Fuel 224 (2018) 489–498

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Fuel
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Full Length Article

Experimental and kinetic modeling of acid oil (trans)esterification in T

supercritical ethanol
⁎
Kallynca Carvalho dos Santos, Fabiane Hamerski, Fernando A. Pedersen Voll, Marcos L. Corazza
Department of Chemical Engineering, Federal University of Paraná, 81531-980 Curitiba, PR, Brazil

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

Keywords: This work reports experimental and kinetic modeling of the coupled esterification and transesterification re-
Biodiesel actions ((trans)esterification) of a model acid oil (a mixture of soybean oil and oleic acid) using ethanol at sub
Supercritical ethanol and supercritical conditions in a continuous tubular reactor. Process variables, namely temperature
Continuous process (220–350 °C), pressure (100–200 bar) and ethanol to acid oil molar ratio (2:1–20:1) as well as the effect of the
Acid oil
initial amount of free fatty acids in the raw material were studied. The best condition for the ethylic supercritical
Kinetics
(trans)esterification of soybean oil with 20 wt% of oleic acid was 280 °C, 100 bar, and ethanol to acid oil molar
ratio of 4:1, where 80% of ester yield was reached in 60 min. It was observed that increasing the free fatty acid
content increased the reaction rate and reaction yield. The proposed autocatalytic kinetic model presented a
good fit in relation to the experimental data.

1. Introduction
Biodiesel is considered as one of the main energy source substitutes
for the fossil fuels. In addition to the environmental benefits, one of the
main advantages of biodiesel is the similarity of its properties to the
petrodiesel, so few modifications are required in the current engine
systems [1]. The conventional method for biodiesel production is the
transesterification of triacylglycerols with a short chain alcohol, for
example, methanol and ethanol, in the presence of alkali catalyst (KOH
and NaOH) generating glycerol as a by-product [2–4]. However, alka-
line transesterification is only suitable for raw materials containing low
free fatty acids (FFA) content (lower than 1 wt%), such as refined ve-
getable oils [1,5]. This specificity of the raw material makes the bio-
diesel production not economically competitive with the petroleum-
based fuel.
An alternative to overcome this disadvantage is the use of cheaper
and low-quality raw materials, such as residual oils, non-edible vege-
table oils and animal fats [6]. The use of these oils also can reduce the
wastes with a potential hazard to the environment [7]. These acid oils
normally present FFA content above the limit allowed for the transes-
terification, what leads to undesirable reactions decreasing the yields of
the desired product [8].
The residual raw material can be processed in a two steps process
(acid esterification as a pretreatment followed by alkaline transester-
ification), in a single reaction in the presence of heterogeneous acid
catalysts or performing the reaction at supercritical conditions. When
the reaction is carried out in two steps, ester yields around 90% are
obtained in about 60 min of reaction using homogeneous catalysts for
both reactions (esterification as pre-treatment and transesterification)
[1,9–12].The disadvantages of a homogeneous catalysis process applied
to biodiesel from acid raw material are the large volumes of neu-
tralization residues, additional products purification steps. The use of a
heterogeneous catalyst can overcome these disadvantages, but it needs
catalysts capable to deal with such raw materials. The heterogeneous
catalysts are less corrosive, easy to separate and reusable [13]. Many
acid catalysts can catalyze simultaneous the reactions involved in acid
oils [6,13,14]. From the results presented by Konwar et al. [6], Zhang
et al. [13] and Boz et al. [14] for example, those authors observed the
versatility of this process, since raw materials with a free fatty acid
content within 5–40% were tested. However, a common feature re-
garding these heterogeneous catalysts is the long reaction times re-
quired to obtain high conversions (higher than 8 h).
Transesterification and esterification (biodiesel production) at su-
percritical conditions have been proposed as a potential technology to
biodiesel production, in which it is possible to produce alkyl esters with
high yields in short reaction times. This technology is more tolerant to
water (moisture) and free fatty acids contents present in the raw ma-
terial than other reaction systems [8]. In addition, either transester-
ification or esterification at supercritical non-catalyzed reaction sys-
tems eliminates the need for a catalyst simplifying the purification steps
[6,15–17].

