Energy for Sustainable Development 43 (2018) 143–161

Contents lists available at ScienceDirect

Energy for Sustainable Development

Review

Biodiesel production in micro-reactors: A review

Appurva Tiwari, V.M. Rajesh ⁎, Sanjeev Yadav
Department of Chemical Engineering, Shiv Nadar University, Tehsil Dadri, Gautam Buddha Nagar, Greater Noida, Uttar Pradesh 201314, India

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

Article history: In recent years, biodiesel, as a renewable and environment-friendly fuel has emerged as one of the most investi-
Received 14 September 2017 gated bio-fuel with a goal to decrease our dependence on petroleum fuels and reduce environmental pollution.
Revised 9 January 2018 The current commercial technique of biodiesel production via transesterification is constrained by high operating
Accepted 9 January 2018
cost and energy requirements, long residence time and limited conversion due to equilibrium limitations. On the
Available online 3 February 2018
other hand, the process intensification using the micro-reactor technology demonstrated an excellent perfor-
Keywords:
mance ascribed to short diffusion distance and high surface area-to-volume ratio that can lead to high heat
Renewable energy and mass transfer rates and improved mixing compared to the conventional reactors. This review provides an
Micro-reactors overview of the current status of biodiesel production in micro-reactors. It includes various types of micro-
Biodiesel reactors used in the production of biodiesel, factors affecting the biodiesel production (i.e., temperature, resi-
Transesterification dence time, alcohol to oil molar ratio, micro-channel size, inlet mixer type, internal geometries, co-solvent, cat-
Bio-fuel alyst type and concentration). This review also includes the factors affecting the liquid-liquid flow patterns
and application of micro-reactor technology in the purification of biodiesel. Some of the critical observations
from this review are, 1) inlet mixer type, channel size, and internal channel geometry (zig-zag, omega, and
tesla shaped channels) have shown a significant effect on mixing in micro-channels. 2) In case of base-catalyzed
transesterification, the biodiesel yield was found to increase up to the reaction temperature of 60–65 °C. 3) Ho-
mogeneous alkaline catalyst (NaOH, KOH, CH3ONa) was preferred for the feedstock with low free fatty acid con-
tent (b1 wt%). However, an acid catalyst with high concentration, a significant amount of methanol and long
reaction time were required for high free fatty acid feedstock (N1 wt%). Therefore, the current research is more
focused on the investigation of heterogeneous catalysts in micro-reactors to develop an ecologically friendly pro-
cess for the production of biodiesel. 4) Also, the reaction temperature and inlet mixer type had shown a signifi-
cant effect on liquid-liquid flow patterns. This review also addressed the following literature gaps; a numbering-
up technique to increase the throughput; catalyst development for high free fatty acid feedstock; continuous pro-
duction of biodiesel in micro-reactors with in-line purification step to meet the energy demand and quality
standards.
© 2018 International Energy Initiative. Published by Elsevier Inc. All rights reserved.

Contents
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
Present state of the art: micro-reactors used in biodiesel synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
Factors affecting biodiesel production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
Effect of reaction temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
Residence time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
Alcohol to oil molar ratio . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
Effects of geometrical configurations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
Effect of channel size . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
Effect of inlet mixer type . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
Effect of internal geometries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
Effect of co-solvent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
Effects of catalyst type and concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
Homogeneous catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
Heterogeneous catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153

⁎ Corresponding author.
E-mail address: vm.rajesh@snu.edu.in (V.M. Rajesh).

https://doi.org/10.1016/j.esd.2018.01.002
0973-0826/© 2018 International Energy Initiative. Published by Elsevier Inc. All rights reserved.
144 A. Tiwari et al. / Energy for Sustainable Development 43 (2018) 143–161

Catalyst-free process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154

Liquid-liquid two-phase flows in micro-reactors for biodiesel production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
Factors affecting flow patterns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
Effect of temperature on flow patterns . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
Effect of alcohol on oil molar ratio . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
Effect of inlet mixer type . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
Purification of biodiesel in micro-reactors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
Scope for future work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 156
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159

Introduction
With the rapid depletion of fossil fuels and increasing environmental
concerns, the need for an alternative fuel that is cheaper, renewable and
environment-friendly is growing consistently. Biodiesel has emerged as
a potential alternative fuel to fossil fuels, which has similar properties to
fossil diesel with some advantages (Freedman, Pryde, & Mounts, 1984;
Van Gerpen, 2005b). Biodiesel is a renewable fuel, less-toxic than con-
ventional diesel and also biodegradable (Al-Zuhair, 2007; Bozbas,
2008; Knothe, Sharp, & Ryan, 2006; Koonin, 2006; Meher, Vidyasagar,
& Naik, 2006). Biodiesel blends with conventional diesel up to B20
(20% biodiesel and 80% diesel) can be used in a diesel engine without
engine modification. However, biodiesel N20% in the blend required
few engine modifications (Canakci, Erdil, & Arcaklioğlu, 2006; Sharma,
Singh, & Upadhyay, 2008; Van Gerpen, 2005a; Xue, Grift, & Hansen,
2011). Biodiesel is produced via transesterification of vegetable oils
or fats with alcohol, typically methanol, in the presence of a catalyst
(Demirbaş, 2003; Van Gerpen, 2005b). The transesterification reaction
takes place in a liquid-liquid two-phase system and the reaction
rate is limited by mass transfer due to immiscibility of oil and alcohol
(Crawford et al., 2008; Guan, Kusakabe, Moriyama, & Sakurai,
2009a). Therefore, an efficient contact between the feed oil and the
alcohol-catalyst mixture becomes crucial for achieving the high rate of
reaction.
Several studies on biodiesel production were carried out using batch
reactors (Dorado, Ballesteros, López, & Mittelbach, 2004; Lotero et al.,
2005; Shah, Sharma, & Gupta, 2004; Vicente, Martınez, & Aracil, 2004;
Xie, Peng, & Chen, 2006; Zhang, Dube, McLean, & Kates, 2003). These
reactors were also commercially used for the production of biodiesel
at industrial scale (Haas, McAloon, Yee, & Foglia, 2006). However,
unfavourable economics and other design and operational issues at
large-scale batch reactors pose challenges to the commercialization of
biodiesel (Maddikeri, Pandit, & Gogate, 2012; Qiu, Zhao, & Weatherley,
2010; Santacesaria, Vicente, Di Serio, & Tesser, 2012). The critical
challenges are, the long residence time of several hours, considerable
investment in equipment and manufacturing floor space, high energy
consumption and low production efficiency (Jachuck, Pherwani, &
Gorton, 2009; Qiu et al., 2010; Slinn & Kendall, 2009; Warabi,
Kusdiana, & Saka, 2004). On the other hand, with these limitations on
a conventional batch process, several alternative highly energy efficient
technologies to produce biodiesel in a continuous mode of operation
were investigated (Maddikeri et al., 2012; Qiu et al., 2010). In recent
years, micro-reactor technology has emerged as a promising technique
for high-efficiency continuous biodiesel production (Xie, Zhang, & Xu,
2012). Micro-reactors are miniaturized reaction systems with reduced
internal characteristic dimensions of 1000 μm–10 μm. Micro-reactors
offer small diffusion distances and large surface area to volume ratio
(10,000–50,000 m2 m−3) and thus lead to high heat and mass transfer
rates. As a result higher conversion is achieved in shorter residence
time (Kashid & Kiwi-Minsker, 2009). Mixing time in micro-reactors is
also considerably reduced due to their reduced internal dimensions.
Moreover, small volume favours micro-reactors to perform highly
exothermic reactions safely with precise control over the operating con-
ditions (Benke, 2014; Burns & Ramshaw, 1999; Kobayashi, Mori, &
Kobayashi, 2006). However, the production capacity of micro-reactors
can be increased by the scale-out approach (Aran & Lammertink,
2013; Geyer & Seeberger, 2008).
Some researchers have successfully applied micro-reactors for
biodiesel synthesis via transesterification (Aghel, Rahimi, Sepahvand,
Alitabar, & Ghasempour, 2014; Buddoo, Siyakatshana, & Pongoma,
2008; Guan et al., 2009a; Martínez Arias, Fazzio Martins, Jardini
Munhoz, Gutierrez-Rivera, & Maciel, 2012; Sun, Wang, Yao, Zhang, &
Xu, 2009; Wen, Yu, Tu, Yan, & Dahlquist, 2009). It was demonstrated
that as compared to conventional batch reactors, higher conversion in
shorter residence time could be achieved in micro-reactors (Dai, Li,
Zhao, & Xiu, 2014; Elkady, Zaatout, & Balbaa, 2015; Guan et al., 2009a;
Martínez Arias et al., 2012; Rahimi, Aghel, Alitabar, Sepahvand, &
Ghasempour, 2014; Santacesaria et al., 2012; Santana, Tortola, Reis,
Silva, & Taranto, 2016; Schürer, Thiele, Wiborg, Ziogas, & Kolb, 2014;
Sun, Ju, Ji, Zhang, & Xu, 2008). It should also be noted that as compared
to conventional reactors, biodiesel could be produced 10 to 100 times
faster in a micro-reactor. Moreover, the requirements of high energy
in the mixing of reactants, ample floor space and standing time for the
separation of products are eliminated using micro-reactors (Buddoo
et al., 2008; Jovanovic, 2006). Although the amount of biodiesel pro-
duced using a single micro-reactor is a trickle, each unit can be num-
bered up to increase the throughput from lab to commercial scale
(Billo et al., 2015; Jovanovic, 2006; Schürer et al., 2016). The process
of transesterification in micro-reactors is observed to be affected by
the operating conditions as well as the type and geometrical param-
eters of micro-reactor (Xie et al., 2012). With this background, the
present review has been organized as following sections: 1) the
present state of the art: the types of micro-reactors used in
biodiesel synthesis with different feedstock have been discussed.
2) The factors affecting biodiesel production in micro-reactors, in
which, the effect of operating parameters such as temperature,
alcohol to oil molar ratio, the effect of co-solvent addition, catalyst
type and concentration as well as the effect of the geometrical
configuration of micro-reactors have been discussed. 3) Liquid-
liquid two-phase flows in micro-reactors for biodiesel production:
flow patterns observed during production of biodiesel and the
factors affecting the flow patterns have been discussed. 4) Purifica-
tion of biodiesel in micro-reactors: the current research techniques
applied for biodiesel separation from glycerol at micro-scale are
mentioned. Finally, the current research gaps that need further
investigations into full-scale commercialization of biodiesel produc-
tion using micro-reactors are also addressed.
Present state of the art: micro-reactors used in biodiesel synthesis
Micro-reactors can be categorized by geometries, fabrication mate-
rial, and techniques. For the production of biodiesel, mainly micro-
tubular and micro-channel reactors have been applied. In general, the
micro-reactor system is composed of a mixer for intensifying mixing
 A. Tiwari et al. / Energy for Sustainable Development 43 (2018) 143–161 145

and a micro-channel or micro-tube for completion of the reaction.
Various combinations of mixers and reaction loop (micro-channel or
micro-tube), fabricated with different materials have been used in bio-
diesel synthesis as shown in Table 1. To demonstrate that the production
of biodiesel is feasible using micro-reactor technology Al-Dhubabian
(2005) developed a micro-reactor with channel dimensions; 23.3 mm
length, 10.5 mm width, and 0.1 mm height as shown in (Fig. 1). Under
operating conditions of 7.2:1 methanol/soya bean oil molar ratio, 1 wt%
NaOH catalyst, at atmospheric pressure and 25 °C, a conversion of 91%
was obtained in 10 min. Similarly, Canter (2006) reported a micro-
reactor with parallel micro-channels cut into a thin plastic plate could
be used for making biodiesel under mild operating conditions. Biodiesel
yield above 90% was obtained at a residence time of about 4 min.
However, the details of the reactor and operating parameters were not
described completely. These works proved that micro-reactors could
be potentially applied for the production of biodiesel commercially.
The findings of Al Dhubabian (2005) and Canter (2006) were sup-
ported by Sun et al. (2008), where they performed transesterification of
pre-mixed rapeseed oil and methanol using KOH as a catalyst in quartz
capillary of 0.25 mm inner diameter and length of 30 m. At a catalyst con-
centration of 1% by weight and methanol to oil molar ratio of 6:1, a fatty
acid methyl ester (FAME) yield of 98.80% was obtained in 6 min at 60
°C. Instead of using a microfluidic mixer the reactants were a premixed
in a tank reactor with constant stirring where the yield reached 81% be-
fore injecting the mixture into the capillary. Hence, the merits of using a
micro-tube capillary as a reactor were not clearly observed.
Guan et al. (2008) carried out continuous production of biodiesel
from sunflower oil using a micro-reactor system consisting of Fluori-
nated ethylene propylene (FEP) tube with an inner diameter of 1 mm
and 160 mm in length and a mixer (split and recombine mixer or a T-
type) to create dispersion. Oil conversion reached 100% in 112 s, using
methanol to oil molar ratio of 23.9:1 and 1 wt% KOH concentration
and split and recombine mixer. It was noted that for complete conver-
sion of oil, the residence time decreased drastically from 600 s to
b240 s when lab scale batch reactor was replaced by a micro-reactor,
under same operating conditions. In their progressive work, Guan

Table 1
Micro-reactors used in the production of biodiesel.

