of enzymatic catalysts in increasing the catalyst loading. In their study, the optimum cat-
transesterification reaction provides remarkable advantages over alyst loading was characterized as 3 wt.% in which the FAME
chemical catalysts. Enzymatic catalysts that are immobilized or sol- content stood at 90%. Higher concentrations of catalyst had
uble lipases are ecofriendly materials, which can be used as ef- negative influence on biodiesel production as the FAME content
ficient catalysts to convert low cost feedstock such as non-edible decreased to 83% in the presence of 4 wt.% of catalyst. According
oils into biodiesel in the presence of high amounts of FFA and to Ezebor et al. [116], increasing catalyst loading leads to product
water. In an enzymatic catalysis, feedstock treatment and catalyst adsorption and finally FAME yield reduction. Chuah et al. [117] ex-
removal are not needed. Moreover, the reaction occurs in mild amined the impact of basic catalyst loading on biodiesel produc-
conditions with low energy consumption, offering a sustainable tion from WCO. They tested various NaOH concentrations ranging
way for biodiesel production. Lipases used as catalyst are mainly from 0.5 to 1.25 wt.% while keeping other reaction factors constant.
originated from biological sources such as microorganisms, plants, Their results revealed that the conversion of triglyceride to methyl
Table 3
Heterogeneous catalysts synthesis and regeneration methods, and their reuse in conversion of various feedstocks into biodiesel.
Catalyst Synthesis method Regeneration Deactivation and Oil feedstock Ref.

reusability
(transesterification yield)
Freshwater mussel shell - Calcination-impregnation-at Calcination in air at 600 °C. 90% in 7th cycle Tallow [94]
900 °C for 4 h.
- Activation at 600 °C for 3 h 80% in 12th cycle
Ni doped ZnO nanocatalyst - Co-precipitation method1 NA2 85% in 5th cycle Castor [95]
- Calcinated at 800 °C
Layered Double Hydroxides - Co-precipitation method3 NA NA Sunflower [96]

and derived mixed oxide
- Calcinated at 450 °C
CaO-ZnO catalytic particles - Catalyst base preparation4 Washed with ethyl alcohol 64% in 2nd cycle Soybean [97]
and hexane, and
calcinated at 300 °C for 3 h
-Calcination method5
CeSO4 +MnSO4 +K2 CO3 - Co-precipitation6 NA NA Soybean [98]
catalyst
- Calcination at 600 °C for 5 h
Eggshell waste-derived CaO - Calcination of Dried and crushed Simple calcination 97–99% in 13th cycle Soybean [99]
catalysts eggshell at 800–1000 °C for 2 h
CaO-SiO2 (3CaO.SiO2 ) - Mechanochemical method NA Sustained its activity up Sunflower [100]
to 4th cycle
- Calcination at 700 °C for 2 h
KOH supported on activated - Dried and activated carbon (at NA 80% in 3rd cycle Corn [101]
carbon 110 °C) was added to KOH in
water, mixed (30 °C, 160 rpm,
24 h), and dried at 60 °C
MoO3 Catalyst synthesis7 and calcination NA ≥90% in 8th cycle Various oils [102]
at 600 (10 °C/min, 4 h)
Acid-activated bentonite - Acid activation8 NA NA Residual olive [57]
SO3 H-functionlized - Catalyst synthesis9 NA NA Residual olive [57]

multiwall carbon - Sulfonation step (98% H2 SO4 ,
nanotubes 110 °C, 3 h)
LiFe5 O8 -LiFeO2 catalyst - Solid state reaction10 NA >94% in 5th cycle Soybean [103]
- Calcination at 600–900 °C
1
1 M aqueous Zinc acetate stirred with 0.1 M Nickel acetate and 8% ammonia solution was added. After 2 h of continuous stirring, the nanocatalyst was precipitated from
homogeneous solution by dropwise addition of 0.4 M NaOH, recovered by filtration, and dried (80 °C for 3 h).
2
Not available.
3
Two liters (L) of precursor solution containing 0.4 M MgSO4 and 0.15 M Al2 (SO4 ) 0.59 Mg-to-Al ratio was added to 0.5 L of distilled water containing Na2 CO3 as pre-
cipitating agent (60 °C, pH 8–10) under continuous stirring. After 20 min, the catalyst was recovered by filtration, repeatedly washed with distilled water (i.e., filtrate pH of
5.5–6), and dried (i.e., 12 h at room temperature, then 70 °C for 1 h).
4
One gram (g) of ZnO stirred with 50 mL of 2 M CaCO3 aqueous solution for 3 h and dried (120 °C, 24 h).
5
Catalyst base was heated (4 °C/min) and kept at 100 °C for 75 min, followed by heating (3.5 °C/min) and keeping at 850 °C for 3 h, and cooling down to 20 °C (3 °C/min).
6
CeSO4 ,MnSO4 , and K2 CO3 (1:1:1 ratio) dissolved into deionized water and precipitated by slow addition of aqueous solution of KOH into the solution while vigorously
stirred at ambient temperature. After 2 h, the solid residue was washed, filtered, and dried at 50 °C.
7
10 mL hydrochloric acid (3.0 mol/L, aqueous solution) was dropwise added to 60 mL of aqueous solution of (NH4 )6Mo7 O24 •4H2 O (166.7 g/L deionized water) in Teflon
liner and stirred for 10 min. After autoclaving (150 °C, 12 h), yellow residue was repeatedly separated by centrifugation and washed with distilled water (10 mL) and finally
dried in an oven (100 °C, 12 h).
8
250 mL 5 N H2 SO4 was slowly added to 50 g bentonite (130 µm particle size) under continuous stirring (95–98 °C, 400 rpm, 2 h). The sample was neutralized by washing
with deionized water and dried in an oven (130 °C, 2 h).
9
Methane (carbon source, 50 mL/min) was decomposed over cobalt-molybdenum nanoparticles supported by nanoporous magnesium oxide (900 °C, 30 min) and the
product swept by hydrogen gas (carrier gas, 250 mL/min) hydrogen. The product was purified with i) HCl (18% solution, 25 °C, 16 h), filtered and repeatedly washed with
distilled water, then ii) dispersed in nitric acid (6 M solution, 70 °C, 6 h), filtered, dried, and heated (400 °C, 30 min).
10
Fe2 O3 and Li2 CO3 (1:1 ratio) were mixed in water and grounded.
Table 4
Recent reports (2016 to 2018) on the application of enzymatic catalysts for converting natural oils and fats into biodiesel.
Feedstock Alcohol Enzyme Conditions Yield Ref.

1 ®
Castor oil Methanol (1:6) 5% Liquid lipase Eversa Transform 35 °C, ≥8 h 94% [107]
Microalgae oil Ethanol (1:3) 10% Liquid Lipolase 100L 30 °C 97% [108]
WCO Methyl acetate (1:12) 6% Lipozyme TLIM 40 °C, 2h 90.1% [109]
Waste oil Methanol (1:6) 40% Novozyme® 435 50 °C, 14 h 72% [110]
Soybean oil Methanol (1:6) ZIF-67 45 °C, 60 h 78% [111]
Citrullus colocynthis oil Methanol (1:5) 14% Novozym 435 43 °C, 3.7 h 97.8% [112]
Rapeseed oil Methanol (1:6) 20% Lipase immobilized on APTES-Fe3 O4 magnetic nanoparticles 45 °C, 5h 89.4% [113]
Soybean oil Methanol (1:4.5) 1.45% CalleraTM Trans L lipase 35 °C, 24 h 96.9% [114]
1
Fig. 3. Schematic steps of enzymatic transesterification.
ester occurred incompletely at catalyst concentrations of less particle sizes have higher surface area; and therefore, could in-
than 1 wt.%, delivering just 63% yield at 0.5 wt.% NaOH. Increasing crease the transesterification reaction by reducing mass trans-
catalyst loading to 1 wt.% improved triglyceride conversion to fer limitations. Rahimzadeh et al. [57] synthesized and compared
97%. In contrast, more catalyst concentration (1.25 wt.%) decreased SO3 H-functionlized multiwall carbon nanotubes with acid acti-
the triglyceride conversion to 90%. The main issue about using vated bentonite and found that the latter had higher biodiesel
high concentrations of basic catalysts is the reaction of FFA with production yield mainly due to its larger pore volume (0.76 vs.
catalyst leading to saponification and water generation, both of 0.25 cm3 /g) and surface area (230 vs. 92.37 m2 /g). However, sepa-
which finally contribute to reduction of biodiesel yield. It has ration of very fine catalysts from reaction medium could be prob-
been also reported that using 3 wt.% of H2 SO4 resulted in 86.4% lematic. Moreover, the application of these catalysts could plug
biodiesel yield whereas higher concentrations of the catalyst (5 packed bed reactors (PBRs) by occupying the spaces between pel-
and 7 wt.%) did not have significant effect on FAME yield [118]. lets. Alternatively, some shape designs (e.g., solid cylinders, hol-
low cylinders with axially extruded holes, etc.) allow synthesizing
larger catalysts with high surface area while at the same time in-
2.1.3. Effect of catalyst shape and size on transesterification
fers higher stability and rigidity. Therefore, it is obvious that the
Catalyst shape and size could influence reaction process as
shape and size of catalysts are among the important criteria for
well as functionality of the system. Generally, catalysts with lower
determining the right packing particles for the reactor technologies 2.3. Mass-transfer
consisting catalyst beds.
The efficiency and the rate of the catalytic transesterification
2.2. Methanol-to-oil molar ratio are considerably diffusion controlled. The slow reactions in initial
and final stages are respectively due to reagents immiscibility and
The alcohol content determines biodiesel yield by preventing reactant unavailability, i.e., catalyst extraction by glycerol. These
transesterification reaction from proceeding in reversible direction phenomena slow down the reaction to the point that is not practi-
at the end of reaction. Various alcohols such as methanol, ethanol, cal for an economic one-step process [124]. The miscibility can be
tert-butanol, butanol, and isopropanol can be applied for transes- improved by application of different types of mixers or agitators
terification of oils. Among them, lower alcohols, i.e., methanol and as well as optimization of mixing intensity, alcohol-to-oil molar ra-
ethanol, are the most common alcohol used in this process. Other tio, pressure, temperature (heating system), and their combinations
alcohols are hardly applied because they are expensive and have thereof.
no economic justification. Methanol is advantageous over other al-
cohols, mainly due to its specific chemical and physical charac- 2.3.1. Mixing system
teristics. For instance, it has the capability to react quickly with Awareness about the effect of mixing intensity on the rate of
triglyceride and dissolve very well in NaOH. The content of water transesterification reaction dates back to early 1980s [119]. In the
in alcohol is also a significant factor in transesterification reaction biodiesel production process, agitation is a vital parameter due to
as excessive water amount can react with triglyceride and causes its critical influence on mixing degree (i.e., turbulence) between
saponification. Generally, it is supposed that high methanol-to-oil immiscible alcohol-oil phase, the mass transfer, and reaction rate
molar ratios facilitates the triglycerides conversion into monoglyc- of alcoholysis. Therefore, in-depth understanding of the impact of
erides and accelerates the transesterification process. Stoichiomet- mixing on the transesterification process is a crucial parameter in
rically, the alcohol-to-oil molar ratio must be 3:1, however, in a the scaling-up and design of reactors.
real reaction system a higher molar ratio is needed to raise the Industrial agitators and mixers for biodiesel production pro-
miscibility of methanol and triglyceride molecules as well as the cess may include: anchor agitators, helix mixers, high-shear
possibility of their contact for improving the final product yield. mixers, magnetic stirrers, mechanical stirrers, turbines agitator,
Moreover, high amounts of methanol are required to dissociate the micro-mixers, motionless or static mixers, two flat-blade paddle
linkage between triglyceride and fatty acid to increase the produc- agitators, and ultrasonic mixers. Moreover, there are other novel
tivity and complete the reaction in a shorter time. In this regard, mixing methods such as mixing with the help of the oscillatory
the formation of alkyl esters is induced in commercial transesteri- frequency in baffled tubes in continuously oscillatory flow reactors.
fication processes by surplus amount of dry alcohol, 6:1 ≤ alcohol- This novel mixing method provides a performance equivalence
to-oil molar ratio [119]. of 80 ideal continuously stirred tank reactors (CSTR) in series,
Glycerol can be easily separated from reaction slurry by settling which is enough to produce biodiesel commercially from rapeseed
or centrifugation since it is essentially insoluble in biodiesel [120]. methyl esters in the presence of 50% excess methanol (0.3–0.5 wt.%
However, when using high alcohol-to-oil molar ratios, glycerol sol- NaOH, 60–70 °C, 15–30 min) [125]. Noureddini et al. [126] analyzed
ubility in biodiesel increases and free glycerol may remain either the influence of motionless and high shear mixers on continuous
as suspended droplets or as small dissolved amount in biodiesel biodiesel production individually and in combination with each
[120]. This can be attributed to the fact that alcohols can func- other. They recorded more than 97% conversion of soybean oil into
tion as co-solvents increasing the solubility of glycerol in biodiesel. FAME when at least one of the mixers was present in the process.
In addition, separation and recycling of the remnant content of However, it was emphasized that the motionless mixer was more
methanol at the end of reaction needs high amount of energy. effective than the high-shear mixer. Sánchez et al. [127] also
Therefore, an appropriate amount of methanol must be determined applied high-shear mixer at 40 0 0 rpm to vigorously increase mass
to avoid yield loss and uneconomic methanol recycling process. transfer in transesterification reaction. In the presence of 1 wt.%
In line with that, Wu et al. [121] probed the NaOH catalyzed- catalyst and methanol-to-oil molar ratio of 6:1, nanodroplets of
transesterification of soybean oil into biodiesel at methanol-to-oil reagents were formed, and subsequently, converted into biodiesel
molar ratios (4.5:1–9:1). The reaction was conducted in a 500 mL within 60 s of dispersion at 22 °C. In another study, a mechanical
3-neck mechanically-stirred flask reactor equipped with condenser stirrer was applied to synthesize biodiesel with American Society
and sampling port. Their findings indicated that a methanol-to-oil for Testing and Materials (ASTM) D 6751 properties through
molar ratio of 7.5:1 resulted in FAME yield of 97.45% after 60 min methanolysis of 50:50 wt.% blend of castor seed oil and waste fish
residence time. The main reason for using the alcohol-to-oil molar oil (0.5 wt.% KOH, 8:1 methanol-to-oil molar ratio, 32 °C, 600 rpm,
ratio higher than 6:1 in this study was the employment of ben- 30 min) with yield of 97.7% [128].
tonite as moisture remover, which could adsorb small amounts Sungwornpatassakul et al. [129] compared static mixer with
of methanol as well. In another study, Sanli et al. [122] exam- mechanical stirrer with respect to reaction rate and droplet size.
ined the effect of alcohol-to-oil molar ratio ranging from 3:1 to In addition to faster reaction rate, the former also formed droplets
20:1 on the transesterification process in the presence of potas- that 90% of them had diameter less than 5 µm. Ji et al. [130] de-
sium hydroxide, sodium methoxide, and potassium methoxide cat- veloped alkaline-catalyzed transesterification method coupled with
alysts. They noted that the highest yield (99.08%) obtained at ultrasonic mixer (19.7 kHz). Similarly, soy-based biodiesel (94.71%
ethanol-to-oil molar ratio of 8:1 and 1.40 wt.% sodium methoxide yield) with ASTM D6751 and IS 15607:2005 standards was ob-
after 2 h. tained using the same type of mixer adjusted at 35 kHz (6.15 wt.%
Behzadi and Farid [123] reported that the transesterification re- KI-impregnated zinc oxide, 10.2:1 methanol-to-oil molar ratio,
action is generally controlled by three important stages, viz. mass 62 °C) [131]. Ultrasound mixing system forms cavities in liquid-
transfer, equilibrium and kinetic of the reaction. Notably, the mass liquid interface, and subsequently creates micro fine bubbles. Then,
transfer in reaction is the slowest stage among the others be- micro jets are developed as a result of asymmetrical collision of
cause of weak immiscibility of methanol and triglyceride. The ki- the bubbles, causing an intensive blending of the liquids [132].
netic of reaction is controlled through a second order mechanism However, appropriate power of ultrasonic mixer must be optimized
with alcohol-to-oil molar ratio of 6:1 or follows a pseudo-first or- according to the size and volume of reactor; otherwise, excess mix-
der mechanism for high ratios like 30:1. ing power generates heat. This heat introduces bubbles in the re-
action system through vaporization of the solvent, which in turn, speed (20 0–80 0 rpm) and biodiesel production yield. The stirrer
sequentially reduce solvent content, the interface area, and the speed considerably controls the mass transfer kinetics with respect
yield of biodiesel. Compared with mechanical stirring, hydrody- to economic transesterification of J. Curcas oil [139]. It has been re-
namic and ultrasonic mixers have lower requirements for catalyst vealed that the influence of stirring rate on the control of biodiesel
(up to three-time less) and shorter reaction times (10–60 min). Hy- production is highest during initial stages of reaction, and then its
drodynamic mixer is even a better mixer than ultrasonic one, al- significance drops as the reaction proceeds. Different kinetics mod-
lowing better mixing for immiscible liquids as well as easier scale- els have been presented for quantification of the impact of rotation
up process regardless of geometric characteristics of reactor. This frequency of mixer on transesterification process [42,46,140–143].
technology provides simultaneous injection of all reagent liquids These models have the ability to predict the reaction evolution
in pre-defined proportions into a vessel through a mixing collec- for only specified mixing scenarios, i.e., single mixing model. This
tor. Therefore, no mixing vessel is required for homogenization and disadvantage was corrected in a methodology proposed by Brásio
both mixing time as well as energy consumption could be reduced et al. [144] who further validated their model by applying it to in-
while precision of portioning could be improved. dependent sets of experimental data previously provided in some
Joshi et al. [133] compared the contribution of hydrodynamic single mixing models.
mixer (high-speed homogenizer, 12,0 0 0 rpm) to heterogeneous
catalyzed-transesterification reaction of soybean and WCOs with 2.3.2. Temperature (heating system)
that of the conventional stirring method with respect to reaction Although there is a controversy regarding the role of tempera-
time. The former delivered microscale turbulence and fine emul- ture in transesterification reaction, operational temperature is con-
sions, reducing the reaction time from 120–180 min to 30 min with sidered by many as an important factor for proper production
same yields of biodiesels. Kolhe et al. [134] used cooking oil as of biodiesel. Table 5 presents the contribution of temperature, in
feedstock and transformed it into biodiesel using hydrodynamic combination with alcohol-to-oil molar ratio, to the transesterifica-
mixer (0.55 wt.% KOH, 4.5:1 methanol-to-oil molar ratio, 20 min). tion reaction rate of different feedstocks.
Compared with stirred tank reactor (STR; 88.5% yield, 60 min), over From Table 5, it can be postulated that at least no economically
5% more conversion of the same feedstock was obtained in three- profitable reaction could be conducted at temperatures below
time faster reaction rate. Yadav et al. [135] utilized hydrodynamic 32 °C. Moreover, the application of temperatures lower than the
mixer for conversion of Thevetica peruviana (Yellow Oleander) oil melting point of oil, for example, 50 °C in the case of palm oil,
into biodiesel (1 wt.% KOH, 6:1 methanol-in-oil molar ratio, 40– would not be practical due to elevated viscosity. Generally, higher
55 °C, 30–45 min) with 97.5% yield. The mixing system included temperatures shorten the reaction time by facilitating mass trans-
a closed loop fluid circuit supported by a 10 L mixing collector, a fer. However, beyond certain limits, the increase in temperature
2.2 kW centrifugal pump, control valve, and 5 cm orifice plates con- either has adverse effects on reactants/reagents (degradation, side-
taining up to seven holes ranging from 1–4 mm pore diameters. reactions, vaporization) or is not cost-efficient. Therefore, optimiz-
Mixing performance has inevitable influence on designing re- ing temperature is necessary for both designing reactors as well as
actors, which is crucial for the development of a homogeneous commercial production of biodiesel. It is noteworthy that the tem-
reaction environment. However, excess mixing reduces the eco- perature near to alcohol boiling point is the optimum temperature
nomic feasibility of process by increasing equipment and operation for non-enzymatic conventional processes. Beyond this tempera-
complexities, interfering with the proper alcohol-to-oil molar ratio ture, both mass transfer and yield of transesterification reaction
by making alcohol less available due to vaporization and/or bub- drop due to loss of one of the reagents, i.e., alcohol through vapor-
ble formation, and ultimately surging production costs because of ization. To address this issue, novel processes have been introduced
higher capital and energy requirement and lower yield of conver- that use heat in combination with pressure (see Section 2.3.3).
sion. As an example, power supply requirements for mild, moder- Freedman et al. [119] reported temperature as a significant
ate, and intense mixing in continuous reactors are 0.1–0.2 kW/m3 , variable for speeding up the transesterification of various veg-
0.4–0.6 kW/m3 , and 0.8–2.0 kW/m3 , respectively [136]. The degree etable oils including cottonseed, peanut, soybean, and sunflower.
of mixing as a result of a moving part is mainly determined by According to their results, the reaction rate was four-time faster
frequency of mixer rotation, and to a lesser extent, by geometry of when conducted at ≥60 °C rather than 32 °C. Darnoko and Cheryan
system, characteristics of mixer (i.e., impeller, direction, etc.), and [44] assessed the influence of temperature (50–65 °C) on the
physical properties of fluid (i.e., viscosity, volume, etc.). For a sys- methylation process of palm oil in a batch system (1 wt.% KOH, 6:1
tem with specific flow characteristics, geometric and power supply, methanol-to-oil molar ratio). They observed that relatively same
the mixing rate can be determined by applying the interrelation of yield of biodiesel was produced in higher temperatures within
two dimensionless numbers as described in Eqs. (2) and (3) [136]: shorter time, compared with lower temperature. Thompson and He
[153] produced canola-based biodiesel by several connected and
pgc
Np = (2) continuously fed static mixers as the reactor. They emphasized that
ρ N3 D5a at a fixed reaction duration of 30 min, the catalyst concentration
below 0.5 wt.% of oil and the temperature of 40 °C were the lim-
ND2a ρ
NRe = (3) iting factors for the progress of transesterification reaction. Aniya
µ et al. [154] studied mass transfer during karanja FAME production.
where Np denotes the power number, NRe the Reynolds number, It was observed that both temperature and time govern the overall
P the mixer power consumption, gc the Newton’s gravity accelera- reaction kinetics in a batch reactor (1 wt.% KOH, 6:1 methanol-to-
tion, ρ the fluid density, N the impeller speed, µ the fluid dynamic oil molar ratio, 600 rpm). A 20 °C increment in the reaction tem-
viscosity, and Da the impeller diameter. perature from 35 °C to 55 °C improved the volumetric mass transfer
Stamenkovic et al. [137] measured size distribution of droplets coefficient by 6.5 times, reaching 20 L/h. Moreover, the methanoly-
during KOH catalyzed-methanolysis of sunflower oil in a stirred sis reaction was initially irreversible at high temperatures due to a
reactor (10 0 0 mL, 10 cm diameter) with two-flat-blade paddle of more dominant equilibrium reaction rate.
7.5 cm in diameter. Using microphotographic technique, it was ob- Some examples of conventional heating systems in biodiesel
served that intensifying agitation forms smaller size drops with production reactors are batch bath, heating coils, and jacketed
less size variations (i.e., droplet size distribution). Similarly, Li et al. reactors. More recently, infrared heater, microwave irradiations,
[138] reported a direct relation between increasing the rotation and radio frequency heater have also been applied as new di-
Table 5
Contribution of temperature to the reaction rate and yield of transesterification of oil with various alcohol-to-oil molar
ratios at atmospheric pressure.
Feedstock Alcohol-to-oil molar ratio Temperature (°C) Reaction time Yield Ref.
Castor seed oil/waste fish oil 8:1 32 °C 30 min 97.6% [145]