⁎
Corresponding author at: Department of Chemical Engineering, Federal University of Paraná, PO Box 19011, Polytechnic Center, Curitiba 81531-980, PR, Brazil.
E-mail address: corazza@ufpr.br (M.L. Corazza).

https://doi.org/10.1016/j.fuel.2018.03.102
Received 17 January 2018; Received in revised form 13 March 2018; Accepted 14 March 2018
0016-2361/ © 2018 Elsevier Ltd. All rights reserved.
K.C. dos Santos et al.
1.1. Transesterification reaction at supercritical conditions
Saka and Kusdiana [18] were the pioneers of the supercritical
method aiming the alkyl esters production. They showed that this
technology has a reaction rate up to 15 times faster than the alkaline
transesterification, proving the efficiency of this new technology for
producing biodiesel. Supercritical technology is a non-catalytic route,
which occurs at high temperatures and pressures (above the critical
point of the solvent). Under these conditions, the thermophysical
properties of the alcohol, such as dielectric constant, viscosity and po-
larity are significantly changed and can be tuned by manipulating the
pressure and temperature of the system [17,19]. However, a major
concerning is the thermal degradation of the alkyl esters at high tem-
perature, mainly polyunsaturated fatty acids.
Silva et al. [20] studied the thermal degradation of biodiesel pro-
duced from soybean oil and ethanol. Using thermogravimetric analysis,
they proved that soybean oil biodiesel is unstable and decompose at
temperatures above 300 °C. As mentioned by Liu et al. [21] and Lin
et al. [22], main decomposition reactions consist of isomerization,
polymerization, and pyrolysis. Ethyl fatty acid esters are relatively
stable up to 275 °C, with the pyrolysis effect being pronounced between
300 and 325 °C [21,23]. Other researchers have shown that even more
parallel reactions are involved at supercritical conditions, such as gly-
cerol dehydration and other less favorable reactions (decarboxylation,
methoxylation, and reformation) [24,25] that generates isomers,
polymers, short chain ester, light hydrocarbons and gases, carboxylic
acids, long chain alkenes, acrolein, acetol and other compounds. Pala-
cios-Nereo et al. [26] proposed to proceed the reaction using a heating
rate for preventing the thermal decomposition of the reactants and
products. In their study, those authors performed three types of reactor
heating: constant temperature reaction (CTR), gradual heating reaction
(GHR), both with a reaction time of 75 min, and hybrid reaction (HR)
combining gradual heating and a phase at constant temperature tota-
lizing reaction time between 65 and 345 min. At CTR they observed a
decrease in the ester yield in reactions above 320 °C. With GHR, de-
gradation was not observed, but low yields were obtained. With the HR
method, the authors obtained yields of 99.9% in 345 min at high tem-
peratures. They evaluated that a heating ramp can minimize the de-
composition of esters.
The supercritical transesterification reaction for different oils, such
as sunflower, palm, and soybean oil has been reported by different
authors [17,26–28]. Optimum conditions have been normally reported
to be within 325–350 °C, 160–350 bar and alcohol to oil molar ratio
33:1–43:1, and the ester yields reached were around 80–90%. Tan et al.
[29] evaluated the transesterification reaction of palm oil in super-
critical methanol (SCM) and supercritical ethanol (SCE). In their study,
they observed that for the same yield, SCE needs more time than SCM,
but the reaction conditions (temperature, pressure and molar ratio) are
milder. In relation to the kinetics of the supercritical transesterification
reaction, some authors considered the overall reaction and others have
used all the three reactions, either reversible or irreversible
[22,28,30–32]. According to these authors, all these kinetic modeling
approaches present good fit to the experimental data.
1.2. Esterification reaction at supercritical conditions
The optimal conditions of the supercritical esterification reaction
are milder than the supercritical transesterification. As presented in the
literature, supercritical esterification normally requires molar ration of
alcohol to acid around 6:1, temperatures below 300 °C and pressures
around 100 bar. Under such conditions, free fatty acid conversions of
90% can be obtained in short times (30–50 min) [33,34]. This occurs
because esterification has higher reaction rates compared to transes-
terification [35]. Moreover, these results can be enhanced by the use of
catalysts, as shown by Lokman et al. [36]. These authors used carbo-
hydrate derived solid acid catalyst in the supercritical methyl
490
Fuel 224 (2018) 489–498
esterification of a palm fatty acid distillate. They obtained ester yields
above 95% in only 5 min of reaction with 1 wt% of the catalyst. Santos
et al. [34] evaluated the experimental and kinetic modeling of super-