Mixer type Reaction loop Reactants Catalyst T (°C) Alcohol/oil Residence Biodiesel Ref.
amount molar ratio time yield (%)
(wt%)

Stirred tank i.d. = 0.25 mm Rapeseed oil + methanol 1% KOH 60 °C 6:1 6 min 98.80% Sun et al. (2008)
l = 30 m
Quartz capillary
Stirred tank i.d. = 0.25 mm Cottonseed oil + methanol 1% KOH 60 °C 6:1 5.89 min 99.40% Sun et al. (2008)
l = 30 m
Stainless-steel capillary
Split and recombine i.d. = 1 mm Sunflower oil + methanol 1% KOH 60 °C 23.9:1 112 s 100% Guan, Kusakabe,
micromixer l = 160 mm Moriyama, and Sakurai
FEP tube (2008)
T-type i.d. = 0.8 mm Sunflower oil + methanol 4.5% KOH 60 °C 23.9:1 100 s 100% Guan et al. (2009a)
l = 300 mm
FEP tube
T-mixer i.d. = 1.5 mm Canola oil + methanol 1% NaOH 60 °C 6:1 3 min 99.80% Jachuck et al. (2009)
l = n.i.
PTFE tube
T-shaped junction dh = 0.24 mm Soya bean oil + methanol 1.2% NaOH 56 °C 17:1 28 s 99.5% Wen et al. (2009)
l = 1.07 m
Stainless-steel
zig-zag channel
Split interdigital i.d. = 3 mm Cottonseed oil + methanol 1% KOH 70 °C 8:1 17 s 99.5% Sun et al. (2009)
micromixer l = n.i.
(SIMM-V2) PTFE tube packed with Dixon
rings
T-Type dh = 0.5 mm Castor oil + ethanol 1% NaOH 50 °C 12:1 10 min 96.70% Martínez Arias et al.
l=1m (2012)
Tesla-shaped PDMS
micro-channel
T-Type dh = 0.5 mm Castor oil + ethanol 1% NaOH 50 °C 12:1 10 min 95.30% Martínez Arias et al.
l=1m (2012)
Omega-shaped PDMS
micro-channel
T-Type dh = 0.5 mm Castor oil + ethanol 1% NaOH 50 °C 12:1 10 min 93.50% Martínez Arias et al.
l=1m (2012)
T-shaped PDMS micro-channel
Zig-zag micro-channel dh = 1.5 mm Soya bean oil + methanol 1.20% KOH 59 °C 8.5:1 14.9 s 99.50% Dai et al. (2014)
mixer l = n.i.
Stainless-steel zig-zag reaction
channel
T-type i.d. = 0.90 mm Soya bean oil + methanol 1.20% KOH 60 °C 9:1 180 s 99% Aghel et al. (2014)
l = n.i.
Stainless micro-tube embedded
with wire coil (30 cm length,
0.5 mm pitch)
Four-way micromixer i.d. = 1.58 mm Soya bean oil + methanol + 1% KOH 57.2 °C 6:1 9.05 s 98.80% Rahimi, Mohammadi,
with 45° confluence l = n.i. hexane (co-solvent) Basiri, Parsamoghadam,
angle Stainless-steel tube and Masahi (2016)
KM micromixer Waste vegetable oil + 1% NaOH 70 °C 12:1 n.i. 97% Elkady et al. (2015)
methanol + THF (co-solvent)

n.i. = no information, i.d. = inner diameter, l = length, dh = hydraulic diameter.

146 A. Tiwari et al. / Energy for Sustainable Development 43 (2018) 143–161

Fig. 1. Schematic diagram of a micro-reactor system with a digital image of the side view of the micro-reactor. Reprinted with permission from Al-Dhubabian (2005). Copyright 2005
Oregon State University.

et al. (2009a) performed transesterification of sunflower oil using a FEP
tube of 0.8 mm in diameter with T-shaped junction. A complete conver-
sion of oil was obtained at 300 mm tube length, 4.5 wt% KOH concentra-
tion, in a residence time of 100 s using the same alcohol to oil molar ratio
and operating conditions as their previous work (Guan et al., 2008).
Jachuck et al. (2009) used a PTFE (Polytetrafluoroethylene) narrow chan-
nel reactor with an internal diameter of 1.5 mm, coupled with a T-mixer
to intensify the biodiesel production process. Conversions higher than
98% were obtained in a residence time of 3 min with NaOH loading of 1
wt% and methanol to canola oil molar ratio of 6:1 at 60 °C.
In the previous works, simple T-flow structures were applied to gen-
erate dispersion in micro-reactors (Canter, 2006; Guan et al., 2009a; Sun
et al., 2008). To investigate another high efficiency passive micro-
structured mixers for biodiesel production, Wen et al. (2009)
developed nine different zig-zag micro-channel reactors, zig-zag-1 to
zig-zag-9. The micro-channel reactors were fabricated on stainless-steel
sheet by electric spark processing and assembled with a T-shaped
three-way mixer. The micro-channels of all reactors were of rectangular
cross-section with the same length of 1.07 m but a different number
of periodic turns (10, 50, 100, 200 & 350) and hydraulic diameter
(240–900 μm) as shown in Table 3. Using the micro-channel reactor
with a smallest hydraulic diameter (240 μm) and most number of turns
(350), a maximum yield of 99.5% was reached with methanol to soya
bean oil molar ratio of 9:1, NaOH concentration of 1.2 wt% in a very
short residence time of 28 s. Based on the same idea, Dai et al. (2014) de-
veloped a micro-reactor in which the conventional T-type mixer used by
Wen et al. (2009) was replaced by zig-zag micro-channel mixers
patterned on stainless-steel sheet along with zig-zag reaction channels.
The mixing and reacting channels were linked through a connecting
channel as shown in Fig. 2. Using a micro-channel of hydraulic diameter

Fig. 2. The configuration of zig-zag micro-channel reactor with zig-zag mixers. Reprinted with permission from Dai et al. (2014). Copyright 2014 American Chemical Society.
 A. Tiwari et al. / Energy for Sustainable Development 43 (2018) 143–161
(A)
Fig. 3. (A) Mixing forms and channel dimensions (width × height) of various micromixers: (a) T-mixer, (b) J-mixer, (c) rectangular interdigital micromixer (RIMM), and (d) split
interdigital micromixer (SIMM-V2). M, an inlet of the methanol phase; O, an inlet of oil. “Reprinted with permission from Sun et al. (2009). Copyright 2010 American Chemical Society.”
(B) PDMS micro-reactor internal geometries: (a) Omega-shaped, (b) Tesla shaped, and (c) T-shaped. Reprinted with permission from Martínez Arias et al. (2012). Copyright 2012
American Chemical Society.
1.5 mm, a biodiesel yield of 99.5% was obtained at a residence time of
14.9 s, methanol to soya bean oil molar ratio of 8.5:1 and KOH concentra-
tion of 1.2 wt% at 59 °C.
Sun et al. (2009) performed experiments on the fast synthesis of
biodiesel from cottonseed oil using high throughput micro-structured re-
actor with various mixer types as shown in Fig. 3(A). The FAME yields ob-
tained using the micromixers were almost twice of the yields obtained
using T- and J-mixers due to more intense mixing in micromixers. Using
rectangular interdigital micromixer (RIMM) a maximum yield of 99.5%
was achieved under the conditions of methanol to oil molar ratio of 8:1,
a reaction temperature of 70 °C, the residence time of 17 s and a flow
rate of 10 mL/min. Similarly, Bhoi et al. (2014) investigated KOH catalyzed
biodiesel production using three different reaction systems having differ-
ent microfluidic junctions, namely, T-type, cross-type and split and
recombine mixer followed by serpentine mixing and reaction channels
etched on a glass chip. It was observed that using methanol to sunflower
oil molar ratio of 10.3:1, conversion above 90% could be obtained in a
residence time of 0.5 min, 1 min, and 5 min with, T-type, cross-type and
split and recombine mixer respectively.
Avellaneda and Salvadó (2011) demonstrated a helicoidal system
comprising a T-mixer for aggregation of reactants and a series of spirals
(i.d. 6 mm) connected consecutively by a fixture, for the continuous
production of biodiesel using pre-treated recycled oil. It was determined
that 89% yield of fatty acid methyl ester could be attained in 13 min at
60 °C, methanol to oil molar ratio of 6:1 and using 0.6 g of NaOH as cat-
alyst per 100 g of oil. For the same yield in the batch reactor, a residence
time of 75 min was required. Santacesaria et al. (2011) proposed the
use of a tubular stainless-steel reactor of 10 mm inner diameter and
20 cm in length with three different packing configurations, that were,
(a) spheres of 2.5 mm diameter, (b) spheres of 2.5 and 1 mm diameters
and (c) spheres of 2.5 and 0.39 mm diameters, forming micro-channels
of about 1000 μm, 500 μm and 300 μm respectively, for studying KOH
catalyzed methanolysis of soya bean oil. Using a methanol to oil ratio
of 6:1 at 60 °C, very high oil conversions were observed in residence
time of b1 min. In their subsequent work, Santacesaria, Di Serio, et al.
(2012) used the same cylindrical tube filled with stainless-steel wool
to obtain a higher void fraction which resulted in increased
productivity.
Martínez Arias et al. (2012) employed different channel geometries
(Omega, Tesla, and T-shaped), as shown in Fig. 3(B) made of polydi-
methylsiloxane (PDMS) using soft lithography process for producing
biodiesel from canola oil and ethanol in presence of NaOH as a catalyst.
147
(B)
The micro-channels were of the quadratic cross-section with width and
height of 500 μm and length of 1 m. For T-, Tesla and Omega shaped
micro-reactors, ethyl ester conversions of 93.5%, 95.3%, and 96.7%
were attained respectively, at alcohol to oil molar ratio of 25:1, catalyst
loading of 1 wt% and a reaction temperature of 50 °C in 10 min. Aghel
et al. (2014) studied biodiesel synthesis using a modified micro-
reactor consisting of a silver wire coil inserted in a stainless-steel tube
of 0.9 mm inner diameter and a micromixer. At T- shaped junction
of micromixer, soya bean oil and methanol were mixed in a molar
ratio of 1:9 with 1.2 wt% of KOH as a catalyst. Using a wire coil with
0.8 mm average diameter, 30 cm length and 0.5 mm average pitch
length, a FAME conversion of 99% was obtained at 60 °C in residence
time of 180 s.
Recently, Santana et al. (2016) performed experiments in a PDMS
based T-junction micro-channel (l × w × h; 41.1 cm × 1.5 cm × 0.2 cm)
reactor. In their experiments, sunflower oil was used as feedstock with
ethanol to produce biodiesel through transesterification with sodium hy-
droxide as a catalyst. It was observed that minimum residence time of 1
min was needed at room temperature for a conversion of 95.8% as com-
pared to the batch process in which 94.1% conversion was achieved in
180 min. In order to increase the conversion and reduce the residence
time, the same group (Santana, Tortola, Silva, & Taranto, 2017) performed
experiments in a PDMS micro-channel (l × w × h; 35.1 cm × 1.5 cm ×
0.2 cm) reactor with internal static elements (1000 μm × 100 μm)
for the improved mixing. It was found that maximum yield
(99.53%) was obtained with 1 wt% catalyst concentration, residence
time of ~12 s and ethanol to oil molar ratio of 9:1 at 50 °C.
Guan, Sakurai, and Kusakabe (2009b) and Rahimi et al. (2016) stud-
ied the production of biodiesel in the presence of co-solvent at room tem-
perature using micro-tube reactors. Guan, Sakurai, and Kusakabe (2009b)
reported biodiesel production at room temperature in the presence of co-
solvent in a FEP tube (0.96 mm i.d) micro-reactor with the T-shaped junc-
tion. Using diethyl ether (DEE) as co-solvent in a molar ratio of 0.73 to
methanol, 1 wt% KOH as catalyst and methanol to sunflower oil molar
ratio of 8:1, a conversion of 93.2% at a tube length of 36 cm was
observed in 93 s. Later, Rahimi et al. (2016) performed transesterification
of soya bean oil in the presence of hexane as a co-solvent using three dif-
ferent four-way micromixers with 0.8 mm inner diameter followed by a
stainless-steel tube with inner diameter of 1.58 mm. The micromixers
were designed with various confluence angles of 45o, 90o and 135o
namely E1, E2 and E3 respectively on a polymethylmethacrylate
(PMMA) flat plate by milling as shown in Fig. 4. The highest FAME
148 A. Tiwari et al. / Energy for Sustainable Development 43 (2018) 143–161