Jatropha oil 7.5:1 65 °C 60 min 99.8%. [146]
Linseed oil 6–9:1 40–60 °C 40 min 88–96% [147]
Linseed 10:1 40 °C 90 min 93.15% [148]
Jatropha oil 30:1 65 °C 60 min 90.8% [71]
Palm oil 6:1 55 °C 30 min 98.8% [43]
Jatropha oil 12:1 90 °C 240 min 97.39% [149]
WCO 12:1 40 °C 1440 min 90.1% [109]
Canola oil 9:1 60 °C 90 min 97.4% [150]
WCO 10:1 50 °C 30 min 88% [133]
WCO 3.4:1 35 °C 2880 min 91.8% [151]
WCO 8:1 60 °C 10 min 99% [132]
Animal fat waste 4:1 50 °C 20 min 96.8% [152]
Canola oil 7.5:1 60 °C 150 min 99.4% [83]
electric heating technologies with improved economic feasibilities. radio frequency heating efficiency. Therefore, pre-heating by con-
Among these novel heating systems, microwave is the most ex- ventional heaters to increase the process temperature to 35 °C was
tensively studied method for biodiesel production whereas radio suggested before application of radio frequency heater. In a sep-
frequency is most economic heating system. In a similar transes- arate study, Liu et al. [160] reported a conversion yield of 96.3%
terification process, the outcome of microwave-assisted system is during transesterification of beef tallow using a radio frequency
advantageous over its thermally heated counterparts in terms of heater (0.6 wt.% NaOH, 9:1 methanol-to-beef tallow molar ratio,
reaction rate and energy consumption. Microwave irradiation im- 5 min). Unfortunately, none of these two studies reported the re-
proves reaction rate by affecting activation free energy and/or in- action temperatures and had no control on it as well.
creasing the frequency of molecular vibrations. The latter factor
leads to an induced molecular mobility. Commonly, microwave- 2.3.3. Mass transfer intensification systems
heating is applied in conjunction with mixing to avoid formation As elaborated earlier, to nullify mass-transfer limitation, either
of hot spots. Leadbeater and Stencel [155] applied a 600 W mi- mixing or heating systems must provide significantly high amounts
crowave heating system with a 5-L vessel for conversion of 3 kg of energy, which is not economically favorable. Moreover, temper-
of an unspecified vegetable oil into biodiesel in the presence of atures higher than boiling point of solvents, for example, 65 °C
either ethanol or methanol (1 wt.% KOH, 6:1 alcohol-to-oil molar in the case of methanol is not practical at atmospheric pressure.
ratio, 50 °C, 1 min). The reaction mixture was continuously stirred Therefore, these systems (i.e., mixing or heating) are applied to-
with the help of an overhead paddle agitator with an unspecified gether and are supported by a number of other intensification sys-
rate. Azcan and Danisman [156] studied the possibility of apply- tems, including addition of co-solvents and/or alternative solvent,
ing 67% of exit power generated by a 1200 W microwave heat- or phase-transfer catalysts (PTCs) to simultaneously cope with
ing system for methanolysis of cottonseed oil (1% wt.% KOH/NaOH, mass transfer limitation in the biodiesel synthesis process as well
6:1 methanol-to-oil molar ratio, 50 °C, 3–5 min). Interestingly, they as to simplify the isolation of catalysts, products, and reagents. For
observed a positive correlation between biodiesel purity (96.1– instance, in alkaline-catalyzed methanolysis, mass transfer limita-
99.4%) and reaction temperature (40–60 °C). Compared with con- tion occurs due to immiscible alcohol and oil phases. This barrier
ventional heating systems, the microwave-assisted process is up can be overcome through converting the system into single-phase
to six-time faster. Surprisingly, a much more reduction in reaction by application of co-solvents, for examples, biodiesel, supercritical
time (360 times) was claimed by Lin and Chen [157] during syn- carbon dioxide (SCCD), hexane, methyl tert-butyl ether, propane,
thesis of biodiesel by microwave heating assisted methanolysis of or tetrahydrofuran. However, the rate of co-solvent-added (single-
pre-esterified jatropha seeds oil (1 wt.% KOH, 6:1 methanol-to-oil phase) methanolysis reaction drastically falls due to drop of system
molar ratio, 65 °C, 200 rpm, 10 s). Milano et al. [158] stated that un- polarity caused by catalyst precipitation [124]. To compensate this
der optimize conditions (0.8 wt.% KOH, 59.6 vol.% of methanol:oil, shift in polarity, alcohol-to-oil molar ratio must be considerably el-
10 0 °C, 60 0 rpm, 7 min), a biodiesel yield of up to 98% could be evated, which makes the process complicated by raising the size of
obtained from alkaline-catalyzed methylation of a blend of Calo- manufacturing plants.
phyllum inophyllum and WCOs (vol. ratio of 3:7) using a 850 W Moreover, it was observed that in an enzyme-catalyzed
microwave-assisted process. During optimizing reaction time (2– methanolysis reaction of canola oil, the yield of biodiesel increases
10 min), they noticed that the reaction time was doubled by every with co-solvent concentration to some point due to miscibility
10 °C drops in the process temperature. improvement, after which they show an inverse relation because
Compared with microwave-heating system, radio frequency of lipase inactivation [161]. Alternatively, phase separation during
heater is more efficient in conversion of electricity into electro- methanolysis can be prevented through application of supercritical
magnetic power with more penetrative characteristics and more methanol (SCM; 9–43 MPa, 200–350 °C), a popular alternative sol-
simple configuration. Heat is quickly generated as the result of di- vent method. Solvents at their supercritical states have gas-like dif-
rect collision of a radio frequency electromagnetic field with an fusivity and liquid-like density. Regardless of catalyst application,
object. Radio frequency heating was efficiently employed by Liu these properties provide an ideal system for convenient, efficient,
et al. [159] for the esterification of WCO with a high amount of and quick production of FAMEs via transesterification of oils even
FFA (3 wt.% H2 SO4 , 80 wt.% methanol, 8 min) as well as its subse- in presence of water and FFAs [49]. The energy consumption of the
quent methanolysis (0.9 wt.% NaOH, 14.2:1 methanol-to-oil molar supercritical technique can be reduced through introduction of co-
ratio, 5 min), yielding 99% biodiesel. They emphasized that temper- solvents as well. Maçaira et al. [162] combined alternative solvent
ature influences the ionic conductivity of reagents, and subsequent method with addition of co-solvent technique through application
of SCM and SCCD as solvent and co-solvent, respectively. This cat- formance of enzymes against adverse effects of short-chain al-
alytic process was used on a fixed-bed reactor for continuous pro- cohols and accumulated glycerol, respectively. Many studies have
duction of biodiesel (yield of 88%) at 200 °C with 2 min reaction applied different combinations of enzymes and ionic liquids for
time. In a similar approach, propane was combined as a co-solvent the production of biodiesel. Among many ionic liquids, 1,3-
with SCM to make soy-based biodiesel production process less dialkylimidazolium salts in water soluble form, i.e., 1-butyl-3-
energy intensive (24:0.01:1 molar ratio of methanol:propane:oil, methylimidazolium tetrafluoroborate, [BMIm][BF4 ]; and water in-
12.8 MPa, 280 °C, 10 min) [163]. soluble form, i.e., 1-butyl-3-methylimidazolium hexafluorophos-
SCM cannot be applied in enzymatic transesterification process phate, [BMIm][PF6 ] have been commonly utilized in various stud-
since its high temperature (up to 350 °C) inactivates enzymes. On ies. [BMIm][PF6 ]-containing 40% enzyme was used to catalyze
the contrary, enzymatic transesterification (20-30 wt.% Novozyme methanolysis of waste oil into biodiesel with 72% yield (6:1
435) could commonly be carried out using normal methanol methanol-to-oil molar ratio, 50 °C, 14 h) [110]. Up to 99% biodiesel
and SCCD (6:1 methanol-to-oil molar ratio, 20 MPa, 45–50 °C) as yield was achieved during Novozyme 435 catalyzed-methylation
acyl acceptor (solvent) and co-solvent, respectively [164]. Com- of sunflower oil using [BMIm][PF6 ] (2 wt.% lipase, 8:1 methanol-
pared with catalyzed-SCM transesterification process, catalyst-free to-oil molar ratio, 1:1 wt. ratio of ionic liquid:oil, 58–60 °C, 10 h).
SCM transesterification involves a more simple, trouble-free, and While in both studies, the efforts to obtain high biodiesel yields
ecofriendly purification step. For instance, tobacco-based biodiesel using another ionic liquid, i.e., [BMIm][BF4 ] ended unsatisfactory
with yields more than 91%, meeting EN14214 standards, was re- [110,174].
portedly produced via catalyst-free SCM methylation of Nicotiana As mentioned earlier, addition of co-solvents and alterna-
tabacum seed oil (43:1 methanol-to-oil molar ratio, 27 MPa, 303 °C, tive solvents methods positively influence the mass transfer of
90 min) [165]. Aboelazayem et al. [166] converted 91% of WCO transesterification reaction by integrating the phases system into
into FAME with EN14214 properties by adapting a non-catalytic single-phase system. A different principle is also applied in PTCs
SCM process (37:1 methanol-to-oil molar ratio, 19.8 MPa, 253.5 °C, approach, in which, an appropriate compound speeds up the
14.8 min). Similarly, a catalyst-free SCM system (5:1 molar ra- reaction between two immiscible liquid reagents through pro-
tio, 9 MPa, 270 °C, 20 min) was applied for in-situ methylation of moting the interphase transfer of species [175,176]. The supe-
wet spent coffee grounds, containing 86.33 wt.% esterifiable lipids riority of this technique over conventional methods is aprotic-
[167]. solvent-free and shorter reaction with easier scale-up process. In
Sakdasri et al. [168] analyzed the commercial feasibility of alkaline-transesterification of oils, the anion transfer between po-
40,0 0 0 t/year FAMEs production from palm oil in two different lar methanol/glycerol and non-polar oil phases, and subsequently
SCM systems; viz. advanced SCM with low alcohol-to-oil molar mass transfer limitation as well as side reactions can be reduced
ratio of 12:1, and conventional homogeneous alkaline-catalyzed via dissolving organic PTCs in the organic phase, i.e., liquid-liquid
SCM with high alcohol-to-oil molar ratio of 42:1 using Aspen PTC (LLPTC) mode [176]. Crown ethers, cryptates, and quaternary
plus® software. Although the advanced SCM required about 1.5- ammonium are commonly applied PTCs in chemistry. Despite the
time higher capital investment than the conventional method (4.91 great adaptability of LLPTC, its application remained undervalued
million USD), it was commercially profitable by providing close to in biodiesel industry. PTC potential in transesterification process
22% greater net present value than manufacturing cost. In contrast, was first noticed during facilitated migration of reactants in the
the conventional SCM was found uneconomic due to the require- presence of a small amount of soap produced due to saponifica-
ment for recycling large amounts of methanol. tion phenomenon [177]. Then, Zhang et al. [176] investigated sev-
Alternative solvent technique can also be performed using ionic eral PTCs containing different anions and cations in methylation
liquids, i.e., organic salts that melt at or below ambient temper- of soybean oil. A biodiesel yield of 96.5 wt.% was achieved in the
ature. These non-volatile, easy-to-produce green solvents could presence of tetrabutylammonium hydroxide or tetrabutylammo-
provide flexible hydrophilicity/hydrophobicity through appropri- nium acetate (1:1 KOH-to-PTC molar ratio, 6:0.2:1 methanol:total
ate modifications in their anion or cation moieties. Therefore, hydroxide:oil molar ratio, 60 °C, 15 min). The most recent study
these designer solvents are highly appreciated for their contribu- in this field was conducted by Hailegiorgis et al. [178], in which
tion in two-phase catalysis via simplifying the catalyst/biocatalyst the reaction rate of in-situ transesterification of J. curcas L. was
dispersion (mass transfer improvement), recovery, and recycling. improved by the application of cetyltrimethylammonium bromide
Wu et al. [169] applied 1-(4-sulfonic acid) butylpyridinium hy- (CTMAB). They reported CTMAB-to-NaOH molar ratio of 1.5:1,
drogen sulfate as ionic liquid for methanolysis of cottonseed oil methanol:biomass of 6.8 vol./wt., NaOH:biomass of 1.3 wt.%, 43 °C,
and achieved 92% yield of conversion. Isahak et al. [170] also and 1.8 h as optimum conditions.
used ionic liquid for the synthesis of choline chloride.ZnCl5 ¯ cat-
alyst for transesterification of palm oil. Yanfei et al. [171] gener-
ated soy-based biodiesel with a yield close to 95% in the presence 2.4. Residence time
of 4 wt.% [(CH3 CH2 )3 N(CH2 )3 SO3 H]HSO4 ionic liquid of oil (14:1
methanol-to-oil molar ratio, 120 °C, 8.7 h). Additionally, 1-ethyl- Another parameter that must be optimized for improving
3-methylimmidazolium methyl sulfate ionic liquid was coupled biodiesel yield is residence/reaction time, which can be defined
with microwave irradiation for in-situ methanolysis of wet alga as the time that chemical species expend in the reactor till the
Nannochloropsis sp. biomass (4:2:1 v/v/w ratio of methanol:ionic reaction is completed or stopped. The required residence time
liquid:wet biomass, 25 min), leading to more than 42% yield of is directly dependent on other parameters that enhance the rate
biodiesel per dry weight of alga [172]. Recently, Ding et al. of transesterification reaction, such as mixing intensity, residence
[173] intensified the transesterification of palm oil by combining time distribution (RTD), and temperature. Unlike batch reactors, in
an ionic liquid 4-(3-methyl-1-imidazolio)-1-butanesulfonic acid hy- which all chemical species have an identical residence time, the
drogen sulfate with microwave-heating system. A yield up to 99% continuous (flow) reactors lead to a phenomenon referred to as
was achieved in the presence of 9.2 wt.% ionic liquid and 11:1 RTD. RTD is generated due to continuous introduction of feedstock
methanol-to-oil molar ratio with 168 W microwave power (equal and removal of the products from these reactors. The RTD of the
to 108 °C) for 6.43 h. flow within a given geometry can be considered as a probability
During transesterification process, further to the above-stated distribution for the time an element of fluid takes to travel within
advantages, ionic liquids can also increase the stability and per- that geometry [179]. In another word, some chemical species stays
less time than other chemicals, and consequently, leave the reac- It should be pointed out that the fatty acid compositions of oils
tors upon their introduction into reactor through product outlet. are immune against transesterification reaction, and hence, their
In two main continuous flow reactors, i.e., CSTRs and plug flow unchanged natures influence some fuel characteristics of biodiesel.
reactors (PFRs), the major reasons of RTD are bypassing stream, As an example, high amount of saturated fatty esters in beef tallow
dead zones, longitudinal mixing induced by vortices and turbu- oil resulted in a biodiesel with higher cloud point than that of soy-
lence, and even the failure of mixing system [180]. It is frequently based biodiesel [191]. The effect of fatty acid composition on cloud
favorable to establish plug flow operation rather than continuous point, cold flow, density, oxidation stability, pour point, and cetane
stirred process since it provides very accurate control of the pro- number of produced biodiesel has also been highlighted in other
cessing history, each element of fluid spends exactly the same time studies [190,192–194]. Generally, cetane number, cold filter plug-
in each condition in the reactor [179]. This reduces by-products as ging point, iodine index, oxidation stability index, and cold flow
compounds of fluid are not, for instance, subjected to higher tem- characteristics improve as the degree of saturation of fatty acid in
peratures for any longer than required for the conversion. It also oil increases. The FFA content can be decreased to the appropriate
greatly decreases the size of reactor. Both undertime and over- amount for transesterification reaction through acid esterification
time processes lead to uneconomic production of biodiesel due process. Pinzi et al. [195] optimized the transesterification of sev-
to uncompleted conversion of oil (lower yield) and higher oper- eral vegetable oils with different fatty-acids compositions (iodine
ating costs with lower productivity rate, respectively. Moreover, values) and FFA contents. They analyzed the influence of fatty acid
biodiesel may be evaporated or even degraded during an unaccept- composition on the production of methyl ester through compari-
able lengthy process under harsh conditions. son of the obtained optima. Accordingly, it was concluded that the
In a batch reaction, the reaction time is the time after which chain length of fatty acids influences biodiesel yield by controlling
the reaction is stopped and mixture is subjected to downstream reaction time, with longer chains slowing the process by two times
processing, i.e., separation, feed recycling, neutralization, and wash- than shorter chains.
ing. In contrast, residence time for a continuous reaction is de- Similarly, higher iodine index of vegetable oils requires higher
fined as reactor volume divided by flow rate. Darnoko and Cheryan concentration of catalyst whereas lower amount of catalyst would
[44] attained that variations of the plot of residence time in com- be required for optimum biodiesel yield from vegetable oils with
parison with produced methyl ester from palm oil in a CSTR was so lower iodine index. Moreover, higher amounts of saturated fatty
that with increasing the residence time, the methyl ester yield in- acids were prone to soap generation in the presence of excess cat-
creased logarithmically. In their study, the optimal residence time alyst. During conventional transesterification of oil, this negative
was 60 min. Other researchers claimed that higher residence time side-product (soap) appears in larger quantities in presence of wa-
could shift the reaction in the reverse side or biodiesel evapora- ter. The other negative effect of presence of water is its contribu-
tion, reducing the overall conversion yields [181,182]. Alamu et al. tion to the introduction of a mass of small bubbles in alcohol-oil
[183] studied 30–120 min reaction time (with 15 min intervals) mixture in combination with agitation, decreasing the mass trans-
for alkaline-catalyzed ethanolysis of palm oil while other param- fer. In addition to lower yield, the operating cost would also be in-
eters were kept constant (1 wt.% KOH, 20 wt.% ethanol, 60 °C) and creased due to problematic separation of glycerol from biodiesel in
a plateau of yield (96%) was observed after 90 min. Falahati and the presence of soap. In contrast to conventional transesterification
Tremblay [184] studied the influence of flux and reaction time reaction, water content would have no significant effect on conver-
in the biodiesel synthesis from various feedstocks by means of a sion yield during biodiesel production by SCM technique and even
membrane reactor. They reported the reaction time as a main in- the yield was reportedly improved with the existence of water at
fluential factor affecting the operating pressure in the reactor. The certain concentrations [196,197].
quantity of unconverted oil in the reactor increased at very low Kwiecien et al. [198] examined the effect of acidity on the
residence time, enhancing the pressure inside the reactor. In an- alkaline-catalyzed methylation process by adding various amounts
other study, Azam et al. [185] investigated the influences of cat- of oleic acid, one of the most abundant fatty acid in vegetable oils
alyst loading and reaction time on biodiesel synthesis from palm (up to 80 wt.%), to artificially increase the acid number from about
oil via micro-tube reactors. The results showed that oil transfor- 0.9 to 12.3 mg KOH/g of oil. In each experiment, they calculated the
mation and FAME yield were proportional to the catalyst loading necessary dose of KOH with respect to acid numbers to keep the
and reaction time. This finding could be explained by the complete concentration of catalyst constant. Under similar reaction condi-
methylation process of oil in response to longer reaction times and tions, the higher acid number of oil deteriorated biodiesel produc-
efficient mixing in micro-tube reactor. Similar results have been tion due to both saponification as well as dissolution of biodiesel
previously observed by Ab Rashid et al. [186] and Rahimi et al. into glycerol phase. It also required higher alkaline catalyst and
[187] who studied FAME synthesis from palm oil and soybean oil longer separation time, both of which are directly correlated with
in a milli- and micro-channel reactors, respectively. economic aspects of biodiesel synthesis [198].
2.5. Composition of oil 3. Reactor technologies
The FFA content of feedstock, its composition, and water con- 3.1. Biodiesel production process modes
centration are critical factors markedly affecting biodiesel yield and
quality. These compounds have detrimental effects on yield dur- There are four main steps in a typical biodiesel production plant
ing biodiesel production process, but the extent of their effects de- via oil alcoholysis with an additional step for treatment of glyc-
pends on production techniques. Generally, higher concentrations erol. In the first step, reagents and reactants are added depend-
of alkaline catalyst would be required in the reaction in order to ing on the process mode into the reactor where the transesterifi-
neutralize high FFA contents (>1%) or decreased yield should be cation of oil takes place under controlled reaction conditions. Upon
expected. Increasing the FFA content from 0% to 4% resulted in completion of the process, the resultant slurry is allowed to stand
2.2% drops in biodiesel yield obtained from WCO [188]. The con- in a settling vessel (decanter) or subjected to centrifugation for
centration of each fatty acid in oil feedstock determines the prop- inducing phase separation in the second step. In addition, other
erties and quality of the triglyceride and the resultant biodiesel. methods of separation such as filtration and sedimentation can be
The physical properties of triglycerides and fatty acids are deter- used [199,200]. In the third step, biodiesel and unreacted alcohol
mined by length of chain and quantity of double bonds [189,190]. are sent to an evaporator or a flash unit to separate alcohol from
Table 6
Comparison of batch, semi-batch, and continuous process modes.
Parameter Batch Semi-batch Continuous
Space requirement High Medium Low
Capital requirement High Medium Low
Operating cost High Medium Low
Product quality Batch-to-batch variation Uniform Uniform
Running time Until chemical equilibrium Until chemical equilibrium Until catalyst inactivation or process maintenance
Production rate Low High Highest
Low selectivity High selectivity High selectivity

Higher versatility Lower versatility Lower versatility
Good flexibility Good flexibility Good flexibility
Reactor application
Simple scale-up Complex scale-up Complex scale-up
Inferior heat transfer Superior heat transfer Superior heat transfer
Suitable for slow reaction Suitable for faster reaction Suitable for quick reaction
biodiesel. Fourth step involves neutralization and purification of ing costs whereas delivering higher quality and uniform products
biodiesel from other undesired compounds such as catalyst, soap, [128].
and unreacted triglyceride by using wet or dry washing methods.
In wet washing which is both water- (2–120 L of wastewater/100 L 3.2. Types of chemical reactors for biodiesel production
of biodiesel) and energy-intensive, the product is neutralized by
acids followed by treatment with water. Treatment of generated Several types of reactors are available for biodiesel production
wastewater and drying the final product are also costly processes. through transesterification of oils, each of which allows different
Dry washing is considered as a more environmental compatible operating conditions with respect to chemical nature of reactants,
approach compared with wet washing but because of using ab- reagents, and products as well as physical parameters of opera-
sorbents and additional equipment, it may not be economical un- tion. These factors, together with the optimum pressure and tem-
der certain industrial circumstances [201]. Alternatively, the crude perature of reaction and production size (reaction mode), define
biodiesel may be purified using membrane filtration which has the choice of reactor. In general, any reactor types should pro-
been discussed in detail in Section 4.3.1. In a subsidiary step, the vide appropriate residence time, heat exchange, and mass trans-
generated glycerol is neutralized, washed using soft water, and di- fer for efficient product formation. Reactors are classified based on
rected towards the glycerol refining section. For feedstocks with phase numbers, existence of mixing systems, and process modes.
high amounts of FFA, the system should be slightly modified with Flow chart of various chemical reactors for biodiesel production is
the incorporation of an acid esterification unit and storage tank shown in Fig. 4.
for the acid catalyst [202]. Batch, semi-batch/semi-continuous, or Table 7 summarizes the operating conditions under which sev-
continuous process modes are available depending on how these eral types of reactors have been proven to perform desirably. The
steps are conducted, each of them having specific cons and pros feasibility of these reactors for application in biodiesel industry is
(Table 6). also highlighted. Although batch STR and CSTR have been reported
The most commonly used method for commercial production to be of low efficiency and difficult to control, they are extensively
of biodiesel is batch-mode process [136]. In a typical batch process, applied at industrial scale due to their simplicity and low cost na-
there are no streams flowing into and out of the reactor during the ture.
process, and therefore, a finite amount of product is synthesized
in a specific period of time. At the end of batch-mode reactor, the 3.2.1. Tubular/plug-flow reactors
entire slurry is sent to separation and purification sections. Semi- The simplest chemical reactor is tubular, also known as pipe
batch process mode is a variation of batch-mode process with a or PFR, in which reactants and reagents are entered in one end,
higher selectivity and better control on reaction temperature, in spent specific time for passing through pipes at a constant ve-
which as the reaction proceeds, one reagent or product may be locity, and mixed while flowing towards the outlet. This mixing
intermittently or continuously added to or removed from the re- can be performed successfully by passing highly turbulent flow
actor, respectively. Moreover, large methanol-to-oil ratios can be through empty pipes and piping fittings (such as elbows). The
maintained by gradual or intermittent introduction of one reagent, length of mixing device as well as its time is significantly reduced
i.e., oil to improve the reaction rate and process yield. The reaction by adjusting pressure. However, more laminar flow operating con-
equilibrium can be broken in favor of biodiesel production through ditions are resulted in tubular reactors when fluid viscosity in-
removal of product as well. Similar to the batch-mode process, the creases. To avoid this, and also to further improve the reaction time
production rate in semi-batch process is limited while operating and size of reactor, side stream additive injection devices (imping-
cost is relatively high. However, like continuous process, the scale- ing jet mixer, spray nozzle, Tee mixer), in-line mechanical mixer, or
up and design is more complex than the batch mode. static mixer can be applied. Static/motionless mixers take advan-
In contrast to the batch-mode process, feeds are continuously tage of stream energy to impose efficient radial mixing of two or
introduced into the flow/continuous-mode reactor while product more immiscible liquids when these fluids pass through it (Fig. 5)
stream leaving the system. In should be noted that biodiesel in- [216,217].
dustry is shifting toward continuous process mode in order to ad- In the simplest configuration (Fig. 5A), static mixing can be ob-
dress disadvantages of batch process operation [203–205]. Despite tained through tubular reactor with horizontal back-and-forth and
of this tendency, batch processes still contribute to major portion vertical upflow-and-downflow configurations. Other configurations
of the biodiesel production plants worldwide as it is the process of (Fig. 5B–F) includes installation of static mixing element inside a
choice in small and medium scale biodiesel synthesis plants. It is tubular channel or a pipe, whose suitability depends on Boden-
worthy of mention that continuous processes offer lower operat- stein number, type of reaction, diameter of reactor, reaction tem-
Fig. 4. Diagram of various chemical reactors for biodiesel production. Background image: courtesy of Bright Path Group, Inc. and Tribologiks, LLC.
Table 7
Characteristics of different types of reactors for the production of biodiesel.
Type of reactor Residence time Mass transfer Temperature control Current status Ref.
Batch stirred tank reactor (BSTR) 1–2 h Medium Difficult Industrial scale [126]
CSTR ≥60 min Good Easy Industrial scale [204,206]
Jet-stirred reactor (JSR) ∼38 min Good Difficult Pilot scale [207]
PFR 19 min Good Difficult Pilot scale [208]
Oscillatory baffled reactor (OBR) 30 min Excellent Easy Pilot scale [209]
Spinning tube-in-tube (STT) <1 min Excellent Easy Industrial scale [209]
Membrane reactor 1–3 h Low Easy Pilot scale [209]
Reactive distillation reactor Several minutes Excellent Easy Pilot scale [209]
Annular centrifugal contactor (ACC) ∼1 min Excellent Easy Industrial scale [209]
PBR 2.8 h Low-Good Difficult Pilot scale [208,210,211]
Fluidized bed reactor (FBR) – Good Easy Pilot scale [212]
Ultrasonic reactor 10–40 min Good Easy Industrial scale [19,177,213]
Hydrodynamic cavitation reactor ∼30 min Good Easy Industrial scale [130]
Shockwave power reactor – Excellent Easy Industrial scale –
Static mixer 30 min Good Easy Lab scale [153]
Micro-channel reactor 28 s–several minutes Excellent Easy Lab scale [209]
Microwave reactor <10 min Good Easy Lab scale [156,214,215]
perature, Reynolds number, and viscosity of fluids. These config- actors with/without static mixing internals provide more efficient
urations are suitable for both low and high viscosity fluids and and economic place for blending when quick mixing, short hold-
the subsequent increase in polar-apolar interfacial area, particularly ups, and low maintenance are desirable.
through local micromixing, significantly facilitates the transesteri- Tubular reactors require lower capital as well as space for con-
fication of oils. Compared with a tank or vessel reactors, pipe re- struction. However, these reactors have a limitation for Reynolds
3.2.1.1. Packed bed reactors. PBRs are popular reactors for the
production of biodiesel by heterogonous catalysts (including ba-
sic, acidic, ion exchange resins, and superacids active catalysts)
with the ability to switch into supercritical mode. Packed bed
can provide a great substrate for enzyme immobilization in the
transesterification process as well. Some support particles such
as magnetic magnetite nanoparticle, poly(stearyl methacrylate-
co-ethylene dimethacrylate) monolith grafted with vinylazlactone,
or polyurethane foam have been successfully utilized in lipase-
catalyzed PBRs [234–236]. PBR is in fact a PFR filled by roughly
equal size of solid packing materials (such as catalysts, activated
carbon, etc.). The catalyst size distribution and bed structure deter-
mine the accessible surface area, void spaces, and therefore, trans-
port and performance of the system. As PBRs consist of fixed or
immobilized bed of catalyst, they are also called fixed bed reac-
tors.
The packing process in these reactors is controlled by (i) phys-
ical characteristics of container (pipe) and particle (catalyst), such
as shape, size, and surface properties; (ii) the intensity, method,
and speed of deposition; and (iii) treatment approach [237]. Un-
desirable flow distribution and pressure variations must be mini-
mized by avoiding particles charging, segregation, and their irreg-
ular distribution during bed generation. Moreover, bed shrinkage
phenomenon as well as packing reproducibility must be improved
by applying appropriate procedures such as snow storm filling
method. During loading, the free fall distance should be <50 cm to
avoid significant damage to catalysts. Compared with PFRs, PBRs
allow higher conversions of oils per unit mass of solid catalysts in
shorter reaction time because the liquid flow is close to ideal plug
flow [238]. A very high operation pressure can be applied in PBRs
with high ratios of L/D because of absence of mixing system. An-
other advantage of PBRs is that the catalysts are fixed in the pipes
(reactors), and hence, no downstream process would be required
for their separation.
In spite of the advantages mentioned, PBRs are suffering from
Fig. 5. Different configurations of static mixing elements which could be used
in tubular reactors, A) Skit-mounted configuration, B) Grid static mixer, C) Heli- several pressure drops during operation attributed to a number of
cal static mixer, D) Cross tube type static mixer, E) Corrugated plate static mixer, factors namely, friction of fluid around as well as its expansion
and F) Lift tab static mixer. Courtesy of StaMixCo-USA/Switzerland http://www. and contraction through spaces among packing particles, length of
stamixco-usa.com/.
reactor, and fluid viscosity. These pressure drops would increase
the operation cost as higher energy in form of pressure would
be required. On the other hand, increasing pressure could break
numbers, which is necessary for appropriate generation of high the catalysts into small fragments. These minute particles could
velocity and suitable turbulence. Therefore, the ratio of length plug the spaces between pellets, and in turn, lead to pressure drop
to diameter (L/D) should be greater than 20 and 200 for tur- again. Therefore, based on intended process, catalysts with resis-
bulent and laminar flows, respectively [218]. It should be noted tant shape configuration and higher surface area must be applied
that the RTD narrows as the ratio of L/D grows [218]. Nar- in PBRs. For instance, solid cylinders are pressure-resistant while
row RTDs as well as large ratios of pipe wall to pipe vol- providing 14.5% < higher surface area as well as 25% less voidage
ume lead to efficient heat transfer. Moreover, these reactors ex- values than spheres of same volume [237]. Raschig rings (hollow
perience significant temperature changes at different points be- cylinders) are even better than solid cylinder owing to their posi-
tween inlet and outlet. To address this phenomenon, appropriate tive influence on system pressure and providing extra surface area
heating systems such as heating jacket or radiation heating ex- (20–30%) [237,239,240]. Nevertheless, the number and size of ax-
change must be used during their application in the transesteri- ially extruded holes must be optimized for better performance of
fication process. Similar to temperature, pressure drop is also ob- hollow cylinders.
served at different points inside tubular reactors, which is cor- The RTD in PBRs narrows with increasing the ratio of bed depth
related with viscosity of fluid, length of pipe, and the presence to the diameter of particle (L/dp ), and is almost negligible at the ra-
of internals. The drop in pressure reduces both mass and heat tio greater than 40 [238]. The application of larger catalyst size as
transfers. well as lower liquid-solid mass transfer coefficients reduces the ef-
Overall, tubular reactors can best be exploited under high pres- ficiency of PBRs [238]. In PBRs, a feed pipe and a distribution hood
sures and continuous mode with steady-state condition of reagents are applied prior to the flow of feedstock into the tube bundle or
injection rates and concentration of small size solid particles (cata- fixed bed in order to prevent flow bypasses. In better words, when
lysts, immobilized enzymes, etc.). The products are separated from there is no formation of flow bypasses, there is a significantly
discharged feed, and then methanol and untreated oils are recy- greater pressure loss in the entrance hood than in the tube bun-
cled to the feedstock storage. The advantages and disadvantages of dle or fixed bed leading to uniform traverse of liquid with equal
various types of PFRs are presented in Table 8 whereas Table 9 pro- residence time in each tube [239]. Although PBRs are considered
vides some examples of these reactors for biodiesel production via as continuous operation, however, since recycling of the ingredi-
transesterification of oil. ents might be necessary in most cases, therefore, by nature they
Table 8
Advantages and disadvantages of various types of PFRs.
Type of reactor Advantages Disadvantages
Oscillatory Flow Reactors - Very low methanol-to-oil ratio, even lower than the stoichiometric - Complicated design and operation in continuous mode
ratio of 3:1 - Still immature for industrial application
- Low capital and operating costs
- High biodiesel yield
- Long reactions in a significantly low length-to-diameter ratio
- Continuous or batch mode
- High mixing intensity
- High heat and mass transfers
Fluidized Bed Reactors - Uniform temperature distribution - High capital and operating costs
- High mixing intensity - Requirement for expensive regeneration equipment
- Continuous or batch process mode - High catalyst attrition and reactor wall erosion
- High heat and mass transfer - Only freely flow catalysts can be applied
- Convenient replacement or regeneration of catalyst - Large pressure drop
- Lower possibility for membrane plugging
Fixed Bed Reactors - Compatible with very high pressure and temperature conditions - Difficult replacement of catalyst
- Higher conversion of oils per unit mass of solid catalysts - Error-prone bed generation process (channeling, uneven flow
- Simple and cost-efficient process distribution, pressure variation)
- High yield - Lower heat transfer and more difficult control of temperature
- Semi-continuous or batch mode - Higher potential of side reactions
Plug-Flow/Tubular Reactors - The simplest chemical reactor - Requirement for a large length-to-diameter ratio
- Compatible with side-stream additive injection devices and other - Operative at stationary conditions
mixers to improve mixing - Inappropriate for slow reaction, i.e., requiring slow mixing
- More efficient and economic than tank-reactors and/or large hold-ups
- Low maintenance
- Low capital and construction space
- Uniform product quality
- Easy to clean
- Efficient use of reactor volume
Trickle Bed Reactors - Continuous separation of products - Lower control on reactor parameters
- No need for separation of heterogeneous catalyst - Prone to channeling and flooding
- Simple operation under high pressures and temperatures - Difficult to scale-up
- Lower catalyst attrition
have to be performed under batch mode [241]. For isothermal pro- from packing particles, i.e., heavier objects sink whereas lighter
cess (such as transesterification of oils), PBRs are commonly used ones float [241]. For selection of proper packing particles, in ad-
in multi-tubular arrangements, in which heat carrier, i.e., liquid dition to intrinsic static characteristics (density, shape, size), dy-
(water, molten salt) or gas externally circulates around the tubes namic behavior of particles with respect to flow of fluid (buoyancy
containing the catalyst and through an external heat exchanger factor, drag coefficient, terminal velocity) must also be considered
[234–236,239]. [242]. At low fluid velocities, the particles in the vessel remain
still as the fluid passes within the voids in the material, similar
3.2.1.2. Fluidized bed reactors. Liquid-solid FBRs, also known as to the PBRs. As the fluid velocity increases and at a specific veloc-
expanded bed reactors, are used for transesterification reaction. ity, drag forces will dominate the weight force so that the particles
These reactors consist of a reservoir for preparing the liquid feed- are capable of initial upward movement. This stage can be con-
stock, prior to being pumped into the FBR column. The column sidered as incipient fluidization and takes places at this minimum
consists of a calming section for equalizing liquid flow, followed fluidization velocity [243]. Once this minimum velocity is sur-
by a distributor, a fluidized bed (i.e., catalyst bed), and freeboard. passed, particles begin to expand and swirl around in fluidized bed
The length of calming section is up to several times of fluidized [244]. Next to fluidized bed is a freeboard that prevents the flow-
column, filled with immobilized packings (rings, saddles, spheres) ing of catalysts out of the column. Based on the operating condi-
or even fluidized bed packing (catalyst, immobilized enzyme), and tions and characteristics of solid phase, different flow regimes such
has a wire screen at the bottom [242]. Distributor must gener- as inverse fluidization, upward fluidization, or vertical moving flu-
ate a sufficiently large frictional pressure drop across itself, com- idized systems (continuous fluidization) can be used. Internal or
pared with the one occurring across the fluidized bed. Above the external liquid-fluidized bed heat exchangers arranged either ver-
distributor, a laterally-directed uniform distribution of longitudinal tically or horizontally may be used to control reaction temperature.
liquid velocity must be formed. Multi-layer metal gauze or sin- Alternatively, a pre-heating line can be used for this purpose. Com-
tered metal glass plate are two examples of good liquid distrib- pared with PBRs, intense mixing in FBRs could cause high attri-
utors [242]. Calming section and distributor reduce or eliminate tion of catalysts due to particle-fluid, particle-particle, and particle-
channeling or bulk circulation in catalyst bed. wall contacts forming solid fines. The elutriation and entrainment
FBRs are similar to PBRs in many ways; however, their main of these solid fines could lead to significant operational challenges
difference is that solid particles in the reaction vessel of FBR are [242].
suspended by the upward-flowing drag of incoming gas or liquid
[242]. In this case, solid particles inside the bed show a liquid- 3.2.1.3. Trickle bed reactor. TBRs provide a structure for contact of
like behavior, allowing even fluid distribution, uniform tempera- solid, liquid, and gas based on gravity or pressure forces. Liquid
ture, and vigorous mixing with higher heat and mass transfers feed is supplied at the top of the column which flows downward
than in PBRs. Moreover, plugging is less likely to happen because over a solid catalyst bed forming droplets or fine films. The pro-
foreign objects can be separated based on their density differences cess may be in either continuous or semi-continuous modes with
258
Table 9
Examples of biodiesel production processes via transesterification of oil using different variations of PFR.
Type of reactor Feedstock Alcohol Packing particle Conditions Yield Highlights Ref.
Oscillatory flow Rapeseed oil Methanol (1:12)1 1.5 wt.% KOH 60 °C, 2 min >95% Significantly enhanced the reaction rate and improved
reactors (OFR), the water tolerance (1 wt.% water).
M. Tabatabaei, M. Aghbashlo and M. Dehhaghi et al. / Progress in Energy and Combustion Science 74 (2019) 239–303
Continuous/ batch
Continuous mode produced higher yield of FAME. [219]
OFR, Batch Neem oil Methanol (1:9) 1% H2 SO4 25–30 °C, 10–15 min NP – [220]
OFR, Batch WCO Methanol (1:6) 1 wt.% KOH 60 °C, 5 min, 4.1 Hz 82% Yield was only dependent on temperature, oscillatory [221]
oscillatory frequency Reynolds number, and Strouhal number.
OFR, Batch WCO Methanol (1:6) 1 wt.% NaOH 60 °C, 30 min, 0.67 Hz 72% A 14% higher biodiesel yield in two-time faster reaction [222]
oscillation frequency process in OFR was attained compared with STR under
similar process condition.
Capillary FBR Canola oil Methanol (1:6) 0.5 g hydrotalcite 300 °C, >0.3 s, 0.15 mL/min 63% Cold methanol and oil were atomized through a sparger. [223]
oil feed rate
Argon was used as supplementary fluidizing gas.
Periodic injections of oxygen gas (after up to 20 min)