critical ethyl esterification of fatty acids with different chain lengths.
They considered that the reaction is self-catalyzed by the free fatty acids
themselves, and this consideration presented a good prediction of the
model in relation to the experimental data.
Some studies show the efficiency of supercritical technology to si-
multaneously convert the triglycerides and fatty acids to ester, i.e., in
the same reactor and condition it is possible to perform the transes-
terification and esterification reaction simultaneously, allowing the use
of residual raw materials [7,19]. Tsai et al. [22] processed waste
cooking oil in a supercritical reactor and concluded that the presence of
free fatty acid in the raw material contributed positively to enhance the
ester yield. In that case, the fatty acid has a dual function: reactant of
the esterification reaction and the catalyst of the transesterification
reaction. However, the literature is scarce regarding the kinetic mod-
eling involving reactions of acid oils with different free fatty acid
contents, which is very important in the process modeling, analysis,
design and optimization.
In the biodiesel production, short chain alcohols such as methanol
and ethanol are generally used. Most of the works have used methanol
due to its low cost and higher reactivity [35,37]. However, methanol is
derived from fossil fuels and its use contradicts the main objective of
biodiesel production, which is to produce a sustainable fuel. For bio-
diesel to be considered a fully renewable fuel it is necessary to use a bio-
alcohol, such as ethanol. Other advantages of ethanol are its higher
miscibility with the oil and the ethyl esters present improved cold flow
properties, lower greenhouse gases emission, they are more biode-
gradable and present higher lubricity. The disadvantage of the ethyl
ester compared to the methyl ester is the higher acid values.
[21,38–40].
Glisic and Orlović [16] presented a review considering the costs
involved in the biodiesel production and for its reduction two factors
must be taken into account, reduction in raw material cost and energy
consumption. The raw material accounts for about 60–80% of the total
biodiesel production cost. The supercritical process presents the cap-
ability to process low added value raw materials with different content
of free fatty acids and water. According to Glisic and Orlović [16], the
economy in the raw material compensates the energy costs to set the
system under the supercritical conditions of the alcohol. The energy of
the system can be optimized from the integration and optimization
involving cold and hot streams and energy supply to the reboiler in
distillation columns. Glisic and Orlović [16] found that the biodiesel
production under supercritical conditions with high molar ratio (42:1)
requires the same amount of energy as a conventional alkaline trans-
esterification process.
In general, it can be observed that the literature has pointed out the
need for high ethanol to oil molar ratios (normally ranged from 25:1 to
42:1) to obtain high ester yields [22,24,28,35]. The main reason pre-
sented is generally the low solubility of triacylglycerols in short chain
alcohols. In the case of acid raw materials (acid oils), the free fatty acids
(FFA) can act as a co-solvent promoting miscibility between the alcohol
and oil. In this case, the FFA might present a similar role of alkyl ester
in the ternary system short chain alcohol + oil + solute (alkyl ester/
FFA) presented by Dagostin et al. [41], favoring the miscibility of the
mixture under ambient conditions and reducing the need for the use of
high molar ratios.
Aiming to understand and improve the biodiesel production from
low-cost raw material and using optimized amounts of ethanol, this
study is focused on the coupled esterification and transesterification
reactions of a model acid oil (soybean oil doped with oleic acid) in a
continuous tubular reactor at low ethanol to acid oil molar ratio. The
influence of different reaction parameters, such as temperature, pres-
sure, initial free fatty acid content in the oil (Ac0) and ethanol to acid
oil molar ratio (Et:AO) on biodiesel yield were studied. A kinetic
K.C. dos Santos et al.
modeling able to predict the supercritical (trans)esterification of acid
oil with ethanol is proposed to evaluate the reactions involved in this
system and its parameters (activation energy and pre-exponential
factor) were adjusted.
2. Material and methods
2.1. Materials
Commercial refined soybean oil (Liza) was purchased in a local
market in Curitiba (state of Paraná, Brazil). Ethanol (99.8%, CAS
number 64-17-5) and oleic acid (90%, CAS number 112-80-1) were
purchased from Neon and Sigma-Aldrich, respectively.
Fatty acid profile of soybean oil was performed using a Shimadzu
chromatograph (GC 2010 Plus), a capillary column (CP-Wax 58 FFAP