Fig. 4. The experimental setup used by Rahimi et al. (2016). Reprinted from Rahimi et al. (2016), with permission from Elsevier.

yield of 98.8% was observed using E1 mixer under optimal conditions and Yoo (2011) developed a continuous bio catalytic membrane
of methanol to oil volumetric ratio of 3:1, hexane to methanol micro-reactor using an asymmetric polyether sulfone membrane with
volumetric ratio of 0.45, reaction temperature of 57.2 °C and 1 wt% a nominal molecular weight limit of 300 kDa (PES 300) as an enzyme
KOH concentration. carrier. Each pore of membrane acted as a particular micro-system in
Several investigations were performed on the continuous catalyst- which biocatalytic transesterification of triolein with methanol oc-
free production of biodiesel using micro-reactors in the presence of curred. With a membrane diameter of 63.5 mm and 0.28 mm thickness,
co-solvent and heterogeneous catalyst under supercritical conditions 80% conversion of triolein to methyl oleate (biodiesel) was acquired in a
(Bertoldi et al., 2009; Silva, Castilhos, Oliveira, & Filho, 2010; Schürer reaction time of 19 min. Kurayama et al. (2010) reported that micro-
et al., 2014, 2016; Trentin et al., 2011). Bertoldi et al. (2009) carried capsules could be used as a micro-reactor for biodiesel production.
out transesterification of soya bean oil using supercritical ethanol with The transesterification of rapeseed oil was carried out by adding meth-
carbon dioxide as a co-solvent in a tubular micro-reactor which was anol to Calcium oxide (CaO) loaded micro-capsules and oil mixture in
made of stainless-steel with an internal diameter of 3.2 mm or 0.76 the batch-type reactor. A maximum FAME yield was reached under op-
mm. The reactions were performed in the absence of a catalyst at the timum conditions of methanol to oil molar ratio of 8:1, 20 wt% of CaO
temperature and pressure ranges from 300 to 350 °C and 7.5 to 20 content in micro-capsule and the temperature of 65 °C.
MPa respectively. In addition, the ranges of oil to methanol molar ratio From the above literature, it is evident that biodiesel production
and co-solvent to substrate mass ratio were also maintained as 1:10 to process is highly intensified applying micro-reactor technology. The
1:40 and 0:1 to 0.5:1 respectively. It was found that the FAEE (fatty
acid ethyl ester) yield was improved at the optimum design and operat- Table 2
ing conditions such as 0.76 mm diameter tube, CO2 to substrate mass Comparison of batch versus micro-reactor plant for production of biodiesel. Reprinted
ratio of 0.05:1, oil to ethanol molar ratio of 1:40 and at 350 °C and 10 with permission from Buddoo et al. (2008).
MPa. Production of biodiesel Batch Micro-reactor Comments
Sootchiewcharn, Attanatho, and Reubroycharoen (2015) produced plant plant
biodiesel from palm oil with supercritical ethylacetate in a stainless- Plant output (tonne/yr) 20,000 20,000
steel micro-reactor with 0.762 mm i.d. and 15.14 m in length. At a Reactor volume (m3) 10 2.4 × 10−3 4167× smaller
temperature of 350 °C, oil to the ethyl acetate molar ratio of 1:50, and Plant footprint (m2) 149 60 60% smaller
ethyl acetate pressure of 20 MPa, biodiesel yield of 78.3% was obtained Surface area to volume ratio (m2/m3) 14.9 2.5 × 104 1678× higher
Productivity (kg/h/m3) 250 10.4 × 105 4167× higher
in 20 min. Recently, Schürer et al. (2014) reported a stainless-steel
Energy input (kJ per kg) 7.1 0.4 18× lower
micro-channel reactor coated with alumina as a catalyst to synthesize bio- Mass transfer coefficient kla (s−1) 10−2–10 10–100 104 higher
diesel under supercritical conditions. A complete conversion of tricaprin Heat transfer coefficient (kJ/m3) 628 2.86 × 106 4554× higher
in residence time of b30 s was observed at 375 °C and 10 MPa pressure. Mixing efficiency (Re) 7 × 105 10 7 × 104 higher
Unlike the conventional micro-tubular and micro-channel reactors Capital cost (Rm) 8.6 6.5 24.4% saving
Manufacturing costs (R/L) 6.60 5.87 11.1% saving
used for biodiesel production, Machsun, Gozan, Nasikin, Setyahadi,
 A. Tiwari et al. / Energy for Sustainable Development 43 (2018) 143–161
residence time of several hours in a conventional stirred tank reactor can
be minimized up to several seconds using a micro-reactor. A comparison
between batch and micro-reactor plant for biodiesel production (Table 2)
exhibited a superior performance of the micro-reactors over the batch
plant regarding productivity, energy input and capital cost for same
plant capacity (Buddoo et al., 2008). However, in most of the studies appli-
cation of this technology is confined to lab scale, producing biodiesel only
in small quantities. Billo et al. (2015) developed a cellular manufacturing
process for fabrication and assembly of a full-scale micro-reactor to pro-
duce biodiesel at the rate of 2.47 L/min and a capacity of 1.2 million L
per year. The scale-up of micro-reactor was done through numbering-
up of individual micro-channel laminae into subassemblies and assem-
blies. Schürer et al. (2016) designed a micro-reactor plant with annual
capacity of 40 t for production of biodiesel under super critical conditions
in the presence of a heterogeneous catalyst. The micro-reactor consisted
of three stainless-steel plates on which the micro-channels were etched
by wet chemical etching. 30 wt% La2O3 supported by γ-Al2O3 was coated
on to the micro-channels as a catalyst. The plates were stacked and sealed
by laser welding. At a reaction conditions of 375 °C and 175 bar and meth-
anol to oil molar ratio of 40:1, a complete conversion of rapeseed oil was
obtained within a few seconds.
Factors affecting biodiesel production
The process of biodiesel production is affected by various factors
depending on the reaction conditions and the geometrical parameters
of micro-reactor used. The effects of these factors are discussed below.
Effect of reaction temperature
The effect of temperature on the transesterification of vegetable oils
has been studied over a wide range of reaction temperatures in micro-
reactors. It was noticed that the temperature of reaction clearly influ-
ences the yield of the biodiesel product (Aghel et al., 2014; Jachuck
et al., 2009; Martínez Arias et al., 2012). Using a micro-tube reactor, it
was found that the conversion of sunflower oil increased with increase
in reaction temperature (Guan et al., 2009a). Martínez Arias et al., 2012
studied the effect of temperature on biodiesel yield using three different
micro-reactors. As the temperature was increased from 30 to 70 °C the
biodiesel yield increased from 67.3 to 89.0%, from 73.9 to 92.2% and
from 75.9 to 92.6% for T-, Omega-, and Tesla-shaped micro-reactors,
Fig. 5. Influence of reaction temperature on yield of ethyl ester using an ethanol/oil molar
ratio of 9:1, NaOH concentration of 1 wt%, and residence time of 10 min in T-, omega-, and
Tesla-shaped micro-reactors. Reprinted with permission from Martínez Arias et al. (2012).
Copyright 2012 American Chemical Society.
149
respectively as shown in Fig. 5. It can be ascribed to enhanced mass
transfer caused by an improvement in alcohol–oil miscibility and in-
creased rate of reaction at elevated temperature (Čerče, Peter, &
Weidner, 2005; Zhou, Lu, & Liang, 2006). Moreover, it was observed
that on increasing the temperature from 46 to 60 °C the percentage in-
crease in conversion was higher at lower catalyst loading in a micro-
channel reactor. At a catalyst loading of 0.25 wt%, the conversion in-
creased by 14.80% while only 2.5% increase in conversion was
obtained for 1 wt% catalyst loading (Jachuck et al., 2009).
Most of the works were carried out at temperatures below the
normal boiling point of methanol. Sun et al. (2009) examined the effect
of reaction temperature on transesterification of cottonseed oil both
below and above the boiling point of methanol using a micro-reactor
with rectangular interdigital micromixer (RIMM). The fatty acid methyl
ester yield increased as the reaction temperature was increased from 60
to 80 °C at methanol to oil molar ratio b9:1. The two-phase slug flow at
60 °C was transformed to gas-liquid two-phase slug-annular flow when
the temperature was raised to 80 °C. However, Aghel et al. (2014) and
Sun et al. (2008) found that when the reaction temperature increases
beyond the optimum level, the biodiesel yield decreases. The fatty acid
methyl ester yield increased from 96.2% to 99.4% as the temperature in-
creased from 30 to 60 °C, but further increase in temperature to 70 °C
resulted in a decrease of FAME yield to 99.1% (Sun et al., 2008). Aghel
et al. (2014) observed an increase in the percentage of FAME yield
with increase in temperature from 55 °C to 60 °C but the yield decreased
rapidly when the temperature was increased from 60 °C to 65 °C. It may
be because of the change in flow pattern from slug to bubble flow and
the accelerated saponification reaction of triglycerides in the presence
of an alkaline catalyst at higher temperatures (Aghel et al., 2014;
Leung & Guo, 2006; Sun et al., 2008). To perform continuous biodiesel
production by two-step acid catalyzed process using acid oil, tempera-
tures N100 °C were needed. Both esterification and transesterification
steps were observed to be positively affected by the reaction tempera-
ture (Sun, Sun, Yao, Zhang, & Xu, 2010).
Even higher reaction temperatures were required for production of
biodiesel under supercritical conditions in micro-reactors (Gonzalez
et al., 2013; Silva et al., 2014; Silva & Oliveira, 2014; Sootchiewcharn
et al., 2015). An increase in the FAEE yield was reported with increase
in the reaction temperature. However, at prolonged residence times,
too high temperatures led to thermal decomposition of the product
(Gonzalez et al., 2013; Sootchiewcharn et al., 2015). Compared to higher
reaction temperatures, when the reactions were carried out at room
temperature, a longer residence time was required to obtain a FAME
yield above 90% (Canter, 2006).
Residence time
The residence time for biodiesel production in micro-reactors varies
with the type of micro-reactor applied. In recent years, several studies
on biodiesel production in micro-reactors have reported that an
increase in residence time is favourable for higher biodiesel yield.
Martínez Arias et al. (2012) transesterified castor oil under the condi-
tions of ethanol to oil molar ratio of 9:1, catalyst amount of 1 wt% at
60 °C in three different micro-reactors. It was observed that for first 4
min of the reaction, with increase in the residence time the biodiesel
yield increased, and after that, the yield attained almost a constant
value as shown in Fig. 6. After a residence time of 15 min, biodiesel
yield of 75.9%, 94.1%, and 93.7% was acquired for T-, Omega and Tesla
shaped micro-reactors respectively. Aghel et al. (2014) observed a sim-
ilar effect of residence time on transesterification of soya bean oil with
methanol using micro-reactor with a wire coil. The percentage of
methyl ester conversion increased from 87.9% to 99% with an increase
in residence time from 20 to 180 s. The conversion increased rapidly
for first 20 to 60 s and then very slightly as the residence time was
prolonged from 60 to 180 s. However, in the study of Sun et al. (2008)
methyl ester yield first increased with increase in residence time from
150 A. Tiwari et al. / Energy for Sustainable Development 43 (2018) 143–161
Fig. 6. Ethyl ester yield of castor oil transesterification carried out in T-, omega-, and Tesla-
shaped micro-reactors at different residence times and using an ethanol/oil molar ratio of
9:1, catalyst amount of 1 wt% and temperature of 50 °C. Reprinted with permission from
Martínez Arias et al. (2012). Copyright 2012 American Chemical Society.
3.68 to 5.89 min then on the further prolongation of residence time the
yield decreased to about 92%. It may have resulted due to weakened
mass transfer (decrease in internal circulations) at prolonged residence
time resulted by a decrease in average velocity for a fixed length of capil-
lary (Dummann et al., 2003; Sun et al., 2008). Under supercritical condi-
tions, the residence time for transesterification of oils in micro-reactors
can be shortened up to a few seconds. Using supercritical methanol in ab-
sence of catalyst, a complete conversion of triglyceride was achieved in a
micro-channel reactor at a residence time of 5 min (Schürer et al., 2014).
However, when the supercritical transesterification was performed in
presence of a heterogeneous catalyst coated on the micro-channels, a
complete conversion was obtained in a very short residence time of
b15 s (Schürer et al., 2014; Schürer et al., 2016).
Alcohol to oil molar ratio
The molar ratio of alcohol to oil is one of the most important param-
eters affecting the yield of alkyl ester. Stoichiometrically, 3 mol of alco-
hol is required for transesterification of 1 mol of oil to yield 3 mol of
alkyl ester and 1 mol of glycerol. However, an excess of alcohol to oil
molar ratio results in greater oil conversions (Freedman et al., 1984).
A linear increase in fatty acid methyl ester yield was observed as the
methanol to cottonseed oil molar ratio was raised from 3:1 to 9:1 be-
tween 60 and 80 °C with 1 wt% KOH catalyst, in a micro-reactor assem-
bly consisting of rectangular interdigital micromixer (RIMM) connected
to a stainless-steel delay loop (Sun et al., 2009). Aghel et al. (2014) ex-
amined the effect of alcohol to oil molar ratio on ester yield with alkali
catalyst using methanol to oil molar ratios of 6:1, 9:1 and 12:1 in two
different micro-reactors, one with an inserted wire coil and other with-
out the coil. The results indicated that increase in a molar ratio from 6:1
to 9:1 led to 4.6% and 7.2% improvement in the percentage of methyl
ester for micro-reactor with and without coil respectively as shown in
Fig. 7. However, as the molar ratio was increased above 9:1, a slight de-
crease in the percentage of methyl ester was observed. This behavior
between methanol to oil molar ratio and ester yield agreed with Sun
et al. (2008) observations. Sun et al. (2008) concluded that in a capillary
micro-reactor when the methanol to soya bean oil molar ratio was in-
creased from 3 to 6, the methyl ester yield increased from 82.1% to
99.3% at 60 °C and 1 wt% KOH concentration. However, a further in-
crease in the molar ratio resulted in a decrease in yield to 95.3%. This un-
expected decrease in fatty acid methyl ester yield was probably because
at too high methanol to oil ratio; methanol acts as an emulsifier that
Fig. 7. Effect of molar ratio (methanol/oil) on FAME%. Reprinted from Aghel et al. (2014),
with permission from Elsevier.
could cause a part of glycerol to remain in biodiesel phase (Leung &
Guo, 2006).
Compared to alkali-catalyzed transesterification higher alcohol to oil
molar ratios were required under acid catalyzed transesterification of
oils with a significant amount of free fatty acid content in oil. A molar
ratio of 30:1 and 20:1 was used for esterification and transesterification
respectively, with sulfuric acid as a catalyst to obtain a yield of 99.5% in a
stainless-steel capillary micro-reactor. In the esterification step, the
conversion of FFA (free fatty acid) increased with increase in methanol
to FFA molar ratio from 10:1 to 30:1. Whereas, in the transesterification
step the yield first increased from 96.1 to 99.9% as the methanol to tri-
glyceride molar ratio was increased from 6 to 20 and then decreased
on further increase in the molar ratio (Sun et al., 2010). Under supercrit-
ical conditions, much higher alcohol to oil molar ratios were required in
comparison to subcritical transesterification (Gonzalez et al., 2013; Silva
& Oliveira, 2014; Trentin et al., 2011). Hence, transesterification in micro-
reactors is positively affected by an increase in alcohol to oil molar ratio,
but too high alcohol to oil molar ratios may lead to a decrease in biodiesel
yield. Moreover, the alcohol to oil molar ratio depends on the type of
micro-reactor applied, reaction conditions (subcritical or supercritical)
and catalyst used for biodiesel production.
Effects of geometrical configurations
Effect of channel size
The micro-channel size in a micro-reactor has a strong influence on
the yield of methyl ester. It could be attributed to different mass transfer
distance and rate between the oil and alcohol phases in various micro-
channel sizes. Using 0.25 mm inner diameter capillary micro-reactor the
methyl ester yield of 98.8% was obtained in a residence time of 6 min at
methanol to oil ratio of 6:1 and 1 wt% KOH concentration while the
yield reached only 96.7% in a residence time of 8.2 min when 0.53 mm
inner diameter capillary micro-reactor was used under same operating
conditions (Sun et al., 2008). Guan et al. (2009a) observed a linear in-
crease in sunflower oil conversion as the micro-tube diameter was de-
creased from 1 mm to 0.8 mm, 0.6 mm and 0.4 mm. A similar relation
between micro-channel size and biodiesel yield was noticed when zig-
zag micro-channel reactors with a hydraulic diameter between 240 and
900 μm were used for transesterification of soya bean oil. The micro-
channel with smallest hydraulic diameter gave the maximum biodiesel
yield as shown in Table 3 (Wen et al., 2009). Kalu, Chen, and Gedris
(2011) studied the effect of channel depth on the performance of the re-
actor using slit channel reactor for biodiesel synthesis. The result indicated
that with a decrease in channel depth from 10, 5 and 2 to 1 mm the
 A. Tiwari et al. / Energy for Sustainable Development 43 (2018) 143–161 151

