Energy Conversion and Management 184 (2019) 475–487

Contents lists available at ScienceDirect

Energy Conversion and Management

journal homepage: www.elsevier.com/locate/enconman

3D printed micro-chemical plant for biodiesel synthesis in millireactors T

a a,⁎ a
Mariana Garcia Mendonça Lopes , Harrson Silva Santana , Vinícius Felix Andolphato ,
Felipe Neves Russoa, João Lameu Silva Jr.b, Osvaldir Pereira Tarantoa
a
University of Campinas, School of Chemical Engineering, Zip Code 13083-852 Campinas, SP, Brazil
b
Federal Institute of Education, Science and Technology of South of Minas Gerais, IFSULDEMINAS, Zip Code 37560-260 Pouso Alegre, MG, Brazil

A R T I C LE I N FO A B S T R A C T

Keywords: A micro-chemical plant implies the production increment of a determined product using micro/millireactor
3D printer disposed in parallel. The flow distributor is responsible for the uniform distribution through these parallel mi-
Numbering-up crodevices. A mal-distribution, resulted from inadequate flow distributors designs, decrease the micro-chemical
Micro-chemical plant plant performance. Hence, the main goal of this paper was to apply 3D printing in manufacturing micro-che-
Biodiesel
mical plant parts and to obtain data on flow uniformity and reaction yield by experimental tests for the increase
of biodiesel production. The methodology consisted of design, printing and assembly of the micro-chemical plant
and experimental tests for flow rate and chemical reaction. The nonuniformity flow coefficient (Ф) values were
obtained for ethanol, sunflower oil and ethanol-sunflower oil mixture. The conical distributor without obstacle
with height of 26 mm (CD26) and the conical distributor with obstacle and height of 52 mm (CDO52) presented
excellent performance (Ф < 1%) for ethanol and sunflower oil flow, respectively, being used in the biodiesel
synthesis scale-up. In the microplant, the pipes used for oil and ethanol followed length/diameter ratios of 39
and 113, respectively, which offered low pressure drop. The flow uniformity deviation obtained in the micro-
plant was 4.2%, and its global yield was 42%, close to a single millireactor operation (50.4%). Thereby, the
biodiesel was produced at 126.4 mL min−1. The developed microplant employed an efficient strategy for bio-
diesel scale-up. Another advantage of the methodology described here is the sharing possibility of files or objects
over the internet. A user anywhere around the world can access the microplant developed here and start pro-
ducing the desired chemical using a 3D Printer.

1. Introduction
The fossil fuel consumption has been generating concerns about
worldwide climate changings. The biodiesel is presented as an alter-
native to the fossil fuel consumption, once it is produced from renew-
able raw materials and animal fats [1]. Biodiesel is a mixture of long
chain fatty acid alkyl esters, produced by the transesterification reac-
tion, i.e., reaction between alcohol and triglycerides, producing esters
(biodiesel) and glycerol in the presence of catalyst. This chemical re-
action aims to reduce the oil viscosity in order to use the biodiesel di-
rectly in combustion engines, without need of major modifications [2].
In macroscale, the transesterification reaction is generally per-
formed in batch reactor. In order to achieve high conversion levels, the
process lasts from minutes to hours [3]. Microreactors are introduced as
an alternative for the biodiesel synthesis, since it presents some ad-
vantages over the batch reactors. The main advantages are the shorter
residence time to achieve high reactant conversion, the lower reactant
amount and the lower generation of residues and energy consumption
[4].
In recent years, several studies about biodiesel synthesis in micro-
reactors have been carried out, exploring the geometry parameters and
process variables (temperature, catalyst concentration and alcohol/oil
molar ratio) in the reaction performance [4–8]. Nevertheless, these
researches focused on the microreactor development and not on the
biodiesel production increment. Concerning the viability of micro-
fluidics processes as an alternative to the conventional batch processes,
the enlargement of the production rate is a fundamental key. This issue
can be achieved using the multiplication of the microreactor unit. The
grouping of microreactors, molding a production unity capable to
provide high conversion level with a large production rate is known as
micro-chemical plant.
Micro-chemical plants can be understood as chemical plants using
micrometric structures, mostly with micro/millireactors, micromixers
and micro-heat exchangers [9]. An example of microplant was pre-
sented by Billo et al. [10], using a multiplication of 14,000 similar
microreactors to produce 2.47 L min−1 of biodiesel. The biodiesel plant

⁎
Corresponding author.
E-mail address: harrison@feq.unicamp.br (H.S. Santana).