CB, 50 m × 0.25 mm × 0.20 □m), flame ionization detector (FID) and
split injection mode (1:10). The injector and detector temperatures
were 250 °C and 280 °C, respectively. The oven temperature was pro-
grammed to increase from 100 °C to 175 °C at a rate of 25 °C.min−1.
After that, the temperature was increased to 230 °C at a rate of
4 °C.min−1 and maintained at 230 °C for 15 min. The carrier gas was
Helium at a flow rate of 22.8 cm3.min−1. The sample was prepared
according to the official method (Ce 2-66) of American Oil Chemists’
Society (AOCS) to convert triacylglycerol and free fatty acids of soy-
bean oil into fatty acid methyl esters (FAMEs). FAMEs were identified
by comparison with retention times of a standard mixture of FAMEs
(Supelco, MIX FAME 37, St. Louis, MO 63103, USA). Results were ex-
pressed as a percentage of each individual fatty acid present in the
sample.
2.2. Experimental procedure
Reactions of acid oil at sub and supercritical ethanol conditions
were performed in a bench-scale continuous tubular reactor. The
system consists of an HPLC pump (Shimadzu, model LC-20AT), stainless
steel tubing (316, 1/16″ OD × 0.91, Swagelok) for preheating the
mixture, stainless steel tube reactor (316, 1/8″ OD × 0.91, Swagelok)
with 22 cm3 of capacity, an electrical furnace (Sanchis Fornos
Industriais, Brazil) with maximum operating temperature of 400 °C,
heat exchanger for cooling the reactor outlet stream. Fig. 1 depicts the
schematic diagram of the experimental set up used for the reactions
evaluated in this work. The pressure in the reactor was controlled by a
backpressure valve at the reactor outlet. The temperature and pressure
were measured by four K-type thermocouples and a pressure transducer
(Huba Control), respectively, connected in a field logger register
(Novus).
Soybean oil with different initial free fatty acid contents of 5, 20 and
35 wt% of oleic acid (Ac0) and ethanol at different initial ethanol to
acid oil molar ratio (Et:AO) (2:1–20:1) were prepared by mixing known
Fig. 1. Schematic diagram of the experimental apparatus used for esterification and transesterification of acid oil at supercritical conditions.
491
Fuel 224 (2018) 489–498
amounts of each reactant, which was stirred using a magnetic stirrer
and thus pumped into the reactor. The molar ratio was calculated ac-
cording to the Eq. (1).
mol of ethanol
Et: AO =
mol of triacylglycerol + mol of oleic acid (1)
Before mixing the acid oil and the ethanol, the reactor was first fed
with pure ethanol until the system reached the conditions of tempera-
ture (220–300 °C) and pressure (100 bar). Therefore, the reaction
mixture was pumped at fixed volumetric flow (5, 2, 1, 0.5 and
0.2 cm3.min−1) and samples were collected at the reactor outlet after
reaching twice the estimated residence time for ensuring the system
reached the steady-state. For each residence time, samples were col-
lected for quantifications of water, glycerol, and free fatty acids by ti-
tration techniques. Another sample was collected and dried (12 h at
60 °C and further 2 h at 100 °C) for the quantification of fatty acid ethyl
esters and acylglycerols by gas chromatography.
2.3. Analytical methods
The water content of the reactants and samples was determined by
volumetric and coulometric titrations using automatic Karl Fischer ti-
trators, KEM MKA-610 and MKC-610 models, respectively. The FFA
quantification was performed by titration according to the method of
American Oil Chemist’s Society (AOCS) official method Ca-5a-40. The
glycerol analysis was performed by the spectrophotometric method, as
proposed by Bondioli and Bella [42].
Fatty acid ethyl esters (FAEE), mono, di and triacylglycerols were
quantified by gas chromatography (GC-2010 Plus, Shimadzu
Corporation) equipped with a Select Biodiesel column (Agilent,
15 m × 0.32 mm × 0.10 □m), flame ionization detector (FID) and split
injection mode (1:10). The injector and detector temperatures were
380 °C and 400 °C, respectively. The initial oven was 50 C and it was
programmed with the following heating ramps 15 °C/min up to 180 °C,
7 °C/min up to 230 °C, and 10 °C/min up to 380 °C, remaining for 6 min.
Helium was used as the carrier gas at a flow rate of 29.2 cm3.min−1.
Samples were prepared according to the European standard EN 14105.
Solvent and derivatizing agent used were heptane and N-methyl-N-tri-
methylsilyl trifluoroacetamide (MSTFA), respectively. The internal
standards were lauric acid, methyl palmitate and tricaprin, corre-
sponding to free fatty acids, fatty acid ethyl ester and mono-di-tria-
cylglycerols, respectively.
The reaction was evaluated in terms of ester yield ( yieldFAEE ) ac-
cording to the equation:
FAEEt
yieldFAEE (%) = 100
3TAGI + FFAI (2)
where TAGI, FFAI refers to the number of moles of triacylglycerols and
free fatty acids at the inlet of the reactor, respectively, while FAEEt
K.C. dos Santos et al. Fuel 224 (2018) 489–498