Table 3 slit interdigital micromixer (SIMM-V2) followed by stainless-steel cap-

Geometric parameters and performances of micro-channel reactors. Reprinted from Wen illary with an i.d. of 0.6 mm. The ester yields obtained using T and J
et al. (2009), with permission from Elsevier.
mixer were almost equal and half of those achieved with the RIMM
Name Section (μm × μm) Hydraulic diameter (μm) Turns Yield (%)a and SIMM-V2 as represented in Fig. 8(a). It may be due to smaller
Zig-zag-1 200 × 300 240 350 97.3 mixer dimensions and more intensified mixing in RIMM and SIMM-V2
Zig-zag-2 300 × 500 375 350 91.3 micromixers. Similarly, three different mixers such as T-type, cross(†)
Zig-zag-3 500 × 500 500 350 81.1 type and split and recombine were used for methanolysis of sunflower
Zig-zag-4 500 × 900 643 350 80.9
oil. Micro-reactor with †-type mixer appeared to be better than the
Zig-zag-5 900 × 900 900 350 77.8
Zig-zag-6 500 × 500 500 10 60.0 micro-reactor with a T-type mixer and the micro-reactor with split
Zig-zag-7 500 × 500 500 50 63.2 and recombine micromixer (Bhoi et al., 2014). Rahimi et al. (2016) de-
Zig-zag-8 500 × 500 500 100 70.2 signed three unlike micromixers with different confluence angles of 45°,
Zig-zag-9 500 × 500 500 200 79.8 90° and 135° namely E1, E2 and E3 respectively (Fig. 4) for biodiesel
a
Reaction conditions: molar ratio of methanol/oil 6, catalyst amount 1% (based on oil production from soya bean oil. The results demonstrated that the reac-
weight), temperature 60 °C, and residence time 28 s. tion was most enhanced in E1 mixer followed by E3 and E2 respectively.
Hence from the above review, it can be concluded that efficiency the
conversion of soya bean oil increased. With increasing depth, the chan- mixer is an effective parameter on the transesterification of oil to fatty
nels approach the batch system and hence are less efficient than shallow acid alkyl ester. It can be attributed to varying dimensions of different
channels. mixers and the flow behavior at the outlet of the mixers. Apart from
the mixer type, Shaaban et al. (2015) investigated the effect of mixer
Effect of inlet mixer type inner diameter and geometry on the yield of fatty acid ethyl ester at
The mixing mechanism has a strong influence on the reaction when same reactor volume, flow rate and residence time using three different
it is carried out between two immiscible liquids. Therefore, the biodiesel inlet mixers T1, T2 and T3 as shown in Fig. 8(b). The T1 mixer recorded
production in micro-reactor is affected by the configuration of mixer ap- highest conversion of 97% in 80 s using 9:1 methanol to oil molar
plied to enhance the mixing of alcohol and oil phase. The microfluidic ratio. This was ascribed to its smaller internal dimensions which led to
systems for biodiesel synthesis consist of an integrated mixer to gener- formation of smaller slugs and increase in interfacial area.
ate dispersion, along with the reaction channel. A FAME yield of 98.80%
was obtained in a residence time of 6 min when instead of a microfluidic Effect of internal geometries
mixer, the reactants were mixed in a batch reactor then injected into Apart from diffusion, advection is another important form of mass
0.25 mm capillary micro-reactor. The yield already reached 81% before transfer in a microfluidic system. The so-called chaotic advection can
the mixture was pumped into the micro-reactor (Sun et al., 2008). significantly improve mixing of oil and alcohol. For passive mixing in
Guan et al. (2008) carried out transesterification of sunflower oil using micro-channels, the chaotic advection can either be introduced by mod-
a T-type and a split and recombine micromixer. The oil conversion ifications in channel geometry or by inserting an obstacle in the channel
was higher when the micromixer was used instead of a T-type mixer. (Nguyen & Wu, 2005). Several studies have been conducted for the pro-
Applying the split and recombine micromixer it was noticed that sun- duction of biodiesel in micro-reactors with simple Y and T structures
flower oil could be completely converted to biodiesel in a residence (Canter, 2006; Guan et al., 2009a; Jachuck et al., 2009). Moreover,
time of as short as 112 s. Even shorter residence time of 14.9 s was ob- there are few efforts on modified channel configurations for biodiesel
served to reach a yield of 99.5% when zig-zag mixer channels with a synthesis. Using a zig-zag micro-channel reactor, the efficiency of biodie-
zig-zag reaction channel (Fig. 2) were used for the production of biodie- sel production process improved significantly. The FAME yield reached
sel using soya bean oil (Dai et al., 2014). 99.5% in few seconds under mild operating conditions (Dai et al., 2014;
Sun et al. (2009) studied the effect of mixer type on the biodiesel Wen et al., 2009). Martínez Arias et al. (2012) investigated the effect of
yields using four different mixers as shown in Fig. 3(A), namely, a T- channel geometries on alkali-catalyzed transesterification of castor oil
mixer, a J-mixer, a rectangular interdigital micromixer (RIMM) and a using a T-shaped, Tesla shaped and Omega shaped micro-reactor. Under