were done for regeneration of catalyst.
Magnetically FBR, WCO Methanol (1:3.7) 10.2% Magnetic 35 °C, 48 h, 136.6 Oe 87% The biocatalyst was recyclable (10 times). [151]
Batch microspheres magnetic field intensity,
cells of 17 mL/min reactant flow
Pseudomonas rate
mendocina,
FBR, Continuous Babassu oil Ethanol (1:12) 12% Novozym® 50 °C, 8 h space-time 98% Simultaneous glycerol removal via Lewatit® GF202 [224]
435 column was conducted.
Resin was regenerated by methanol.

Two-stage PBR, Coconut/macaw Ethanol (1:12) Immobilized 50 °C, 14 h space-time 96–97% A simultaneous glycerol-removing column, Lewatit® GF [225,
Continuous oils Burkholderia 202 was annexed to the reactor. 226]
cepacia lipase on
SiO2–PVA
The half-life time of the immobilized lipase was

1512–1540 h due to removing glycerol.
PBR, Continuous Linseed oil Diethyl ether and 160 g CaO 30 °C, 1.37 mL/min flow 98% PBR was combined with co-solvent technique (Diethyl [227]
methanol rate ether).
(1:9.5:11.3)
PBR, Continuous Soybean oil Methanol (1:42) Dixon rings 22 MPa, 350 °C, 0.12 and 91% PBR was combined with alternative solvent additive [228]
0.067 mL/min oil and technique, i.e., supercritical methanol.
methanol flow rates
A 27% higher biodiesel yield was obtained contain with
basic PFR, i.e., no packing material.
PFR, Continuous Soybean oil Ethanol (1:40) No catalyst 20 MPa, 350 °C, 15 min 80% – [229]
(continued on next page)
Table 9 (continued)
Type of reactor Feedstock Alcohol Packing particle Conditions Yield Highlights Ref.
PFR, Batch Canola oil Ethanol (1:40) No catalyst 20 MPa, 350 °C, 30 min 98% Biodiesel production under supercritical condition was [230]
carried out.
Thermal energy was efficiently recovered because of

spiral configuration of reactor.
PFR, Continuous Palm oil Methanol (1:5 v/v) 4–12 g/L KOH 60 °C, 20 L/h oil flow rate, ND Integration of ultrasound clamp as a mixing device [231]
ultrasound clamps improved the process efficiency of short length PFR.
(16 × 400 W, 20 kHz
frequency)
PFR, Continuous Canola oil Methanol (<1:5 1.5 wt.% CH3 NaO 60 °C, 30 min, 1.1 L/min ND Integration of 34 fixed left- and right-hand helical static [153]
v/v) flow rate mixers to the reactor was performed.
The reactor dimensions were L = 300 mm and ID=4.9 mm.

PFR, Batch Corn oil Methanol (1:4.3) 1.8 wt.% KOH 26–30 °C, 30 min, 7.2 L/min 98% Integration of 20 helical static mixers (L = 12 mm and [129]
flow rate Din = 8 mm) to the reactor was done.
The reactor dimensions were L = 260 mm and ID=8 mm.

PFR, Continuous Soybean oil Methanol (1:6) 1–2 wt.% KOH 60 °C, <1 min, 75–98% Various static mixer elements were attached to the [217]
1.4–8.3 mL/min flow rate reactor.
The reactor dimensions were L = 200 mm and ID=10 mm.

Trickle bed reactor Sunflower oil Methanol CaO packed bed 100 °C, 3.8 and 4.1 mL/h 98% Easy and continuous separation of products was achieved. [232]
(TBR), Continuous (1–2 diameter methanol and oil flow
and 125 mm rates
thickness)
TBR, Continuous Rapeseed oil Methanol Ca/Al composite 65 °C, 0.3 and 0.6 mL/min 94% Easy and continuous separation of products was obtained. [233]
oxide-based methanol and oil flow
catalyst (Bed rates
volume of 91 mL)
1
Alcohol-to-oil molar ratio, unless specified otherwise.
259
a different study, Meng et al. [233] carried out the methanolysis

of rapeseed oil in a TBR consisting of a packed bed of alkaline het-
erogeneous Ca/Al composite oxide-based catalyst with a 91 mL cat-
alyst bed volume. A biodiesel yield of 94.5% was achieved using re-
spective methanol and oil flow rates of 0.3 mL/min and 0.6 mL/min
at 65 °C. The advantages and disadvantages of TBRs are previously
presented in Table 8.
3.2.1.4. Oscillatory flow reactors. OFR are another type of vertical or

horizontal continuous tubular reactors consisting of one or several
tubes (continuous OFR; Fig. 7) each with equally distanced baffles.
Bellows, diaphragms, or pistons at one or both of tube/s ends are
used to generate oscillatory flow with periodic changes in flow di-
rection (Fig. 7). A vortex mixing is produced and fills almost the
whole cross section of baffles’ downstream cavity because of di-
recting or obstructing fluids by the baffles. This phenomenon also
occurs in the opposite side of the baffles after reversing the bulk
flow. The flow reversal cycle is repeated causing an efficient mixing
due to interaction with the opposite vortices formed in the previ-
ous oscillation cycle [245]. Technically, in OFRs, each zone located
between two baffles acts as a stirred tank. Therefore, a relatively
ideal PFR can be obtained by implementing a sufficient number of
baffles in series [125]. The interaction of bulk and imposed oscilla-
tory velocities controls the RTD through intensifying radial mixing,
which in turn improves heat and mass transfer under low shear
and convenient global mixing conditions [125,209,246,247]. In gen-
eral, OFR configuration allows vigorous mixing control using baffle
geometry and feeding pulsation.
Standard meso-OFRs contain tubes of less than 15 mm in diam-
eter and commonly orifice baffles, requiring low bulk flow rates
of several millimeters per hour to maintain plug flow. Moreover,
various baffle geometries such as central axial, helical, integral,
Fig. 6. Lab-scale configuration of TBR for biodiesel production [233]. With permis-
and wire wool configurations are available for meso-OBRs to max-
sion from Elsevier. Copyright© 2018. imize mixing characteristics or to minimize frictional loss (Fig. 8)
[245,248]. Integral baffle configuration provides very smooth con-
concurrent or countercurrent flow of gas and liquid flows. Various striction and is generally used for shear-labile reactions while the
equipment designs are possible for TBRs; however, the examined central axial baffle has found applications for single phase reac-
design for biodiesel production consists of a tubular tank with a tions and provides higher shears than the integral one. In contrast,
support structure (wire mesh, sieve plate) for packed bed hetero- wire wool configuration and helical baffles with a central insert
geneous catalyst close to the bottom of the reactor (Fig. 6). The design are advantageous for facilitating inter-phase dispersion of
hold-up of the liquid, and hence, biodiesel yield can be improved two-phase liquid-liquid systems (such as methanol and oil in the
by increasing the height of packed bed as well as by decreasing transesterification reaction). Other helical baffles can also be ap-
feed flow rate. The oil is fed from top of the column whereas the plied in various oscillation conditions for the production of an ef-
methanol can be fed from either top or bottom points. The desired ficient plug flow.
temperature, i.e., higher than boiling point of methanol is main- Unlike conventional PFRs, mixing in OFRs is directly depen-
tained by heating jackets (exterior heaters) on the reactor wall or dent on oscillatory conditions rather than Reynolds number of the
heating coil in the packed bed (interior heaters). Moreover, the un- bulk flow through the reactor. This would make possible success-
reacted methanol is separated from products by a separate heating ful completion of time-consuming reactions, such as transesterifi-
system placed at the bottom of TBRs. As the result of this heating cation of oil, in continuous compact tubular type reactor with sig-
system, methanol is completely vaporized at this point and starts nificantly short L/D ratios. Consequently, these advantages lead to
rising in the column. A gas distributor breaks the methanol vapor lower capital cost, lower operation cost (control, pumping, main-
into bubbles prior to its direct introduction into the packed bed tenance), improved yield of biodiesel, and lower reaction time. In
catalyst, which causes intense mixing and dispersion of oil droplets OBRs, ratio of baffle spacing, open area of baffle flow, oscillatory
within the bed before they are collected and refluxed by an up- and bulk flows, Reynolds numbers, Strouhal number, and velocities
stream condenser. Similarly, an even distribution of liquid through- ratio of oscillatory to bulk flows determine the oscillatory condi-
out the bed is maintained by using a bubble cap, fine layer of inert tions and the fluid mechanics. The first two parameters control
particles, or sieve plate distributor prior to packed bed. eddy expansion and width, respectively, with optimum length of
There are two outlets in TBRs; one on top of the reactor for baffles to reactor inner diameter of 1–2 (lb /D; commonly 1.5) and
methanol gas recycling while the other one is located at the bot- square ratio of baffle constriction diameter to reactor inner diam-
tom of the reactor for liquids (products and unreacted oil). The eter of 0.2–0.4 [245,249]. An efficient mixing can be obtained by
application of TBR configuration for transesterification of oils into thinner baffles (1–3 mm), since thicker ones lead to vortex distor-
biodiesel has been reported in a few studies only. For instance, tion from lengthy surface adhesion [250]. Moreover, it has been
Son and Kusakabe [232] continuously produced sunflower-based stated by Ni and Stevenson [251] that smaller gap sizes between
biodiesel with 98% yield using a TBR with a calcium oxide packed the tube and baffles increases the axial dispersion coefficient, per-
bed (1–2 mm in diameter and 125 mm in thickness) at 100 °C, haps by preventing the generation of a second vortex ring. Com-
methanol flow rate of 3.8 mL/h, and oil flow rate of 4.1 mL/h. In pared with PFRs which require Reynolds number of 2100 for gen-
Fig. 7. Continuous oscillatory baffled reactor and different flow patterns in an oscillatory flow baffled reactor.
flow, mainly diffusion, rather than a turbulence flow, making the

movement of chemical species predictable and the reaction calcu-
lable [256]. However, for an efficient molecular diffusion, a lengthy
path is required. To address this challenge and to facilitate molec-
ular diffusion while the diffusion path is shortened, passive mi-
cromixers could be employed to improve contact surface between
two or more liquids [257]. This type of micromixers can be applied
as microfluidic working with no need for external force. They are
categorized with respect to the arrangement of mixed phases into
Dean vortices, droplet, injection, and lamination (parallel and se-
Fig. 8. Different geometries of meso-oscillatory reactor: A) Internal baffles, B) Cen- rial) [257,258]. Moreover, some passive mixing channels with spe-
tral axial baffles, C) Round-edged helical baffles, D) Sharp-edged baffles, E) Sharp- cial geometries, called chaotic advection, can also induce advection
edged helical baffles with a central insert, F) Wire wool baffles [200]. With permis- through breaking, folding, splitting, and stretching (Fig. 9).
sion from Elsevier. Copyright© 2018.
In parallel lamination, the inlet streams are split into sev-
eral narrow sub-streams, which are subsequently merged into one
eration of flow separation, i.e., transition to turbulent flow, meso- stream as laminae. Under this concept, the basic configurations are
OBRs produce similar conditions with oscillatory Reynolds number T-shaped or Y-shaped micro-channels (Fig. 9) [257].
of just 50 [245,246,252]. For biodiesel reaction screening purpose Serial lamination micromixers use the same concept as parallel
(such as selection/comparison of solid catalysts), novel meso-OBRs lamination micromixers, i.e., splitting the inlet streams and joining
with lower diameters (4.4-5 mm) than the above-mentioned stan- them later. However, in serial lamination micromixers, the merging
dard ones could be applied to save construction as well as feed- occurs horizontally first, followed by vertically [257].
stock costs. In these OBRs, oscillatory Reynolds number of 10 is In injection micromixers, the oil stream is split into sub-
sufficient to generate turbulent flow [245]. streams. Then, alcohol is injected through an array of nozzles that
It should be mentioned that axi-symmetrical vortex rings are are present on the top of one stream [257]. Droplet micromixers
formed in each baffle cavity during each fluid oscillation with use an internal flow field for the production and transportation of
oscillatory Reynolds numbers of 100 and 250 in novel- or stan- the mixed liquids droplets by capillary effects, pressure, and flow
dard meso-OBRs, respectively [245,252,253]. These chaotic, non- instability between two immiscible liquids [257,259,260].
axisymmetric, and intensely mixed flows generated within cavities Although clogging and corrosion impose considerable chal-
could enhance axial mixing in a way similar to STRs. Velocity ratio lenges in the application of micro-channel reactors, the main dis-
of oscillatory to bulk flows must be more than one for efficient full advantage of using these reactors for biodiesel production is their
flow reversal [246]. The Strouhal number is in inverse relationship very small liquid capacity [255]. A process known as numbering-up
with eddy formation; hence, a Strouhal number lower than 0.13 is used to address this issue by increasing the number of channels,
would be required for an intense eddy formation and the subse- and hence, volumetric capacity [255]. However, the shortcomings
quent appropriate vortex generation in the adjacent baffle cavities associated with this solution are channels arrangement in the re-
[245,254]. actor as well as uniform distribution of fluids through them. Kobe
Steel Company designed a large-capacity micro-channel reactor,
3.2.1.5. Micro-channel reactors. Mirco-channel reactors (also known called stacked multichannel reactors (SMCR® ), to solve these prob-
as micro-reactors or micro-structured reactors) use numerous nar- lems with the help of plates consisting of parallel multi-channels
row channels of millimeter range diameter allowing high surface- on either side. The channels on both sides are then connected to
to-volume ratios and short diffusion distances for effective heat each other through a through-hole. Either T-shaped or Y-shaped
and mass transfer. According to Table 10, such configuration re- mixing can be applied by combining channel configurations in the
sults in rapid reaction rates with high yields of up to 99.5–100%. mixing part. A characteristic flow pattern in micro-channel reac-
Accurate temperature control, continuous mode, energy efficiency, tor is slug flow, i.e., the alternate arrangement of immiscible fluids
and quick phase separation are among its other advantages [255]. (methanol and oil) in channels and large specific interfacial area.
All of these features are ascribed to the occurrence of a laminar Other flow conditions including two-layer flow and annular flow
Table 10
Micro-channel assisted biodiesel production via transesterification of oil.
Feedstock Alcohol Catalyst Reactor configuration Conditions Yield Ref.
Cotton seed oil Methanol (1:8)1 1 wt.% KOH SIMM-V2 micro-mixer, ID: 70 °C, 44 s 94.7% [263]
0.6 mm, L: 14 m, 2.5 mL/min
flow rate
Cotton seed oil Methanol (1:20) 3 wt.% H2 SO4 SIMM-V2 micro-mixer, ID: 100 °C, 7 min (first step) and 99.5% [264]
0.6 mm, L: 14 m 120 °C, 5 min (second step)
Soybean oil CO2 (as supercritical – ID: 0.571 mm, L: 97 m 20 MPa, 325 °C 84% [265]
fluid) and ethanol
(1:0.2:20)
Soybean oil Methanol (1:9) 0.2 g/mL NaOH in Slit channel micro-reactor 55–65 °C, 3 min 100% [266]
methanol with channel dimensions of
1, 1.5, and 2 mm.
Soybean oil Methanol (1:9) 1.2 wt.% KOH T-shaped plexiglass 60 °C, 3 s 98% [187]
micro-mixer, ID: 0.8 mm
Pork lard Methanol (1:6) 1.3 wt.% KOH T-mixer micro-reactor, ID: 65 °C, 5 s 95.4% [267]
0.5 mm, L: 1.2 m
Sunflower oil Ethanol (1:9) 1 wt.% NaOH Two micro-mixer designs (L: 75 °C 91.5% [268]
35 mm; W: 1500 lm, H:
200 lm): T-micromixer
(micromixer without static
elements) and MSE
(micromixer with static
elements).
Sunflower oil Methanol (1:6) NaOH Tubular micro-reactor carried 60 °C, 4 min ∼99% [269]
out using stainless steel
tubing with an ID: 710 µm
and L: 5 m
Soybean oil Methanol/hexane vol. KOH Micromixers designed with 57.2 °C, 9 s 98.8% [270]
ratio of 0.55 (1:6) confluence angel of 45
Palm oil Methanol (1:24) NA Packed-microchannel reactor; 65 °C, 8.9 min 99% [271]
Dimension of microchannel
reactor section was
60 × 1 × 0.5 mm
Soybean oil Methanol (1:9) 2 wt.% KOH ID: 0.9 mm, wire coil inserted 60 °C, 3 min 99% [272]
(L: 30 cm, average pitch
0.5 mm)
1
Fig. 9. A) T-shape mixer in parallel lamination, B) Y-shape mixer with obstacles on wall, and C) a zig-zag-shaped channel in chaotic advection micromixer.
are also possible (Fig. 10). The main factors affecting the final re- tal research works conducted on biodiesel production using micro-
sult of the reaction in the aforesaid systems were reported to be channel reactors.
micro-channel size, mixing mechanism, residence time, and reac-
tion temperature [255].
3.2.2. Rotating reactors
Martinez et al. [261] compared the impact of different inter-
Mechanical agitation facilitates the mass and heat transfer, de-
nal geometries (omega, T-shaped, Tesla) on the performance of
creases the hold-up of reactants and reagents, and allows the uti-
micro-channel reactors for ethanolysis of castor oil. Among them,
lization of more efficient (usually costlier) materials in the fabri-
the Tesla-shaped micro-channel reactor showed the most favorable
cation of resulting smaller-sized reactors. Rotating reactors have
performance by reaching 96.7% biodiesel yield. In another study
single or multiple rotating elements with various configurations
on the mass transfer simulation of biodiesel production in micro-
(discs, impellers, tubes, etc.) and rotational characteristics (power,
channel reactors, higher residence time and lower micro-channel
speed). Various types of rotating reactors suitable for transesterifi-
reactor height (higher ratio of surface area to volume) were found
cation of oil have been discussed in this section.
as significant factors [262]. Table 10 summarizes recent experimen-
Fig. 10. Different flow patterns in a micro-channel reactor.
3.2.2.1. Stirred tank reactors. In general, a STR is a cylindrical vessel

equipped with a central shaft which harbors one or more stirrers.
Lack of mixing is usually observed in tanks of large sizes especially
when multiphase reactions occur. This poor mixing can affect the
rates of mass transfer and reaction [273]. Two forms of catalyst dis-
persion in a stirred tank are considered, including heterogeneous
and homogeneous forms. Heat transfer in stirred tanks is managed
through external jackets or by applying coils inside the tank. Al-
though the application of internal coils provide higher rates of heat
transfer in system, it can cause some issues such as increasing the
possibility of fouling, disturbance of mixing, and difficulties in re-
actor cleaning.
Various methods have been developed to enhance mixing in
STRs. For example, bottom to top movement of mixture is hin-
dered by using vertical wall baffles fasten on the inner wall of
the tank. The four most common stirrer types used in reactors are Fig. 11. A schematic illustration of a typical batch stirred reactor.
turbine, impeller, monolithic, and foam stirrers [274]. Additionally,
more complicated stirrers such as Rushton stirrer can also be used
to improve the mixing intensity. Rushton stirrer is a kind of turbine Batch reactors are classically composed of a mixed tank in
mixers that has been in use since 1940s [274]. This stirrer consists which a reaction is initiated by adding the reactants and cata-
of six vertical blades placed on a disc, generating a radial flow in lysts and proceeds during a determined time. Batch reactors were
mixture. Physical characteristics of mixture and geometry of vessel extensively used at the initiation of chemical industry era dating
mainly determine the power properties of this stirrer [275]. back to the seventeenth and the eighteenth centuries. Along with
Gas-distributing inlets can also be used for improving the mix- the development of the chemical industry in the twentieth cen-
ing rate in stirred tanks [274]. For instance, gas-inducing impellers tury, continuous reactors were introduced and employed in vari-
could introduce an unreactive gas phase to the liquid phase in a ous industries. In spite of that, batch reactors still possess some
reactor in order to enhance mixing and productivity [276]. In a significant kinetic features as well as advantages making them as
CSTR with a gas-inducing impeller, electrical capacitance tomog- an important system for various reactions (Table 6).
raphy (ECT) could also be used for monitoring the gas flow in the Batch reaction systems are frequently developed by direct scale
liquid phase and consequently to increase the efficiency of the gas up from laboratory trials. If the feed concentration and reaction
distribution in the system, further improving mixing times and re- temperature are kept identical to the lab operational condition,
action parameters [277]. Another type of mixing system used in similar residence time is often needed for the same reaction since
CSTRs is the monolithic stirrer suitable for reactions with dispersed the reaction rate (kmol/hr/m3 or lb mol/hr/ft3 ) does not vary with
catalysts. This type of stirrer consists of a ceramic part with many the reactor volume. The minimum required reactor volume could
channels placed in parallel. The first idea for developing monolithic be determined on the basis of the yearly desired production rate
stirrers was presented by Albers et al. [278] for low viscose mix- and the time for a complete batch cycle, including times for charg-
tures. Immobilization of enzymatic catalyst or other types of cata- ing the reactants, heating, reaction, product discharge, and clean-
lysts inside the channels may be an advantage of monolithic stir- ing. A slightly larger reactor than standard size might be chosen
rers. In addition, there is no need for catalyst separation step while for a different run schedule or increases in production rate [238].
immobilizing the catalysts inside the channels [279,280]. A critical factor to reach high productivities in batch systems is
Solid foam stirrer is a more recent stirrer, which consists of two the precise calculation of the time required for complete conver-
foam blocks with a reticulated structure. The blocks possess high sion of reagents into products. In a batch system, optimum tem-
surface area providing an ideal situation for catalyst immobiliza- perature profiles are determined through the chemistry of reac-
tion. It has been demonstrated that tanks equipped with foam stir- tion. For instance, in exothermic reversible reactions, temperature
rer present higher yields of liquid-solid and gas-liquid mass trans- is adjusted to increase with initiation of reaction so that the pro-
fer [281,282]. Some examples of STRs are presented in Table 11. cess proceeds in the desired pathway. Thereafter, the temperature
Batch stirred tank reactor. As mentioned earlier, BSTR was the decreases with certain time to inhibit the reduction in chemical
premier biodiesel production technology and is still very popular equilibrium constant. The temperature profile is different for en-
for industrial-scale production processes. For a batch process in a dothermic reversible reactions. Under this condition, temperature
ideally stirred tank, the reaction rate is the same as the changes increases quickly as much as possible to the highest amount be-
in reactants or product/s concentrations [238]. Fig. 11 represents a cause raise of chemical equilibrium constant depends on tempera-
schematic illustration of a typical batch stirred reactor. ture elevation.
Table 11
Application of STRs for biodiesel production via transesterification of oil.
Reactor Feedstock Alcohol Catalyst Conditions Yield Ref.
BSTR Triolein oil Ethanol (1:6)1 1% KOH 25 °C, 1800 rpm, 5 min 70% [283]
BSTR Castor oil Ethanol (1:16) 1% NaOCH2 CH3 30 °C, 400 rpm, 30 min 99% [284]
BSTR Jatropha oil Ethanol (1:6) 2% NaOH 25 °C, 300 rpm, 2 h ∼100% [285]
CSTR Palm oil Methanol (1:6) 1% KOH 60 °C, 60 min 97.3% [204]
CSTR Rapeseed oil Methanol (1:6–7.8) KOH 60 °C, 3–8 mL/min flow rate 98.6% [286]
JSR Soybean and sunflower Methanol (1:6) 1% NaOH ∼35 °C, 5 min, two impinging >90% [207]
oils (85:15 wt.%) injectors, 5 mm nozzle diameters,
15 cm internozzle space
JSR WCO Methanol (1:15) 4% KOH/γ -Al2 O3 65 °C, 3 h, two impinging injectors, 76% [287]
millimetric particle 2 mm nozzles diameter, 0.5 or 1 cm
internozzle space, 4 L/min
volumetric flow rate
1
In a batch operation, the concentration of reagents is in their