https://doi.org/10.1016/j.enconman.2019.01.090
Received 22 November 2018; Accepted 23 January 2019
Available online 10 February 2019
0196-8904/ © 2019 Elsevier Ltd. All rights reserved.
M.G.M. Lopes et al.
Nomenclature
Abbreviatures
3D 3 Dimensional
ABS Acrylonitrile Butadiene Styrene
PLA Polylactic Acid
FDM Fused Deposition Modeling
CDO conic distributor with obstacle
CD conic distributor without obstacle
SI Supplementary Information
Symbols
D diameter, mm
H height, mm
L length, mm
N total number of outlets/millireactors
has 35 manifolds with 8 modules. In each module, 50 microdevices
were coupled. The fabrication process lasted 3 months and was divided
in 7 steps.
In recent literature other examples of micro-chemical plants are
found. Iwasaki et al. [11] applied a microplant composed by 8 stainless
steel reactors in the methyl-acrylate polymerization. The microplant
presented control system and was continuously operated for 6 days at a
maximum flow rate of 1.83 mL min−1. Togashi et al. [12] used a micro-
chemical plant composed by 20 microreactors arranged in parallel in 4
modules (each module with 5 microreactors), in order to conduct three
distinct reaction processes. The flow uniformity and the flow rate were
evaluated continuously for 4 h, and the pressure drop remained con-
stant with a production rate of 10 mL min−1. Su et al. [13] experi-
mentally analyzed the photo-catalytic reaction performance of a gas-
liquid mixture in the microreactor scale-up. The authors observed that
the pressure drop effect on the distributor was important to ensure a
good flow distribution, allowing compatible yield between scaled-up
and single microdevice operations. Yap et al. [14] studied the perfor-
mance of the three-phase hydrogenation in a module composed of 8
millireactors. The system reached an average yield of 83% for a flow
rate of 20 µL min−1, 40 µL min−1 and 2.9 mL min−1 for each phase.
Han et al. [15] presented a microplant consisted of a 5-module-system
with 400 microchannels to the microfluidic droplet-based scale-up used
in wastewater treatment. The authors also mentioned the importance of
flow uniformity in the scale-up to maintain a uniform droplet size
through the multiple microchannels. All the aforementioned examples
reinforce the importance and relevance of micro-chemical plant de-
velopment for microdevices scale-up.
Despite the successful use of micro-chemical plants in some pro-
cesses, the scale-up configuration and the reactant distribution to the
microreactors are still a considerable challenge. A microplant for bio-
diesel production can be developed using a configuration with micro/
millireactor disposed in parallel [12,13,15]. This configuration allows
operation with different temperature and pressure, and it is flexible
maintenance and replacing of operating units. The uniform flow dis-
tribution by the microdevices in parallel is an essential parameter for
micro/millireactor scale-up. The flow mal-distribution is caused by
inadequate flow distributors, reducing the microplant performance
[16]. Thereupon, the flow distributor has as main goal to provide
uniform flow over the parallel microdevices, supporting a compatible
performance of the microplant regarding the achieved in a single mi-
crodevice [17]. Accordingly, literature researches approach mostly the
flow distributor aiming the reactants division to the microreactors
unities [13,16,18–22]. Our group recently developed conical dis-
tributors with 4 outlets [23]. Good performance was observed for water
476
Energy Conversion and Management 184 (2019) 475–487
p pression, kg m−1 s−2
Q flow rate, mL min−1
u velocity, m s−1
β flow ratio
β̄ average flow ratio
µ viscosity, kg m−1 s−1
ρ density, kg m−3
Ф non-uniformity flow coefficient, %
A fatty acid peak area
Re Reynolds number
Δp pressure drop, Pa
FAEE percentage of ethyl esters, %
Subscripts
i outlet/Millireactor
global module
m average
with flow rate deviations below 1%. It was evaluated the fluid dynamic
behavior of water, ethanol and sunflower oil by CFD simulations. Re-
levant information was obtained about the occurrence of preferential
flow paths. After the development of an efficient flow distributor, field
engineers and researchers need to think about the microdevice. Higher
production rates can be reached if scale-up is combined with increase of
reactors dimensions, from “micro” to “milli”, for example, without
missing mass and heat transfer characteristics obtained in microscale
[24].
The manufacturing of a micro-chemical plant components, such as
flow distributors, structure support and micro/millireactor, requires
time and resources. The 3D printing, i.e., layer by layer additive man-
ufacturing of physical object directly from digital object, allows, in few
hours, the production of devices using low cost raw material [25,26].
Zhang et al. [27] presented some advantages of 3D printing use in
microdevice manufacturing over the conventional fabrication methods
(e.g. soft lithography): 3D printer allows developing complex geome-
tries at microscale, with low fabrication costs, decrease in development
time, diversity of raw materials and custom designs. Moreover, Bara
et al. [28] and Mardani et al. [29] highlighted that this technique al-
lows a fast fabrication, with material savings and custom designs, in-
cluding mountable pieces, favoring part replacement according to de-
mand.
Thereupon, this research aims to apply 3D printing technique in the
development of flow distributors, microplant structure support and
millireactors for the scale-up of biodiesel synthesis, performing an ex-
perimental analysis of flow rate, flow uniformity and reaction efficiency
in the designed distributors and in the scaled unit. Therefore, the study
novelty was the manufacturing of a micro-chemical plant for scale-up of
biodiesel synthesis using 3D printing technique and to show its per-
formance, comparing with other micro-chemical plants presented in
literature. To the authors' knowledge, this is the first time that a che-
mical plant is made by 3D printing. We believe that 3D printing will
enable the manufacture of chemical plants anywhere and according to
the required demand. Using a 3D printer, anyone can manufacture their
own chemical plant and produce their chemical compounds.
2. Design and 3D printing
The 3D printing was performed using the Sethi3D S3 printer
(Sethi3D, Campinas, SP, Brazil). Firstly, the model slicing (i.e. division
of the digital 3D model into hundreds or thousands of horizontal layers)
was carried out with the Simplify3D software. The Acrylonitrile-
Butadiene-Styrene (ABS) polymer was used in flow distributor and
support structure printing and the Poly-Lactic Acid (PLA) polymer was
M.G.M. Lopes et al. Energy Conversion and Management 184 (2019) 475–487

used in the millireactors printing. The printing process was made from Table 1
the polymers heating to their melting points: 235 °C (ABS) and 205 °C Printing data for the distributors.
(PLA). Then, the melted polymer was extruded and deposited, layer by Distributor 3D printing data
layer, until the complete part confection. This printing technology is
known as Fused Deposition Modeling (FDM). Printing timea (min) ABS mass (g) ABS cost (US$)