(a) (b)

Fig. 8. (a) FAME yields of different micromixers at 60 °C for a methanol to oil molar ratio of 8:1, a KOH concentration of 1 wt%, a total flow rate of 1 mL/min, and a residence time of 44 s:
(T) T-mixer, (J) J-mixer, (RIMM) rectangular interdigital micromixer, (V2) (SIMM-V2) split interdigital micromixer. Reprinted with permission from Sun et al. (2009). Copyright 2010
American Chemical Society. (b) Specifications of the micromixers used by Shaaban, El-Shazly, Elkady, and Ohshima (2015). Reprinted with permission from Shaaban et al. (2015).
152 A. Tiwari et al. / Energy for Sustainable Development 43 (2018) 143–161
Table 4
Ethyl ester yields for different volumetric rates using ethanol/oil molar ratio of 9:1, catalyst
amount of 1 wt% and temperature of 50 °C. Reprinted with permission from Martínez
Arias et al. (2012). Copyright 2012 American Chemical Society.
Geometry Volumetric rate Residence Ethyl ester conversion (%)
(mL/h) time
(min)
Castor Ethanol T-shaped Omega
oil shaped
Transsection (μm × μm), 15.0 8.1 1 58.9
500 × 500 hydraulic 7.5 4.1 2 69.4
dia, 500 μm 5.0 2.7 3 73.1
3.8 2.1 4 74.7
3.0 1.6 5 71.1
2.1 1.1 7 75.1
1.5 0.8 10 73.4
1.0 0.5 15 75.9
same operating conditions, the Omega and Tesla shaped micro-reactors
resulted in higher ethyl ester conversions, followed by T-shaped micro-
reactor as shown in Table 4. It can be ascribed to chaotic flow in Tesla
and Omega micro-reactor which favoured better contact between the
oil and alcohol phase.
Recently, Aghel et al. (2014) developed a micro-reactor with an
inserted wire coil to improve the mixing efficiency. Compared to a sim-
ple T-shaped micro-reactor used in their previous work (Rahimi et al.,
2014), the micro-reactor equipped with wire coil produced a higher
percentage of FAME at the same reaction conditions. Similarly, the effi-
ciency of micro-channel reactor with static elements (MSE) in terms of
the mixing and reaction was also compared with plain T-shaped micro-
channel reactor without static elements. It was found that the micro-
channel with static elements showed superior performance of mixing
index and oil conversion due to induced changes in the direction
of flow, disturbances in boundary layer and formation of vortex
(Santana et al., 2017). From the above review, it is noticeable that better
conversion in micro-reactors with modified micro-channel structure
can be obtained as a result of chaotic mixing in comparison to laminar
mixing in simple T and Y micro-channels.
Effect of co-solvent
The biggest obstacle in the transesterification of vegetable oil is
immiscibility of alcohol and oil phase that slows down the reaction
significantly. In order to overcome slow reaction rates caused by the ex-
tremely low solubility of the alcohol in the triglyceride phase, addition
of an organic co-solvent has been recommended by Meher et al.
(2006). Several works on transesterification of triglycerides to fatty
acid alkyl ester using an organic co-solvent have been performed at
micro-scale to take the advantages of micro-reactors simultaneously
(Elkady et al., 2015; Guan, Sakurai, & Kusakabe, 2009b; Rahimi et al.,
2016). An improved process was investigated for methanolysis of sun-
flower oil with co-solvent in a micro-tube reactor. At a methanol to oil
molar ratio of 8:1 and 25 °C, oil conversion was considerably high in
the presence of co-solvent (Diethyl ether, DEE) as compared to conver-
sion obtained without co-solvent. It was observed that the flow was ho-
mogenous at the entrance of the micro-tube and with the formation of
immiscible glycerol the homogenous flow was disturbed (Guan,
Sakurai, & Kusakabe, 2009b).
Using Tetrahydrofuran (THF) as co-solvent, transesterification of
waste vegetable oil was observed at methanol volumetric ratio ranges
of 0.2 to 1 in a KM micromixer. As shown in Fig. 9, an increase in the bio-
diesel yield was seen with an increase in the THF to methanol volumet-
ric ratio. A maximum yield of 97.30% was obtained at THF to methanol
volumetric ratio of 0.3:1. However, while increasing the ratio above
0.3:1, no noticeable increase in the yield was found. In particular, THF
was chosen because its boiling point of 67 °C is only two degrees higher
Tesla
shaped
67.1 69.2
79. 3 83.8
87.5 88.8
88.3 91.5
89.7 91.1
88.5 91.7
87.4 92.2 Fig. 9. Effect of co-solvent volumetric ratio (THF/methanol) on percentage biodiesel yield.
91.4 93.7 Reprinted with permission from Elkady et al. (2015).
than that of methanol. Therefore, at the end of the reaction, the
unreacted methanol and THF can be co-distilled and recycled (Elkady
et al., 2015). Rahimi et al. (2016) studied the influence of co-solvent
(hexane) to methanol volumetric ratio on the FAME content. Using an
E1 mixer (see Fig. 4), an increase in the percentage of FAME from 81%
to 88% was reported as the co-solvent to methanol volume ratio was in-
creased from 0.1 to 0.4 at 45 °C, 2:1 oil to methanol volumetric ratio and
9 s residence time. However, on further increasing the ratio, the FAME
content decreased. It may be due to dilution of reactants at large
amounts of co-solvent (Mohammed-Dabo, Ahmad, Hamza, Muazu, &
Aliyu, 2012; Pardal, Encinar, González, & Martínez, 2010; Zhang, Jin,
Zhang, Huang, & Wang, 2012).The addition of co-solvent to alcohol to
overcome the immiscibility improves the contact between the alcohol
and oil phase but increases the number of downstream purification
steps.
Effects of catalyst type and concentration
Depending on the characteristics of feedstock, the nature of catalyst
employed plays an important role for transesterification of triglycerides
to biodiesel. The production of biodiesel can be carried out by acid, alkali
or enzyme-catalyzed processes or in the absence of catalyst using super-
critical methanol. The alkali and acid catalysts include both homoge-
neous and heterogeneous catalysts. Homogenous alkaline catalysts are
most commonly used to catalyze transesterification due to their low
cost, shorter reaction times and high conversion under mild operation
conditions (Casas, Fernández, Ramos, Pérez, & Rodríguez, 2010;
Demirbas, 2007; Freedman, Butterfield, & Pryde, 1986; Wang, Ou, Liu,
& Zhang, 2007). However, the process involving homogeneous alkaline
catalysts needs feedstock with free fatty acid content b1 wt%. In the case
of high FFA levels, a considerable amount of alkaline catalyst reacts with
FFAs to form soaps which hinder biodiesel purification process and dis-
turbs the flow patterns in micro-reactors (Guan et al., 2010).
Although alkali catalyzed, reactions are much faster compared to
acid catalysts, to overcome the difficulties due to soap formation acid
catalyzed transesterification is preferable when high content of FFA
(N1 wt%) is present in the oil. The acidic catalysts yield high biodiesel
content for high FFA feedstock, but it is greatly ignored due to long reac-
tion times, high catalyst concentration and a large amount of methanol
requirement (Sun et al., 2010). The heterogeneous catalysts are still
under development, and only a limited number of investigations have
been done on heterogeneous catalysts for the production of biodiesel
in micro-reactors (Kurayama et al., 2013; Kurayama et al., 2010;
Machsun et al., 2011; Schürer et al., 2014; Schürer et al., 2016). The het-
erogeneous catalyzed process exhibits some advantages, such as good
tolerance to free fatty acids, simple product purification, no waste
water treatment and mild operating conditions but because of high pro-
duction cost and short lifetime, their application for biodiesel produc-
tion is limited (Gorji, 2015; Sun et al., 2010).
 A. Tiwari et al. / Energy for Sustainable Development 43 (2018) 143–161
Apart from catalyzed process in micro-reactors, research has been
done using supercritical alcohols for biodiesel synthesis (Silva et al.,
2012; Farobie, Sasanami, & Matsumura, 2015; Gonzalez et al., 2013;
Schürer et al., 2014; Schürer et al., 2016; Silva et al., 2014;
Sootchiewcharn et al., 2015). However, the high cost of the production
process in the supercritical process due to strict demand of equipment
and high temperature and pressure requirements is a major limitation
(Chen et al., 2008). Besides the type of catalyst, the concentration of cata-
lyst used in the reaction has an optimum value below which the reaction
remains incomplete, and an excess catalyst amount may lead to reinforc-
ing the lateral saponification reaction (Dunn, 2001). The optimum con-
centration of catalyst depends on the operating parameters as well as
catalyst type (Gorji, 2015). Several investigations on the effect of catalyst
concentration on biodiesel yield in micro-reactors have been performed
(Guan et al., 2009a; Kaewchada, Pungchaicharn, & Jaree, 2016; Rashid,
Uemura, Kusakabe, Osman, & Abdullah, 2014). A similar influence as ob-
served for the conventional batch process was observed in micro-
reactors.
Homogeneous catalysts
The majority of research for biodiesel production using micro-reactor
technology has been done using low FFA feedstock or pre-treated feed-
stock in the presence of homogeneous alkaline catalysts. On the contrary,
transesterification of high acid value oils catalyzed by homogeneous acid
catalyzed has not been explored much. It may be due to simplicity, and
strong catalytic activity of an alkali-catalyzed process in which the reac-
tion proceeded in a single step while using acid catalyst required removal
of water as it may hinder the transesterification process to some extent
(Guan, Teshima, et al., 2009; Sun et al., 2010). However, use of alkali cat-
alyst is limited to oils with low acid content because of the formation of
soaps when a great amount of free fatty acid is present which disturbs
the flow behavior in micro-channels.
Alkaline catalysts. In micro-reactors, potassium hydroxide and sodium
hydroxide are the most investigated homogeneous base catalysts for
transesterification of vegetable oils. Sun et al. (2008) used KOH as a cat-
alyst, with methyl alcohol to convert the cottonseed oil into biodiesel.
By varying the concentration of catalyst at a constant methanol to oil
molar ratio of 6, residence time of 6 min and 60 °C reaction temperature,
they concluded that an increase in KOH concentration from 0.40 wt% to
1 wt% led to an increase in methyl ester yield from 86% to a maximum of
99.3% but with further increase in KOH concentration the FAME yield
decreased to 94.80%. This reduction in FAME yield was ascribed to sa-
ponification of oil with KOH since an increase in soap concentration
was observed from 0.2 to 0.34 wt%, when catalyst concentration was in-
creased from 1.0 to 1.2 wt%. Similarly, the influence of catalyst amount
was studied on transesterification of soya bean oil with three different
KOH concentrations of 0.6, 1.2 and 1.8 wt%. The results indicated that
the percentage of methyl ester increased when the catalyst concentra-
tion was raised from 0.6 to 1.2 wt% while a slight decrease in the propor-
tion of methyl ester was observed when a KOH concentration of 1.8 wt%
was used (Aghel et al., 2014).
Dai et al. (2014) performed series of experiments using KOH as a cat-
alyst in the range of 0.8–1.5 wt% for converting soya bean oil to methanol
in a zig-zag micro-channel reactor. A maximum yield of 99.5% was ob-
tained at 59 °C using 1.2 wt% KOH and 8.5:1 methanol to oil molar ratio
in 14.9 s. Kaewchada et al. (2016) and Azam, Uemura, Kusakabe, and
Bustam (2016) carried out KOH catalyzed transesterification of palm oil.
It was noted that an increase in the concentration of catalyst positively af-
fected the biodiesel yield. When NaOH is used as a catalyst, the reaction
temperature applied is usually low to avoid emulsification and saponifica-
tion (Xie et al., 2012). Experiments were conducted using four different
NaOH concentrations from 0.25 to 1 wt%, for transesterification of canola
oil in a small channel reactor. The residence time, methanol to oil molar