M Nj
represents the number of moles of fatty acid ethyl esters at the reactor
outlet. OF = ∑∑ (Yijtexp−Yijtcalc )2
j t=1 (14)

2.4. Kinetic modeling In this equation, and Yijtexp Yijtcalc

are the experimental and calculated
content values (wt%) of each component at the experimental point t for
Kinetic of acid oil reactions with ethanol at sub and supercritical each kinetic curve j , M is the number of kinetic curves and Nj is the
conditions of alcohol (Tc = 240.75 °C and Pc = 61.48 bar) were mod- number of experimental data for each kinetic curve. The components i
eled considering the three soybean oil transesterification reactions (Eqs. used in the objective function were DAG, MAG, FFA and FAEE. To
(3)(5)) and the esterification of acid oleic (Eq. (6)). All reactions were evaluate the correlation between the model calculations and the ex-
considered reversible, elementary and self-catalytic by the free fatty perimental data was used the root mean square deviation (rmsd ), Eq.
acid present in the reactant mixture, as shown below: (15), where NOBS is the number of total experimental runs.
k1 M Nj
TAG + ET + FFA ⥫
⥬ FAEE + DAG + FFA
k−1 (3) ∑∑ (Yijtexp−Yijtcalc )2
j t=1
k2
rmsd =
NOBS (15)
DAG + ET + FFA ⥫
⥬ FAEE + MAG + FFA
k−2 (4)
The differential equations that describe the set of reactions in the
k3 tubular reactor according to the proposed mechanism for all compo-
MAG + ET + FFA ⥫
⥬ FAEE + GLY + FFA
k−3 (5) nents are the following:

k4 dCTAG
FFA + ET + FFA ⥫
⥬ FAEE + W + FFA = −r1
dτ (16)
k−4 (6)

where TAG , DAG , MAG , ET , W , FAEE , FFA and GLY represent tria- dCDAG
= r1−r2
dτ (17)
cylglycerol, diacylglycerol, monoacylglycerol, ethanol, water, fatty acid
ethyl ester, free fatty acid and glycerol, respectively, ki and k−i are the dCMAG
forward and backward kinetic rate constants of each reaction i . = r2−r3
dτ (18)
The mass-balance in the continuous tubular reactor for a generic
component A (Eq. (7)) and the reaction rates for each reaction (Eqs. (8) dCGLY
= r3
(11)) in terms of molar concentrations were written as follows: dτ (19)

dCA dCFAEE
= rA = r1 + r2 + r3 + r4
dτ (7) dτ (20)

1 dCET
r1 = k1 ⎛⎜CTAG CET CFFA− CDAG CFAEE CFFA⎞⎟ = −r1−r2−r3−r4
dτ (21)
⎝ keq,1 ⎠ (8)
dCFFA
= −r4
1 dτ (22)
r2 = k2 ⎜⎛CDAG CET CFFA− CMAG CFAEE CFFA⎞⎟
⎝ k eq,2 ⎠ (9) dCW
= r4
dτ (23)
1
r3 = k3 ⎜⎛CMAG CET CFFA− CGLY CFAEE CFFA⎞⎟
keq,3 (10) In this work, the residence time was calculated as proposed by
⎝ ⎠
Santos et al. [34]:
1 VR q̇
r4 = k 4 ⎛⎜CFFA CET CFFA− CW CFAEE CFFA⎞⎟ τ= with υ =
⎝ k eq,4 ⎠ (11) υ ρmix ,R (24)
−3
where Cj are the molar concentration of each component j [mol.cm ], where VR is the reactor volume (22 cm3), υ is the volumetric flow, q̇ is
τ is the residence time [min], ri are the reaction rates of each reaction i the mass flow measured at the end of the reaction of each residence
[mol.min−1.cm−3] and keq,i are the equilibrium constants of each re- time [g.min−1] and ρmix ,R is the density of the initial mixture at reactor
action i , which are described by the ratio between forward and back- temperature and pressure conditions [g.cm−3]. PC-SAFT state equation
ward kinetic rate constants (Eq. (12)). was used to determine the density of the triolein, representing the
soybean oil and oleic acid. PC-SAFT parameters of pure components
ki
keq,i = were taken from the literature [34,44]. The accurate equation of state
k−i (12)
proposed by Dillon and Penoncello [45] was used for the density of
Forward and backward kinetic constants of all self-catalyzed reac- ethanol calculations at each reaction condition. The mixture density
tions were calculated by an Arrhenius-type expression, as indicated in was calculated considering an ideal solution. The kinetic model was
Eq. (13). implemented in Matlab® and the ode23s subroutine was used to solve
the differential equations system (Eqs. (16)(23)).
−E
ki = 10 ki0exp ⎛ ai ⎞
⎝ RT ⎠ (13)
3. Results and discussion
3 −1 2 −1
Pre-exponential factors ki0 [(cm .mol ) .min ], and the activa-
tion energies Eai [kJ.mol−1] of each reaction i were fitted using the The characterization of soybean oil used in the experiments pre-
experimental kinetic data measured. For the kinetic parameters esti- sented the following fatty acid profile: linoleic acid (56.86%), oleic acid
mation, the objective function (OF ) (Eq. (14)) was initially minimized (21.57%), palmitic acid (10.94%), linolenic acid (6.15%), stearic acid
using the stochastic Particle Swarm Optimization (PSO) algorithm [43] (3.31%) and 1.17% others.
and thus the solution was refined using the fminsearch subroutine, Table 1 shows the experiments performed at different conditions of
available in the MATLAB® software. temperature (T), pressure (P), initial free fatty acid content in the