CDO13 32 9.08 0.35

CDO52 44 12.74 0.49
2.1. Flow distributors CD26 34 9.91 0.38

The flow distributors previously developed in Lopes et al. [23] were
used in the experimental runs of ethanol and sunflower oil and the flow
test of the micro-chemical plant. The details of the distributors are
provided in Fig. 1, with inlet diameter, D1 = 6.79 mm, outlet diameter,
D2 = 3.10 mm and distributor base diameter, D3 = 23.56 mm.
The CDO present an obstacle diameter of D4 = 10.08 mm (Fig. 1b).
The internal obstacle drives the reactant flow towards the outlets. The
CD was built with a height of H = 26 mm (CD26) and the CDO designs
present heights of H = 13 mm (CDO13) and H = 52 mm (CDO52). The
printing data for the distributors are summarized in Table 1.
2.2. Support structure
The support structure was developed using SketchUp software from
modular concept, which allows modifications of millireactor number of
units according to the production demand, without the necessity of
reprinting the entire structure. The details and dimensions of support
structure are provided in the Supplementary Information (SI) in Figs.
S1, S2 and S3.
The structure was divided in three parts: supporting pillars, milli-
reactor support and fixing rods. Each structure plate is composed by
four pillars, one millireactor support and two fixing rods, admitting
only one millireactor, as shown in Fig. 2.
The blocks of the supporting pillars have internal cavities for the
connection of several units. The blocks also have triangular gaps to
couple the fixing rods. The rods lock the millireactor support in the
blocks, molding a supporting pillar. The assembled plate provides a
stable base for the supporting structure scale-up, as illustrated in Fig. 3.
Since the designed distributors have four outlets, a four-plate structure
was assembled in order to support the four millireactor used in bio-
diesel synthesis. Table 2 provides data of supporting structure parts
printing.
a
Printing time relative to the 3D printer used (Sethi3D S3). It should be not
assumed as absolute.
2.3. Millireactor
The millireactors were also developed using SketchUp software. The
design presents channels with rectangular cross section, sloped at 45°, a
strategy used for printing quality enhancement. The millireactor has 11
channels (Fig. 4a), with width of 3 mm and height of 2 mm (Fig. 4b),
hydraulic diameter (Dh = 4As / Pw ,where As is the cross-sectional area, in
mm2, and Pw is the wetted perimeter, in mm) of 2.4 mm and channel
length of 195 mm (total length of 2145 mm). The printing time required
to manufacture the millireactor, shown in Fig. 4c, was 6 h and 14 min,
with an estimated cost of US$ 3.56 of PLA polymer. The details and
dimensions of the millireactor are given in Supplementary Information
(Fig. S4).
3. Materials e methods
3.1. Materials
The materials used in flow rate test and biodiesel synthesis were:
sunflower oil from Campestre Indústria e Comércio de Óleos Vegetais LTDA
(São Bernardo do Campo, Brazil), with acidity index of 0.04 mg of
KOH/g of oil; ethanol (99.5%, P.A.) from Dinâmica Química
Contemporânea LTDA; sodium hydroxide (P.A., micropearls) from Êxodo
Científica®; hexane (P.A.) from Anidrol®.
3.2. Flow distributor
The flow rate tests were carried out using ethanol and sunflower oil
in the experimental configuration, shown in Fig. 5. The fluids were
pumped from 1L beakers through flexible pipes Masterflex® (Tygon Lab

Fig. 1. Conical distributors: (a) without obstacles with dimensions; (b) with obstacles with dimensions; (c) printed model using Sethi3D S3 printer, with details of
inlets and outlets.

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M.G.M. Lopes et al. Energy Conversion and Management 184 (2019) 475–487

Fig. 2. Support structure module: (a) supporting pillars; (b) millireactor support; (c) fixing rods.

– L/S 17) using two peristaltic pumps Masterflex® L/S® (Fig. 5a). The Table 2
distributor was placed in a support rod, held with a clamp, to keep the Printing data for the supporting structure part.
level throughout the experimental test and to allow sample collecting. Part (quantity) Printing timea ABS mass ABS cost (US
Flow rates of 50–200 mL min−1 were adjusted for each pump. The (min) (g) $)
outlet flow rates were measured in graduated tubes of 10 mL and
Supporting pillar (2 units) 74 28.92 1.07
chronometers. The outlet flow rate runs were performed in triplicates.
Millireactor support (1 unit) 61 21.40 0.79
For ethanol and sunflower oil mixture, the flow rates were adjusted Fixing rods (2 units) 19 7.01 0.26
in the peristaltic pumps to provide the ethanol/oil a molar ratio of 9.
Thus, the ethanol/sunflower oil flow rates were 30/50, 50/90, 100/ a
Printing time relative to the 3D printer used (Sethi3D S3). It should be not
180, 120/220, 150/270, 170/310 and 200/360 mL min−1, adjusted in assumed as absolute.
each pump. Since ethanol and sunflower oil are immiscible, each vo-
lume fraction was visually determined by a 10 mL test tube aided by a the reaction test using two heat plates (models: Novatecnica and IKA®
blue dye added to ethanol. The flow rate measurements were conducted C-MAG HP7) in the sunflower oil and the ethanolic solution pumping
using 10 mL test tubes and a chronometer. The results refer to average systems. Four tests were performed, varying flow rate and temperature.
values from triplicate runs. The reaction test samples were collected in triplicates, at the distributor
The transesterification test in the distributor was performed for an outlets and analyzed later.
ethanol/oil molar ratio of 9 and sodium hydroxide catalyst of 1% w/w
(ethanolic solution), according to operating conditions of Santana et al.
[4]. The flow rates were 50 and 360 mL min−1 for sunflower oil, and 30 3.3. Millireactor
and 200 mL min−1 for ethanolic solution. The reaction temperatures
were 25 °C and 50 °C. The system temperature was kept constant during The millireactor was fed with ethanolic solution and sunflower oil
using peristaltic pumps. The influence of temperature, ethanol/oil

Fig. 3. Modular supporting structure with capacity of four millireactors: (a) lateral view; (b) frontal view.

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M.G.M. Lopes et al. Energy Conversion and Management 184 (2019) 475–487

Fig. 4. Millireactor for biodiesel synthesis: (a) superior view of channels in SketchUp; (b) cross sectional view of the rectangular channels; (c) superior view of 3D
printed millireactor.

molar ratio and catalyst concentration were studied by the use of a
Central Composite Rotatable Design (CCDR), as described in Table 3.
Table 4 summarizes the flow rates of oil and ethanolic solution for each
ethanol/oil molar ratio evaluated for a residence time of 10 s.
3.4. Micro-chemical plant
Firstly, the microplant assembly, using the printed parts, was car-
ried out, as shown in Fig. 6. Tygon Masterflex® flexible pipes were
employed to connect the distributor outlets to the millireactor inlets.
The millireactors were coupled to the supporting structure. All con-
nections were sealed with plastic adhesive for PVC to prevent fluid

Fig. 5. (a) Experimental apparatus for flow rate tests of distributors, (b) ethanol configuration, and (c) sunflower oil configuration.