ratio (6:1), temperature and pressure of reaction were kept constant for
each catalyst loading. The results indicated that the use of higher catalyst
153
concentration led to higher triglyceride conversion. However, the rate
of change of conversion on catalyst loading was negligible at catalyst con-
centrations above 0.75% (Jachuck et al., 2009). Martínez Arias et al. (2012)
carried out biodiesel synthesis in three different micro-reactors i.e. a T-,
Tesla, and Omega shaped micro-reactors using different NaOH concentra-
tions (0.5, 1.0, and 1.5 wt%) for each micro-reactor. The residence time,
temperature and ethanol to castor oil molar ratio were held constant at
10 min, 50 °C and 9:1 respectively. It was observed that with an increase
in catalyst concentration from 0.5 to 1.5 wt% the yield of ethyl ester in-
creased from 50.6 to 79.1%, from 54.3 to 96.2% and from 56.3 to 98.9%
for T-, Omega and Tesla shaped micro-reactors, respectively. Likewise,
NaOH was tested as a catalyst in a range of 0.5 to 2 wt% for biodiesel pro-
duction from waste vegetable oil in a KM micromixer. A maximum yield
of 95% was achieved with 1 wt% catalyst concentration. Using 0.5 wt% cat-
alyst concentration the oil conversion was observed to be incomplete
while biodiesel yield decreased significantly as the NaOH concentration
was increased above 1 wt% (Elkady et al., 2015). Santana et al. (2016)
studied the relation between fatty acid ethyl ester percentage and catalyst
concentration. The results indicated that the percentage of FAEE (fatty
acid ethyl ester) yield increased slightly from 89.13% to 89.89% when
the NaOH concentration was increased from 0.2 to 0.85 wt%, but it dimin-
ished when NaOH concentration was higher than 0.85%.
Crawford et al. (2008) performed transesterification of triolein cata-
lyzed by sodium methoxide in a commercial Syrris 250 μL micro-reactor.
Using a 0.1 M catalyst concentration, a complete conversion of triolein to
methyl oleate was obtained at room temperature in 2.5 min. It has been
reported that compared to sodium hydroxide (NaOH), sodium methoxide
(NaOCH3) is more efficient because it is disintegrated into CH3O− and
Na+ and does not form water as in the case of NaOH/KOH. Additionally,
in contrast to sodium hydroxide the required amount of sodium
methoxide is about 50% lower, but due to its high cost it is not used widely
(Shahid & Jamal, 2011).
Acid catalysts. Despite the fact that alkaline catalysts are very efficient
and common for production of biodiesel, these catalysts do not exhibit
good results when the acid value and water content in oil are high
(N1 wt%). The water contents and acid values of most of the non-
edible and cheap feedstock are higher than performance range of base
catalysts. In such cases, acid catalysts are preferred (Fukuda, Kondo, &
Noda, 2001). Sulfuric acid is the most widely used acid catalyst, which
can be used to conduct both esterification and transesterification
simultaneously.
Acid catalyzed transesterification of high FFA oils in micro-reactors
has not been examined much. Sun et al. (2010) carried out production
of biodiesel with acid oil as a feedstock by a two-step sulfuric acid cata-
lyzed process in a micro-reactor assembled with a split interdigital
micromixer (SIMM-V2) and a 0.6 mm i.d. stainless-steel capillary
delay loop. Esterification of oleic acid and transesterification of cotton-
seed oil with methanol were investigated as model reactions to explore
optimum condition for the two-step process. Based on these reactions,
an acid catalyzed two-step process was developed with the first and
second steps conducted separately under the optimized esterification
and transesterification conditions. The results indicated that the
acid value of the acid oil was reduced from 160 to 1.1 mg KOH/g,
with a methanol to the acid molar ratio of 30, the H2SO4 concentration
of 3 wt%, and a residence time of 7 min at 100 °C in the first step. The
final FAME yield reached 99.5% with a methanol to triglyceride molar
ratio of 20, the H2SO4 concentration of 3 wt%, and a residence time of
5 min at 120 °C in the second step. Thus, biodiesel can be produced in
a residence time of b15 min by an acid catalyzed process in a micro-
reactor. However, higher concentration of catalyst is required for acid cat-
alyzed transesterification compared to base catalyzed transesterification.
Heterogeneous catalysts
Homogeneous catalysts are very efficient and are most frequently
used in biodiesel production. However, these catalysts require excessive
154 A. Tiwari et al. / Energy for Sustainable Development 43 (2018) 143–161
washing for their removal from the final product and subsequent treat-
ment of waste water. As a result, a lot of water, energy and time are con-
sumed. Besides that, these catalysts cannot be reused (Fukuda et al.,
2001). The use of heterogeneous catalysts offers several advantages
over homogeneous catalysts, such as; simple product separation, simple
catalyst recovery, catalyst reusability, less energy requirements and less
added cost of purification (Atadashi, Aroua, Aziz, & Sulaiman, 2013).
Biodiesel synthesis in micro-reactors applying heterogeneous catalysts
is still under investigations. To the best of our knowledge only heteroge-
neous alkaline and enzyme catalysts have been examined to catalyze
transesterification of oils in micro-reactors. Kurayama et al. (2013)
used CaO loaded micro-capsules as a micro-reactor for biodiesel
production from rapeseed oil. The micro-capsules were prepared by
encapsulation of CaO particles with butanol modified alginate as a
shell material using co-extrusion technique. It was suggested that
CaO-loaded micro-capsules could be successfully reused for three
times without the loss of the catalytic activity. Under supercritical con-
ditions, the application of heterogeneous catalyst coatings in micro-
channels for biodiesel production was first investigated by Schürer
et al. (2014). They performed experiments on transesterification of
tricaprin under supercritical conditions using alumina as a catalyst,
coated onto stainless-steel micro-channels by applying wash coating
process. A complete conversion was obtained in a very short residence
time of the 30 s. In their successive work, Schürer et al. (2016) designed
a small-scale heterogeneous alkali catalyzed (30 wt% La2O3 supported
by γ-Al2O3) plant with annual capacity of 40 t for biodiesel synthesis
under supercritical conditions. The implementation of heterogeneous
catalyst to micro-reactors minimized the residence time significantly.
Machsun et al. (2011) used a bio catalytic membrane micro-reactor
with immobilized lipase in the pores of an asymmetric polyether sul-
fone (PES) membrane for transesterification of triolein with methanol.
Each membrane pore acted as a micro-reactor in which the reaction oc-
curred. A maximum conversion of 80% was observed in a residence time
of 19 min. No activity decay of immobilized lipase was observed over a
period of 12 days of continuous operation.
Catalyst-free process
In the catalyst-free process, transesterification of oils is performed in
the absence of catalyst using supercritical alcohol at extremely high
pressure and temperature (Demirbaş, 2002; Kusdiana & Saka, 2001;
Saka & Kusdiana, 2001; Schürer et al., 2014; Warabi et al., 2004). Biodie-
sel production by the catalyst-free supercritical process has several
advantages over catalytic processes, including higher reaction rates,
easier separation, and purification of products, environment friendli-
ness and more tolerance to the presence of water and free fatty acids
(Kusdiana & Saka, 2004; Rathore & Madras, 2007).
Bertoldi et al. (2009) and Trentin et al. (2011) carried out continuous
biodiesel production in a stainless-steel micro-tube reactor through
catalyst-free transesterification of soya bean oil in supercritical ethanol
in presence of CO2 as a co-solvent. Bertoldi et al. (2009) performed ex-
periments in temperatures between 300 and 350 °C, pressure from 7.5
to 20 MPa, oil to ethanol molar ratio of 1:6 to 1:40, co-solvent to sub-
strate mass ratio from 0:1 to 0.5:1. An appreciable yield was obtained
at 350 °C and 10 MPa pressure, using oil to ethanol molar ratio of 1:40
and CO2 to substrate mass ratio of 0.05:1. Trentin et al. (2011) used
the similar experimental reaction system previously used by Bertoldi
et al. (2009) but a different range of operating parameters. In the inves-
tigated experimental range it was observed that temperature, pressure,
and co-solvent to substrate mass ratio had a positive effect on FAEE
(fatty acid ethyl ester) yield and significant yields were achieved at
325 °C, 20 MPa, oil to ethanol molar ratio of 1:20, 0.8 mL/min substrates
flow rate and CO2 to substrate mass ratio of 0.2:1. Sootchiewcharn et al.
(2015) investigated the production of FAEE from refined palm oil with
supercritical ethyl acetate in a micro-reactor. A biodiesel yield of 78.3%
was obtained at oil to ethyl acetate molar ratio of 1:50, the temperature
of 350 °C and 20 min of residence time. Using supercritical methanol,
Schürer et al. (2014) performed transesterification of tricaprin in
stainless-steel micro-channels. A complete conversion was achieved in
residence time of 5 min at 40-fold excess of methanol, 200 bar reaction
pressure and 375 °C reaction temperature. However, by application of
heterogeneous catalyst under supercritical conditions the required
pressure was reduced to 100 bar and a residence time of b30 s was re-
quired for 100% conversion.
Liquid-liquid two-phase flows in micro-reactors for
biodiesel production
It is crucial to study hydrodynamics in the multiphase reactor be-
cause different flow patterns influence mass transfer and axial disper-
sion, which affect the conversion and selectivity of the reactions.
Depending on the volumetric flow ratio of the two phases and total
flow rate, different flow patterns can be attained in micro-channels. In
two phase liquid-liquid system the conventional flow regimes include
as droplet (Fig. 10A), parallel (Fig. 10B), or slug flow (Fig. 10C). For
liquid-liquid two-phase mass transfer limited reactions, application of
slug flow has been suggested (Burns & Ramshaw, 2001; Dummann
et al., 2003; Kashid et al., 2005). In slug flow, the mass transfer between
two immiscible phases is significantly intensified due to the presence of
internal circulations (Burns & Ramshaw, 1999, 2001; Kashid et al., 2005;
Khan, Günther, Schmidt, & Jensen, 2004). These internal circulations are
induced as a result of shear force between the two liquid phases as well
as by liquid/wall friction (Malsch et al., 2008). It has been reported that
enhanced mixing and rapid reaction rates can be achieved using seg-
mented flow with internal circulations (Burns & Ramshaw, 1999; Tice,
Song, Lyon, & Ismagilov, 2003).
Using a quartz capillary micro-reactor, Sun et al. (2008) observed
that the methanol and oil phases were separated from each other
forming a slug flow due to high interfacial forces between the two
phases. An alternating long oil slug and a short methanol slug was
formed at the capillary inlet. They also reported a presence of a thin
methanol wall film surrounding the oil slug due to superior wettability
of methanol phase. The dimensions of oil slugs decreased with a de-
crease in capillary diameter suggesting an increased mass transfer at
smaller channel diameters due to an increase in interfacial area. As the
reaction between the two phases progressed, a similar alternative slug
flow of methyl ester and glycerol was seen at the outlet part of the cap-
illary. However, the flow patterns in the middle of capillary were not
clearly identified and the effect of reaction conditions and geometrical
configurations of micro-reactor were not investigated. Assuming droplet
flow could occur in tubular micro-reactor, Lopez-Guajardo et al. (2017)
suggested application of the droplet flow to achieve high interfacial area