maximum amounts at the beginning of the reaction which causes
a high reaction rate that needs high heat transfer load. The pro-
cess must be checked frequently because the batch system is a
time-varying process in which main parameters can change with
time. Thus, applying control planning such as “gain scheduling”
is needed during the process. A non-linear model is used for an-
alyzing batch reactors while in a condition close to steady-state
level which occurs in continuous systems, a linear model is usually
used [288]. The non-linear behavior of batch process contributes to
complexity in reaction kinetics that leads to inaccurate measure-
ments. Consequently, this would prevent complete optimization of
conditions to obtain maximum productivity and economic benefits.
Overall, a batch system can be operated optimally through two ap-
proaches. The first is to specify optimal set points of significant
process parameters such as temperature of reaction and the sec-
ond step is to monitor the system through a controlling approach
to obtain the optimal profile [289,290]. Modeling errors are usually
unavoidable due to external disturbances and complex conditions
of batch systems affecting the final products yield. To solve these
problems in control process, often on-line optimization has been
used to efficiently estimate the desired profile [291]. Examples of
BSTR for biodiesel synthesis using transesterification of oil are pro-
vided in Table 11.
CSTR. A CSTR is simply a vessel equipped with feed input (inlet),
product outlet (output), an agitator, as well as cooling and heating
jacket. It is more suitable for the industrial scale biodiesel produc- Fig. 12. Stirring packed bed reactor [138]. With permission from Elsevier. Copy-
tion [206] due to several benefits over batch operation as elabo- right© 2018.
rated in Table 6. This reaction system can make products contin-
uously every time it is run, whereas a typical BSTR is operational
for only about half the time of CSTR. CSTR can be integrated with for concentration of reactants/reagents in both vessel contents and
other reactor types to improve effectiveness. For example, PBR in stream of products. The rate of conversion and quantity of reac-
the forms of columns have been integrated with mixing/rotating tants are in a reverse relation, in better words, a high rate of con-
nature of CSTR reactors to develop a simple rotating PBR (RPBR) version needs a low amount of reactants. Apparently, the reaction
(Fig. 12). The enhancement achieved in mass transfer in RPBRs is rate is highly dependent on primary throughput of reagents. This
due to the decline in boundary layer of reactants over the hetero- issue can be solved thorough increasing the volume of reactor ves-
geneous catalysts, and the subsequent reduction in mass transfer sel [288].
resistance [292]. More complex RPBRs are discussed in detail in The design of appropriate controlling strategy, which is im-
Section “3.2.2.2”. portant for achieving maximum conversion possible with mini-
In the CSTR configuration, controlling temperature is straight- mum cost, is very challenging in CSTRs due to highly second or-
forward than in the BSTR configuration due to the fact that the der complex non-linear dynamics [242]. Accordingly, external dis-
reaction rate is fixed and the heat release rate does not vary with turbance attenuation, one relative degree, state estimation, and
time [238]. Finally, conversion and selectivity may show batch-to- zero dynamics are four difficult issues in controlling CSTR. Feed-
batch variations in a batch reaction system, whereas they are more back linearization, general predictive control, multi-model control,
likely to be fixed in a CSTR system with appropriate controlling proportional-integral-derivative controller, Taylor-linearization, and
means [238]. A CSTR system is generally modeled with respect to terminal sliding mode control model have all been used for con-
conditions in which there are no variations in temperature, controlling different parameters of CSTRs applied for biodiesel produc-
centration, or reaction rate throughout the vessel. Composition and tion [293–297]. Zhao et al. [297] have designed two new output
temperature of output stream are exactly the same as the mix- integral terminal sliding mode strategies, namely sign integral ter-
ture in the tank throughout the reaction. This feature is also true minal sliding mode control and fraction integral terminal sliding
wire screen was used to prevent their washing from this cham-
ber. The volumetric flow rate of 4 L/min was found as the optimum
value for suspending the catalyst within the chamber and elimi-
nating external mass transfer resistance [287]. It was found that
jet velocity and Reynolds number were appropriately raised at this
flow rate. Similar to the previously explained study [207], the low-
est diameter of examined nozzle (2 mm) also provided better yield
of biodiesel by providing a higher Reynolds number. The internoz-
zle distance influenced the collision of the jets; and therefore, sus-
pension of the solid catalyst within the chamber. The distances of
0.5 and 1 cm were reportedly appropriate for the complete suspen-
sion of catalyst, and hence for the maximum reaction rate [287]. A
biodiesel yield about 76% was obtained under optimum transes-
terification conditions (4 wt.% KOH/γ -Al2 O3 , 15:1 methanol-to-oil
ratio, 65 °C, 3 h) [287].
Fig. 13. Simplified diagram of jet flow stirred reactor. Redrawn from [207]. With Overall, JSRs are more suitable for heterogeneous catalyzed-
permission from Elsevier. Copyright© 2018. transesterification reactions, compared with mechanical stirrers
due to protecting structures of solid catalysts.
mode control, with powerful robustness to system disturbances. 3.2.2.2. Rotating/spinning tubes reactors. Rotating tube reactors.
In a different study, an event triggered sliding mode control was Rotating tube reactors (RTRs) use tubular geometry with low shear
designed by Sinha and Mishra [298] for maintaining the tempera- stress. To fulfill that, they rotate a moveable hollow cylinder with
ture and concentration states of an CSTR at equilibrium points. This a typical rotational speed of less than 10 0 0 rpm. In these reactors,
controller was in a relaxed status when the predefined conditions a sheared thin liquid film (0.7–1.4 mm in thickness) is formed,
were not violated and could provide stability in the system with which improves mass and heat transfers by significantly elevating
lower computational load and cost within a short period of time. the ratio of surface area to volume (about 10 0 0:1) as well as
Jet-stirred reactors. The main advantage of JSRs over PFRs and generating a small conduction path length [48,302]. Therefore,
shock tubes is that both time and space are zero-dimensional together with low pressure drop over the cylinder as well as sim-
whereas in the latter two reactors, only one parameter can be ple design, RTRs are capable of providing a suitable basis for bulk
zero-dimensional. Potentially, the mixing time is shorter than res- transesterification processes. This technology has been successfully
idence time and both can be dissociated from each other in a JSR. examined by Lodha et al. [302] for continuous production and
In contrast, mixing and residence times can never be separated separation of canola-based biodiesel in the presence of NaOH.
in PFRs [299,300]. However, JSRs have been rarely employed for They injected a mixture of methanol and oil into an RTR and
biodiesel production from natural oils and fats. controlled the temperature by means of cooling/heating jacket.
As an example, Reyes et al. [207] developed a self-heating batch Under optimized conditions (1.5 wt.% NaOH, 1:6 methanol-to-oil
transesterification reaction system using two-impinging-jet-flow as molar ratio, 900 mL/min flow rate, 40–65 °C, 670 rpm, 45 s), a high
hydrodynamic agitation driving force and converted soybean and oil to biodiesel conversion rate of 97.6% was obtained. The result
sunflower oils (85:15 wt.% blend) into biodiesel in the presence of was very promising compared with membrane reactors (480-time
1 wt.% of NaOH at methanol to-oil molar ratio of 6:1 (Fig. 13). They longer residence time, 147.5-times lower flow rate) as well as
obtained more than 90% relative biodiesel yield in the first 5 min CSTRs (eight-time longer residence time, 2.4-times lower flow
of the process while this value was increased to 98% after 60 min rate) [302–304].
of residence time. The reactor consisted of a 9-L tank connected to Rotating bed reactors. RPBR (Fig. 14) are the most common type
two centrifugal pumps at the conical bottom. These pumps forced of rotating bed device in HiGee technology that has been men-
the mixture to pass through two injectors located in the top part of tioned in the literature. Other rotating devices are also possible
the reactor wall. This configuration generated dual opposite radial which include blade packing rotating packed bed, counter-flow
jet flows in internozzle distance of 15 cm to produce a local zone concentric-ring rotating bed, crossflow concentric-baffle rotating
of high mass transfer with small size droplets of oil due to the col- bed, rotating fluidized bed, rotating zigzag bed, rotating bed with
lision of oil jets at that space. They also examined four nozzle di- blade packing and baffles, single-block rotating packed bed, split-
ameters ranging from 5 to 13 mm and argued that nozzles size had packing rotating bed, two-stage counter-current rotating packed
an inverse relationship with Reynolds number and reaction tem- bed [305]. RPBR is an intensified variation of PBR in which a
perature. More specifically, the highest initial Reynolds number of centrifugal force is applied to facilitate alcohol-oil interface, mi-
6470 was delivered by nozzle diameter of 5 mm. This could be as- cromixing (molecular scale mixing of two liquids), and mass trans-
cribed to the high temperature of the mixture in response to high fer while reducing both height and volume of the conventional
friction created which in turn lowered density and viscosity of the PBR up to 10.5–11.1 times [306]. It has been reported that mass
mixture, and consequently led to flow increments [207]. transfer coefficients have inverse relations with average lifetime
In a more recent study using JSR configuration, Ghasemi and of liquid film [306]. In fact, a resistance is observed when sur-
Molaei Dehkordi [287] used KOH/γ -Al2 O3 millimetric particles for faces of two immiscible fluids (such as alcohol and oil) are ap-
accelerating the transesterification process of WCO. The millimet- proaching each other, forming a liquid film [307]. In the case of
ric size catalyst eliminated some drawbacks associated with their pure miscible liquids, zero lifetime of liquid film, i.e., no resis-
conventional smaller size counterpart, viz., leaching of potassium tance is encountered and the surfaces immediately mix and van-
moiety into the solution, dropping of activity in recycled catalyst, ish. In RPBRs, the most important part of the reactor for mass
and separation difficulty. However, intense mixing was required to transfer is the end-effect zone of packing. More specifically, RPBR
overcome the external mass transfer resistance all over the solid produces a high energy dissipation region and passes the liquid
catalyst particles [287,301]. Therefore, they applied two-impinging- stream through it [308,309]. This part extend from the inner edge
jet technique in the JSR to deliver vigorous micromixing of reaction of the packing to the capture site of liquid, by the rotary pack-
mixture. The catalyst was located in the reaction chamber and a ing [306]. Maximum relative velocity, between liquid and rotat-
the rotational speed which can in droplet, film, or pore flow forms
at low, medium, or high centrifugal forces, respectively [310]. The
process is completed by flowing the stream of liquid into the hous-
ing and leaving the reactor through outlets [309].
RPBR efficiency depends on operational parameters, including
flow rate of liquid, speed of rotation, volumetric ratio of two liquid
streams, and fluid viscosity; as well as design parameters, includ-
ing packing (length, inner and outer radii, type, porosity), liquid
distributor (pipe, premixed, impinge), and liquid velocity charac-
teristics [308,309]. Rotational speed has a linear relationship with
segregation index, to some point, after which its influence is non-
linear [309]. Micromixing is facilitated at higher rotational speeds
by providing higher energy dissipation [309]. Similarly, the flow
rate of liquid and the volumetric ratio of two supplied liquid
streams have more or less inverse relationship with segregation
index. In contrast, viscosity has a proportional relationship with
segregation index and at higher viscosities, the average size of liq-
uid fragments increases whereas the deformation and shrinkage
of liquid elements are reduced at a given energy dissipation rate
[309,311].
The application of RPBRs for the transesterification of oils is
still immature. It has been expressed that RPBRs can enhance the
transesterification reaction by intensive mixing of reactants and
Fig. 14. A schematic drawing of a rotating packed bed reactor. Redrawn from [309].
reagents within a short time [292,301]. More specifically, the mi-
With permission from Elsevier. Copyright© 2018. cromixing time and RTD of liquid are about 10−4 s and within
several seconds [308, 312]. The subsequent centrifugation results
in glycerol phase separation and heterogeneous catalyst recovery
(in the case of its application). This strategy has been success-
fully performed for continuous production of biodiesel from ho-
mogeneous or heterogeneous-catalyzed methanolysis of soybean
oil [292,301]. KOH catalyzed-methylation of soybean oil (3 wt.%
KOH, 6:1 methanol-to-oil molar ratio, 60 °C) was conducted un-
der continuous flow rates of methanol (69 mL/h) and oil (271 mL/h)
Fig. 15. Three most common patterns of liquid distribution in a rotating pack bed at 900 rpm centrifugation. Yield and productivity of 97.3% and
reactor; A) Distribution pipes, B) Premixed distributor, and C) Impinging stream dis- 0.83 mol/min were achieved with 43.2 s residence time, respec-
tribution [309]. With permission from Elsevier. Copyright© 2018. tively [292].
Spinning tube-in-tube reactors. STT reactor or inline high shear
mixer is another reactor with tubular geometry which was
ing packing, tears and shears the liquid in this section. Conse- patented by Richard Holl in 2010 [313]. It works by quickly ro-
quently, smaller droplets and thinner liquid films are formed en- tating one tube inside another concentric fixed tube to generate
hancing surface area, and hence, volumetric mass-transfer coeffi- high shear micro-mixing. Major components of the system are ro-
cients are surged 10–100 times [306]. The high gravitational force tor (rotating cylinder), stator (stationary cylinder), two inlets, and
(50 0–250 0 rpm) improves the speed of reaction, which is already one outlet. Stator encompasses rotor with a narrow annual gap
speeded up because of packed bed process. of 0.25–0.44 mm between them. Once reactants and reagents are
RPBRs’ lower capital and space requirements as well as its pro- entered into this small annual space, the Couette flow and high
cess intensification power justify its higher energy consumption rate of shear induces instant mixing of the two liquids and their
for rotation. RPBR consists of a motor mounted either on the side subsequent movement as a coherent thin film through the gap.
or underneath the reactor according to the rotation axis. It spins This leads to a very large interfacial contact area which in turn
a ring-shaped cylindrical packed bed rotor (moving part) with or increases the reaction rate [314]. The enhanced rate of reaction re-
without a series of concentric perforated baffles placed in a cylin- duces reaction time and energy consumption in the form of mix-
drical casing, i.e., housing (static part) (Fig. 14). The center of ro- ing. The reactor volume and centrifugal force are typically 10–
tor is a hollow structure called as eye that distributes liquid. The 10 0 0 mL and 30 0 0–12,0 0 0 rpm, respectively.
packing bed is composed of three sections, viz., inner rim (im- In the biodiesel production processes using STT reactors, two
pingement zone), bulk zone, and outer rim. Both rims have a high separate streams of oil and methanol/catalyst are fed into the re-
liquid hold-up whereas the bulk zone has a high liquid distribu- actors from their individual inlets. STT fluid flow is depicted in
tion and lower hold-up. The introduction of alcohol and oil into Fig. 16. Fluids flow through the slots or holes around the rotor
the rotating packed bed can be performed by three approaches and stator and pass through a gap between rotating and station-
(Fig. 15), viz., distribution pipes spraying droplets of alcohol and ary parts of the reactor. High shear interaction of the two reactants
oil separately, premixed distributor spraying droplets of previously leads to elimination of mass transfer resistance and improves heat
mixed alcohol and oil feed, or impinging stream distribution jet- transfer as well. It may be assumed that STT reactors may not be
spraying alcohol against oil in the eye of the rotor [309]. The liquid an appropriate option for large-scale production of biodiesel due to
streams then sharply collide, i.e., impinge with the rotating packed their low reaction volume. However, these reactors have been al-
bed in its first 7–10 mm in length (also called the impingement ready utilized by COSTELLO Company for industrial scale biodiesel
zone). Subsequently, the liquid is fed in the same direction as of production (Fig. 17) [209]. The commercial version of STT system,
centrifugation rotation towards the outer rim. The rate of pass- i.e., CryonTM Reactor allows rapid scale-up as well as instant mix-
ing the alcohol-oil mixture through the bulk zone is dependent on ing of alcohol and oil for trans/esterification reactions (Fig. 18). This
flows across the surface of spinning disc are directly controlled

by rotational speed, which forms characteristic finite-amplitude
waves (concentric, spiral) and sophisticated interfacial dynamics
[274,315] (Fig. 20). An increase in the liquid flow rate and/or ro-
tational speed triggers radial velocity growth [316]. This excellent
fluid dynamics allows a continuous and efficient production of
chemicals using a compact SDR operating under appropriately high
rotational speeds. Moreover, SDR provides a great degree of control
on side-reactions, and hence, increases the process yield while re-
duces the cost of downstream purification. Both homogeneous re-
actions and heterogeneous catalysis (i.e., disc as the catalysis sup-
port) can be conveniently performed by SDRs [315].
Wave formation in SDRs can be further intensified through the
application of a temporally and spatially varying electric field with
specific intensity and electrode geometry [318]. Further improve-
ment was done in a SDR variation known as rotor-stator spinning
disc reactor (RSSDR), consisting of three discs, i.e., one rotating disc
(rotor) and two stationary discs (stators) [319]. The rotor is placed
between the stators with an axial distance of 1 mm with a speed of
Fig. 16. Depiction of spinning tube in tube fluid flow. Courtesy of Bright Path up to 4500 rpm. Later, another variation of SDR was also patented
Group, Inc. and Tribologiks, LLC. [320], consisting of two rotatable discs each with an input and an
output. The first rotatable disc was larger and contained a hollow
disc-shaped cavity where the second smaller rotatable disc with
process can support rapid (<1 s) continuous process in a single re- channeled cavity was located. Both discs had an input and an out-
actor with single pass delivering minimal soap formation and high put and were concentric about an axis at a distance of 0.05 mm.
conversion yield. The discs were counter-rotating or co-rotating with a rotational
According to COSTELLO Company, the application of STT reac- speed of up to 50 0 0 rpm to provide efficient multi-phase contact-
tor can increase the process yield up to 3% while providing higher ing.
feedstock flexibility. The process requires about 33% lower capital Studying disc radius and rotational speed of disc and volumet-
cost, no requirement for water wash step and hence save water ric flow rate of liquid is important for scale-up process of SDRs
recovery costs, and occupy low space. because they determine liquid film thickness as well as residence
time. In the case of scaling-up of the RSSDR, it is important to
increase the number of rotors-in-series rather than the diame-
3.2.2.3. Spinning disc reactors. Spinning disc reactors (SDRs) take
ter of rotor. This is because increases in the latter would result
advantage of thin liquid flow (≤100 µm) for perfect heat and mass
in a significant surge in energy consumption [274,321,322]. Dur-
transfer (Fig. 19). The thickness and radius of liquid film that
Fig. 17. Spinning tube in tube schematic view. Courtesy of Bright Path Group, Inc. and Tribologiks, LLC.
Fig. 18. Spinning tube in tube for biodiesel production; A) The system, and B) CryonTM Reactor. Courtesy of Bright Path Group, Inc. and Tribologiks, LLC.
Fig. 19. A sample of spinning disk reactor for biodiesel production. Redrawn from [317]. With permission from Elsevier. Copyright© 2018.
ing transesterification of oil using SDRs, the liquid feedstock is in- stresses, mixing intensity, and hence, the conversion. The optimum
troduced into the center of reactor chamber containing rotatable gap distance led to 55% conversion at room temperature. Simi-
disc. Consequently, a liquid film with thin, unstable, and wavy larly, Wen and Petera [325] investigated the potential of a two-
characteristics is distributed across the disc. The movements of disc SDR for intensifying the biodiesel production process. The two
liquid within this film is plug flow and from center to the pe- flat discs were concentric with a gap of 0.2 mm between upper ro-
riphery [318,323]. A two-disk spinning reactor (one rotating and tating disc and lower stationary disc. Methanol and triglycerides
one stationary) was studied by Qiu et al. [324] for continuous was coaxially fed along the center line of stationary and rotating
NaOH-catalyzed transesterification of canola oil (1 wt.% catalyst, discs. They noticed that despite the lower residence time, increas-
6:1 methanol-to-oil molar ratio, 10 0 0 rpm, 30–50 °C, few seconds). ing the rotational speed improved the conversion process. More
They observed a 20–40 folds shorter reaction time than BSTR un- recently, Chen and Chen [317] applied a SDR for continuous soy-
der similar conditions. They also argued that conversion was most based biodiesel synthesis (1.5 wt.% NaOH, 6:1 methanol-to-oil mo-
importantly influenced by sick surface morphology, rotation speed, lar ratio, 773 mL/min flow rate, 60 °C, 2400 rpm, 2–3 s). Under such
feed rate, and the intra-disk gap. Among them, the most influen- optimum conditions, a yield of up to 97% was achieved with a pro-
tial parameter was found to be the intra-disk gap (optimum dis- duction rate of 1.86 mol/min. The findings of these studies high-
tance of 0.1 mm), which was inversely correlated with local shear lighted the suitability of SDR and its intensification capability for
ric, composite) containing organic [i.e., cellulose acetate, polyacry-

lonitrile, poly(dimethylsiloxane), polysulfone, poly(vinylidene di-
fluoride)], inorganic materials (i.e., carbon, ceramic, α -Al2 O3 /TiO2 ,
ZnO2 /C), or their hybrid (i.e., organic-inorganic membranes) have
been investigated [328,332–338]. The above-mentioned conven-
tional configurations are the most common systems for mem-
brane housing and for preventing the negative impact of operating
pressure. Plate-and-frame membranes have a planar arrangement,
which is mainly in rectangular form providing a moderate aspects
ratio (surface-to-volume ratio). Some disadvantages of this config-
uration are possibility of plugging at flow stagnation points, diffi-
Fig. 20. Wave formation in SDR with respect to rotor speed; a) 200 rpm, and b) cult cleaning, and high cost [339]. While hollow fibers offer high
600 rpm [315]. With permission from John Wiley & Sons, Inc. Copyright© 2018. membrane aspect ratios and low energy utilization; however, they
are susceptible to plugging by particulates. In addition, the replace-
ment of the whole module is inevitable due to possible fouling of
simple and efficient synthesis of biodiesel in a small production fibers [340].
space. Asymmetric membranes differ from their composite counter-
parts in the number of building materials. In another word, asym-
3.2.3. Simultaneous reaction-separation reactors metric membranes are produced from a single material whereas
This group of reactors combines chemical reactions with si- composite membranes include at least two structural elements
multaneous extraction of products from reactants and unreacted produced from two different materials.
reagents in a single unit operation, an intensification method also Various membranes have successfully been applied for the re-
known as reactive separation process. This intensification process tention of glycerol (0.261–10 wt.%) from crude biodiesel with or
is generally used for equilibrium reactions, for example, trans- without the presence of alcohol and/or oil. After passing crude
esterification. The separation of product changes the equilibrium biodiesel through these membranes, glycerol content in permeates
of the reaction in favor of products formation. Moreover, these was reportedly dropped to about ∼0.01–0.19 wt.%, corresponding to
reactors provide excellent mixing, and hence, better quality and glycerol rejection percentages of more than 90–99.6 [328,341,342].
higher yield of conversion are achieved. Two classes of reactors, The mechanisms of glycerol retention could be reversed micelle
viz., membrane reactors and annular centrifugal contactors (ACCs), formation by glycerol or glycerol and soap molecules in microfil-
and one technology, i.e., reactive distillation using simultaneous re- tration, swelling of glycerol droplet by adsorption of added wa-
action and separation principle for biodiesel production are dis- ter in ultrafiltration, or simply by sieving effect in nanofiltration
cussed in this section. Other types of reactive separation tech- [328,334,341–343]. It should be noted that the amount of glycerol
nologies, including reactive absorption and distillation, reactive ad- in crude biodiesel plays a significant role in biodiesel quality on
sorption, reactive chromatography, and reactive extraction have not the permeate side, possibly due to the action of trapped glycerol
been covered in this review due to space limitations. as filter aid.
Inorganic membranes are more frequently studied for the sep-
3.2.3.1. Membrane reactors. Membranes offer a selective way to aration and purification of biodiesel, compared with their organic
transport the target substances through them, which could be used counterparts. This is because inorganic membranes are chemi-
in separation of liquids, vapor, and gasses with different mass cally inert and provide unique surface characteristics with good
transfer rates [326]. The intensification of biofuel production pro- resistance against microbial contamination while also withstand
cesses with membranes is becoming increasingly attractive [327]. harsh industrial operation conditions such as high temperature,
However, the application of membrane separation technology in mechanical stress, and organic solvent [340,343]. Despite many
biodiesel production process is relatively a new concept [328]. considerable advantages of inorganic membranes, some critical
It can be applied as either complementary step (i.e., separation disadvantages of these membranes including brittleness, compli-
and purification method) or integrated process (i.e., simultaneous cated sealing at high temperatures, difficult scale-up, low aspect
reaction-separation reactor) in the transesterification process of oil ratio, low selectivity (with few exceptions), and high capital and
for biodiesel synthesis. In general, membranes are classified based maintenance costs hinder their industrial application [343,344].
on their geometry, separation basis, and nature and are used for Therefore, the application of organic membranes such as poly-
enhancement of biodiesel quality to meet, for examples, DIN EN meric nanofiltration and reverse osmosis are recommended [343].
14214 and/or ASTM D6761 standards for biodiesel with 100% pu- It should be noted that polymeric membrane materials are pH-
rity. The selection of the right membrane type for a given process labile; and therefore, the pH of biodiesel must be reduced from
depends on various parameters such as reaction condition, pro- 12.4 to below 8.7 to avoid physical damage to membrane structure
ductivity, separation method, lifetime, and the cost of membrane [338,343].
[326]. Saleh et al. [334] efficiently reduced the glycerol content of
Separation and purification of biodiesel via membrane tech- crude biodiesel from 0.04 wt.% to as low as 0.013 wt.% (59–71%
nology have significant advantages, compared with conventional glycerol rejection) using ultrafiltration membrane of polyacryloni-
methods. This ecofriendly technology produces low amounts of trile, supported on frame-and-plate configuration. The ultrafiltra-
wastewater and utilizes low energy. Moreover, membrane can be tion was conducted with molecular cut-off of 100 kDa at pH 7,
used as a mean for the treatment of wastewater generated during 25 °C, 0.55 MP with the cross flow velocity of 0.6 m/s. Under
separation and purification of biodiesel [329,330]. Membranes are these optimum conditions, the membrane flux was 10 L/m2 /h. The
resistant to organic solvents and occupy a small area for their oper- permeate was taken whereas the retentate was recycled back to
ation. In addition, membrane reactors could provide higher quality the feed tank. This biodiesel purification process required slight
biodiesel vs. conventional separators [331]. For the separation and amounts of water for improvement of the two-phase system, and
purification step, three configurations (i.e., hollow fiber, plate-and- hence, very low amount of wastewater (1 kg water/500 L of the
frame, tubular), three membrane processes (i.e., microfiltration, treated FAME) was generated [334]. It is worth mentioning that
ultrafiltration, nanofiltration), and two structures (i.e., asymmet- the efficiency of separation is generally decreased with increased
concentrations of methanol in this step due to increasing glycerol