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M.G.M. Lopes et al. Energy Conversion and Management 184 (2019) 475–487

Table 3
Operating variable ranges for CCDR analysis.
Variables Levels

−1.68 −1 0 1 1.68

Temperature (°C) 25 40 50 60 68
Ethanol/Oil molar ratio 5 7 9.5 12 14
Catalyst concentration (%) 0.2 0.46 0.85 1.25 1.5

Table 4
Flow rates for sunflower oil and ethanolic solution (mL min−1) for the different
ethanol/oil molar ratios.
Ethanol/oil molar ratio Sunflower oil flow rate Ethanolic solution flow rate

5 57.44 17.79
7 52.47 22.76
9.5 47.36 27.88
12 43.15 32.08
14 40.28 34.95
leakage during the operation. In the distributors, one inlet was used for
fluid intake, while the other remained closed. The microplant flow rate
test was performed for the ethanol-oil mixture, aiming to determine the
volume fraction of ethanol at each millireactor. Flow rates of
140 mL min−1 and 160 mL min−1 for ethanol and sunflower oil, re-
spectively, were adjusted in the peristaltic pumps, providing the
ethanol/oil molar ratio of 14.
The transesterification reaction in the microplant was carried out
using an ethanolic solution with 0.85% w/w of NaOH and an ethanol/
oil molar ratio of 14 at 50 °C [4]. Both fluid streams (ethanolic solution
and sunflower oil) were pre-heated at 50 °C using heat plates and then
pumped at 140 mL min−1 and 160 mL min−1, respectively. Distributors
CD26 and CDO52 distributed the ethanolic solution and sunflower oil,
respectively, to the four millireactors. Samples were collected in tri-
plicates at millireactor outlets for posterior analysis.
The fatty acid ethyl esters (FAEE) determination of all samples and
the quantification of flow uniformity (Ф) are detailed in the
Supplementary Information.
4. Results and discussion
This study was divided in two parts. The first one consisted in the
distributors performance evaluation, regarding their use in the scale-up
of biodiesel synthesis. From this analysis, the microplant configuration
was defined, using one or two distributors. The second part consisted of
Fig. 7. Nonuniformity flow coefficients for CDO13, CDO52 and CD26 in
ethanol flow experiments.
operation and performance tests of the developed microplant.
4.1. Ethanol flow distribution
The nonuniformity coefficient (Ф) for the ethanol flow rate test
using the three distributors designs are presented in Fig. 7. The dis-
tributors presented good performance for ethanol flow, with deviations
below 3%. Gomes et al. [18] obtained deviations below 4% in experi-
mental runs for water in a conical distributor, considered optimal.
Therefore, the CDO13, CDO52 and CD26 designs, which presented
average Ф of 0.95%, 0.38% and 0.36%, respectively, can be considered
optimal flow distributors, providing good ethanol flow uniformity in
the investigated flow range. The nonuniformity coefficient decreased
with the flow rate increment in CDO13 and CDO52 distributors. For the
range of 300–400 mL min−1, Ф < 0.5% were noticed for CDO13. The
CDO52 shows a nonuniformity coefficient of 1.1% for 100 mL min−1,
which was decreased to 0.14% at 340 mL min−1. In the CD26 dis-
tributor, an increment from 0.19% to 0.65% was observed for a flow
rate increase from 100 to 240 mL min−1, gradually decreasing to Ф =
0.2% at 400 mL min−1.
Similar relationship between the nonuniformity coefficient and the
flow rate was noticed for distributors CDO13 and CDO52, with highest
deviations of 2.64% and 1.1%, respectively, at 100 mL min−1. For the
distributor CD26, the highest deviation (0.65%) was noticed at

Fig. 6. Micro-chemical plant for biodiesel synthesis: (a) peristaltic pumps; (b) CD26 distributor; (c) CDO52 distributor; (d) Tygon flexible pipes; (e) support structure;
(f) millireactors; (g) ethanolic solution – ethanol and sodium hydroxide; (h) sunflower oil; (i) heat plates.