and intense local mixing for higher conversions. At a constant methanol
volume of 3.97 × 10−7 m3, the highest interfacial area was reported for
droplet flow as shown in Table 5. Yeh, Huang, Cheng, Cheng, and Yang
(2016) devised a millimetrically scaled device that employed a droplet-
based co-axial fluidic system to complete alkali-catalyzed
transesterification for biodiesel production. The large surface area-to-
volume ratio of the droplet-based system, and the internal circulation in-
duced inside the moving droplets, significantly enhanced the reaction
rate of immiscible liquids i.e. soya bean oil and methanol. The droplet-
based co-axial fluidic system performed better than other methods of
continuous-flow production. This study demonstrated the high potential
of droplet-based fluidic chips for energy production.
Factors affecting flow patterns
Effect of temperature on flow patterns
Temperature clearly influences the methanol-oil two-phase flow be-
havior in micro-channels as the miscibility of oil and methanol increases
with increase in temperature (Čerče et al., 2005; Zhou et al., 2006). Guan
et al. (2009a) used a transparent fluorinated ethylene propylene (FEP)
tube to observe the flow pattern during biodiesel production under
 A. Tiwari et al. / Energy for Sustainable Development 43 (2018) 143–161
Fig. 10. Scheme of flow patterns of the reactants during the synthesis of biodiesel in the tubular micro-reactor: (A) droplet flow; (B) parallel flow; (C) slug flow. Reprinted with permission
from López-Guajardo et al. (2017). Copyright 2017 Taylor & Francis.
different reaction conditions. In order to obtain a clear view of flow,
methanol was dyed with inert red phloxine B which is also soluble in
glycerol but insoluble in oil. The flow patterns were observed at differ-
ent temperatures for two different alcohol to sunflower oil molar ratios
of 4.6 and 23.9. A gradual change in flow patterns was observed with in-
crease in temperature from 20 to 60 °C. When the methanol to oil molar
flow ratio was 4.6, at 20 °C a clear segmented flow was formed 400 mm
apart from the tube inlet and then fine red droplets composed of meth-
anol and glycerol were observed in oil slugs which agglomerated and
merged into the methanol segment to form larger red segments near
the exit region of tube (Fig. 11a). On the increase in temperature, the ag-
glomeration of segments began closer to the tube inlet (Fig. 11b). At 60 °C
the agglomeration started at 100 mm from the inlet of the tube, and a
quasi-homogenous phase was formed at the outlet region of the micro-
tube (Fig. 11c). When the tube outlet was cooled to room temperature,
the quasi-homogenous segments were separated into a segmented flow
of red segments containing methanol and glycerol, and oil segments con-
taining unreacted oil and FAMEs. For methanol to oil molar ratio of 23.9,
agglomeration of the red droplets appeared at 100 mm and 50 mm
from reaction inlet at 20 °C and 60 °C respectively. Hence, the time re-
quired to reach the quasi-homogenous phase became shorter as the tem-
perature is increased.
Previous research on biodiesel synthesis studied flow patterns up to
temperatures below the boiling point of methanol. Sun et al. (2009)
used a rectangular interdigital micromixer (RIMM) coupled with poly-
vinyl chloride (PVC) tube to examine the flow behavior both below
and above the boiling point of methanol. At 60–65 °C a fully developed
droplet flow of methanol dispersed in oil phase was seen at the outlet of
the mixer. As the temperature was increased, the flow transformed into a
mixture of many droplets and a small number of bubbles at 70 °C and to a
mixture of many bubbles and a smaller number of droplets at 75 °C. Fi-
nally, at 80 °C a gas-liquid two-phase slug-annular flow (Yue, Chen,
Yuan, Luo, & Gonthier, 2007) was formed. At the outlet part of the tube,
a two-phase slug flow was observed between 60 and 70 °C and however,
some methanol bubbles were seen in the slugs at 70 °C. At 75 °C, a gas-
Table 5
Estimated total interfacial areas for different flow patterns with a constant methanol vol-
ume of 3.97 × 10−7 m3. Reprinted with permission from López-Guajardo et al. (2017).
Copyright 2017 Taylor & Francis.
Flow Volume of single N° droplets-lugs Total interfacial area
pattern droplet-slug (m3) in TMR (m2/m3)
Drop flow 4.2 × 10−15 9.45 × 107 6.00 × 104
Slug flow 4.82 × 10−10 822 1.46 × 103
Parallel flow N.A.a N.A.a 6.31 × 102
a
N.A.: not available.
155
liquid two-phase slug-annular flow, similar to that at 80 °C during all re-
action times, was formed. Thus, the reaction temperature has a significant
influence on the flow behavior.
Effect of alcohol on oil molar ratio
It has been reported that alcohol to oil molar ratio strongly affects
the flow patterns (Guan et al., 2009a; Sun et al., 2009). At a methanol
to oil molar ratio of 4.6, short methanol segments dispersed in long oil
segments were observed. When the methanol to oil molar ratio was in-
creased to 23.9, the number of methanol segments per unit length of the
tube slightly decreased compared to the number of segments at 4.6
methanol to oil molar ratio as shown in Fig. 11. Moreover, the length
of methanol segments increased, while the length of oil segments de-
creased. The formation of red droplets containing glycerol and methanol
and their aggregation was more intense for methanol to oil molar ratio
of 23.6, and a complete conversion was obtained at 300 mm from tube
inlet (Guan et al., 2009a). Sun et al. (2009) reported that on increasing
the methanol to oil molar ratio from 3:1 to 15:1 at 60 °C, the droplets
of glycerol at the outlet part of the tube are enlarged gradually. Thus,
depicting higher conversion at higher methanol to oil molar ratio.
Effect of inlet mixer type
The mixer type also has a strong influence on the flow pattern in
micro-reactors. Sun et al. (2009) observed the flow patterns at the out-
let of four different types of micromixers, namely, a T-mixer, a J-mixer, a
rectangular interdigital micromixer (RIMM) and a slit interdigital
micromixer (SIMM-V2). As shown in Fig. 12, a uniform slug flow with
methanol slug dispersed in oil phase was formed at the outlet T-mixer
and J mixer, whereas a mixture of some slugs and many methanol drop-
lets appeared at the outlet of RIMM and SIMM-V2. Hence, the contact
area between the methanol and oil phase was significantly increased
using RIMM and SIMM-V2 resulting in higher FAME yields. Similarly,
Bhoi et al. (2014) investigated the flow in micro-reactors with three dif-
ferent mixers, a T-type, a cross (†) type, and a split and recombine mixer
at various flow rates and constant methanol to oil molar ratio of 10.3:1
during methanolysis of sunflower oil. The flow pattern for micro-reactor
with T-mixer was mainly a parallel flow with intermittent droplets
which were formed due to interface instabilities. This parallel flow
existed for a complete range of flow rates depicting no change in the
interfacial area with the flow rate. For micro-reactor with the †-type
junction, a mixture of slug and droplet flow was observed at a flow rate
of 0.5 mL/min. When the flow rate was decreased gradually, short
slugs were seen at 0.25 mL/min which continued up to a flow rate
of 0.10 mL/min. As the flow rate was decreased further to 0.07 and
0.05 mL/min annular flow was observed. Hence, in the flow rate range
of 0.05 to 0.5 mL/min, three different flow patterns were observed for a
156 A. Tiwari et al. / Energy for Sustainable Development 43 (2018) 143–161
Fig. 11. Total flow patterns in a transparent FEP micro-tube reactor (inner diameter = 0.8 mm, length = 1000 mm). Total flow rate =8.2 cm3/h. Arrows stand for the flow direction.
Reaction temperature: (a, d) 20, (b, e) 40, and (c, f) 60 °C. Methanol/oil molar ratio: (a–c) 4.6 and (d–f) 23.9. Reprinted with permission from Guan et al. (2009a). Copyright 2009
American Chemical Society.
cross-type junction. For micro-reactor with split and recombine mixer, at
flow rates equal to 0.05, 0.07 and 0.20 mL/min a slug flow was seen while
parallel flow with intermittent droplets was observed at a flow rate equal
to 0.10, 0.15, 0.25 and 0.5 mL/min.
Purification of biodiesel in micro-reactors
Transesterification of oils in the presence of methanol in micro-
reactors involves the formation of FAME and glycerol as the reaction
progresses. Separation of glycerol phase from biodiesel is a major step
to meet the quality standards. As both FAME and glycerol are immisci-
ble, they have to be separated from each other by density difference in
batch process. In the conventional batch process, an emulsion of biodie-
sel and glycerol is formed which is hard to break and consequently the
separation of the two phases is considerably slow. However, traces of
glycerol remain in the biodiesel phase after phase separation. Conven-
tionally, this small amount of glycerol is removed from the biodiesel
phase through washing followed by drying to remove the moisture
(Perez et al., 2014; Shahid & Jamal, 2011). For microfluidics devices
with small dimensions the separation of two phases on the basis of den-
sity difference is inappropriate due to negligible gravitational forces.
Separation and purification in microfluidic devices have gained
much importance in recent years (Hartman & Jensen, 2009; Jahnisch,
Fig. 12. Flow patterns in the transparent PVC tubes (inner diameter 1.2 mm) at the outlets
of different micromixers: (a) T-mixer, (b) J-mixer, (c) rectangular interdigital micromixer
(RIMM), (d) split interdigital micromixer (SIMM-V2). Reprinted with permission from
Sun et al. (2009). Copyright 2010 American Chemical Society.
Hessel, Lowe, & Baerns, 2004; Naleini, Rahimi, & Heydari, 2015; Sahoo,
Kralj, & Jensen, 2007; Singh, Renjith, & Shenoy, 2015) but only limited
work has been performed on purification of biodiesel product in
micro-reactors (Xie et al., 2012). Crawford et al. (2008) used a Syrris
Flow Liquid-Liquid Extraction (FLLEX) module for in-line continuous
separation of fatty acid methyl esters and glycerol. The FLLEX module
consisted of a microfluidic channel fitted with a polytetrafluoroethylene
(PTFE) membrane designed by Kralj, Sahoo, and Jensen (2007). The
separation was achieved by the addition of water to the mixture leaving
the micro-reactor chip at a rate of 100 μL/m in the FLLEX module. The
hydrophobic biodiesel phase was able to traverse the membrane
pores, while the aqueous phase containing glycerol and methanol did
not. According to a review article by Xie et al. (2012), Sun (2010)
performed the separation of biodiesel from glycerol by washing in a
micro-separator with channel dimensions of 500 × 500 × 500,000 μm.
A sandwich flow pattern between the water and raw biodiesel was
observed in the separator. The glycerol content in the final biodiesel
product was decreased to 0.02%. Purification of biodiesel in micro-
reactors is still under development and new technologies are needed
for continuous separation of biodiesel from glycerol. Several phase sep-
aration techniques have been developed and implemented for separa-
tion of two liquid phases (Fig. 13) which may be investigated for
separation of biodiesel from glycerol at micro-scale (Tsaoulidis, 2015).
Scope for future work
It is evident from the reported literature that production of biodiesel
through transesterification of oils with alcohol in the presence of a
catalyst have been investigated experimentally using various types of
micro-reactors, micro-tubes and micro-channels. Moreover, the advan-
tages of micro-reactors were also demonstrated and the potential of
micro-reactors for small-scale production of biodiesel fuel, rather than
large-scale centralized production using batch reactors. Through the re-
duced footprint of the entire production system which can be made
possible through the application of micro-reactor, the portable biodiesel
 A. Tiwari et al. / Energy for Sustainable Development 43 (2018) 143–161 157