solubility in FAME [334].
Torres et al. [338] prepared polymeric nanofiltration compos-
ite membranes, named PVDF-12SI, by covering the surface of
asymmetric membrane of poly(vinylidene difluoride) with 12 wt.%
poly(dimethylsiloxane) solutions in hexane. Interestingly, PVDF-
12SI could tolerate harsh conditions (pH ∼12, 60 °C, 1.5 MPa) of
ethyl ester purification with high stability permitting flux recovery
ratios of up to 0.95 after 20 cycles of use. Under these conditions,
PVDF-12SI rejected 70% of the glycerol and 69% of the total glyc-
eride with a membrane flux of 7.4 L/m2 /h.
The oily nature and viscosity of crude biodiesel mask the
good selectivity and impurities rejection of solvent resistant
nanofiltration membranes by minimizing biodiesel permeation and
membrane performance efficiency [337]. Nevertheless, the flux
permeation may be increased by application of organic-inorganic
membranes [337,345]. Such type of void-free membrane is gen-
erated by dispersion of inorganic particles into polymeric matrix.
Some examples of inorganic particles incorporated into polymeric
membranes to form organic-inorganic membranes are hydrotalcite,
multiwall carbon nanotubes, ZrO2, and Zr(SO4 )2 [337,346,347]. In-
organic phase can be used as carrier of catalytic sites (in the case
of catalytic membrane in membrane reactors) and/or as support to
improve membranes characteristics. Other advantages of organic-
inorganic composite membranes are fouling resistance, and good
hydrophilicity and selectivity [337]. Peyravi et al. [337] added dif-
ferent concentrations of functionalized multiwall carbon nanotubes
in the polyimide casting solution for fabrication of nano-composite
solvent resistant membranes. They used these membranes for
purification of laboratory synthesized canola-based biodiesel and
achieved up to 100% glycerol removal (pH 7, 25 °C, 0.5 MPa). Fig. 21. Some possible roles of membranes in catalytic membrane-reactors for
Transesterification membrane reactors are a type of simulta- biodiesel synthesis through alcoholysis of oil; A) Improved yield by extractor mem-
neous reaction-separation intensification process in which the re- brane, B) Improved selectivity by distributor membrane, C) Flow-through inert
membrane, and D) Flow-through catalytic membrane with immobilized catalysts
action is integrated with in situ membrane separation. In the on or within the membrane. Abbreviations: A: Alcohol; B: Biodiesel; C: Catalyst;
biodiesel production process, membrane system prevents passing D: Diglyceride; DGR: Diglyceride reaction step; G: Glycerol; M: Monoglyceride;
glycerol molecules or rejects the unreacted triglyceride molecules MGR: Monoglyceride reaction step; O: Oil (triglyceride); RR: Remnant (unreacted)
from biodiesel stream [333]. Overall, compared with conventional reagents/reactants; TGR: Triglyceride reaction step.
methods of biodiesel production, the application of membrane re-
actors provides lower operating cost because there is no need for
additional intermediate steps. Cao et al. [333] synthesized biodiesel brane participates in the reaction to generate biodiesel permeate
from various substrates with different FFA contents via continu- [352,356] (Fig. 21D). Technically, this configuration involves the im-
ous membrane reactors. They obtained high yields of final prod- mobilization of desired catalyst on or into a suitable membrane
uct with lower amount of glycerol in comparison with the conven- (such as ceramic or polymeric membrane), which acts as micro-
tional batch techniques [348,349]. Some other examples of mem- structure catalyst carrier and may also perform separation task in
brane reactors applied for transesterification of oils have been pre- the case of integration of pervaporation technique (see further in-
sented in Table 12. formation at the end of this section) or hydrophilic polymeric ma-
Membrane reactors have two simultaneous functions, viz. pro- trices (glycerol, methanol, and water separation) [351,356]. Me-
ceeding transesterification reaction, and separation of undesired chanical and thermal stability of these membranes can be im-
compounds such as alcohol, catalysts, and glycerol from biodiesel proved through cross-linking technique with appropriate amount
stream. These roles can be fulfilled through three most pop- of a suitable compound. Cross-linking is also applied for the gen-
ular membrane reactor configurations (Fig. 21), namely, extrac- eration of catalytic membrane by introducing catalytically active
tor membrane-reactor, distributor membrane-reactor, and flow- site(s) for performing reactions. For example, the application of
through membrane-reactor [354,355]. In the first configuration, the cross-linking agents containing sulfonic groups, which also act as
yield of equilibrium-limited reactions is improved by selective reactive sites, produces more stable catalytic membrane for biodiesel
moval of the generated products by membrane so that the reaction synthesis by alcoholysis of oil [356].
is shifted towards the products formation (Fig. 21A). The second As mentioned earlier, membrane reactors can also be classi-
configuration selectively regulates the concentration of one reac- fied based on the position of catalyst and membrane into (i) in-
tant/reagent that is required in successive reactions with the help ert membrane reactor and (ii) catalytic membrane reactors. The
of membrane (Fig. 21B). Therefore, distributor membrane-reactor catalyst is physically separated from the membrane in the inert
minimizes the side reactions or further conversion of the desired membrane reactors and the membrane (e.g., ceramic membrane
products. In the case of flow-through membrane-reactors, inert or with a microporous structure, carbon membrane, etc.) does not
catalytic membranes could be used. In the former, the inert mem- directly participate in the reaction, but acts as a barrier to reac-
brane only acts as mixing system by forcing reactants and reagents tant, reagents, and some products. In contrast, in the latter mem-
to flow through the membrane (Fig. 21C) while in the latter, which brane reactor type, either the catalyst is dispersed in the mem-
is the most common configuration used for biodiesel synthesis brane or membrane itself acts as catalyst. Homogeneous catalysts,
by alcoholysis reaction in membrane reactor, the catalytic mem- glycerol, and biodiesel are soluble in methanol whereas the lipid
Table 12
Application examples of membrane reactor for biodiesel production via transesterification of oil.
Feedstock Operation mode Alcohol Catalyst Membrane characteristics Reaction conditions Yield Ref
Catalytic membrane reactors
Soybean oil Batch Methanol (1:5 v/v) Solid acid (sulfonic Flat sheet poly(vinyl alcohol) membrane 60 °C, 0.1 MPa, 29 h ND [350]
groups and acidic modified with sulfossucinic acid,
active sites) 0.8 mmol/g Bronsted acid sites
Eruca sativa Gars Batch Methanol (1:95)1 H3 PW12 O40 Agarose membrane with 38 wt.% embedded 65 °C, 8 h, 33 mL/min feed flow rate ∼90% [351]
H3 PW12 O40 , SA: 16 cm2
Soybean oil Continuous Methanol (1:9) Na2 SiO3 and Polypropylene nonwoven fabric membrane 60 °C, 65 min, 1 mL/min feed flow >97% [352]
N-[(2-hydroxy-3- modified with Na2 SiO3 and rate
trimethylammonium) N-[(2-hydroxy-3-trimethylammonium)
propyl] chitosan propyl] chitosan chloride, pore
chloride size:10–50 µm, SA: 7.95 m2 /g
Inert membrane reactors
Canola oil Semi-continuous Methanol (1:11–46) 0.5 wt.% NaOH Tubular carbon membrane, pore size: 55 °C, ∼0.21 MPa, 2–3.1 h, 88.9– [332]
0.05–1.4 µm, ID: 6 mm, L: 12 cm, SA: 3.3 mL/min methanol flow rate 98.7%
0.022 m2
Canola oil Continuous Methanol (1:23.9) 1 wt.% NaOH Tubular composite ceramic (TiO2 support), 65 °C, 0.276 MPa, 60 min, 50 mL/min 55–60% [333]
300 kD molecular weight cut-off methanol-catalyst feed rate,
50 mL/min oil feed rate
Canola oil Continuous Methanol (1;24) 0.5 wt.% NaOH Composite ceramic (TiO2 support) 65 °C, 0.46 MPa, 5 min, 50 mL/min >98% [335]
methanol feed flow rate, 50 mL/h
oil feed flow rate
Palm oil Continuous Methanol (1:1 v/v) 157.04 g KOH supported Tubular ceramic TiO2 /Al2 O3 membrane, pore 70 °C, 0.21 cm/s cross flow 94% [336]
on activated carbon size:0.05 µm, D: 16 mm, L: 40 cm, SA: circulation velocity
per unit volume of the 0.0201 m2
reactor
Soybean oil Continuous Methanol (1:24) 0.27 g/mL MCM-41 Ceramic membrane, ID: 6 mm, L: 20 cm 80 °C, 0.08 MPa, 4.15 mL/min 84.1% [353]
supported circulation velocity
p-toluenesulfonic acid
Canola oil Semi-continuous Methanol 1 wt.% NaOH Tubular carbon membrane, pore size: 70 °C, ∼0.14 MPa, 6 h, methanol feed 96% [303]
0.05 µm, ID: 6 mm; L: 12 cm, SA: 0.022 m2 flow rate 3.2 mL/min, circulate
speed 15.2 mL/min
Canola oil Semi-continuous Methanol 2 wt.% H2 SO4 Tubular carbon membrane, pore size: 70 °C, ∼0.14 MPa, 6 h, methanol feed 64% [303]
0.05 µm, ID: 6 mm; L: 12 cm, SA: 0.022 m2 flow rate 6.1 mL/min, circulate
speed 15.2 mL/min
1
Alcohol-to-oil molar ratio, unless specified otherwise.
271
droplets are suspended in the mixture. Inert membrane reactor pass the substances is solution-diffusion, which is observed in non-
prevents unreacted lipid to pass through it because the molecular porous membranes [362].
size of lipid molecules differs with soluble elements of the mixture The process flow diagram of a typical inert membrane reac-
[333,348]. tor for biodiesel synthesis by transesterifying oils is depicted in
From simultaneous reaction-separation process, catalytic mem- Fig. 22. This configuration normally comprises a packed or flu-
brane reactors are better choice than inert membrane reactors idized bed of catalysts (in the case of heterogeneous catalyst) or
[354,357]. Catalytic membrane performs separation and conver- a feedstock/catalyst mixing chamber (in the case of homogeneous
sion through interaction between functional groups of membrane catalyst).
and specific molecules in a mixture. Agarose, polypropylene, and The critical parameters which could impact membrane-based
poly(vinyl alcohol) are some examples of membrane that have biodiesel production include temperature, alcohol-to-oil molar ra-
been respectively applied as supports for catalytically active com- tio, catalyst dosage, residence time, as well as membrane thickness
pounds including Tungstophosphoric acid (H3 PW12 O40 ), Na2 SiO3 and pore size. The optimum temperature for biodiesel synthesis
and N-[(2-hydroxy-3-trimethylammonium) propyl] chitosan chlo- via a membrane reactor is 50–70 °C depending on oil droplet size
ride, and acid sulfosuccinic for biodiesel production via transes- [336,363]. Higher temperatures decreases FAME yield by compli-
terification of oil (Table 12). In the transesterification process by cating the separation of alcohol and lipid phases due to increases
this type of membrane, methanol and glycerol generate bonds in the homogeneity of the system. It has been demonstrated that
with OH groups of the membrane and are eliminated from the elevation in methanol to-oil molar ratio enhance the process yield
reaction slurry whereas biodiesel and unreacted lipids are re- in membrane reactor and the common methanol to-oil molar ratio
jected by the membrane due to their different chemical struc- in a separation membrane reactor is 24:1 [333,336]. The separation
tures [334,350]. The suitability of poly(vinyl alcohol) for fabrica- quality in a membrane reactor also depends on catalyst dosage. In-
tion of catalytic membranes is due to its inherent ability to be creasing the catalyst loading can enhance the reaction conversion
functionalized by acidic functional groups [350]. Poly(vinyl alco- through elimination of mass transfer limitation in a membrane re-
hol) and Nafion membranes were experimentally compared with actor [336]. Otherwise, more residence time will be required to
each other for transesterification of soybean oil. According to compensate for the low amount of catalyst. Another critical fac-
the results obtained, poly(vinyl alcohol) showed better charac- tor in membrane reactors is the membrane pore size, which is de-
teristics as a basic substance for catalytic membrane fabrication termined with respect to the molecular size of the compounds of
[358]. the reaction mixture. In the transesterification reaction, oil droplets
Membrane reactors, particularly organic synthetic hallow fiber have an average size of 12–1400 µm [333]. Therefore, the pore size
or plate-and-frame membranes, can act as good carriers of lipase of membrane should be in the range of 0.05–1.4 µm to prevent
used in enzymatic transesterification. More specifically, lipase can passing of oil molecules to the permeate stream [333]. The stage
be immobilized on membrane to form catalytic membrane reactors of a reaction is a main factor to determine the membrane thick-
through adsorption, covalent binding, entrapment, microencapsu- ness. Accordingly, at the initiation of the process, the conversion
lation, or their combination thereof [359]. However, it should be rate increases with reducing the membrane thickness. However,
noted that the activity of enzyme could be reduced due to loss of the membrane thickness has no effect on the reaction rate and
enzyme during immobilization process [360]. Moreover, reaction conversion at the end of process.
processes with immobilized enzymes have lower mass-transfer,
compared with enzyme-free reactions. Despite these drawbacks, 3.2.3.2. Reactive distillation reactors. Traditionally, in reversible
improved stability of immobilized enzyme leads to higher eco- liquid-phase reaction, the synthesis of products is induced accord-
nomic profitability of overall production process [360]. ing to Le Chatlier’s principle through recovering of one or more
Among the different enzyme immobilization techniques intro- products in a separate process with the help of distillation [364].
duced, adsorption is the most simple and cost-effective technique Thereafter, the unreacted reagents are recycled back into the re-
[360]. In this method, lipase is adsorbed on the surface of mem- actor for further conversion into products. Alternatively, surplus
brane through the weak linkages of hydrogen bonds, hydrophobic amount of one reagent (such as alcohol) is added to the process
interaction, ionic binding, and van der Waals interaction. However, to obtain higher desired product yields (such as biodiesel) by bet-
this method is also associated with some drawbacks including enter conversion of other reagents (such as oil) at the expense of
zyme loading limitation and convenient desorption of enzyme by higher cost of distillation and recycling process. In contrast, this
aqueous solvent or even due to ionic strength, pH, and tempera- goal can be achieved via continuous removal of the products al-
ture of the reaction [359,360]. Covalent binding of lipase to various lowing neat operation of transesterification of oil, i.e., at the stoi-
organic and inorganic carriers is considered as the most advanta- chiometric molar methanol to-oil ratio of 3:1, pulling the equilib-
geous immobilization technique in terms of improved stability of rium to efficient conversions. Although this conventional process
enzymes, high loading capacity, and minimized enzyme leaching is effective for overcoming equilibrium limitations, it significantly
issue. Nevertheless, this method is time-consuming and often re- increases both capital and operating costs up to several times. Re-
quires harsh conditions such as toxic coupling reagents that may active distillation (Fig. 23) is a breakthrough process engineered
inactivate enzyme [360]. Overall, very little is available in the pub- by merging chemical reaction and product separation (i.e., distilla-
lished literature on the use of enzymatic membrane reactors for tion) in a reactive distillation column and could address the above-
transesterifying oils. mentioned challenges.
Another technique known as pervaporation may also be cou- Technically, in reactive distillation, as the separation is induced
pled with inert or catalytic membrane reactors to separate mix- by thermal driving forces through distillation, the process is appli-
tures of liquid by partial vaporization. Separation based on this cable when there is a difference in chemicals’ boiling point or va-
technique employs a non-porous dense membrane, composed from por pressure [366]. In an ideal scenario, one product is the heaviest
zeolite or polymer [361]. In this method, separation occurs based and the other one is lightest with reactants as intermediate boiling
on relative rates of permeation mediated by specific membrane. components [364,366]. The size of the reactive distillation column
Pervaporation separation is mostly used for removal of organic can be greatly lowered by a deliberate addition of an appropri-
substances from an organic or aqueous mixture. The most distin- ate entrainer, which selectively reacts with one compound for its
guishable feature of pervaporation method is that both permeation simple removal from solution, or increasing the column pressure.
and evaporation occur in one module. The main mechanism to The process integrates enthalpy exchange, mass flow, multiple cat-
Fig. 22. Process flow diagram of a typical inert membrane reactor for biodiesel synthesis by transesterifying oils.
Fig. 23. Basic process flow diagram of a reactive distillation column-based biodiesel production plant. Adopted from [365].
alyst systems, liquid and vapor traffic over the catalyst, and sep- cles packed bed is intensified by integrating crimped wire meshes
aration into one unit [364]. Reactive distillation has many socio- into the design with catalyst held between their layers [238]. The
economic and environmental advantages, including safer process, transesterification reaction proceeds in the container of agitated
lower capital (small and simple plant size) and operating costs (20- fluid on the distillation trays while aerating with alcohol (com-
time faster, maximum conversion, lower energy consumption, long monly methanol) vapors produced in a re-boiler. Finally, the prod-
uninterrupted process), and lower emission, over conventional se- ucts, reagents, and reactants, leave the reactive zone and enter one
quential processes. of the two distillation zones, either rectifying or stripping zones,
From the operation point of view, a reactive zone is placed be- based on their volatility differences leading to their purification.
tween a rectifying zone and a stripping zone [238]. The distillation The rising methanol vapor, produced from unreacted methanol in
column may be packed or be built from a set of distinct stages the re-boiler, takes part in the reaction while also contributing to
(trays). Typically, heavier reagents should be supplied at the top of system agitation (through bubbling) and stripping water from the
the reactive zone whereas the lighter reagents should be supplied reaction. This causes increasing concentrations of water and prod-
at the bottom of the reactive zone. In the case of biodiesel produc- ucts (glycerol, FAME) towards the top (rectifying zone) and bottom
tion, the preheated alcohol and oil can be fed separately into the (stripping zone) of the distillation column, respectively (Fig. 24). In
reactive zone at different stage points or they can be mixed in a the rectifying zone, methanol and water are enriched, sent to con-
pre-reactor to bring the system close to chemical equilibrium, and denser, and separated from each other with the help of decanter.
then, the mixture of products, reagents, and reactants is fed to the Water is removed from the system as distillate whereas methanol
mentioned zone [238]. is recycled back as a reflux and feeding stream. In the stripping
In the case of heterogeneous catalyzed-transesterification, bas- zone, the products, i.e., biodiesel and glycerol are enriched, fol-
kets or screens are placed between trays of column to confine lowed by their heating in a re-boiler and pumping to decanter
the catalyst particles. An alternative solution would be the ap- (settling tank). In the settling tank, biodiesel is separated from the
plication of a packed bed prepared with standard catalyst shapes mixture and then methanol is separated from glycerol and other
such as rings and saddles. The countercurrent flow in small parti- impurities in a flash drum. Methanol is recycled back as vapor into
pared with a reactive distillation with upstream recycling because

of the lower total investment cost and energy requirement [307].
However, a higher production cost was recorded in the absence
of upstream recycle (i.e., alcohol recovery). Overall and based on
the data presented, it could be deduced that despite the higher
total production cost of biodiesel production using reactive distil-
lation without recycling upstream, this process would be the most
economical one in terms of return on investment and net present
value.
Noshadi et al. [370] continuously converted WCO into
biodiesel in a reactive distillation column using methanol in
the presence of catalyst 12-tungestophosphoric acid hexahydrate
(H3 PW12 O40 •6H2 O). Under optimum conditions (10 wt.% catalyst,
67.9:1 methanol to-oil molar ratio, 116.2 mol/h total feed flow,
1.3 kW re-boiler duty), a 94% biodiesel yield was achieved with re-
cycling the catalyst and pure methanol from the product stream
and condenser, respectively. This unacceptable large methanol to-
oil ratio about 70 may be ascribed to the shortcoming of this re-
search in considering the temperature of reactive distillation col-
umn. In better words, more favorable results could have been
obtained if the authors had considered higher temperature val-
ues beyond the sub-optimal range considered, i.e., 20–30 °C. More-
over, the total flow rate range considered in this study was 115–
150 mol/h with the optimum value recorded at 116.2 mol/h. The
proximity of the optimum point to the minimum limit of the range
Fig. 24. Separation of water, biodiesel, and glycerol in reactive distillation column could be indicative of the weakness of the boiler duty in delivering
by rising methanol vapor within the column. high heat energy to quickly raise the temperature of the column.
It is noteworthy that feed temperature as well as boiler duty must
be carefully assessed as they determine the process yield by di-
system. Glycerol can be deliberately purified in another distillation rectly influencing methanol availability, reaction rate, or biodiesel
column. If homogeneous catalyst is used, it is introduced at top of degradation.
column with water and methanol, which must be later decanted He et al. [205] designed a bench-scale reactive distillation sys-
from water and recycled back to the column [364]. tem containing 20 sieve-trays for continuous production of up to
Reactive distillation is an active field of study for many sci- 75 mL/min biodiesel (90.7% yield) by methanolysis of canola oil
entists, concentrating on the process control as well as operation at 65 °C. The catalyst, i.e., KOCH3 was introduced into the system
conditions, i.e., agitation intensity, catalysts loading and concen- as a mixture (32 wt.%) in methanol feed stream of 11.64 mL/min.
tration, condenser, re-boiler duties, feed inlets ratios, reflux ratios, The methanol-oil ratio was 4:1 and oil flow rate was 70 mL/min.
and temperature profiles. The hold-up of about 5 min makes this proposed reactive distil-
The economic profitability of reactive distillation can be signif- lation reactor up to 12–36 times faster than the existing indus-
icantly increased by improving heat exchange efficiency and the trial batch reactor processes. In another study by Prasertsit et al.
ability of the system to maintain, adsorb, and recycle back the [371], a simple lab-scale reactive distillation packed column was
energy in the form of heat, for example, using thermal coupling applied for KOH catalyzed-methylation of palm oil (1 wt.% KOH,
method. Such novel integrated process is suitable for a variety of 4.5:1 methanol-to-oil molar ratio, re-boiler temperature of 90 °C,
feedstock (palm fatty acid distillate, WCO, and animal tallow) and 5 min hold-up in column). Up to 93% biodiesel was produced un-
is associated with reduced heating and cooling demands by 43% der these conditions with a requirement for 25% less fresh feed
and 47%, respectively [367]. Petchsoongsakul et al. [368] designed methanol than the conventional process.
a single reactive distillation column, packed with amberlyst-15 in
top and CaO/Al2 O3 in bottom as two heterogeneous catalysts, for 3.2.3.3. Annular centrifugal contactors. ACC, also known as centrifu-
combined esterification and transesterification processes to con- gal reactor/contactor, has been developed since more than four
tinuously produce biodiesel from WCO. The column required four decades ago. Its prototype was designed at the Savannah River Lab-
esterification and 20 transesterification stages when operated at oratory, and Argonne National Laboratory modified it further to
atmospheric pressure (0.1 MPa). They reduced the reactive stages produce ACC. Monostage ACC uses single unit for mixing and sep-
from 24 to 8 stages (three esterification stages, five transesterifica- aration of liquids by means of a vertical centrifuge. Multistage ACC
tion stages) by increasing the column pressure to 0.3 MPa. More- has several mechanical stages and is simply formed by intercon-
over, the developed hybridization process required a net specific necting several monostage ACCs. The separation is performed due
energy of 216 kWh/kmol biodiesel, which was 8 and 449 kWh/kmol to difference in the specific mass, i.e., density between liquids. The
biodiesel lower than that of two reactive distillation columns in se- process begins with feeding two immiscible liquids through two
ries and conventional process, respectively. separate inlets located close to the top of ACC into narrow annu-
Simasatitkul and Arpornwichanop [369] applied the reactive lar spaces between the stationary housing wall and spinning ro-
distillation to convert from palm fatty acid distillate into biodiesel tor. This gap defines the intensity of mixing, liquids volume hold-
and improved the performance of both reaction and separation up, and residence time [372]. In this region, liquids are mixed and
phases. Their simulation outcomes showed that a reactive distil- chemical reactions occur. Then, the fluid is directed through radial
lation system could discount not only production cost but also to- stationary vanes in the housing base toward the rotor bottom, i.e.,
tal investment cost in comparison with a conventional two–step beginning of separation zone working by action of the spinning ro-
catalyzed system. In addition, they also concluded that a reactive tor. The fluid rotation in a vortex manner is prevented by these
distillation without upstream recycling offered more benefits com- vanes. Subsequently, the mixed liquids are accelerated toward the
wall as soon as they enter the separation zone with a speed cor-
responding to that of the rotor. The high-speed rotation facilitates
the phases separation by about 300 times, compared with grav-
ity conditions [372]. Moreover, it causes an upward movement of
fluid in the separation zone which extends from diverter disk to
the lighter phase weir [372–374]. This extended zone allows the
required transition time for the formation of a sharp liquid-liquid
interface, which in turn split off by flowing over their respective
weirs and exit through their respective outlets by gravity. At this
point, first mechanical stage is completed and each phase either
enters into next mechanical stage and so on (in the case of mul-
tistage ACC) or collector (in the case of monostage ACC). A suit-
able heavy phase weir ring, together with proper rotational speed,
is used for positioning the interface midway between the lighter
fluid weir and the heavier fluid undercurrent at the uppermost
point of the separation zone [374]. This separation strategy is ro-
bust in response to slight changes in liquid ratios or flow rate as
the efficiency of separation is not reduced by considerable shift in
distance of interface position. In contrast, bulk flow rate, density,
and viscosity of two liquids with respect to reaction temperature
and rotational speed must be considered for an optimized per-
formance. Moreover, it should be mentioned that Taylor number
which defines the significance of inertial forces (centrifugal forces)
depends on rotation direction, radius ratio of the cylinders, and
column height.
The main challenge in ACC is their uncontrollable and ex-
tremely low residence time (up to 10 s) that does not allow com-
plete transesterification reaction. This drawback can be partially
addressed by using additional delay loops and processing. Alter-
natively, Wardle [372] reported that an improvement in mixing
zone residence time and generation of smaller droplet size could
be obtained through operating ACCs at less than half of its maxi-
mum capacity with a four straight vane design. This approach low-
Fig. 25. Schematic cross section of the ACC designed and fabricated by CINC Indus-
ers the flow rates, and hence, increases hold-up volume as well
tries [267].
as overall performance in processes with kinetic limitation [310].
Nu-Energie, LLC with cooperation of Oak Ridge National Laboratory
developed a novel ACC to increase the residence time to several an internal clean-in-place system, allowing easy and quick cleaning
minutes [375–377]. For this purpose, they decreased the pump- of the reactor with no need for disassembling.
ing rate from the outer chamber to inner chamber by modify- The performance of the CINC ACC, particularly CINC V02, for
ing the inlet between the mixing and separation zones. Addition- continuous synthesis of biodiesel has been examined by some sci-
ally, this variation of ACC could provide convenient reagent ad- entists. For instance, Kraaj et al. [378] fed a CINC V02 with two
dition (methoxide/methanol), online sampling, and monitoring of separate feed streams; a stream of sunflower oil and a solution
the transesterification reaction due to incorporation of recircula- of sodium methoxide in methanol, with flow rates of 12.6 mL/min
tion and sampling zones into the design [375,376]. For batch pro- and 3.1 mL/min, respectively. Under optimum conditions (1 wt.%
duction of biodiesel by this modified ACC, two liquid phases, i.e., CH3 NaO, 6:1 methanol-to-oil molar ratio, 60 °C, 2400 rpm), a con-
soybean oil and methanol including base catalyst were separately tinuous production of biodiesel with a yield of 96% was deliv-
supplied to the reactor. They were mixed and reacted with each ered. Similarly, Abduh et al. [379] achieved a biodiesel yield of 98
other in the mixing zone (0.6 wt.%, 5.1:1 methanol-to-oil molar mol% with a volumetric production fatty acid ethyl ester (FAEE) of
ratio, 0.26 MPa, 80 °C, 3600 rpm, 2 min) and then, the immiscible 112 kg/m3 liquid /min through sodium ethoxide catalyzed-ethylation
products, i.e., methyl esters and glycerol were recovered in the sep- of J. curcas L. oil at optimum conditions (1 wt.% C2 H5 ONa, 6:1
aration zone and collected by their respective weirs. It was re- ethanol-to-oil molar ratio, 60 °C, 2100 rpm, 28 mL/min oil flow rate,
ported that after a single-pass, ASTM specifications for bound acyl- 10.3 mL/min ethanol flow rate containing dissolved C2 H5 ONa) in
glycerides were reached; higher quality biodiesel could be achieved a CINC V02. In this study, the ACC provided a similar conversion
through the second and third passes of the biodiesel obtained in yield corresponding to about 57% less than standard yield that
the previous pass with minor addition of methanol [375]. More- obtained with optimized batch reactor. However, the process was
over, the yield could be increased to as high as 95% by a total of found suitable for small-scale mobilized biodiesel units with ap-
10 min residence time, i.e., five consecutive stages (5 × 2 min) with preciable robustness, size, and flexibility in production.
addition of methanol only in first stage [375,376]. It was also re-
ported that at 60 °C and 4200 rpm and by increasing the pressure 3.2.4. Cavitational reactors
of system, a continuous production of ASTM-passed biodiesel in Two types of energy, acoustic or flow energy, are used in cavi-
the ACC could be achieved with 1 min residence time [375]. tational reactors to intensify chemical processes through the cavi-
CINC Industries also designed a series of liquid-liquid ACC with tation phenomenon [380]. The other two types of energy, i.e., optic
a capacity of 1.9–757 L/min (Fig. 25). This series provides a good or particle energy are not appropriate for induction of good chemi-
environment for batch or continuous chemical processes and per- cal and physical intensification of reactions [380]. The formation of
forms neutralization and separation in one-step with optimum cavities, their subsequent growth, and their collapse release huge
mass transfer to reduce solvent usage. The device is equipped with energies over a very small area leading to large energy densities,
which in turn efficiently improve the physical and chemical charac-