480
M.G.M. Lopes et al.
240 mL min−1. This different behavior could be related to the obstacle
presence, since the CD26 design does not have the internal element. A
difference between the adjusted and real pumping flow rates was ob-
served in the experiments, as summarized in Table 5.
The inlet and outlet flow rates were not equal in the ethanol system
possibly due to the fluid evaporation in the distributor, as shown in
Fig. 8. The system accessories and characteristics (bends, distributor
height on the fixing rod, ethanol reservoir height) can decrease the flow
pressure until it reaches the ethanol vapor pressure (7999.3 Pa at
26 °C), contributing to ethanol evaporation. Santos et al. [30] purposely
used an orifice plate to cause ethanol evaporation and produce bio-
diesel by hydrodynamic cavitation. The authors observed that higher
flow rates promoted greater amount of ethanol evaporation. This be-
havior is also observed in the present research. Table 5 shows the in-
fluence of distributor height and presence of the obstacle in vaporized
ethanol amount. For the distributors with obstacles (CDO13 and
CDO52), the mass imbalance was greater to that noticed for CD26
distributor. The higher the distributor is, the greater is the ethanol
evaporation. Accordingly, the CD26 distributor presented superior
performance for ethanol flow, since it provided the lowest average
nonuniformity coefficient (Ф = 0.36%) and the smallest mass im-
balance.
4.2. Sunflower oil flow distribution
Fig. 9 presents the nonuniformity coefficient results for the sun-
flower oil flow. The average Ф for CDO13, CDO52 and CD26 dis-
tributors were 1.25%, 0.34% and 0.89%, respectively. All three designs
can be considered optimal distributors for oil, since they provided good
flow uniformity (low Ф values). For this case, the obstacle did not affect
the flow uniformity. However, the distributor height influenced the
flow uniformity. Higher devices provided superior flow distribution.
Based on the results, the CDO52 distributor presented superior perfor-
mance for oil flow rate, with the average nonuniformity coefficient of
0.34%.
In the oil flow test, no direct correlation between Ф and flow rate
was observed, as shown in Fig. 9. Therefore, the Reynolds numbers (Eq.
(1)), written in flow rate terms, were estimated to investigate the
viscosity effect on the oil flow uniformity.
4ρQ
Re =
πμD (1)
−3 −1
where ρ is the density, in kg m , Q is the flow rate, in m s , D is the
3
diameter, in m, and μ is the dynamic viscosity, in Pa s. The fluid
properties were obtained for 25 °C: ethanol: ρ = 786 kg m−3;
μ = 0.0011 Pa s; sunflower oil: ρ = 914.96 kg m−3; μ = 0.0549 Pa s).
Analyzing the Reynolds number presented in Table 6, the pre-
dominance of viscous forces over inertial forces in the sunflower oil
flow was noticed. Despite the increase from 100 to 400 mL min−1, the
Reynolds number rises only from 3.91 to 15.62, characterizing an es-
sentially viscous laminar flow. Accordingly, the flow rate has no great
influence in the flow uniformity of the viscous oil. Comparing the
Reynolds numbers of sunflower oil and ethanol flow tests, the viscous
force predominance becomes more evident. Since ethanol presents
lower viscosity, the flow rate (inertial effects), affects the flow pattern,
and, consequently, the ethanol flow uniformity, as observed in Section
4.1.
4.3. Mixture flow distribution
The experimental runs of ethanol-oil mixture aim to evaluate each
component distribution at the outlets of the distributors. The experi-
mental results of ethanol volume fraction are presented in Fig. 10. The
expected volume fraction of ethanol was 0.36 at each outlet.
The highest ethanol volume fraction was noticed in the outlet
number 4, due to its position compared to the distributor inlets, as
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Energy Conversion and Management 184 (2019) 475–487
shown in Fig. 11. Therefore, ethanol flowed through a preferential path,
named outlet 4. The increment of flow rate reduced the trend towards a
preferential path, increasing the volume fraction distribution over the
other outlets. The smallest difference of volume fraction over the out-
lets was noticed for the total mixture flow rate of 560 mL min−1
(200 mL min−1 of ethanol, and 360 mL min−1 of oil) for all three dis-
tributors. This behavior can be attributed to the fluid recirculation
provided by the high flow rate at inlet, allowing the fluid mixing inside
the device, decreasing the preferential path of ethanol. Despite the
superior flow uniformity at higher flow rates, the experimental values
in all outlets remained far from the expected ideal distribution
(α = 0.36). The distributor height and the obstacle presence did not
influence the volume fraction distribution at outlets.
Fig. 12 presents the nonuniformity coefficients for ethanol volume
fraction (Ф). A slight increase in Ф was observed from the minimum
flow rate. Above 340 mL min−1 , the Ф considerably decreased in all
distributors. The flow rate increment benefited the flow uniformity due
to higher fluid mixing. Despite the flow uniformity increase, the
minimal values of Ф were 17.4% (CDO13), 8.8% (CDO52) and 9.2%
(CD26). However, these nonuniformity coefficients were much higher
than 1% (obtained for the single-phase flow) and considering that the
millireactor is fed by the distributor outlets, the different ethanol flow
rate provided for the millireactors would imply in different perfor-
mance of each device in the biodiesel synthesis, an undesirable beha-
vior for the microplant. Su et al. [13] presented the importance of flow
uniformity to obtain a compatible yield in each microunit, allowing the
scale-up. Accordingly, the flow distributor did not exhibit good per-
formance for ethanol-oil mixture distribution (Ф ≫ 1%).
Moreover, it is important to keep the chemical reaction progress
only inside the microreactors, in order to control process variables,
allowing the desirable performance in the scale-up. Su et al. [13] and
Nagaki et al. [21] used parallel microreactor to scale-up a gas-liquid
photo-catalytic reactor and a synthesis of an intermediate compound of
Valsartan, respectively. In both studies, the reactants distribution was
performed by flow distributors, and the reaction occurred only inside
the microreactors. In this context, the biodiesel synthesis occurrence in
the distributors was verified.
The chemical reaction tests were carried out at minimum
(80 mL min−1) and maximum (560 mL min−1) flow rates, using the
ethanol-oil mixture at 25 °C and 50 °C. The CDO52 distributor was used
based on its superior performance for the mixture distribution. Fig. 13
presents the biodiesel yield at each distributor outlet.
Biodiesel was produced in all distributor outlets for the four oper-
ating conditions evaluated, even in ambient condition. The temperature
increment favored the biodiesel synthesis due to the increase in
ethanol-oil miscibility and the reaction dependence on temperature.
The increase of flow rate also enhanced the biodiesel yield. The
average yield was 17.64% (25 °C, 80 mL min−1), 30.56% (50 °C,
80 mL min−1), 35.98% (25 °C, 560 mL min−1) and 54.77% (50 °C,
560 mL min−1). Despite the lower residence time of the fluid mixture,
the higher flow rate favored the reaction, providing higher FAEE yield
at 50 °C. This can be attributed to higher fluid recirculation inside the
Table 5
Ethanol flow rates from experimental measurements in CDO13, CDO52 and
CD26 distributors.
Ethanol flow rate (mL Distributor
min−1)
CDO13 CDO52 CD26
100 91.01 ± 1.34 90.13 ± 0.43 93.44 ± 0.54
200 182.11 ± 0.76 178.44 ± 0.76 200.83 ± 1.63
240 218.17 ± 1.65 210.09 ± 2.15 234.84 ± 2.42
300 268.52 ± 1.62 262.09 ± 2.59 287.34 ± 1.57
340 300.55 ± 3.76 294.92 ± 2.02 325.86 ± 5.45
400 353.17 ± 0.93 348.22 ± 5.64 381.48 ± 2.27
M.G.M. Lopes et al. Energy Conversion and Management 184 (2019) 475–487

Fig. 8. Ethanol condensation inside the distributor pipe inlet.

up was proposed with a two-distributor configuration, each one pro-

viding a single-phase fluid feed. The CDO52 and CD26 designs ex-
hibited superior distribution performance to sunflower oil and ethanol
flows, respectively. These two designs were used in the microplant
scale-up.