Fig. 13. A schematic of separation devices during liquid-liquid plug or parallel flow. (a) Phase separation using a Y-splitter Xue et al. (2011), (b) phase separation by capillary forces
(Angelescu, Mercier, Siess, & Schroeder, 2010), (c) phase separation during parallel flow (Aota, Mawatari, & Kitamori, 2009) and (d) rhase separation by wettability combined with
pressure balance (Scheiff, Holbach, & Agar, 2013). Reprinted with permission from Tsaoulidis (2015). Copyright 2015 Springer.

system could be easily installed in the fields where oil-producing feed-
stock exists rather than transporting feedstock. Thus, avoiding the
transportation cost and loss of oil due to inevitable drying and spilling
of the feedstock oil while in transit. However, in reviewing the pub-
lished research on biodiesel production in micro-reactors, most of the
production scale was relatively small and limited effort has been done to-
wards the development and scale-up of micro-reactors for production of
biodiesel at pilot scale (Billo et al., 2015; Schürer et al., 2016). The
throughput of a single unit of micro-reactor is too low to meet the produc-
tion rates at industrial scale. Hence, the scale-up of micro-reactors units is
highly desirable and this can be achieved using the concept of
numbering-up.
Numbering-up is the multiple, parallel repetitions of micro-reactor
units to increase the throughput without altering the microfluidic flow
properties (Schenk, Hessel, Hofmann, Löwe, & Schönfeld, 2003). The
concept of numbering-up becomes important to prove the applicability
of micro-reactor at industrial scale. Kashid, Gupta, Renken, and Kiwi-
Minsker (2010) demonstrated the different numbering-up techniques
such as external numbering-up and internal numbering-up as shown
in Fig. 14(a & b). In internal numbering-up the two liquid phases are

(c)

Fig. 14. Numbering-up concept for two-phase micro-reactor. (a) Internal numbering-up and (b) external numbering-up. Reprinted with permission from Kashid et al. (2010). Copyright
2010 Elsevier Ltd. (c) Splitting distributor developed by Adamson, Mustafi, Zhang, Zheng, and Ismagilov (2006). Reprinted with permission from Adamson et al. (2006). Copyright 2006
Royal Society of Chemistry.
158 A. Tiwari et al. / Energy for Sustainable Development 43 (2018) 143–161
mixed at the junction and the mixture is distributed in several parallel
channels. The advantage of internal numbering-up is that only a single
pumping system and one mixing element is required. However, equal
distribution of two phase mixture in parallel channels is a challenging
task. In external numbering-up several mixing elements are arranged
in parallel and the two phases are mixed in each mixing element inde-
pendently. Hence, in external numbering-up performance of single
micro-reactor is ensured along with increased throughput but require-
ment of multiple independent reaction systems limits the use of this
strategy. In recent years, a new numbering-up strategy of designing a
splitting distributor has emerged in which a single micro-channel is fab-
ricated on a plate through etching and branched into multiple micro-
channels to form a tree like structure as shown in Fig. 14(c). Splitting
distributors ensure better flow uniformity as compared to external
and internal numbering-up solutions (Adamson et al., 2006; Al-
Rawashdeh et al., 2012).
To overcome the disadvantages of internal and external numbering-
up, Schenk et al. (2004) developed a first liquid-flow splitting unit
which ensured the flow equidistribution. The flow equipartition was
achieved by building up a pressure barrier. It was equipped with six
docking stations and three dampening elements for six micro-devices.
Separation-layer mixers were chosen as micro-devices, since the carry-
ing out of fouling-sensitive reactions was considered as one major appli-
cation of the flow splitting unit. Kashid et al. (2010) developed a
capillary micro-structured reactor, numbered-up for six capillaries to
investigate the effect of interfacial tension on the mass transfer perfor-
mance for various operating conditions. To reduce the equipment cost
and size, they integrated internal numbering-up approach for distribut-
ing single phase fluids and external numbering-up for two-phase
contacting. Yue et al. (2010) developed an external numbering-up ge-
ometry of a parallel micro-channel contactor with two constructal dis-
tributors to study the flow distribution and mass transfer
characteristics during CO2-water flow. Each distributor comprised of a
dichotomic tree structure that fed 16 micro-channels. It was found
that constructal distributors could ensure a nearly uniform distribution
of the two phases when the ideal flow pattern was slug-annular flow.
Hoang et al. (2014) designed a splitting distributor for uniform distribu-
tion of bubbles over the exit channel. They observed that all bubbles at
the junctions will be broken if the value of capillary number is greater
than a critical value i.e. Ca N Cacritical. Kriel, Woollam, Gordon, Grant,
and Priest (2016) performed experimental numbering-up of microfluidic
chips from one to five and then ten in an extraction module to extract
Platinum (IV) Chloride using a secondary amine. The extraction perfor-
mance was observed to remain unchanged with increasing throughput.
Al-Rawashdeh et al. (2012) developed barrier-based distributor which as-
sured flow uniformity and no channelling between the two phases. With
large constrictions in the upstream a flow uniformity of N90% was ob-
served. Hence, it is evident from the reported literature that several at-
tempts were made to numbering-up the channels using different
techniques. However, application of these techniques for production of
biodiesel were not explored.
Most of the current researches on biodiesel production in micro-
reactors were performed through transesterification of low free fatty
acid (FFA) edible oils using homogenous base catalysts to avoid the
formation of soaps. A confined work has been done on biodiesel produc-
tion using low-cost non-edible feedstock with high FFA content. The
conventional process of two-step acid-base transesterification for
biodiesel production using high FFA feedstock is yet to be applied at the
micro-scale. Alternative design and modifications of the microfluidic de-
vices for continuous removal of soap have to be carried out for biodiesel
production using oil with high FFA, which may minimize the cost of
production. Moreover, to overcome the difficulties due to soap formation
development of alternative catalysts with good tolerance to FFA and
adaptability at micro-scale needs to be investigated. From the above
review, it is evident that the current research is focused on increasing
the production efficiency through application of micro-reactors. However,
additional studies are required for in-line continuous purification of
biodiesel to meet the industrial quality standards.
Conclusions
• In recent years, biodiesel has gained significant importance with an
aim to replace fossil diesel fuel. It is evident from the reported litera-
ture that many nations of the world are commercially producing bio-
diesel using conventional reactors. However, conventional technique
for biodiesel production faces several challenges of long residence
time, high investment in equipment and manufacturing floor space,
high cost of operation and energy requirements and low production
efficiency. Micro-reactor technology can be successfully applied to
overcome these challenges. Attributed to small diffusion distances
and large surface area to volume ratio in micro-reactors, heat, and
mass transfer are significantly intensified, thus resulting in higher
conversions in shorter residence times. Moreover, the energy require-
ments in the mixing of reactants, ample floor space and standing time
for the separation of products are also eliminated.
• Production of biodiesel through transesterification in micro-reactors is
observed to be affected by operating parameters such as temperature,
alcohol to oil molar ratio, the effect of co-solvent addition, catalyst
type and concentration. Additionally, the geometrical configuration of
micro-reactors as well as the flow regime have significant effect on
the biodiesel yield.
• Production of biodiesel in micro-reactors has been investigated for a
wide range of temperatures. Most of the reported work has been
performed below the boiling temperature of methanol (60–65 °C).
For alkali catalyzed transesterification the biodiesel yield increases
with increase in temperature up to an optimum temperature beyond
which the yield decreases. This can be ascribed to accelerated
saponification reaction of triglycerides in the presence of an alkaline
catalyst at higher temperatures. However, to perform acid catalyzed
transesterification and transesterification under supercritical
condition, temperature above 100 °C and 300 °C were required
respectively.
• Apart from the temperature it is important to optimize the residence
time for the reaction. The residence time for biodiesel production
varies with the type of micro-reactor applied. However, at prolonged
residence time resulted by a decrease in average velocity for fixed
length micro-channel may cause a decrease in internal circulations
leading to weakened mass transfer. Hence, a decrease in the yield
may be noticed at decreased flow velocities. Similarly, under super-
critical conditions the biodiesel yield decreases due to decomposition
of the reactants and products at too long residence time.
• Alcohol to oil molar ratio is another important factor that affects the
yield of biodiesel during transesterification. Methanol and ethanol
are most investigated for biodiesel production in micro-reactors.
Under base catalyzed transesterification, most of the researchers
obtained the maximum yield at alcohol to oil molar ratio of 6:1.
However, the yield varied with the type of micro-reactor used.
When the alcohol to oil molar ratio was increased above the optimum
value a decrease in the biodiesel yield decreases. This unexpected
decrease in yield is probably because at too high alcohol to oil molar
ratio; the alcohol acts as an emulsifying agent which causes a part of
glycerol to remain in biodiesel phase. Compared to base catalyzed
transesterification a high alcohol to oil molar ratio of up to 20:1 may
be required for acid catalyzed transesterification. Even higher excess
alcohol to oil molar ratio (up to 40:1) is required for transesterification
under supercritical conditions.
• The reaction temperature, residence time and alcohol to oil molar ratio
depend upon type of catalyst, and catalyst concentration. For biodiesel
production in micro-reactors generally homogenous base catalysts are
used. Most of the researchers have used Potassium hydroxide (KOH)
or Sodium hydroxide (NaOH). For feedstock with high free fatty con-
tent acid catalyst (H2SO4) is preferred over base catalyst. However,
 A. Tiwari et al. / Energy for Sustainable Development 43 (2018) 143–161
high reaction temperature, residence time and alcohol to oil molar
ratio are required for acid catalyst. The application of heterogeneous
catalyst makes the catalyst separation obsolete but requires high dura-
bility of the catalyst. Heterogeneous catalyst micro-reactors are still
under development.
• Catalyst free process using supercritical alcohol can also be used to
accelerate the transesterification but the high cost of the production
process in the supercritical process due to strict demand of equipment
and high temperature and pressure requirements is a major limitation
for this method. The conversion efficiency is further improved when
supercritical transesterification is performed in presence of a co-
solvent or a heterogeneous catalyst.
• The geometrical configurations of micro-reactor i.e. channel size, inlet
mixer type and internal geometry of the channels also affect the ester
yield significantly. Shorter dimensions of channel lead to shorter diffu-
sion distances between the reactant molecules which enhances the
mass transfer. Hence, with decrease in the channel size (hydraulic di-
ameter) the yield of product increases. However, small dimension of
channels may lead to low throughput therefore apart from diffusion,
advection can be used to intensify the transesterification reaction
through improved mixing of oil and alcohol.
• Micro-reactors in which chaotic advection is induced by modifications
in channel geometry like application of zig-zag, omega, tesla shaped
channels or by inserting an obstacle in the channel tend to provide
higher yields. Moreover, the yield of biodiesel also depends on the
inlet mixer type. It can be attributed to varying dimensions of different
mixers and the flow behavior at the outlet of the mixers. The nature of
flow between the two phases determines the surface area to volume
ratio. The droplet-based flow performs better than other methods of
continuous-flow production.
• Optimization of operating parameters and design of micro-reactor is
necessary to gain higher productivity. However, for biodiesel produc-
tion in micro-reactors, there are some issues still needed to be tackled
with, including the numbering-up of micro-reactor from lab to pilot
scale, design, and development of micro-reactors for handling high
free fatty acids feedstock and heterogeneous catalyst micro-reactors.
Furthermore, continuous biodiesel purification using an integrated
microfluidic device is still under development. More design and sur-
face modification of the microfluidic devices have to be carried out
to meet the quality standards.
Acknowledgement
The authors would like to thank Shiv Nadar University for financial
assistance to carry out this work.
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