teristics of reaction [380]. In better words, as a result of the simul-
taneous incidents of cavitation (at ambient conditions) within the
reactor, local hot spots with over hundred mega Pascal pressure
and thousands Celsius temperature are formed. The cavitation also
facilitates the transport process (mixing intensity) through promo-
tion of micro-turbulent eddies, shock waves, and acoustic stream-
ing (liquid micro-circulation) [380–382]. Additionally, free radicals
responsible for chemical transformation are probably formed un-
der this condition. Maximum size and life of the cavity are the two
important characteristics of any cavitational reaction which respec-
tively determine the amount of pressure pulse upon collapse of the
cavity and active volume of the reactor [380,383]. Therefore, vari-
ous parameters must be optimized to increase these quantities for
maximum intensification of the process [380]. During the transes- Fig. 26. Hexagonal configuration for ultrasound assisted biodiesel production reac-
terification of oils, very fine emulsions are generated due to distor [390]. With permission from Elsevier. Copyright© 2018.
ruption and mixing caused by cavitational collapse near or at the
two liquids interface. Consequently, the surface area at which alco-
hol, catalyst, and oil interact with each other is increased, followed reactor design (Fig. 26). They successfully decreased the reaction
by an increase in the reaction rate. The advantages of cavitation time to 15 min with a yield as high as 93%, compared with a
as an emulsifying technique is the generation of smaller and more 3 h conventional stirring process with a biodiesel yield of 75%.
stable emulsions than conventional techniques in the presence of However, further improvements in yield were not economically
little to no surfactant, which is perfect for biphasic systems or PTC feasible due to higher costs of downstream processes.
technique. Ultrasonic horn reactors are the most common sonochemical
reactor design [380], which typically utilize an immersion type of
3.2.4.1. Sonochemical/ultrasonic reactors. These reactors are based transducers to produce very high pressure intensities next to the
on acoustic cavitation which involves sonochemistry, i.e., enhanc- horn. The intensity is lowered exponentially by increasing the dis-
ing chemical reaction due to modification in pressure through the tance from horn depending on the operating frequency and power
passage of sound waves. The most common sound waves are ul- input [391]. The efficiency of this sonochemical reactor design is
trasound in the range of 16 kHz to 100 MHz [380]. Complete si- enhanced either by constraint of liquid within longitudinal high-
nusoidal waves including both expansion (positive pressure) and intensity region or vigorous mixing of liquid. Two variations of
constriction (negative pressure) generate sonoluminescence bub- this design are sonochemical reactors with concentrator horn and
bles (vacuum micro regions filled with reagent vapors). In con- those with telsonic horn (with radial vibrations) [392,393]. Com-
trast to the number of cavitation bubbles, the size of cavitation plex scale up, erosion and particle shedding on the surface of emis-
bubble, and hence, energy released by bubble implosion has an sion tip, and cavitational blocking are among the main disadvan-
inverse relationship with the ultrasonic frequency. Cavitation oc- tages of this design and its variations.
curs as the formed bubbles expand and collapse [384]. With re- Bhangu et al. [394] speeded up Candida rugosa-derived lipase-
spect to biofuel production, ultrasound-assisted technologies have catalyzed transesterification of canola oil from 22–24 h to 90 min
been proven to be beneficiary far beyond the scope of esterifica- by applying a 3.5 cm ultrasonic horn (40 W, 20 kHz frequency). The
tion/transesterification reactions [385]. It is crucial to appropriately second common sonochemical design, i.e., ultrasonic bath (cleaner)
select energy intensity in relation with average behavior of bub- reactor consists of an ultrasonic bath encompassing the bottom of
bles, control active cavitation population (cavitational efficiency), the reactor. The irradiation of the working liquid is conducted by
and provide uniform distribution of the ultrasonic activity for an single or multiple transducers. This configuration limits the active
efficient utilization of ultrasonic energy as well as cavitational ef- zone to a vertical plane on top of the transducers with the high-
fects [380,385]. Every ultrasound-assisted reaction consists of three est intensity at the center of transducer [380]. Therefore, increasing
main steps [386]. In the first step, electrical energy is converted the bottom surface area of the reactor increases the irradiating sur-
into mechanical energy by means of piezoelectric or piezomagnetic face, and hence, improves the emission of sonochemical energy in
transducers. Then, acoustic energy is transmitted from the emis- the reactor. Consequently, a higher pressure intensity is obtained
sion tip to the medium in the second step, followed by energy con- with lower ultrasonic intensity at the end of the cavitation pro-
version to the final form leading to the chemical transformation in cess [395]. Other configurations or sonochemical designs include
the last step. Any energy loss during these three steps reduces the (i) tubular reactors with one transducer and one reflector at oppo-
overall process efficiency [386]. site ends or one transducer at each end, (ii) transducers on each
Different aspects should be considered while designing side of a hexagon, and (iii) parallel plate reactors each irradiating
ultrasound-assisted reactive systems including angle, depth with different or same frequency [380].
and position of probe with respect to geometry, size and working Sonochemical reactors result in better transesterification op-
capacity of reactor, quantity and output densities of transducers, eration parameters, including lower alcohol-to-oil molar ratios,
as well as skin morphology and shape of probe [387–389]. For lower catalyst concentrations, lower temperatures, shorter resi-
example, cavitational blocking phenomenon, which is observed dence times, than conventional processes [382]. For homogeneous
when power densities near to the emission tip are very high, can catalyzed-batch transesterification processes, the intensification is
be avoided by using several low-output transducers. Moreover, mainly achieved by replacing magnetic or mechanical stirring de-
in multi-transducer systems, lower erosion and particle shedding vices with ultrasonic probes. Feedstock streams of catalyst and
is observed as the ultrasonic intensity is concentrated on the raw substances are generally mixed in an individual pretreatment
central axis and away from the vessel walls [380]. Manickam chamber. Ultrasonic irradiation step could be followed by different
et al. [390] compared single, dual, and triple sonochemical fre- downstream separation/purification scenarios. The process flow di-
quencies and obtained the highest yield of palm oil conversion agram of a typical of homogeneous ultrasound-assisted biodiesel
into biodiesel using triple frequency operation in the hexagonal production system is represented in Fig. 27.
Fig. 27. A typical process flow diagram of homogeneous ultrasound-assisted biodiesel production system.
Georgogianni et al. [396] compared different homogeneous and tinuous biodiesel processing equipment based on ultrasound tech-
heterogeneous catalysts during ultrasound-assisted synthesis of nology. In their technology, the oil is heated (45–65 °C) and con-
rapeseed biodiesel. Amongst Mg-MCM-41, Mg–Al hydrotalcite, K- tinuously mixed with catalyst by adjustable pumps and an inline
impregnated zirconia, and NaOH, the last catalyst led to the lowest static mixer. The mixture receives 5–30 s ultrasonic cavitation ex-
mass resistance and highest efficiency. Sequential ultrasound and posures (up to 16 kW power, 20 kHz) by passing through the flow
microwave irradiation was studied by Hsiao et al. [397] for con- cell. Then, it enters a reactor column for allowing the transester-
verting rapeseed oil into biodiesel in the presence of NaOH in a ification reaction to complete (60 min retention time). Finally, the
step-wise process of 1 min ultrasound and 2 min microwave irra- mixture is subjected to centrifugation to separate the biodiesel and
diation. They reported that the method quite was successful for glycerol [413].
biodiesel production due to lower energy requirements, lower op-
eration temperature, as well as elimination of mechanical stirring 3.2.4.2. Hydrodynamic cavitation reactors. The second type of cavi-
and cooling systems. tational reactors is hydrodynamic cavitation reactors, mainly con-
Sáez et al. [398] emphasized on the significance of appropriate sisting of a pump and a constriction channel or interface, located
fatty acid compositions of oil feedstocks for batch sonochemical at the downstream of the pump’s discharge. Similar to sonochem-
biodiesel production (20 kHz frequency). Accordingly, shorter hy- ical reactors, these reactors also enhance the reaction rate through
drocarbon chains and higher saturation resulted in higher produc- cavity formations by pressure variations. These pressure variations,
tion of FAME and lower glyceride concentrations vs. when longer unlike acoustic cavitation, are generated by using specific geome-
hydrocarbon chains and unsaturated fatty acids were used. They try of the system that causes velocity variation when a high flow
also emphasized that the combination of three ultrasound am- of fluid passes through the constriction channels/interface (orifice,
plitude cycles (generated by an ultrasonic probe at 20 kHz fre- throttling valve, venture, etc.) [414]. This passage elevates the ve-
quency, 50% amplitude, and 70% duty cycle) with two 5-min ag- locity of stream at the expense of its pressure. A permanent loss
itation intervals conducted at 900 rpm for 13 min and 48 s at 50 °C in pressure is resulted because of the generation of eddies mo-
was an efficient method for transesterification of vegetable oils tion. Once pressure drops below the cavitation threshold pressure
[352]. Recently, a high-frequency, energy-efficient piezoelectric ul- (vapor pressure in the liquid at reaction temperature) millions of
trasonic reactor was introduced and analyzed from technical, en- cavities are produced [380]. As the stream proceeds, the pressure
ergetic, exergetic, exergoeconomic, and exergoenvironmental view- recovers partially and the cavities collapse leading to an intense
points and optimized using advanced soft computing techniques local agitation [380,415]. The number of cavities can be modified
[11,132,399,400]. by opening the valve fully or partially. Moreover, flow rate can be
Table 13 presents more examples of sonochemical production controlled with the help of a bypass [416]. Irreversible loss in pres-
of biodiesel. Accordingly, it can be deduced that methanol, calcium sure head and friction as well as turbulence loss are the principal
oxide, and potassium hydroxide are the most frequently used al- factors affecting the cost of fluid pumping.
cohol, heterogeneous catalyst, and homogeneous catalyst, respec- The advantages of hydrodynamic cavitation reactors are their
tively. It is worth mentioning that alcohol molecular size and struc- simplicity with respect to design, structure, operation, main-
ture could have significant effect on the transesterification reaction tenance, and immediate scale-up [416]. Moreover, this type of
[283]. More specifically, as the number of carbons in alcohol struc- reactors provides a specific reaction or physical condition through
ture increases, transfer of ester molecules formed in the glyceride modification of pressure and temperature pulses. These pulses can
phase will be hindered more [283]. Additionally, primary straight be adjusted by manipulation of bubble behavior through physical
chain alcohols are the most suitable structure of alcohols among and geometrical parameters, for examples, discharge pressure,
primary, secondary, and tertiary alcohols [401,402]. diameter ratio of constriction channel to pipe, and the dimensions
Arisdyne System, Inc. has developed a commercial retrofit of the pipe located downstream of the constriction channel [416].
biodiesel reactor, called controlled flow cavitation (CFCTM ) process, In contrast to linear pressure change in the case of permanent
based on sonochemical cavitation to form micro droplets and sub- orifice, a rotating valve can be applied to exert a sinusoidal varying
sequent emulsion. The process provides a tight control with re- pressure field on bubbles that are generated at the shear layer.
peatable droplet size distribution, delivers lower amount of mono- Additionally, bubbles with more violent collapse (large pressure
glycerides with no increase in catalyst concentration, and reduces and temperature pulses) can be obtained through installation of
residence time and catalyst consumption (up to 25%) [413]. The ad- two or three successive orifices to develop a fluctuating pressure
vantages of this add on the reactor are efficient and rapid process, field at the shear layer [416]. Compared with acoustic cavitation,
simple installation, little pipefitting and small space requirements, hydrodynamic cavitation leads to lower erosion issues because the
and low maintenance. Similarly, Hielscher Company supplies con- cavitation takes place at the shear layer in bulk [416]. An intense
278
Table 13
Examples of sonochemical reactors used for transesterification of different oils into biodiesel.
Feedstock Alcohol Catalyst Conditions Ultrasonic specifications Yield Highlights Ref.
Homogeneous catalyzed transesterification of oil

Jatropha oil Methanol (1:5)1 0.5 wt.% KOH Ambient temperature, 100 W (50% amplitude), 97.6% Higher yields and 10–20 times faster [403]
7 min 20 kHz, pulse 0.3 s cycle downstream separation was achieved in
comparison with the conventional
transesterification.
The ultrasound radiator was compatible with
CSTR and plug flow systems.
Silybum marianum oil Methanol/ethanol (1:8) 1.5 wt.% KOH 60 °C, 20 min 250 W, 40 kHz 95.7% The production of FAEE required 50% longer [404]
residence time and 20 °C higher reaction
temperature while delivering 3.4% lower
biodiesel yield than FAME production.
Palm oil Ethanol (1:9–11) 1.5–1.7 wt.% KOH 35–40 °C 1.5 kW, 20 kHz 92% The process was continuous mode. [405]
Higher temperatures led to reduction of
viscosity and consequently reduction of
cavitational activity.
When the primary cause of the activation was
cavitational collapse, a low operating
temperature was advantageous.
Higher values than the reported reagents
molar ratios led to the lower accessibility of
ethoxy groups to triglycerides.
Muskmelon oil Methanol (1:6.6) 1.15 wt.% KOH 41.9 °C, 3.56 min 400 W, 20 kHz 97.9% Artificial neural network approach provided [406]
superior simulating efficiency than response
surface methodology.
Heterogeneous catalyzed transesterification of oil
Sesame oil Methanol (1:6.7) 1.8 wt.% Ba(OH)2 31.9 °C, 40.3 min 1.2 kW, 20 kHz 98.6% Higher temperatures than the optimum value [407]
retarded the extent of cavitational effect
and reaction rate.
Artificial neural network showed more
accurate prediction over response surface
methodology.
Palm oil Methanol (1:9) 8 wt.% CaO 60 min 120 W, 20 kHz 92.7% – [408]
Jatropha oil Methanol (1:11) 5.5 wt.% CaO 64 °C 35 W, 35 kHz 95% Alcohol-to-oil molar ratio and catalyst [409]
concentration were reportedly influenced
the efficiency due to the formation of
methoxy ions.
Ultrasound sonication had marked impact on
the transesterification reaction but no effect
on the esterification reaction.
Four times higher activation energy was
required for the heterogeneous-catalyzed
reaction than its homogeneous counterpart.
Jatropha crude oil Methanol (1:20) 20 wt.% activated 60 °C, 40 min 300 W, 20 kHz (with 10 s 87.3% High tolerance to FFA and water contents in [410]
carbon-supported on and 3 s off working the oil was observed.
heteropolyacid pattern)
Soybean oil Methanol (1:7) 7 wt.% Magnetic 54 °C, 80 min 4.5 W/mL (27 W), 20–25 97.9% Magnetic catalysts were reused for five [411]
NaSiO3 @Fe3 O4 /C kHz reactive cycles with 94.9% recovery with
biodiesel yield more than 80%.
Replacement of soybean with Jatropha oil
resulted in 94.7% yield under same
conditions.
(continued on next page)
Table 13 (continued)
Feedstock Alcohol Catalyst Conditions Ultrasonic specifications Yield Highlights Ref.
Soybean oil Methanol (1:10) 6 wt.% CaO 62 °C, 60 min 35 W, 35 kHz 90% Three-phase heterogeneity of the system [412]
increased the activation energy compared
with the homogeneous-catalyzed system.
At temperatures close to boiling point of
alcohol, sonochemical system facilitated the
reaction through ultrasonic micro-streaming
rather than cavitation bubble.
Canola oil Methanol (1:7.5) 5.3 wt.% CaO 60 °C, 2.5 h 40 W 99.4% – [83]
1
279
of micro-cavities and heat and/or mass transfer, a process known

as shockwaves. The cavitation is controlled and is away from the
metal surfaces to minimize the corrosion damage (Fig. 29B). Hydro
Dynamics, Inc. supplies SPRs in various models for biodiesel pro-
duction with annual input capacity ranging from 3–495 kton based
on continuous flow and 95% uptime [423]. Various feedstocks such
as beef tallow, poultry fat, and low-grade soybean oil can be uti-
lized and the process can be handled either in batch or continuous
mode. SPRs also have the advantages of the conventional hydrody-
namic cavitation reactors mentioned in the previous section.
3.2.5. Microwave reactors

Microwave is an electromagnetic base irradiation with wave-
lengths ranging from 0.01 to 1 m and the corresponding fre-
quencies of 0.03 to 300 GHz [424]. The advantages of microwave
irradiation (i.e., simple control, time and thermal efficiencies, clean
products, and less downstream processing) as well as microwave-
effect were partially explained under Section 2.3.1. In spite of its
promising features, one of the main problems associated with
microwave reactors is the difficulty of controlling power and
Fig. 28. Formation, growth and collapse of the cavity [209]. With permission from
Elsevier. Copyright© 2018. temperature, and hence, low process reproducibility [425,426]. A
microwave reactor consists of a microwave source equipped with
a power supply and controls (the duty cycle) that transfer the
turbulence and the subsequent uniform cavitation throughout the electromagnetic energy through either coaxial cables (for lower
reactor allow efficient conduction of reactions requiring milder power) or waveguide (for higher power) into the chemical reactor,
conditions of pressure and temperature. Interestingly, hydrody- enclosed within an applicator (a metallic cavity) [426,427]. The
namic cavitation requires up to 10 times lower energy input reactor vessel or tube can be constructed from various materials
per unit of reactant/reagent volume than ultrasound cavitation such as polytetrafluoroethylene, polyether ether ketone, quartz, or
[380,416]. Compared with conventional mixing processes, hydrody- silicon carbide which are transparent or adsorptive of microwave
namic cavitation is a more cost-effective alternative as it reduces energy, allowing heating of reactants/reagents directly or indirectly,
the energy consumption by more than half [417]. Formation, respectively. In commercial microwave ovens, stirrers are used or
growth, and collapse of hydrodynamic cavities (Fig. 28) release an the reactor vessel is rotated to homogenize the electric field profile
energy density equal to 1 × 1018 kW/m3 [418]. [426,428]. These reactors are also equipped with online pressure
Pal et al. [417] used a hydrodynamic cavitation system con- and temperature control systems and have a specific geometry
sisting of a feed tank, a pump, an orifice, and control valves to design with respect to the penetration depth. All commercial
produce biodiesel with Thumba (Citrullus colocyntis) oil. The pro- microwave reactors support pressures and temperatures up to 3–
cess achieved 80% yield within 30 min residence time. Same pro- 8 MPa and 250–300 °C, respectively [426]. Generally, the reaction
cess approach was reported by Gole et al. [419] who esterified is completed within several minutes, although microwave reactors
and transesterified non-edible Nagchampa oil. In the transester- have the ability to be operated for longer times (several hours).
ification step, 20 min treatment of pre-esterified oil with 1 wt.% Biodiesel production can be assisted with microwave energy
KOH and 6:1 alcohol-to-oil ratio yielded 92.1% biodiesel. Sunflower through two main routes, including oil extraction from some
oil was successfully transesterified into biodiesel (1% w/w NaOH, feedstocks [429,430] and transesterification reaction of oil into
6:1 methanol-to-oil ratio, ∼8450 rpm, 0.86 L/min inlet flow rate, biodiesel. The second route has been discussed hereafter in which
3.5 min) with a yield of 88% using hydrodynamic cavitation re- microwave irradiation is mainly used as an alternative for heat-
actor [420]. Bokhari et al. [421] also used a hydrodynamic cavi- ing system (see also Section 2.3.2). Conventional heating, i.e., wall
tation for cleaner synthesis of rubber seed (Hevea brasiliensis) oil heating and microwave heating have been illustrated in Fig. 30.
methyl ester. They synthesized FAME with 96.5% yield in 50 L pi- The thermal energy is produced due to dipole reorientation (po-
lot hydrodynamic cavitation reactor consisting of orifice plate with larization) [432]. Under this condition, atomic or electronic polar-
21 holes of 1 mm each and inlet pressure of 0.3 MPa (1 wt.% KOH, ization, i.e., displacement of electrons around atoms or nuclei oc-
6:1 alcohol-to-oil molar ratio, 55 °C, 18 min). Compared with me- curs trillion times per second when polar molecules are exposed
chanical stirring, hydrodynamic cavitation resulted in up to 4.9, 5, to microwave irradiations. Heat is generated as a result of fric-
and 6.5 times higher rate constant, less reaction time, and higher tion between rotating molecules. The other two mechanisms for
energy efficiency, respectively [421]. It should be pointed out that microwave heating are Maxwell-Wagner and conduction [432,433].
pressures beyond the optimum condition could lead to the chocked The best alcohol as acyl acceptor for microwave-assisted
cavitation phenomenon in which downstream is filled with a cav- biodiesel production is methanol due to the presence of –OH group
ity cloud resulting in liquid scape without collapsing, and conse- providing polar characteristics as well as anchoring behavior [434].
quently reduced microturbulence and conversion [422]. Consequently, more localized rotation of methanol molecules in-
duces more superheating capability. This allows more rapid reac-
3.2.4.3. Shockwave power reactors. SPRs (Fig. 29A) are in fact rotat- tion with better performance and lower costs than other alcohols,
ing hydrodynamic reactors that have a rotor with dead ended cav- for example ethanol [435]. The sustainability of microwave-assisted
ities (Fig. 29C). Low pressure zones are created at the bottom of biodiesel production system was studied through comparison of
the cavities due to rotor spinning [423]. Therefore, micro-cavities the electrical energy demands of microwave generator and mixers
are formed as the mixture of methanol and catalyst is fed into the during biodiesel production with the electricity generated through
machine housing and passed through the specially designed rotor the combustion of the produced biodiesels [424]. Based on the re-
[209]. The collapse of these low pressure zones leads to collapse ported findings, the microwave-assisted biodiesel production gen-
Fig. 29. A) Shockwave power reactor, B) Schematic of its working principle, and C) rotor with dead ended cavities. Courtesy of Hydro Dynamics, Inc. https://www.
hydrodynamics.com.
Fig. 30. Conventional wall heating vs. microwave heating [431].
erated an extra electrical energy of 1.66 kWh per kg of biodiesel 4. Environmental sustainability, economic viability, and
after combustion. policy-making aspects of biodiesel
Scares et al. [436] obtained an ethyl ester yield of 84% by trans-
esterifying soybean oil in a continuous flow microwave reactor un- 4.1. Economic aspects and impacts of biodiesel production
der optimum conditions (1 wt.% NaOH, 9:1 ethanol-to-oil molar
ratio, 42.5 L/h flow rate, 56.4 °C, 33 s, 10 0 0 W microwave power). The total investment cost for any biodiesel production plants
Panadare and Rathod [437] also investigated the microwave- includes capital investment and operating costs. Briefly, the former
assisted enzymatic (lipase 435) synthesis of biodiesel from WCO could be estimated through different methods, viz., class 1 (i.e.,
and dimethyl carbonate. The reaction was completed in 4 h, result- detailed estimates), class 2 (i.e., definitive estimates), class 3 (i.e.,
ing in a biodiesel yield of up to 94%. Milano et al. [158] successfully preliminary estimates), class 4 (i.e., study estimates), and class 5
transesterified a mixture of Calophyllum inophyllum and WCO (yield (i.e., order-of-magnitude estimates) [440,441]. Of these, study esti-
of about 97%) using Anton Paar Monowave 400 high-performance mate is the most commonly applied approach for determination of
microwave reactor (0.77 wt.% KOH, 59.6 vol.% methanol-to-oil ratio, the cost of capital investment for biodiesel production [440–443].
60 0 rpm, 10 0 °C, 7.15 min). Thirugnanasambandham and Sivakumar This approach is useful for preliminary feasibility assessment of
[438] also obtained a high conversion yield of 99.5% by transester- different scenarios [440] with respect to the direct plant costs
ifying cotton seed oil in the presence of undetermined amount of (i.e., piping, instrumentation, electrical facilities, auxiliary facilities,
KOH (17:1 ethanol-to-oil molar ratio, 70 °C, 380 rpm, 12 min, 270 W equipment installation, and yard improvement) and equipment
microwave power). purchasing costs [441]. Therefore, the accuracy of this estimation
Microwave irradiation has also been used for in situ transes- greatly relies on the precise design of the complete process flow,
terification of microalgae in combination with ultrasound or ionic selection of equipment type (their construction materials and
liquid (see Section 2.3.3) [172,439]. For instance, Ma et al. [439] di- size), considering their most updated and adjusted prices, and
rectly transesterified Chlorella vulgaris microalgae in the presence execution of energy and material balances [440,441,444].
of heterogeneous KF/CaO catalyst in a ultrasound-microwave- Total equipment costs for biodiesel production have been es-
assisted process. A biodiesel yield of 93% was reached under the timated by different researchers [440,442]. For instances, Turton
optimum conditions (12 wt.% catalyst, 8:1 methanol-to-oil molar et al. [440] used the formula C° R = 15,0 0 0 V.55 (V is volume) for
ratio, 60 °C, 45 min). calculation of the fixed on board cost of each type of equipment
investigated in the design whereas Haas et al. [442] developed an
estimation method based on Chemcost Capital Cost and Profitabil- It is worth to mention that the extension of biofuels (such as
ity Analysis Software as well as Cost Data Online (i.e., Richardson biodiesel) industry has indirect and direct economic impacts on
Construction Estimating Standards). In addition to the direct plant the related markets such as energy, forestry, and agriculture [448–
costs and equipment purchasing costs, other criteria determining 451]. For example, as a result of land-use change, over-zealous
the total investment cost include direct (i.e., materials and labor biodiesel production may have noticeable economic consequences
for installation) and indirect (i.e., purchased taxes, insurance and on the prices of forest products, land values, agricultural com-
transportation, contractor fee, auxiliary facilities, and construction modities, fossil fuel energy, and food and feedstuffs [448]. Even-
overhead) expenses. Therefore, following the screening of the alter- tually, commercial production of biodiesel may economically influ-
native processes by study estimates, the capital cost required for a ence country spending resulted from any biofuel competitiveness
profitable process is estimated using preliminary estimates by in- policy. The increase in government expenditures and decrease in
corporation of the mentioned criteria on the basis of percentage its revenue may also negatively affect national development pro-
allocation of the total equipment purchasing cost [440,441]. For in- grams.
stances, a percentage allocation method has been used in Chilton
and Holland methods for estimating direct plant costs for biodiesel 4.2. Biodiesel policies and mandates
production processes [445].
Another cost associated with any biodiesel production plants is As mentioned earlier, the current higher price of biodiesel com-
the operating cost which includes costs of repairs, maintenance, pared with fossil-based diesel substantially impedes its widespread
labor, utilities, and raw materials. Of these, raw materials (e.g., al- production and application by private sectors. More specifically, an
cohol, oil, catalyst, wash water, etc.) constitute the largest frac- individual might be a staunch supporter of biodiesel but they are
tion of the operating cost [441]. The cost of raw materials for any not willing to pay a cent more for a liter of biodiesel. Regard-
given plants could be estimated by knowing the capacity of the less of price, the place of biodiesel as a fuel could negatively be
biodiesel production plant and the final proportions of these ma- under vigorous political pressure by oil-rich countries or oil com-
terials in the transesterification reaction. Moreover, utilities con- panies. In another word, every liter of biodiesel sold is a liter of
sumption could be estimated according to the energy balance of petrodiesel that is not (i.e., the product of an oil company). On
transesterification reaction and is dependent on size and type of this basis, the biodiesel industry could not stand alone without a
equipment and the applied process [441,446]. As mentioned ear- strong policy supporting it. It should be noted that a single pol-
lier, the current high cost of biodiesel is mainly due to the high icy on biodiesel industry could not be applied worldwide as ef-
cost of feedstock, which may hinder its large-scale production as ficiency and success of any legislated policy depends on various
well. As an example, the cost of feedstock for small and large socio-economic criteria (e.g., the energy state of country, popu-
scale biodiesel production plants contributed up to 75% and 90% of lation, economics, public acceptance, unemployment rate, etc.,) of
the total production cost, respectively [440,441]. In another study the destination country. For example, the success of Brazilian bio-
[442], soy feedstock cost amounted approximately to 88% of the fuel policy could not be replicated in India owning to the frequent
total biodiesel production expenses scored. Typically, annual oper- failures of monsoon and seasonal variations [452]. Therefore, Na-
ating cost of a biodiesel plant is the sum of the costs of raw (i) tional Biodiesel Mission was launched by government of India in
material, (ii) utilities, (iii) miscellaneous materials (1% fixed capi- 2003 based on the Committee on Development of Biofuel’s report.
tal investment, FCI), (iv) maintenance (10% FCI), (v) operating la- The goal was the exploitation of 13.4 million ha wastelands for
bor (manning estimates), (vi) labor (20% of operating labor), (vii) Jatropha-based biodiesel in two phases including experimentation
supervision (20% of operating labor), (viii) overheads (50% of op- and demonstration, and Jatropha cultivation, biodiesel production
erating labor), (ix) capital charges (15% FCI), and (x) insurance and and marketing [452]. In 2006, the government mandated oil mar-
taxes (4% FCI) [440,441]. The sum of items i-iii stands for variable keting companies for buying standard biodiesel at Rs. 26.5 (0.38
cost, while the sum of items iv-x indicates fixed cost. The sum of USD/L), including all taxes, in specific centers [452]. Despite these
these two costs (i.e., variable and fixed costs) determines the di- efforts, the National Biodiesel Mission put an end and up to this
rect production cost which is equal to annual production cost in date, noticeable commercial production of biodiesel in India was
biodiesel production plant without R&D. If R&D is considered, the unsuccessful [452]. These were due to unscientific cultivation and
annual production cost is increased by 5%. By dividing annual pro- maintenance of Jatropha oil feedstock and lack of trust between
duction cost by plant capacity, unit production cost is determined industry players and farmers. Nevertheless, the main constraint
[440,441]. was the price of biodiesel production which was 20–50% higher
Overall, different technologies require different equipment and than the purchase price determined in the biodiesel purchase pol-
may consume different raw materials; therefore, result in different icy [452]. Consequently, National Policy on Biofuels was adopted
total cost of investment for biodiesel production. Nevertheless, the by the government of India. According to its 2018 approved policy
operational biodiesel production systems around the world cannot [453], the biofuel feedstocks were further expanded and farmers
deliver a cost-competitive diesel fuel with the current technologies were allowed (with National Biofuel Coordination Committee’s ap-
and feedstocks. Therefore, the present manufacturers of biodiesel proval) to sell food feedstocks during the surplus production phase
have been incentivized by offering government supports ranging to biofuel companies. The policy supported the foundation of sup-
from subsidies and tax exemption to mandatory application of ply chain mechanisms for production of biodiesel from WCO, non-
biodiesel as diesel extender and imposing taxes on petrodiesel. It is edible oilseeds, and short duration crops. Eventually, synergistic ef-
obvious that the proper production and consumption of biodiesel forts were encouraged by defining responsibilities and roles of each
have obvious environmental benefits (i.e., GHG emission reduction) department or ministry involved with respect to biofuels [453].
and possible positive economic impacts (i.e., job creation) on coun- The expected outcome from such policy would be cleaner envi-
tries. For example, National Biodiesel Board [447] analyzed the US ronment, health benefits, infrastructural investment in rural areas,
economy in 2013 with respect to biodiesel production (6435.2 mil- employment rate improvement, increase in farmers’ income, and
lion L). Accordingly, this production had an economic impact of decreased dependency on energy import [453].
$16.8 billion, supported about 62 thousand jobs, and paid $2.6 bil- On the other hand, the main justifications of the European
lion wages. In the same study [447], it was reported that produc- Union for development and coordination of a mandatory biofuels
tion and consumption of 4277.5 million L of biodiesel could ap- policy at continental level have been environmental criteria (e.g., at
proximately abate 10 million metric tons of CO2-eq in the US. least 20% CO2 abatement by 2020, compared with 1990) and fuel
security [454]. The Directive on the promotion of the use of biofu- transport since 2009 with a biofuel target of 6.25% [16,458]. In
els or other renewable fuels for transport was introduced in 2003, 2016, the contribution of biofuels to the transportation sector in
setting 2 and 5.75% of biofuel shares in transport fuel by 2005 and Germany was up to 4.7% (with double counting) out of the 6.9%
2010, respectively [454]. In the same year, Member States were share of the renewable energies [458]. The two most widely ap-
allowed for biofuels tax reductions and exemptions under certain plied biofuels were biodiesel and ethanol with 59% and 35% of all
conditions defined by the Energy Taxation Directive. Despite some the biofuels consumed, respectively [458]. Germany plans to de-
success, the share of biofuel stood at 1.4% in 2005, 0.6% lower than crease its GHG emissions from fossil fuels in the transport sec-
the set point [454,455]. Therefore, “A European Union strategy for tor up to 6% in 2020 and to maintain it at that level for 5 years
biofuels” was released by the European Commission in 2006 to fa- (i.e., until 2025) by blending the required amounts of biofuels (not
cilitate biofuels developments by setting out seven strategic policy from animal fats and oil) with no double-counting criteria [458].
areas. This communication included “support to developing coun- Nevertheless, the application of conventional biofuels capped at
tries”; “research and development”; and “discussing the opportuni- 6.5% and the mandatory application of advanced biofuel will be in
ties and biofuel demand improvements” [454]. In 2007, the Europe place in 2020 and will reach up to 0.5% in 2025. This plan clearly
Union endorsed the “Renewable Energy Roadmap” for turning the shows Germany‘s agenda shifting from an energy mandate to a
Europe into a low-carbon and highly energy-efficient economy by GHG abatement since 2015. Parallel to this, the 1.55 €/L and 0.7
increasing the share of renewable and sustainable energies up to €/L penalties of diesel equivalent for violating fuel suppliers until
20% by 2020. In line with this, the minimum share of biofuels for 2014 were replaced by 470 €/tCO2-eq of GHG not saved [458].
phasing out diesel and petrol in the transport sector was targeted Overall, regardless of the scope, the success of any sustainable
at 10% [454]. The endorsement was further supported with some biofuel policy program substantially depends on the strict legal
legal measurements, i.e., Climate and Energy Packages legislated obligations and effective implementation. Nevertheless, a support-
and adopted in 2008 and 2009, respectively [456]. However, dif- ive agricultural policy is also needed to improve the biofuel feed-
ferent stakeholders and Member States weakened the position of stock amount and cost.
liquid biofuels in the transport sector in the original proposal dur-
ing negotiations for legislation by stating that renewable resources 4.3. Biodiesel tradeoffs and feedstock sustainability
(i.e., bioelectricity, biohydrogen, biodiesel, etc.) must source 10% of
the energy (i.e., not only diesel and petrol) in the transport sector Despite the substantial advantages of biodiesel, some negative
[454]. impacts are also associated with its application including (i) net
Recently, the energy and climate objectives for 2030 set in 2018 GHGs from direct or indirect land-use change (LUC), (ii) impacts
increased the share of renewable energies up to 32% of total energy on tropical forests and biodiversity, (iii) threat to food security and
consumption in all sectors with a minimum GHG emission reduc- food price (i.e., food vs. fuel debate), and (iv) competition for wa-
tion targeted at 40% [457,458]. More specifically, the exchange of ter resources (i.e., drink vs. drive debate) [463]. Theses tradeoffs of
the total transportation energy by renewable ones were agreed to biodiesel production/utilization can be at least minimized, if not
be 14% with 3.5% share of advanced biofuels (such as WCO and/or eliminated, through observing sustainability criteria encompassing
animal fats derived biodiesel) [458]. It should be noted that in both careful selection/evaluation of feedstock/technology used for sus-
2020 and 2030 Renewable Energy Directives (REDs), the WCO and tainable biodiesel production as well as by the implementation of
animal fats derived biofuels could count double towards the re- appropriate policies.
spective targets of 10% and 14% renewable energy sources. Marine Among such criteria, those related to feedstock are of out-
and aviation sectors were exempted from these mandates; how- most importance given the fact that the majority of the above-
ever, the application of each unit of biofuel in these sectors could mentioned disadvantages of biodiesel are attributed to this
be counted at 1.2 times of other transportation sector [458]. domain. Feedstock evaluations must be multi-criteria based con-
The encouraging mechanisms for biofuels production and considering the geographical as well as societal features of a given
sumption range from total or partial tax exemptions (or fossil fuels territory. Moreover, such evaluations should take into account
taxation) for making the price of biofuels lower than fossil fuels to carbon footprint, water footprint, impact on food/water security,
force blending of biofuels. The latter mechanism was adopted by economic feasibility (both cultivation and conversion processes),
many European countries to avoid revenue losses by governments and quality attributes of respective biodiesel (i.e., cloud point, flash
in expense of transport users [454,459]. An alternative mechanism point, pour point, calorific value, cetane number, etc.). It is also
was established by Fuel Quality Directives in which State Mem- critical to consider highly diverse biodiesel feedstocks to prevent
bers were ordered to reduce their fossil fuel lifecycle emissions up dependency on certain resources both regionally and globally
to 6% of 2010 by 2020 while at the same time allowed the ap- [464]. In line with that, different oil feedstocks used for biodiesel
plication of greater amounts of biofuels as petrol and diesel ex- production have been investigated with respect to oil yield as well
tenders. This mandate could motivate fuel suppliers for consuming as carbon and water footprints (Table 14) and the properties of
more biofuels in their products as blends to decrease GHG emis- the resultant fuels (Table 15).
sions level [454,460]. The European Union farmers were also mo-
tivated by Common Agricultural Policy to grow energy crops by 4.3.1. Edible and non-edible oil crops
providing 45 €/ha subsidy (under Energy Crop Scheme) and by al- Further increases of the global biodiesel production capacity ei-
lowing the cultivation of these crops on set-aside lands (constitut- ther requires more exploitation of non-agricultural lands such as
ing 10% of a farmer land under European Union agricultural law), forests for growing more biodiesel feedstock crops (i.e., direct LUC)
that were terminated in 2008 and 2010, respectively [454]. In 2015, or increasing the diversion of already cultivated feed or food crops
the European Union Indirect LUC Directive made an amendment to towards biodiesel industry (i.e., indirect LUC). LUC could in general
RED transport target for encouraging the non-food-based-biofuels contribute to altered GHG emissions due to the following modifica-
by capping the contribution of conventional feed- and food-based tions in; the aboveground and underground biomass, the emission
biofuels at 7% [458,461]. of N2 O from soil, and the soil carbon stocks [544]. These modifica-
In 2008, Germany (2,477,983 toe), France (2,020,690 toe), and tions may render biodiesel production not sustainable with respect
United Kingdom (691,335 toe) were the top three highest con- to emission reduction of GHGs and carbon payback. For example,
sumers of biodiesel in the European Union [462]. Germany, for ex- the conversion of peatland or natural rain forest for oil palm cul-
ample, has mandated the application of biofuel in rail and road tivation requires 320 or 57 years carbon payback by palm-based
284
Table 14
The comparison of sustainability aspects of different oil feedstocks for biodiesel production with respect to oil yield as well as carbon and water footprints.
Alternatives Oil yield (kg oil/ha) Oil content (%) Carbon footprint1 (g CO2 -eq/MJ) GHG mitigation (%)2 Water footprint3 (m3 /ton) Ref.
Edible oils
Canola oil (Brassica napus L.) 1094–1376 40–50 4.56 (+)51.6 (LUC included) 5846.5∗ 6666 (Australia)∗ [465-469]
Coconut oil (Cocos nucifera L.) 2200–2925∗ 63–65 NA NA 2671 [465, 470]
Olive oil (Olea europaea L.) 1432∗ 15–16 NA NA 2969 [465, 470]
Palm oil (Arecaceae) 5000 30–60 51.53 (+)38–41 1057 [470-472]
Rapeseed oil (Brassica napus L.) 1000 38–46 58.91 (+)29.7–32.5 1935 1482 (Germany) [465, 470, 473, 474]
Safflower (Carthamus tinctorius L.) 350–650 20–45 21.65 (+)78 6938 [465, 470, 475]
Sesame (Sesamum indicum L.) 256–310∗ 52–63 NA NA 8969 [465, 470]
Soybean oil (Glycine max L.) 375 15–20 51.5 (+)45.4 (LUC included) 2107 1442 (Italy) [465, 466, 470, 473]
Sunflower oil (Helianthus annuus L.) 305–696 25–42 NA NA 3165 [470, 476]
Non-edible oils
Camelina oil (Camelina sativa L.) 403–706∗ 30–45 18 (+)80 (LUC included) NA [477, 478]
Castor oil (Ricinus communis L.) 350–1200 40–45 22.145∗ (+)75–90 9598 [470, 479, 480]
Cotton oil (Gossypium spp. L.) 320–640∗ 16 NA NA 3589 [470, 481]
Croton oil (Croton megalocarpus) 1800 40–45 NA NA NA [465, 482]
Field Pennycress oil (Thlaspi arense L.) 349.6–699.2∗ 53.6 13–41 (+)56–85 NA [483, 484]
Jatropha oil (Jatropha curcas L.) 1590 35–40 23.5–44 (+)61.6–72 3222 (Brazil) [465, 473, 485, 486]
Jojoba oil (Simmondsia chinensis L.) 1578 44–59 66 (combustion excluded) NA 12,344 [465, 487-489]
Karanja (Pongamia pinnata L.) 225–2250 27–39 343.06 (-)22.5 1300 [465, 490, 491]
Linseed oil (Linum usitatissimum L.) 380–1320∗ 38–44 NA NA 5005 [465, 470]
Mahua (Madhuca indica/longifolia) 2700 35 38.45 (+)87.57 NA [465, 492, 493]
Moringa oil (Moringa oleifera L.) 681–1192∗ 38–40 18.61–21.07∗ NA NA [465, 494, 495]
Patchouli oil (Pogostemon cablin L.) 99–124 2.5–3.5 NA NA NA
Polanga oil (Calophyllum inophyllum L.) ∼5000 65–75 NA NA NA
Pranajiwa oil (Sterculia foetida L.) 350 34 NA NA NA [496, 497]
Rubber oil (Hevea brasiliensis L.) 120 40–50 ∼15–45 (combustion excluded) (+)70–86 13,325 [465, 470, 496, 498]
Waste oils
WCOs – – 27.93–32.49 43–51 NA [499]
NA: Not available.