4.4. Biodiesel synthesis in millireactors

Before the scale-up procedure, the biodiesel synthesis was carried

out in a single unit of the millireactor at operating conditions listed in
Table 7. This step provides important information about the biodiesel
yield, since according to Su et al. (2016), it is fundamental that the
scale-up device provides similar yield of a single millireactor.
For the residence time of 10 s, the maximum biodiesel yield (fatty-
acid ethyl ester percentage - FAEE(%)) observed was 73.51%. The
minimum FAEE% was 8.99%. Table 7 summarizes the effect of each
operating variable on the biodiesel yield. It was noticed the dependence
of reaction performance on the interaction among the operating vari-
Fig. 9. Nonuniformity flow coefficients for CDO13, CDO52 and CD26 in sun- ables in all runs. Several researches about biodiesel synthesis verified a
flower oil flow experiments.
positive relationship between the temperature and the chemical reac-
tion efficiency, i.e. the increment of temperature resulted in the oil
Table 6 conversion increase, due to the increment of the ethanol-oil miscibility
Reynolds numbers for the experimental flow tests of ethanol and sunflower oil. and the temperature dependence of the chemical reaction rate
Flow rate (mL min−1) [5,31–33]. This behavior was observed in the runs 3 and 4. The FAEE
(%) raised from 42.73% to 59.83%, with the increment of the tem-
100 200 240 300 340 400 perature from 40 °C to 60 °C. In the runs 9, 10 and central points, the
increment was 42.62% (25 °C) to 55.56% (68 °C).
Reynolds number
Sunflower oil 3.91 7.81 9.37 11.72 13.28 15.62 The runs 1 and 2, 5 and 6, and 7 and 8 exhibited an inverse effect of
Ethanol 167.44 334.87 401.85 502.31 569.29 669.75 the temperature on the biodiesel yield. The decrease of FAEE (%) with
the increment of temperature was also observed by our research group
Santana et al. [4] and by Velickovic et al. [32]. The temperature in-
distributor, enhancing fluid mixing. fluence depends on its interaction with the molar ratio and the catalyst
Different biodiesel yields were noticed at each distributor outlet. concentration. In runs 1 and 2 (ethanol/oil molar ratio of 7 and catalyst
This behavior reinforces the importance of good flow uniformity to concentration of 0.46%), the biodiesel yield decreased from 65.19%
obtain the expected reaction performance in each millireactor, and (40 °C) to 48.82% (60 °C), in contrast with runs 3 and 4 (ethanol/oil
subsequently, a successful scale-up procedure. molar ratio of 12 and catalyst concentration of 0.46%). The only dif-
Based on the results for mixture distribution (Ф ≫ 1%) and the re- ference about this pair of runs was the ethanol/oil molar ratio. For runs
action occurrence inside the distributor, the biodiesel microplant scale- 5 and 6, and 7 and 8, the increase of temperature and molar ratio

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M.G.M. Lopes et al. Energy Conversion and Management 184 (2019) 475–487

Fig. 10. Ethanol volume fraction (α) at distributor outlets: (a) CDO13; (b) CDO52; (c) CD26.

Fig. 11. Inferior perspective of CDO52 in SketchUp software with details of inlets and outlets.

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M.G.M. Lopes et al. Energy Conversion and Management 184 (2019) 475–487

Table 7
Effects of temperature, ethanol/oil molar ratio and catalyst concentration on
biodiesel yield – FAEE (%).
Runs Temperature (°C) Ethanol/oil Catalyst concentration FAEE (%)
molar ratio (% w/w)

1 40 7 0.46 65.19
2 60 7 0.46 48.82
3 40 12 0.46 42.73
4 60 12 0.46 59.83
5 40 7 1.25 73.51
6 60 7 1.25 69.34
7 40 12 1.25 65.70
8 60 12 1.25 8.99
9 25 9.5 0.85 42.62
10 68 9.5 0.85 55.56
11 50 5 0.85 61.18
12 50 14 0.85 50.42
13 50 9.5 0.20 47.45
14 50 9.5 1.50 62.20
15 50 9.5 0.85 53.46
16 50 9.5 0.85 59.30
Fig. 12. Nonuniformity coefficient for ethanol volume fraction in CDO13,
17 50 9.5 0.85 53.34
CDO52 and CD26 distributors.
Bold value represents the maximum and minimum values obtained for the
synthesis of biodiesel in a single millireactor.

procedure. Accordingly, it is possible to define the optimal operating

conditions in order to achieve high yields in the micro-chemical plant.

4.5. Numbering-up of millireactors for biodiesel synthesis

The biodiesel synthesis scale-up was performed from the paralleli-

zation of millireactors, as shown in Fig. 6. The support structure was
assembled to arrange the millireactors. Tygon Masterflex® flexible pipes
were used to connect the distributors to the millireactors.
Su et al. [13], Yap et al. [14] and Tanaka et al. [34] highlighted the
importance of the pressure drop effect (flow resistance) on flow uni-
formity in scaled-up units. The pressure drop through the piping con-
nection (distributor–millireactor) was calculated according to Hagen-
Poiseuille Equation (Eq. (2)):
128LμQ
Δp =
πD 4 (2)

where Δp is the pressure drop, in Pa, μ is the dynamic viscosity, in Pa s,

Q is the flow rate, in m3 s−1, L is the pipe length, in m, D is the pipe
Fig. 13. Biodiesel yield (in fatty acid ethyl esters - FAEE (%)) at CDO52 outlets.
diameter, in m. The complete description of the mathematical model
used for the pressure drop calculation is detailed in the Supplementary
resulted in the FAEE (%) reduction. This behavior was related to the Information (SI). The main challenge in the first scale-up step was the
increment of the catalyst concentration, favoring parallel reactions, and minimization of flow resistance. Therefore, flow tests were performed
consequently, reducing the biodiesel yield. analyzing the influence of the length-to-diameter ratio, L/D, on the
The superior reaction performance was 73.51%, below the obtained pressure drop of each fluid stream.
from previous studies, 95.8% [4] and 99% [31], for residence times of Initially, a similar L/D was employed for both fluid streams, using
about 60 s and 12 s, respectively. However, the printed millireactors D = 3.1 mm and L = 630 mm (L/D = 203.2) for an ethanol/oil molar
operate at 75 mL min−1, whereas the microreactors of [4] and [31] ratio of 14. The results are summarized in Table 8.
made in PDMS (polydimethylsiloxane) were operated at an average of The results showed the expected behavior. Since ethanol and oil
0.58 mL min−1, an increase about 130 times. Moreover, the millireactor present different viscous characteristics, according to Eq. (2), the vis-
channels exhibited lower pressure drops due to larger cross section cous fluid generates higher pressure drop, resulting in a preferential
dimensions (millireactor: width = 3.0 mm and height = 1.0 mm; mi- path for the oil, taking a short-cut with less flow resistance, instead of
croreactor: width = 1.5 mm and height = 200 µm). flowing along the millireactor. As observed in Fig. 14, the oil stream
The larger channel dimensions of the millireactor implicate in lower
interfacial area, reducing the mass transfer rate. Another consequence Table 8
of the milliscale is related to the longer molecular diffusion path, re- Length-to-diameter ratio (L/D) on pressure drop of ethanol and oil piping.
ducing the reaction yield. These factors contributed to the observed
Fluid Stream L/D ratio Δp (Pa)
decrease on yield. The millireactor performance can be enhanced using
micromixer inside the millichannels, and will be approached by our Ethanol 203.2 193.59
research group in future studies. 112.9 107.55
Finally, the obtained experimental data provided information about Sunflower oil 203.2 10172.65
the chemical reaction efficiency, a fundamental key for the scale-up 39.8 226.65