1
Well-to-wheel life cycle assessment (crop cultivation, biodiesel production, biodiesel combustion, etc.).
2
Overall GHG mitigation relative to conventional petroleum diesel.
3
The sum of global average blue and green virtual water.
∗
Values estimated in the present study using the available literatures.
Table 15
Fuel properties of biodiesel (B100) obtained from different oil feedstocks.
Alternatives Cetane number Flash point ( °C) Cloud point ( °C) Pour point ( °C) Calorific value (MJ/kg) Carbon residue (wt.%) Ref.
Edible oils
Canola oil (Brassica napus L.) 61.5 182–186.5 −3 −9 to −8 39.5 NA [500,501]
Coconut oil (Cocos nucifera L.) 51–57.4 100–118.5 0–1 −4 to −3 38.3 0.01 [500,502–504]
Olive oil (Olea europaea L.) 61 173.8 NA NA 41.35 NA [503,505]
Palm oil (Arecaceae) 52–62 164–214.5 13–15 14–15 40 0.03–0.07 [500,506-508]
Rapeseed oil (Brassica napus L.) 56 170–180 −4 to −2 −12 37 1.1 [506,507]
Safflower (Carthamus tinctorius L.) 49.8–53.14 166.8–187 −5 −24 40.3–41.3 NA [503,505,509]
Soybean oil (Glycine max L.) 45–51.5 178–202.5 −5 to 1 −9 to 0 40 1.74 [500,507,510]
Sunflower oil (Helianthus annuus L.) 45.5–58 192–220 2 0 38.2–39.5 ≤0.01 [503,511–513]
Sesame (Sesamum indicum L.) 40–53 110–185 −5 −18 to −8 34.6–40.9 NA [471,505,514]
Non-edible oils
Camelina oil (Camelina sativa L.) 46 >160 −2 to 3 −8 to −4 39.1 0.02 [464,515–517]
Castor oil (Ricinus communis L.) 43.7 160–260 −27.8 to −12 −45 to −30 37.9–39.8 0.028 [464,479,506,518–520]
Cotton oil (Gossypium spp. L.) 41.2–59.5 181.8–243 1.7 −15 to −10 39.5–40.3 0.42 [503,505,521,522]
Croton (Croton megalocarpus) 40.7–46.6 164–189 −4 to −3 −9 to −2 39.8 NA [482,500,523]
Field Pennycress oil (Thlaspi arense L.) 59.8 NA −10 −18 NA NA [483]
Jatropha oil (Jatropha curcas L.) 46–57.1 135–238 4–13 2–6 38.5–42 0.02 [464,500,507,508,522,524]
Jojoba oil (Simmondsia chinensis L.) 63.5 61–75 6–16 −6 to 6 42.8–47.4 NA [464,522]
Karanja (Pongamia pinnata L.) 52–58 150–187 13–15 −3 to 5.1 35.6–38 0.15 [464,506,522,525,526]
Linseed oil (Linum usitatissimum L.) 28–35 108 1.7 −18 to −4 37.7–39.8 NA [522]
Mahua (Madhuca indica/longifolia) 51–52 127–129 3–5 1–6 39.4–39.9 0.2 [464,522,526]
Moringa oil (Moringa oleifera L.) 67 162–176 17–21 17–19 40.1–43.28 NA [494,500]
Patchouli oil(Pogostemon cablin L.) NA 118.5 <−33 <−33 44.2 NA [500]
Polanga oil (Calophyllum inophyllum L.) 56.2–57.3 140–170 −1 to 14 0–4.3 39.2–41.3 0.18 [500,508,522,526,527]
Pranajiwa oil (Sterculia foetida L.) 57.9 130.5–179 −3 to 3 −3 to 3 40.42 NA [500,527,528]
Rubber oil (Hevea brasiliensis L.) 37–49 130–187 1–5 −8 to −2 36.5–41 0.126 [81,464,518,522,529,530]
Waste oils
Animal waste fats 44–74 106–174 −5 to 14 −6 to 15 38.76–40.23 0.024–0.21 [531–538]
WCOs 50–54.43 120–235 −1 to 9 −16 to −3 38.2–40 4.0 wt.% [67,499,539–543]
285
biodiesel, respectively [545]. While only eight years of palm-based ing process. Although, this water consumption can be minimized
biodiesel production could mitigate the carbon debt in the form of (∼20 mL/each liter of biodiesel) through adopting various advanced
GHG emission from LUC of the logged-over forest [545]. It should technologies, biodiesel production still require huge amounts of
be noted that the reduction of vegetation of managed and natural water for the cultivation of oil feedstocks. The latter water con-
ecosystems as well as the organic carbon storehouses in the soils sumption has raised drink vs. drive arguments and is partially
must be minimized in order to achieve a sustainable production blamed for water crisis severity.
of biodiesel in terms of GHGs mitigation. On the same basis, it is The water footprint of any crops can be calculated by consider-
recommended to grow native perennial crops in abandoned agri- ing their consumption of blue, green, and gray virtual-water [470].
cultural or degraded lands for biodiesel production [546]. The blue virtual-water content represent the amount of evapo-
Microalgae have also been promoted as promising triglyceride rated rainwater while the green virtual-water content stands for
source for sustainable biodiesel production, if their limitations to the amount of ground and surface water consumed during the cul-
commercialization would be overcome. For instance, cheap con- tivation process [470]. They all directly depend on irrigational, ge-
centrated CO2 supply point together with other essential resources ographical, and climatic variables. The gray virtual-water of a crop
such as fertilizers are necessary for efficient cultivation of mi- refers to the amount of polluted water generated during the crop
croalgae [27,547]. On this basis, nitrogen and phosphorous nutri- cultivation and is mainly related to agricultural practices [470]. In
ents must be totally recycled back and ideally the system ability general, some oilseed crops yield appropriately under rain-fed con-
for nitrogen bio-fixation should be granted. Another constraint on ditions and require limited irrigation facilities at the critical growth
the way of large-scale algal biodiesel is freshwater and its limited points, i.e., sowing, flowering, and seeding [555]. Such crops if in-
supply considerably reducing the yield of production [547]. These digenous to arid or semi-arid areas or genetically-modified to be
constraints make the near-future commercial application of algal so could serve as sustainable biodiesel feedstocks with respect to
biodiesel almost impossible. Therefore, in this section the main water footprint.
focus is placed on other viable feedstocks for biodiesel produc- Table 14 presents the data on global average water footprint
tion, i.e., animal fats and vegetable oils. The carbon footprint of (blue and green) of some oil feedstocks used for biodiesel produc-
any crop-based biodiesel could be estimated through an analy- tion [470]. It should be noted that the water footprints of these
sis known as life cycle assessment (LCA), involving all the stages crops may vary in different parts of the world as evapotranspi-
from the production of a given feedstock to the combustion of its ration of crops could be affected by climatic conditions. For ex-
respective biodiesel and could be further completed by consider- ample, soybean consumes 602 m3 /ton (61 m3 /GJ) water in Brazil
ing LUC [466,548,549]. LCA is in fact directly related to agricul- but its water consumption increases to 979 m3 /ton (99 m3 /GJ) and
tural practice efficiency (field practices, yield, transportation, etc.) 1360 m3 /ton (138 m3 /GJ) under the climatic conditions present
[550] as well as biodiesel production efficiency. It should be noted in the United States and Zimbabwe, respectively [556]. Therefore,
that in general, biodiesel combustion emits roughly equal GHG the Brazilian priorities for biodiesel feedstocks (based on water
emissions to what fixed during the growth of its respective feed- footprint) would be coconut, 444 m3 /ton (49 m3 /GJ); groundnuts,
stock (biomass). However, the utilization of fossil fuels in various 426 m3 /ton (51 m3 /GJ); sunflower, 972 m3 /ton (54 m3 /GJ); soy-
stages of crop cultivation and/or biodiesel production could lead bean, 602 m3 /ton (61 m3 /GJ), palm oil, 1502 m3 /ton (75 m3 /GJ),
to a final carbon debt. According to the European Union’s policies and rapeseed, 1460 m3 /ton (214 m3 /GJ) [556]. While based on the
and regulations, i.e., RED, LCA of biodiesel from any given feedstock data provided by Berger et al. [557] on blue virtual-water foot-
must confirm a minimal GHG-emissions reduction of 35%, com- print of some crops, the European priorities for biodiesel feed-
pared with GHG emissions arisen from the synthesis and applica- stocks would be rapeseed, soybean, and sunflower consuming 41.8,
tion of conventional fuels, to be considered as sustainable [551]. 302.3, and 426.2 million m3 water for the production of about 6.17,
Four major biodiesel feedstocks include palm oil, rapeseed, soy- 2.88, and 0.58 million L of biodiesel (each 31 L of biodiesel is equal
bean, and sunflower seed. Of these, rapeseed biodiesel is the most to 1 GJ), respectively. Based on these results, it could be concluded
extensively used biodiesel; however, this crop is currently culti- that the application of irrigated sunflower for biodiesel synthesis
vated using an intense application of nitrogen-containing fertilizer. is a total waste of water, particularly in Spain where 275.2 million
Up to 3–5% of the provided N2 is emitted in the form of N2 O m3 water is used for the production of only 0.9% of the total Eu-
with a 296-time stronger global warming potential than CO2 [552]. ropean feedstock required for synthesis of 250.3 × 105 GJ biodiesel
In contrast, soybean cultivation does not require any nitrogen- [557].
containing fertilizers, and hence, its cultivation is more favorable Overall, edible oils, despite their low FFA contents (i.e., no es-
than rapeseed in terms of economic and GHGs emissions. The cul- terification pretreatment requirement), could not be used for sus-
tivations of palm and soybean are mostly concentrated in biodiver- tainable biodiesel production even if economically feasible, due to
sity hotspots [553]; therefore, any further expansions in their pro- violently triggering food/water vs. fuel debates and threating bio-
duction may further jeopardize tropical forests and consequently diversity in some cases as well. Therefore, non-edible oils are ar-
threaten their associated native biodiversity [463]. Cerrado and the guably more agronomically-justified (i.e., lower water, soil, fertil-
Amazon (in the case of soybean) in South America, and Indone- izer, pesticide requirements) and more environmentally-efficient
sia’s and Malaysia’s rainforests (in the case of palm) in Southeast (i.e., less LUC, more CO2 sequestration) feedstocks than edible ones
Asia are at the highest risk of the above-mentioned destructions as long as they are cultivated on marginal and waste lands, i.e.,
[544,554]. lands that are poor for other crops [464,558–560]. A good exam-
On the other hand, a popular debate allegory, i.e., food vs. fuel ple could be jatropha plant (life-cycle of 30–50 years) which effi-
has also been raised due to increasing food prices in this mil- ciently grows and yields oil seeds (after 2–3 years) even in sandy
lennium. More specifically, biodiesel production may decrease the and saline soils with 250 mm annual precipitations [506]. Castor
availability of foods by either direct absorption of food/feed feed- shares similar ecological requirements with jatropha and could be
stocks and/or reducing the production of food/feed crops due to intercropped with it to compensate for the low income of jat-
indirect LUC as well as soil depletion. In addition, increasing water ropha cultivation in its initial 2–3 years of plantation [506]. Cas-
demands for agricultural expansions as well as population growth tor biodiesel has one of the lowest cloud point (−12 to −27.8) and
have already raised severe water crisis worldwide [463]. As men- pour point (−32 to −45) amongst all the biodiesel produced ever
tioned earlier, biodiesel production plants generate up to 1.2 L of (Table 15). Rubber plant is another non-edible oil seed produc-
wastewater per each liter of purified biodiesel during wet washing tree that has been extensively studied as a biodiesel feedstock
[81,518,529]. Its oil-rich kernel (40–50% oil content) constitutes up ity over both environmental and societal aspects. Therefore, it is
to 50–60% of the seed and the extracted oil can be efficiently con- the responsibility of those few companionate individuals to im-
verted into biodiesel via one-step (i.e., alkaline-catalyzed transes- prove the former aspect of biodiesel production and application
terification) or two-step process (i.e., FFA esterification followed by while making its production more environmentally sound. One ap-
alkaline-transesterification) [81,518,529]. proach is to force and encourage via legislations, subsidies, or their
Non-edible oil crops respond well to cultivation in rotation with combinations defined by policy makers. Alternatively, the more in-
food/feed crops, through converting fallow-crop system to crop- teresting approach could be scientific solutions either by intro-
crop system, i.e., more intensive cropping system. The latter sys- ducing novel economically-viable oil crops and/or by improving
tem significantly improves agronomic and economic aspects [561], the characteristics of already-known oil crops. Both approaches re-
such as land availability, minimizing LUC and food insecurity. For quire careful and comprehensive investigation with periodic up-
instance, Chen et al. [561] studied a three-year replicated rota- dates on improvements in terms of alternative feedstocks, their
tion system, in which Camelina and winter wheat were rotated cultivation practices, and their conversion into biodiesel. More
in the Northern Great Plains. Compared with fallow-wheat sys- specifically, the latter approach involves the presentation of some
tem, 13% less wheat yield (365 kg/ha) were conveniently offset by environmentally-friendly oil crop species with appropriate charac-
the production of 907 kg/ha Camelina [561]. Camelina has a short teristics for biodiesel production, such as through identification of
life-cycle (2–3 months) and low requirement for water, delivering naturally drought- and pest-resistant, high oil-yield crops (prefer-
up to 45% non-edible oil (290–400 kg/ton) [561,562]. Fröhlich and ably non-edible) that require minimum agricultural practices fol-
Rice [515] reported relatively similar fuel economy for Camelina- lowed by the introduction of agronomic techniques and technolo-
based biodiesel and diesel oil based on vehicle trials. Niger seed gies to exploit the best out of their cultivations. Castor, karanja, ja-
oil (Guizotia abyssinica L.) is another non-edible crop option which tropha, linseed, and polanga are some examples of this approach.
is well-adapted to poor acidic soils. This oil crop matures within Moreover, this approach could involve traits improvements (oil
about four months and can be cultivated in rotation with some traits, agronomic traits) through natural selection or recombinant
food crops such as maize and wheat [563]. A seed oil content of technology, the latter commonly referred to as genetically modi-
up to 30% can be delivered, whereas the remaining high protein fied crops. This may even decrease the feedstock cost through co-
meal could be used as animal feed [563]. Despite these advantages, production of high-value recombinant products [465]. For instance,
biodiesel production from this oil crop seems unfeasible because of a transgenic low-palmitic-acid (<5%) and high-oleic-acid (>85%)
its low seed yield (5–10 kg/ha) as well as the application of whole soybean was developed by Graef et al. [510] showing stability to-
seed as birds’ food in many countries. wards environmental stresses such as production on irrigation and
It is interesting to note that the production cost of non- non-irrigation schemes. Moreover, oil properties and consequently,
edible oils for castor (1188 kg oil/ha), jatropha (1590 kg oil/ha), fuel characteristics of the resultant biodiesel were also efficiently
and karanja (225–2250 kg oil/ha) oils are estimated at 0.12, 0.39, improved compared with the conventional soybean oil biodiesel,
and 0.25 USD/kg, respectively, whereas soybean oil (375 kg oil/ha) i.e., cetane number (from 47.2 to 51.5), cloud point (from −1
production costs 1.64 USD/kg [506,529,564]. Although palm oil to −5 °C), pour point (from 0 to −9 °C), and total glycerol (from
(50 0 0 kg oil/ha, 0.19 USD/kg) and rapeseed oil (10 0 0 kg oil/ha, 0.34 0.097 to 0.068 wt.%) [510].
USD/kg) could economically compete with the above-mentioned
non-edible oils [506,565], they are associated with several short- 4.3.2. Biodiesel production under biorefinery concept
comings mentioned earlier. An untapped non-edible oil feedstock Biodiesel could be produced in a sustainable way under recy-
for biodiesel could be polanga (65–75% seed oil content) with cling or biorefinery concept from residual oils or crops, such as oil
an oil yield of about 50 0 0 kg/ha, i.e., equal to palm oil yield refinery waste oil streams (acid oil, soapstock, fatty acid distillate,
[508,566]. In a thorough investigation, Dinh et al. [507] compared oil crop pomace) as well as other waste oil feedstocks (animal fats,
algae, jatropha, palm oil, rapeseed, and soybean as biodiesel feed- WCO, brown or yellow grease, residual oil from food/fruit process-
stock based on economical, sustainability (cultivation feasibility ex- ing industry, etc.) (Table 16). Collection, transportation, and treat-
cluded), and technical criteria. According to the results of analytical ment mainly determine the cost of these promising feedstocks. For
hierarchy process technique, soybean was the most economic op- instance, leftover apricot or plum stone from fruit processing in-
tion but was interior from the environmental (GHG emissions, land dustry could provide low-cost oil feedstock for biodiesel produc-
usage, water consumption) and biodiesel quality (cetane number, tion through either one-step process and/or two-step process as
cloud point, carbon residue) perspectives. Moreover, although palm they contain 44.7–57.8 or 32–45.9% oil, respectively. Plum stone
oil was the best feedstock in term of biodiesel quality, it was only oil content is relatively similar to those of sunflower and rape-
slightly better than soybean in terms of environmental aspects. seed but about 1.6–3.1 times higher than that of soybean seeds
Overall, algae followed by palm oil had the highest total ranks [569]. The possibility of conducting one-step biodiesel production
based on their suggested priority structure using the analytical process from some of these oil feedstocks indicates their low acid
hierarchy process technique. In a simulated study [567], jatropha value (FFA contents). Apricot kernel oil biodiesel has been synthe-
biodiesel (USD 0.15/L) followed by WCO biodiesel (USD 0.23/L) had sized by Wang [570] displaying a cetane number of 47.2–51.23 and
lower production costs compared with the other investigated oil flash point of 173 °C whereas that obtained from plum kernel oil by
feedstocks (i.e., palm, microalgae, tallow). Overall, it could be de- Kostić et al. [569] showed 57 and 155 °C, respectively. These stud-
duced that non-edible oils would be better biodiesel feedstocks ies found kernel oil, from the leftovers of fruit processing indus-
than edible oils. However, they also could lead to food/feed and try, promising biodiesel feedstocks as long as efficient oil recov-
water insecurity, to a much lesser extent than edible oil plants ery techniques are conducted. Nevertheless, appropriate genotype
though. Therefore, full exploitation of non-edible oil as sustainable must be selected and established by agricultural studies as well
feedstocks for biodiesel production still requires some improve- as by cloning techniques to further improve both productivity and
ments with respect to agricultural practices, post-harvest technolo- quality of these fruits including their kernel.
gies, and processing techniques [464,568]. Soapstock is a by-product of oil refinery industry, produced
Currently, biodiesel costs about 1.5–3 times higher than diesel, when crude vegetable oil is refined from FFAs by agitation with
of which the price of oil feedstocks, as mentioned earlier, could alkali. The typical generation rate of soapstock is about 6% of the
contribute up to 70–95% of the production costs [67,543]. Unfortu- total crude oil input [580]. The high lipid content of soapstock,
nately, for many entrepreneurs, economic aspects have the prior- together with its low market value of about 0.11 USD/kg dried
Table 16
Some examples of biodiesel production under biorefinery concept with respect to feedstock, industries, and technologies involved as well as the generation of value-added
products.
Feedstock Integrated industries Value-added products Technologies involved Ref.
Castor plant Ethanol and biodiesel industries –Ethanol –Simultaneous saccharification and [571]
-Biodiesel fermentation of residual castor plant
(149.6 g biodiesel and 30.1 g -Ethanolic transesterification of castor oil
ethanol per each kg of biomass)
Saussurea heteromalla Ethanol and biodiesel industries –Ethanol –Simultaneous saccharification and [572]
-Biodiesel fermentation of residual biomass
(112.2 g biodiesel and 42 g ethanol -Methanolic transesterification of
per each kg of biomass) Saussurea heteromalla oil
Oil feedstocks Food, fuel, and cosmetic industries –Biodiesel –Transesterification of oil [573,574]
-Dihydroxyacetone -Oxidation, hydrogenolysis, aqueous phase
-Hydroxypyruvic acid reforming, or fermentation of glycerol
-Ethylene glycol from biodiesel industry.
−1,2-propanediol
-Propanediols
-Ethanol
-Polyhydroxyalkanoates
-Docosahexaenoic acid
Olive oil residue Vegetable oil refinery and –Edible olive oil –Oil extraction techniques [57]
biodiesel industry -Biodiesel -(Trans)esterification of residual olive oil
wastes from oil refinery industry
Microalgae Food and biofuels industries –Pigments –Various extraction methods or biological [27,575,576]
-Proteins processes
-Vitamins -Transesterification of extracted oil
-Biodiesel -Fermentation of microalgae carbohydrate
-Ethanol content
-Biogas -Anaerobic digestion of microalgae
residues
Chlorella minutissima Food and biodiesel industries –Lutein –Ethanol-hexane based solvent extraction [577]
-Biodiesel followed by parallel saponification and
transesterification
Palm oil (Bio) energy and agriculture –Biodiesel NA1 [578]

industries -Electricity
-Heat
-Biofertilizer
Mucor circinelloides Enzyme, biodiesel, ethanol, and –Hydrolytic enzyme NA [579]