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M.G.M. Lopes et al. Energy Conversion and Management 184 (2019) 475–487

Fig. 14. Biodiesel synthesis micro-chemical plant: (a) numbered millireactors; (b) details of oil flow through the ethanol/blue dye inlet pipe at millireactor 2.

pushes the ethanol backward to the CD26 distributor (Fig. 14b). This the deviation noticed in the biodiesel microplant were over 1%, this
phenomenon interferes in flow uniformity and, subsequently, in the two-distributor configuration provided a superior flow uniformity than
reaction yield. Therefore, an additional step was required aiming at the the one-distributor configuration, which the smallest deviation was
minimization of oil pressure drop at the millireactor inlet. 8.8% at 560 mL min−1. Moreover, the pressure drop influenced the
The pressure drop was reduced by the L/D ratio in the oil piping. flow uniformity of the scale-up unity, since low deviations (below 1%)
Thereby, the pipe length was shortened from 630 mm to 260 mm, while were noticed in the individual distributor tests.
its diameter was increased from 3.1 mm to 6.4 mm. The L/D ratio de- After the verification of admissible flow uniformity in the micro-
creased from 203.2 to 39.8. Also, an adjustment in the ethanol piping plant, the chemical reaction was carried out. Firstly, it was necessary to
was necessary. The length of this stream decreased to 350 mm, resulting verify the yield of a single millireactor, providing a performance cri-
in the L/D ratio of 112.9. terion. According to Su et al. [13] the yield of each millireactor of the
Using the configuration of L/D = 38.9 for the oil, and L/D = 112.9 microplant must be compatible with the performance of a single re-
for the ethanol, and an ethanol/oil molar ratio of 14, the microplant actor. The performance test in a single millireactor was conducted
operated for 30 min without showing oil flow toward the ethanol inlet isothermally at 50 °C, catalyst concentration of 0.85% w/w and
pipe. (Remark: the influence of L/D on the pressure drop was performed ethanol/oil molar ratio of 14 (run 12, Table 7). The ethyl esters (bio-
only for the ethanol/oil molar ratio of 14, therefore, the biodiesel diesel) yield was 50.4%. The biodiesel synthesis reaction results in the
synthesis in the micro-chemical plant was carried out at this condition microplant are summarized in Table 9. In the millireactors 1 and 4, the
and not at the optimal operating conditions observed for a single mil- biodiesel yield was 51.2% and 52.3%, respectively, close to the single
lireactor). millireactor operation. However, the millireactors 2 and 3 provided
After the initial operating run, the flow rate tests were performed in
the microplant in order to evaluate ethanol volume fraction and flow
uniformity in the millireactors. Fig. 15 presents the ethanol volume
fraction at each millireactor outlet. The ideal expected ethanol volume
fraction, based on the inlet flow rate of reactants, was 0.47 at each
millireactor.
Note that flow rates at millireactors outlets were 141 mL min−1 for
ethanol and 159 mL min−1 for sunflower oil, that is, the ethanol did not
evaporate by cavitation, confirming the assertive choice to use the
distributor CD26. Higher ethanol volume fractions were noticed in
millireactors 2 and 3, with an average value of 0.51 and 0.53, respec-
tively. The millireactors 1 and 4 showed an average ethanol volume
fraction of 0.34 and 0.42, below the expected ideal value of 0.47. The
distinct ethanol distribution by millireactors can be attributed to de-
viations resulted from the scale-up procedure, resulting in different flow
rates. The average deviation observed for ethanol volume fraction was
4.2%, an acceptable value. Yap et al. [14] observed deviations below
1% in the flow distributor tests for a three-phase system, however, in
Fig. 15. Experimental results for ethanol volume fraction (α) in the microplant
the micro-chemical plant, the deviations increased up to 7%. Despite
operation.

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M.G.M. Lopes et al. Energy Conversion and Management 184 (2019) 475–487

Table 9 enlargement to the millireactor scale was conducted using channel

Experimental results of flow rate and biodiesel synthesis yield in the micro- cross section dimensions of 3 mm × 2 mm, against 500 µm × 500 µm of
plant. the microreactors employed by Billo et al. [10]. Another advantage is
Millireactor Total flow Biodiesel yield – Residence Ethanol related to the manufacturing time. Billo et al. [10] spent three months
rate (mL FAEE (%) time (s) volume to conclude the microplant fabrication. The microplant described here
min−1) fraction composed by flow distributor, support structure and four millireactor
units can be manufactured in 40.4 h by 3D printing process.
Single unita 75 50.40 10.00 0.47
1 49.33 51.24 14.60 0.34 Another benefit of 3D printing is that the digital data file (G-code)
2 66.49 43.16 10.83 0.51 allows the microplant manufacture in any location with a suitable 3D
3 115.41 31.28 6.24 0.53 printer. Accordingly, (G-code) files or 3D objects could be stored and
4 69.47 52.33 10.36 0.42
sent via internet. Therefore, a user anywhere around the world can
a access the developed microplant and start producing the desired che-
Single unit: operation of a single millireactor unit, providing a performance
criterion. mical using a 3D Printer.
The microplant developed in this work showed higher production
biodiesel yield of 43.2% and 31.3%, respectively. rates regarding the reported in literature, of 1.83 mL min−1,
The biodiesel yield in the millireactor can be related to the residence 10 mL min−1 and 2.9 mL min−1 by Iwasaki et al. [11], Togashi et al.
time. The millireactors were designed for a residence time of 10 s. [12] and Yap et al. [14], respectively. Considering the observed ad-
However, the real residence time in millireactors 1 and 3 were different vantages, the strategy presented by this study provided an efficient way
from 10 s. Thus, even with a smaller amount of ethanol (34% v/v - for the scale-up of biodiesel synthesis.
millireactor 1), the residence time of 14.6 s resulted in superior bio-
diesel yield (51.24%). In contrast, the millireactor 3 with only 6.24 s of
5. Conclusion
residence time resulted in the lowest biodiesel yield of 31.28%, even
with the higher availability of ethanol (53% v/v, very close to the ideal
The distributor designs CD26 (conical distributors, with height of
of 47% v/v). These results reinforce the strong influence of residence
H = 26 mm) and CDO52 (conical distributors with obstacle, with
time in biodiesel yield. Comparing the millireactors 1 and 4 (α = 0.42
height of H = 52 mm) showed superior performance for ethanol and
and residence time of 10.36 s), a similar performance can be noticed.
sunflower oil flow, respectively, with average nonuniformity coeffi-
Millireactor 4 presented both ethanol volume fraction and residence
cients (Ф) of 0.36% and 0.34%. These distributor designs were classi-
time (or total flow rate) very close to the expected. Despite the milli-
fied as optimal distributors (Ф < 1%). The ethanol-oil mixture flow
reactor 2 showed a residence time close to the ideal of 10 s, its per-
uniformity resulted in high flow deviations (Ф ≫ 1%). Also, the che-
formance was below the expected (43.2%). This behavior can be at-
mical reaction occurrence was observed in the distributor. Based on
tributed to the excessive ethanol volume fraction (0.51), affecting
these results, the biodiesel synthesis scale-up microplant was config-
negatively the reaction yield. Finally, based on Table 9, the flow uni-
ured with two flow distributors (CD26 and CDO52), one for each fluid
formity influence on each millireactor performance was observed,
stream. The length-to-diameter ratios (L/D) were 38.9 for oil and 112.9
causing deviations in ethanol volume fraction and in residence times.
for ethanol. The L/D ratios were based on pressure drop and correct
The heat loss of the system was disregarded in the millireactor
flow direction of the streams. The microplant operated for 30 min
performance analysis. This consideration was based on the low re-
without present oil flow deviation towards the ethanol inlet pipe. The
sidence times (approximately 10 s) of the fluids and relative high flow
ethanol volume fraction deviation in the microplant flow rate test was
rate, promoting a fast fluid transportation from the heat source (fluid
4.2%, evidencing the pressure drop importance in the flow uniformity.
reservoir) to the millireactors.
The reaction test in the microplant using four millireactors showed
The global yield obtained in the microplant module was calculated
biodiesel yield of 51.2% (unit 1), 43.2% (unit 2), 31.3% (unit 3) and
according to Eq. (3), adapted from Su et al. [13]:
52.3% (unit 4). The difference between units 1 and 3 was attributed to
n
Qi the flow uniformity deviation in the scaled microplant, affecting
FAEEglobal (%) = ∑ NQm
·FAEEi ethanol volume fraction and residence time in the millireactors. The
i=1 (3)

where FAEEi is the ethyl esters yield at each millireactor, in %, Qi is the

outlet flow rate at each millireactor, in mL min−1, Qm is the average
outlet flow rate of the millireactors, in mL min−1, and N is the number
of millireactors used in the scale-up.
The 4-millireactor module presents a global yield of 42%, near to
the single millireactor operation yield of 50.4%, as shown in Fig. 16.
Since the global yield is weighted by the individual flow rate of the
millireactor, a slight difference in the reaction yield was noticed be-
tween the global and individual millireactor results. This difference is
mostly due to millireactors 1 and 3. Despite the higher yield obtained in
millireactor 1 (51.2%), its flow rate was very low (49 mL min−1)
comparing to the other devices. The millireactor 3 presented a high
flow rate (115 mL min−1), however, the biodiesel yield was only
31.3%. Considering a global yield of 42%, biodiesel was produced at
126.4 mL min−1 in the developed microplant using 3D printing.
Billo et al. [10] used 14,000 units to produce 2470 mL min−1 of
biodiesel. To achieve the same production rate using the 3D printed
microplant, only 79 millireactors would be required, corresponding to
20 modules of 4 millireactors. This simple scale-up is attributed to the
parallel disposition of the millireactors and, mostly, to the development Fig. 16. Fatty Acid Ethyl Ester (biodiesel) percentage obtained in individual
of optimized flow distributors. Moreover, the microreactor size units and global microplant yield.

486
M.G.M. Lopes et al.
global yield of the module was 42%, close to the single millireactor
operation (50.4%). The biodiesel production rate of the 4-millireactor
microplant was 126.4 mL min−1. The parallel operation of the milli-
reactor units, the optimized flow distributor development and the 3D
printing manufacture of the microplant parts were an efficient strategy
for biodiesel synthesis scale-up.
6. Future research
In future researches, the global yield enhancement of the microplant
module should be approached, using more efficient millireactors, as the
devices presented by Santana et al. [31]. The microplant instrumenta-
tion aiming to achieve accurate data of pressure, temperature and flow
rate in the entire microplant also must be performed. These data can
assist better flow uniformity and, subsequently, superior reaction per-
formance. Moreover, numerical studies of the microplant could predict
the fluid flow behavior, improving the global performance of the
modules. Finally, new optimal distributors design with a great number
of outlets in order to achieve higher production rates should be carried
out.
Acknowledgments
The authors acknowledge the Unicamp Scholarship Program,
CAPES and the financial support provided by FUNCAMP (Unicamp
Foundation, Process). The authors would like to thank the financial
support provided by CNPq (National Council for Scientific and
Technological Development, Process 404760/2016-3) and FAPESP (São
Paulo Research Foundation, Process 2016/20842-4).
Competing interests
The authors declare the following potential competing financial
interests - our team filed a patent covering the technology described in
this manuscript concerning the conical distributors, millireactors and
support structure presented in the present research: “SISTEMA DE
ESCALONAMENTO DE PROCESSOS QUÍMICOS, DISTRIBUIDOR
CÔNICO DE FLUIDO, ESTRUTURA DE SUPORTE DE MILIRREATORES
E MILIRREATOR”; Inventors: H.S. SANTANA, M.G.M. LOPES, V.F.
ANDOLPHATO, F.N. RUSSO, J.L. SILVA Jr., M.V.R. ESTEVOM, O.P.
TARANTO; Patent number: BR1020180090437, filed on 05/04/2018.
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.enconman.2019.01.090.
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