food industries -Biodiesel
-Ethanol
-Carotenoids
-Nutritional biomass as food
1
Not available.
soapstock (20% of the crude soybean oil price) makes it an at- Waste animal fats (WAFs) such as beef tallow, chicken fat, duck
tractive feedstock for biodiesel production [581]. Once soapstock tallow, lard, mutton fat, etc. are another group of waste oils that
is H2 SO4 -treated, acid oil containing long-chain FFAs along with can be used as biodiesel feedstock. A cheap by-product of meat
traces of other compounds are generated. Other by-product of oil industry is tallow, produced in a centralized manner in slaughter-
refinery industry is fatty acid distillate generated in the final de- ing houses, processing facilities or by rendering operations. Beef
odorization stage. All of these low-cost by-products can be con- tallow, for example, can be divided into edible and non-edible
verted into biodiesel. For example, Haas [581] successfully synthe- fats and the latter is traditionally used as animal feed supplement
sized soybean soapstock methyl esters with promising fuel proper- (main market), soap, and lubricants [584]. In recent years, the
ties, i.e., flash point of 169 °C, carbon residue of 0.01 wt.%, cetane trade of tallow as well as its shipment for the above-mentioned
number, 51.3, and cloud point of 6 °C. Moreover, biodiesel pro- applications has been negatively affected by risk of transmission
duction cost was decreased by 23%, compared with soy-based of bovine spongiform encephalopathy. However, these tallowate
biodiesel. Alternatively, the oil crop residues from oil refinery feedstocks can be safely converted into value-added product, i.e.,
may also be further processed and used as biodiesel feedstock. biodiesel costing about 0.38 USD/L [584]. It should be noted that
For instance, olive pomace oil has been successfully converted higher transesterification reaction temperature is commonly re-
into biodiesel reducing up to 43–51% GHG emissions relative to quired for the conversion of WAFs into biodiesel than vegetable
petroleum-based No. 2 diesel [499,582]. It has also been argued oils due to high saturated fatty acid (SFA) content of WAFs (up
that the total carbon footprint of olive pomace oil biodiesel could to 61.1%) [538]. An exception is chicken fats (30–33% of SFA) that
be further decreased by improving agricultural practices as 48–60% tend to be liquid or in semi-solid form. Chicken fat (i.e., skin and
of the emissions were attributed to these practices [499]. Resid- visible fat) is another largely available leftover from the meat in-
ual olive oil has similarly been considered as biodiesel feedstock dustry in leading poultry-producing countries, constituting up to
to increase the economic profitability of olive oil refinery plant 8–20% of chicken carcass weight and have direct relationship with
[583]. chicken weight [585]. For example, considering Iran chicken pro-
duction (2.5 million ton/annum) and Iranian people tendency to pharmaceutical industries unless it is purified. Nevertheless, the
buy larger chickens, up to 500 ton/annum chicken fat is produced. purification steps are highly expensive with respect to operation
The oil can be conventionally extracted from chicken fat by melt- and equipment costs [574]. Alternatively, crude glycerol can be
ing technique (90–100 °C) or by more recent techniques utilizing used as a feedstock for synthesis of a number of different chemi-
microwave heating or ultrasonic irradiations [586], followed by its cals through (i) reduction or oxidation process, or (ii) reaction with
one-step or two-step process conversion into biodiesel. other chemicals, forming other three carbon molecules or new
An alternative feedstock considered under the biorefinery con- chemical species, respectively. The application of cheap oxidizing
cept is WCO whose conversion into biodiesel would provide a safe agents (e.g., oxygen, air, bleach, hydrogen peroxide) for transform-
and economic disposal method for this waste as well. WCO is ing glycerol allows inexpensive production and in turn, industrial
largely produced (11 million ton/annum in the US only) as a left- application of some value-added products including, Glyceric, Hy-
over from preparation or cooking of foods and is no longer suit- droxypyruvic, Mesoxalic and Tartronic acids, and Dihydroxyacetone
able for the consumption by humans or animals [67]. WCOs may compounds [594,595] (Table 17). Additionally, aqueous phase re-
be divided into yellow and brown greases, typically containing less forming (i.e., moderate pressure, low temperatures) could be ap-
than and more than 15% FFAs, respectively. They could be consid- plied for breaking glycerol into gaseous (i.e., containing mainly
ered as promising biodiesel feedstocks because they are cheap and H2 ) and liquid (i.e., acids, alcohols, aldehydes, esters, ketones, etc.)
readily available. For example, yellow grease of soybean oil is avail- phases. Among them, 1,2-propanediol (Table 17) is used in syn-
able at a market value of about 0.27 USD/L in 2018 [587] compared thesis of polyurethanes, polycarbonates, polyesters, resistant textile
with virgin soybean oil price of about 0.67 USD/L in the same fibers and carpet, food products (i.e., solvent for flavoring and col-
year. The production of biodiesel from WCO could be at very rea- oring), emulsifiers, other solvents, and plasticizers [595,596]. More-
sonable price even in oil-rich countries such as Iran (∼0.61 USD/L over, 1,2-propanediol is applied as component in cosmetics, lu-
biodiesel) [67]. bricants, hydrolytic fluids, and anti-freezing agents [574]. Another
WCO has relatively same physicochemical characteristics to group of compounds, i.e., polyglycerols and their esters could be
those of virgin cooking oil but with higher FFAs and water obtained through etherification of glycerol for application in cos-
content, requiring an appropriate pretreatment before alkaline- metics, food additives, and surfactants [594]. The halogenation of
catalyzed transesterification reaction. Some pretreatment tech- glycerol leads to production of epichlorohydrin (significant feed-
niques for removing FFAs from WCO include (solid)acid-catalyzed stock in papermaking industry) with 1,3-dichloropropanol as an in-
trans(esterification), glycerolysis, silica gel pretreatment, and vac- termediate, consuming hydrochloric acid (i.e., chlorination agent)
uum distillation [588–591]. Vacuum distillation is used to trap FFAs and lower water while generating lower chlorinated residues [597].
when their content is between 3 and 15%. Glycerolysis process Anaerobic digestion, fermentation, pyrolysis, and gasification of
involves the addition of glycerin to retrieve FFAs in the form of glycerol are also possible [598]. The main product of anaerobic di-
monoglycerides at ∼204.5 °C [591]. Acid or solid acid is generally gestion of glycerol (or its co-digestion with other feedstocks) is
used for WCOs with higher than 15% FFAs content and converts CH4 with acetate, butyrate, and propionate as major intermediates
FFAs to esters. The main advantage of solid acid over acid esterifi- [599]. Whilst the fermentation of glycerol delivers some similar
cation is its immiscibility with oil, and hence, no purification step compounds to anaerobic digestion (i.e., acetate, butyrate, and H2 ),
and consequently no wastewater treatment are required. It should it also generates butanol, ethanol, and lactate [574]. The products
be noted that even oil feedstocks with high FFAs (such as WCOs, of low temperature pyrolysis of glycerol mainly include acetalde-
non-edible oils) can be directly converted into biodiesel using su- hyde, formaldehyde, and acrolein whereas ethylene, H2 O, CO2 , and
percritical method (see Section 2.3.3) for simultaneous conversion CH4 are dominant at higher temperatures [574,594]. On the other
of FFAs and triglycerides into biodiesel. From the quality perspec- hand, gasification process decomposes glycerol into H2 and syn-
tive, a proper pretreatment process guarantees similar characteris- gas which are suitable for energy application [600]. In addition
tics of biodiesels produced from WCO and virgin cooking oil [588]. to gasification and aqueous phase reforming, H2 could be pro-
In an interesting study on the various aspects of WCO biodiesel duced from glycerol (i.e., in 4:1 ratio) by auto-thermal reforming
using LCA, Moecke et al. [592] considered WCO-based biodiesel and steam/water reforming processes [601,602]. Similarly, a num-
(200 L/day) production in a plant in the vicinity of Pinheira Beach ber of different fuel additives could be formed from chemical mod-
(Santa Catarina, Brazil). They advocated the economic, environ- ification of glycerol via acetalization, etherification, ketalization, or
mental, and societal gains of the plant for the community. How- methylation process (Table 17). Ketal derivatives of glycerol could
ever, based on their results, oil collection was the most polluting stabilize biodiesel with respect to oxidation, iodine, and viscosity
stage of biodiesel production (92.1% contribution) in terms of to- while improving its cold-flow characteristics [603]. An engineered
tal GHG emissions (2.23 tCO2-eq /t biodiesel). This highlights that a bacterium, Escherichia coli strain YL15 efficiently consumes glycerol
well-managed collection system must be implemented to increase to metabolize fatty acids forming glycerol esters with a yield of
the carbon pay efficiency as well as economic profitability of the 813 mg/L [604]. Isobutylene and 1-butene could be used for ether-
WCO-based biodiesel plants through reducing fuel consumption ification of glycerol for the production of some biodiesel additives
for feedstock collection. For example, total CO2-eq emission from including dibutoxy glycerol as well as propyl glycerol ethers and
biodiesel production could be decreased by up to 23% reaching 1.72 butyl glycerol ethers, respectively [605,606].
tCO2-eq /t biodiesel in the same study [592] if fossil fuel (petroleum) Overall, upgrading biodiesel-derived glycerol not only could
was replaced by B50 (biodiesel 50%) in the WCO-vehicle collection economize the production of biodiesel but also could mitigate
system. Alternatively, centralized WCO-based biodiesel production its environmental impacts. Table 17 tabulates some glycerol-based
plants could be by the decentralized ones to minimize the envi- value-added products as well as their potential commercial appli-
ronmental and even economic burdens associated with waste col- cations.
lection and transportation [593].
An important consideration in further economizing any 4.4. Social acceptance of biodiesel
biodiesel production chains would be glycerol upgrading for pro-
duction of value-added products and hence, reducing the biodiesel There have been significant efforts for the introduction of low-
production cost. Crude glycerol (containing water, salts, alcohol, carbon biofuels such as biodiesel into the transport sector. The lev-
biodiesel, mono and diglycerides, FFAs, soap, etc.) generated dur- els of success were different from country to country and even
ing biodiesel production cannot be applied for cosmetic, food, and one community to another. Regardless of the cost, other social ac-
Table 17
Different glycerol upgrading methods for synthesis of value-added products with their potential industrial applications [574,594–596,607–611].
Conversion method Value-added product Application Industry
–Monoacylglycerides
–Diacylglycerides
Acetalization
-Diacetin
-Triacetin
–Butyl glycerol ethers
-Di-butoxy glycerol
Etherification
-Propyl glycerol ethers
-Glycerol tert-butyl ethers
Fuel additives Fuel industry
−2-butanone-glycerol
-Methyl hexonoate
Ketalization
-Fatty acid formal glycerol
ester
-Solketal
–Glycerol dimethoxy ether
Methylation
-Glycerol tert-butyl ethers
–Manufacturing of sunless tanning lotions

–Dihydroxyacetone Cosmetic and food industries
-L, D-serine synthesis
–Flavoring agent in cheese
–Hydroxypyruvic acid -Synchronization of fruit maturation Food industry
-L, D-serine synthesis
Oxidation –Glyceric acid –Skin disorder treatment Pharmaceutical and detergent

industries
-Production of biodegradable fabric softener
–Tartronic acid –Adjuvant for tetracycline absorption in blood Pharmaceutical and chemical
-Scavenging dissolved oxygen in alkaline water industries
–Mesoxalic acid –Precursor in organic synthesis Chemical industry
Hydrogenolysis –Ethylene glycol –Production of monobasic alcohols and alkanes Various industries
Aqueous phase reforming with −1,2-propanediol –Production of various chemical species Food, fuel, and cosmetic
no hydrogen addition industries
–Acrolein –Production of D/L-methionine, acrylic acid, acrylic acid Various industries

esters, glutaraldehyde, detergents, and herbicides
Dehydration
–Healthcare diet for animals and human
Pharmaceutical, food, and
−3-hydroxypropionaldehyde -Chemical fixation of biological tissues
chemical industries
-Food preserving agent
–Polyglycerols and –Production of cosmetics, lubricants, food additives, and Fuel, food, and cosmetics
polyglycerol esters surfactants industries
–Glucosyl glycerol NA1 Food and cosmetics industries
Etherification
–As nonionic surfactants and emulsifiers in dairy
Food, fuel, and cosmetic
–Glycerol monoesters products, margarines, bakery products, and sauces
industries
-As texturing agent in lotions and creams
-As plasticizing and lubricant agent in machinery oil
formulation
–Di and triglycerides –Fuel additives Fuel industry
–Monoacetin; production of cryogenics, biodegradable

Esterification or
–Glycerol acetates polyester, explosives, and (tanning) leather Various industries
transesterification
-Diacetin; printing ink, softening agents, plasticizer, and
dye solvent
-Triacetin; production of perfumes, and photographic
films, and as viscosity and cold flow improver of
biodiesel and antiknock additives for gasoline
–Efficient solvent for resins and plastics

Transesterification –Glycerol carbonate Chemical industry
-Production of glycerol ethers by reacting with alcohols,
phenols and carboxylic acids in presence of heat
Halogenation –Epichlorohydrin Synthesis of elastomers, epoxide resins, and sizing agents Paper industry
1
Not available.
ceptance criteria (discussed hereafter) of any biofuels play decisive in Finland. Interestingly, none of the respondents considered biofu-
roles in its commercial feasibility. els as the most ideal energy carrier. More specifically, up to 50% of
Public awareness, opinion, and knowledge could contribute to the respondents raised fuel vs. food debate while others had either
the social acceptance of any biofuels including biodiesel. Moula not enough information on biofuels or disappointed by their un-
et al. [612] studied the social acceptance of biofuels for transport availability or high prices at fuel stations. Similar results (i.e., avail-
ability at fuel stations and price) were obtained by Gracia et al. soap as side-product. Methanol is the most common type of alco-
[613] who examined Spanish biodiesel market for identifying pa- hol for economic biodiesel production. Alcohol-to-oil molar ratios
rameters influencing biodiesel acceptance in the transport sector. of above six are often used to induce the formation of biodiesel.
If these two parameters were comparable to those of diesel, about The most commonly used process mode for commercial pro-
50% of car drivers would definitely consume biodiesel. The number duction of biodiesel is still batch operation. However, continuous
of biodiesel users would drop to 20% or 30% when only one of the process mode requires lower space, capital, and operating cost
mentioned factors were comparable to that of its fossil counter- while it also guarantees a product with uniform quality. This pro-
part (i.e., availability or price, respectively) [613]. Nevertheless, the cess mode is suitable for quick reaction and provides superior
study emphasized that the use of biodiesel was also avoided due to heat transfer and high selectivity compared with the batch pro-
lack of knowledge (i.e., only 20% of the car drivers surveyed knew cess mode. Accordingly, the biodiesel industry is shifting toward
what biodiesel was). Generally, higher degree of willingness-to-pay the continuous process mode to address the drawbacks associated
for renewable energy projects could be found in people (mainly with the batch process operation.
younger females) with higher environmental awareness, and more It is clear that there is no perfect reactor technology for trans-
income and education [613,614]. esterifying natural oils and fats since each technology has its own
From a different viewpoint, Amin et al. [615] studied the so- pros and cons. In the majority of developed transesterification re-
cial acceptance of biodiesel with respect to Malaysian stakehold- actors, various process intensification techniques have been em-
ers’ willingness to commit palm-based biodiesel development and ployed to improve the economic profitability of the process. In
commercialization. Intriguingly, it was determined that perceived general, BSTRs have been extensively applied at industrial scale
benefits (e.g., health and social aspects) were the most signifi- due to its simplicity and low-cost fabrication, even though they
cant direct predictor for stakeholders’ attitude towards biodiesel. suffer from low efficiency and serious instability. It should be men-
The other important interconnected determinants were willingness tioned that ACCs, shockwave power reactor, STT reactor, and ultra-
for engagement in biodiesel technology (i.e., knowledge, awareness, sonic reactor have also been reached or applied at industrial scale
etc.), trust in key players (i.e., scientists, industry, and policy mak- to date for transesterification of natural oils and fats into biodiesel.
ers), attitude towards technology, and perceived risk (e.g., environ- Tubular reactors provide a more efficient and economic plat-
mental, human health, moral, and societal issues) [615]. form for blending when quick mixing, short hold-ups, and low
In conclusion, the social acceptance must be improved in par- maintenance are desirable. Although tubular reactors require lower
allel to biodiesel development and commercialization. Whatever capital and space for construction, they have a limitation for
the reasons are behind social repellents of biodiesel (i.e., lack Reynolds numbers. Moreover, these reactors experience significant
of knowledge, perceived risks, negative attitude towards technol- temperature and pressure changes at different points between in-
ogy, biodiesel unavailability or high price, and lack of trust), they let and outlet, negatively affecting heat and mass transfer coeffi-
must be carefully assessed and addressed properly. It should also cients. In rotating reactors, intense mechanical agitation facilitates
be noted that these concerns have different magnitudes of ef- mass and heat transfer and decreases retention time of reactants
fect among people with different social status. Finally, whilst the and reagents. The main problems associated with these reactors
concerns about price and availability could be partially removed are their lower efficiency as well as the difficulty of process con-
through mandatory policies, these policies would be ineffective if trol. Using reaction-separation reactors, better quality and higher
the other above-mentioned social acceptance concerns were not yield of conversion could be achieved due to excellent mixing. Nev-
sufficiently addressed. ertheless, upscaling these reactors for commercial application is
slightly difficult and complex. Cavitational reactors provide more
5. Concluding remarks and future prospects narrowly dispersed and more stable emulsions than the conven-
tional techniques, which in turn boost the reaction rate. These re-
Different types of transesterification reactors (tubular/plug-flow actors require lower alcohol-to-oil molar ratios, lower catalyst con-
reactors, rotating reactors, simultaneous reaction-separation reac- centrations, lower temperatures, and shorter residence times than
tors, cavitational reactors, and microwave reactors) employed for the conventional STRs. However, complex scale up and cavitational
converting natural oils and fats into biodiesel as well as their lim- blocking are the main disadvantages of these systems. Simple con-
itations and deficiencies have been comprehensively reviewed in trol, time and thermal efficiencies, clean products, and less down-
this article. In order to better understand the mechanisms behind stream processing are the main advantages of microwave reac-
each reactor technology, the effects of the main influential param- tors. However, difficulty in controlling power and temperature and,
eters on the transesterification process have also been discussed in thereby, low process reproducibility is the main problems associ-
detail. Biodiesel production has been scrutinized from the biofuel ated with microwave reactors.
policies and mandates, economic aspects and impacts, and feed- Generally speaking, the interest in advanced transesterification
stock sustainability perspectives. Moreover, biodiesel production reactor is growing due to the need for reducing capital cost, energy
under biorefinery concept utilizing waste-oriented oils and glycerol and water consumption, space requirement, reaction time, waste
upgrading to various value-added products have been elaborated streams, and environmental burdens while improving biodiesel
as well. It is worth mentioning that the present article is the first quality and boosting conversion efficiency. Nevertheless, the main
to comprehensively review and discuss all the above-mentioned barriers for the commercial application of advanced transesteri-
aspects as a whole (Table 18). fication reactors applied for converting natural oils and fats into
Overall, the economic profitability of biodiesel production via biodiesel are their high construction costs and difficult scalability.
transesterification reaction markedly depends on various process Accordingly, it is vital to develop inexpensive and scalable versa-
parameters, viz. process intensification method, quantity and type tile transesterification reactors that are applicable to various feed-
of alcohol, quantity and type of catalyst, composition of oil, resi- stocks with different qualities. In addition, emerging technologies
dence time, and temperature. Among acidic, basic, and enzymatic have a chance to replace the traditional ones, if they are proved to
catalysts applied to speed up the transesterification process, basic be economically profitable and environmentally sustainable using
catalysts are the most promising type tolerating harsh operating advanced engineering approaches.
conditions while accelerating the reaction up to 40 0 0 times. How- It should be noted that the appropriate selection of sustain-
ever, a high concentration of basic catalyst as well as the presence able feedstock is the most crucial criterion in biodiesel produc-
of water and free fatty acid decreases biodiesel yield by forming tion feasibility as feedstock makes up the majority of produc-
Table 18
Comparison of the present review article and the review papers published over the last 5 years (since 2014) on biodiesel production and processing technolo-
gies.
Ref. Production methods Process parameters for transesterification A1 Reactor technologies Sustainability/feasibility B2
C3 D4 E5 F6 G7 H8 I9 J10 K11 L12

√ √ √ √ √ √ √ √ √ √ √ √
This Study 18 reactor types ✗
√ √ √
[616] ✗ ✗ ✗ ✗ ✗ ✗ Short note on 3 reactor types ✗ ✗ ✗ ✗
√ √
[617] ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗
√ √ √
[618] ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗
√ √ √
[619] ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗
√ √
[620] ✗ ✗ ✗ ✗ ✗ ✗ ✗ 1 reactor type ✗ ✗ ✗ ✗
√
[621] ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗
√ √ √
[622] ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗
√ √ √ √ √
[623] ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗
√ √
[624] ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗
√
[625] ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗
√ √ √
[626] ✗ ✗ ✗ ✗ ✗ ✗ 1 reactor type ✗ ✗ ✗ ✗
√ √ √ √
[627] ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗
√ √ √
[628] ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗ ✗
1
Mass-transfer intensification.
2
Combustion, engine performance, and/or emission.
3
Catalyst (types and concentration).
4
Molar ratio.
5
Temperature.
6
Mixing.
7
Residence time.
8
Feedstock (oil) composition.
9
Feedstock type.
10
Feedstock sustainability.
11
Economic feasibility and impact.
12
Biodiesel policy.
tion cost. Apart from the economic considerations, any sustain- [5] Aghbashlo M, Tabatabaei M, Rastegari H, Ghaziaskar HS, Valijanian E. Ex-
able feedstock for biodiesel production must be classified as non- ergy-based optimization of a continuous reactor applied to produce val-
ue-added chemicals from glycerol through esterification with acetic acid. En-
edible (i.e. not triggering food vs. fuel debate) while requiring ergy 2018;150:351–62.
low water footprint (i.e., not triggering water vs. fuel debate) [6] Aghbashlo M, Tabatabaei M, Rastegari H, Ghaziaskar HS. Exergy-based sus-
for its cultivation and oil extraction. Moreover, such a feedstock tainability analysis of acetins synthesis through continuous esterification
of glycerol in acetic acid using Amberlyst® 36 as catalyst. J Cleaner Prod
should confirm a minimal GHG-emissions mitigation of 35% in 2018;183:1265–75.
comparison with GHG emissions arisen from the synthesis and [7] Aghbashlo M, Tabatabaei M, Jazini H, Ghaziaskar HS. Exergoeconomic and ex-
application of petroleum fuels. The production of biodiesel un- ergoenvironmental co-optimization of continuous fuel additives (acetins) syn-
thesis from glycerol esterification with acetic acid using Amberlyst 36 cata-
der biorefinery concept can also address some‫ ‏‬c‫ ‏‬ontroversial is-
lyst. Energy Convers Manage 2018;165:183–94.
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2282.
duction from waste-oriented oils is a good example for this
[9] Hosseinzadeh-Bandbafha H, Tabatabaei M, Aghbashlo M, Khanali M,
approach but requires an elaborated management for feedstock Demirbas A. A comprehensive review on the environmental impacts of
collection. diesel/biodiesel additives. Energy Convers Manage 2018;174:579–614.
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The authors would like to thank University Technology MARA ergetic and technical optimization of a piezoelectric ultrasonic reactor ap-
(UiTM), Iranian Biofuel Society (IBS), Agricultural Biotechnology Re- plied to synthesize biodiesel from waste cooking oil (WCO) using soft com-
puting techniques. Fuel 2019;235:100–12.
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Techno-economic comparison of three biodiesel production scenarios en-
hanced by glycerol supercritical water reforming process. Int J Hydrogen En- Meisam Tabatabaei is an Associate Professor of En-
ergy 2019. vironmental Biotechnology (University Technology Mara
[599] Chen Y, Wang T, Shen N, Zhang F, Zeng RJ. High-purity propionate pro- (UiTM), Malaysia) and is the founding Editor-in-Chief of
duction from glycerol in mixed culture fermentation. Bioresour Technol Biofuel Research Journal (BRJ) in Canada. Meisam has
2016;219:659–67. been working closely with the United Nation Develop-
[600] May A, Salvadó J, Torras C, Montané D. Catalytic gasification of glycerol in ment Program (UNDP) to promote waste-oriented bio-
supercritical water. Chem Eng J 2010;160:751–9. fuels in the developing world. Since 2016, he has been
[601] Avasthi KS, Reddy RN, Patel S. Challenges in the production of hydrogen the lead collaborator of the Lancet Commission on Public
from glycerol–a biodiesel byproduct via steam reforming process. Procedia Health and Climate Change (UCL, UK) and has published
Eng 2013;51:423–9. over 240 publications including original research papers
[602] Schwengber CA, Alves HJ, Schaffner RA, da Silva FA, Sequinel R, Bach VR, and reviews in journals such as The Lancet (Impact Fac-
et al. Overview of glycerol reforming for hydrogen production. Renew Sustain tor: 59.102), Progress in Energy and Combustion Sciences
Energy Rev 2016;58:259–66. (Impact Factor: 26.467), etc. (Citations: >5600, h-index:
Arash Mollahosseini (MBA, M.Sc.) is currently a Ph.D.

39, i10 index: 129; June 2019, Google Scholar). He is also an invited professor at
candidate in the Department of Chemical and Biologi-
Lebanese University. Dr. Tabatabaei has been listed on the Web of Science Highly
cal Engineering in the University of Saskatchewan. Be-
Cited Researchers List (Top 1% scientists in the world) in Engineering Category since
fore joining the USask, Arash was a researcher of environ-
2017. He is the Editor of the Book Volumes “Biogas: Fundamentals, Process, and Oper-
mental engineering in the AR Membrane Research Team
ation” and “Biodiesel: from Production to Combustion” which have been published by
(Babol University of technology, Mazandaran, Iran) and
Springer Nature in 2018 and is on the Editorial/Advisory Board of International Jour-
Biofuel Research Team (BRTeam). He received his M.Sc. in
nal of Life Cycle Assessment (Springer), Data In Brief (Elsevier), MethodsX (Elsevier),
2011 and his MBA in 2014. Since the commencement of
Frontiers in Energy Research, and Energy Sources, Part A: Recovery, Utilization, and
his Ph.D. back in 2018, Arash’s main research interests in-
Environmental Effects (Taylor & Francis). Dr. Tabatabaei is also the Guest Editor of
clude the application of membranes inbiomedical indus-
Special Issues in Renewable & Sustainable Energy Reviews (Elsevier) and Energies
try as well as in separation processes for environmental
(MDPI). Meisam is the Co-Editor-in-Chief of the Elsevier Book Series on Biomass
applications and upstream water-energy nexus.
and Biofuels.
Mortaza Aghbashlo is an Associate Professor at the Fac- Mehdi Hosseini (1984) received his B.Sc. and M.Sc. in
ulty of Agricultural Engineering and Technology, Univer- Mechanics of Agricultural Machinery Engineering and
sity of Tehran, Iran. He has received University of Tehran’s Mechanics of Biosystem Engineering from the Urmia Uni-
award for Excellence in Research in 2008, 2012, and 2017. versity in 2010 and 2012, respectively. Mehdi joined Bio-
His research interests primarily include renewable en- fuel Research Team (BRTeam) in 2010 and has been col-
ergies, biofuels, exergy-basedanalyses, and sustain abil- laborating with BRTeam ever since.
ity assessment. With over 120 technical publications in
highly referred journals such as Progress in Energy and
Combustion Sciences, Fuel, Energy, Renewable and Sustain-
able Energy Reviews, etc., Mortaza is an established re-
searcher in renewable energy technologies, engineering
thermodynamics, and thermal engineering. He is also the
Co-Editor of the Book Volume “Biodiesel: from Production
to Combustion” which has been published by Springer Nature in 2018 and is on the Mohamad Mojarab Soufiyan (1989) received his B.Sc.
editorial board of Biofuel Research Journal. and M.Sc. in Mechanics of Agricultural Machinery Engi-
neering and Mechanical Engineering of Biosystems from
Mona Dehhaghi (1988) holds a PhD degree in Microbi- the Urmia University and University of Tehran in 2013
ology from the University of Tehran and passed her PhD and 2016, respectively. Mohamad’s main research inter-
sabbatical in the Maquarie University (Sydney, Australia). ests include process engineering and exergy-based anal-
Her main research interests include microorganisms isola- ysis of biofuels and renewable energies production sys-
tion and identification, bioproducts, biorefinery, and bio- tems. He joined Biofuel Research Team (BRTeam) in 2016
fuels. She has already published several articles and book and has been collaborating with BRTeam ever since. He
chapters. Although her main focus during PhD was on has also been serving Biofuel Research Journal as graphic
drug discovery, she could quickly adapt to biofuel re- and design artist since 2016.
search thanks to her strong background in applied micro-
biology. Since joining Biofuel Research Team (BRTeam) in
June 2018, she has managed to publish several articles in
a number of highly referred journals such as Renewable
Energy and Renewable and Sustainable Energy Reviews.
Hamed Kazemi Shariat Panahi (1988) received his Mas-

ter of Science in Microbiology from the University of
Tehran. He continued his research activities in the same
university on bioremediation as well as on microbial
metabolites production, extraction, and purification from
2014 to 2017. In 2018, he joined Biofuel Research Team
(BRTeam) for exploring the field of biofuels. Currently, his
research activities are devoted to the production biofuels
and other value-added products under biorefinery scheme
via thermochemical and biochemical processes. Hamed
has published several articles in highly referred journals
such as Renewable Energy and Renewable and Sustain-
able Energy Reviews.
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Progress in Energy and Combustion Science 74 (2019) 239–303

Contents lists available at ScienceDirect

Progress in Energy and Combustion Science

Reactor technologies for biodiesel production and processing: A review

1. Biodiesel production. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240

1. Biodiesel production 1.1. Physical approaches

Method Advantage Disadvantage

Fig. 1. Schematic steps of base-catalyzed transesterification.

Fig. 2. Schematic steps of acid-catalyzed transesterification.

Feedstock Alcohol Catalyst Conditions Yield Ref.

Catalyst Synthesis method Regeneration Deactivation and Oil feedstock Ref.

Layered Double Hydroxides - Co-precipitation method3 NA NA Sunflower [96]

Acid-activated bentonite - Acid activation8 NA NA Residual olive [57]

SO3 H-functionlized - Catalyst synthesis9 NA NA Residual olive [57]

Feedstock Alcohol Enzyme Conditions Yield Ref.

Fig. 3. Schematic steps of enzymatic transesterification.

Castor seed oil/waste fish oil 8:1 32 °C 30 min 97.6% [145]

2.5. Composition of oil 3. Reactor technologies

Parameter Batch Semi-batch Continuous

Space requirement High Medium Low

Capital requirement High Medium Low

Operating cost High Medium Low

Product quality Batch-to-batch variation Uniform Uniform

Production rate Low High Highest

Low selectivity High selectivity High selectivity

Type of reactor Advantages Disadvantages

Argon was used as supplementary fluidizing gas.

Periodic injections of oxygen gas (after up to 20 min)

Resin was regenerated by methanol.

The half-life time of the immobilized lipase was

Thermal energy was efficiently recovered because of

The reactor dimensions were L = 300 mm and ID=4.9 mm.

The reactor dimensions were L = 260 mm and ID=8 mm.

The reactor dimensions were L = 200 mm and ID=10 mm.

a different study, Meng et al. [233] carried out the methanolysis

3.2.1.4. Oscillatory flow reactors. OFR are another type of vertical or

flow, mainly diffusion, rather than a turbulence flow, making the

Feedstock Alcohol Catalyst Reactor configuration Conditions Yield Ref.

Fig. 10. Different flow patterns in a micro-channel reactor.

3.2.2.1. Stirred tank reactors. In general, a STR is a cylindrical vessel

Reactor Feedstock Alcohol Catalyst Conditions Yield Ref.

In a batch operation, the concentration of reagents is in their

flows across the surface of spinning disc are directly controlled

ric, composite) containing organic [i.e., cellulose acetate, polyacry-

concentrations of methanol in this step due to increasing glycerol

Catalytic membrane reactors

Inert membrane reactors

pared with a reactive distillation with upstream recycling because

which in turn efficiently improve the physical and chemical charac-

Feedstock Alcohol Catalyst Conditions Ultrasonic specifications Yield Highlights Ref.

Homogeneous catalyzed transesterification of oil

Feedstock Alcohol Catalyst Conditions Ultrasonic specifications Yield Highlights Ref.

of micro-cavities and heat and/or mass transfer, a process known

3.2.5. Microwave reactors

Fig. 30. Conventional wall heating vs. microwave heating [431].

NA: Not available.

Feedstock Integrated industries Value-added products Technologies involved Ref.