492
K.C. dos Santos et al. Fuel 224 (2018) 489–498

Table 1
Experimental conditions for simultaneous esterification and transesterification of acid soybean oil in ethanol.

Run T [°C] P [bar] Ac0 [wt%] Et:AO Mole fraction** ρmix,R [g.cm−3]

Ethanol Oil Oleic acid

1 283 ± 1 102 ± 3 20 2:1 0.6994 0.1697 0.1308 0.5749

2* 278 ± 1 103 ± 1 22 4:1 0.7909 0.1125 0.0965 0.5407
3 283 ± 2 102 ± 2 20 5:1 0.8238 0.0995 0.0768 0.4804
4 280 ± 1 100 ± 1 22 8:1 0.8909 0.0590 0.0500 0.4157
5 280 ± 1 101 ± 1 20 20:1 0.9524 0.0269 0.0208 0.3326
6* 221 ± 3 100 ± 2 22 4:1 0.7864 0.1151 0.0985 0.7221
7* 249 ± 1 100 ± 2 20 4:1 0.7783 0.1252 0.0965 0.6782
8* 299 ± 1 102 ± 2 20 4:1 0.7787 0.1249 0.0964 0.4453
9 279 ± 1 202 ± 1 20 4:1 0.7912 0.1178 0.0910 0.6832
10 280 ± 1 100 ± 2 5 4:1 0.7909 0.1799 0.0292 0.5445
11 280 ± 1 102 ± 3 35 4:1 0.7908 0.0786 0.1306 0.4996
12 319 ± 2 101 ± 1 22 4:1 0.7902 0.1129 0.0968 0.3764
13 321 ± 1 102 ± 1 22 4:1 0.7896 0.1133 0.0971 0.3773
14 350 ± 1 101 ± 2 22 4:1 0.7897 0.1132 0.0971 0.3323

*
Data set used in the parameters estimation procedure; **Uncertainty in mole fraction u(x) = 0.0003. Legend: Ac0 refers to the initial free fatty acid content in oil; Et:AO is the ethanol to
acid oil molar ratio and ρmix,R is density of the reactant mixture estimated at average conditions in the inlet of the reactor.

reactant oil (A), ethanol to acid oil molar ratio (Et:AO), initial molar
fraction of components and the density of the mixture at the initial
conditions (inlet reactor). Temperature and the pressure values are
presented by the average and standard deviation of collected data along
each experiment.
Reactions at temperatures above 300 °C were not used in the kinetic
modeling due to the possible occurrence of degradation reactions, as
suggested in the literature [20,21,23–25]. The kinetic parameters were
adjusted using four kinetic set varying the temperature from 220 to
300 °C (Runs 2, 6, 7 and 8 in Table 1) and fixing the initial oleic acid
content in the soybean oil around 20 wt%, pressure of 100 bar, and
ethanol to acid oil molar ratio of 4:1. The pre-exponential factors and
the activation energies adjusted are shown in Table 2. The methanol
transesterification reaction in the range of 200–320 °C for different oils,
sunflower oil [22] and soybean oil [46], as reported by those authors,
presented activation energy of 85.5 and 92.52 kJ.mol−1, respectively.
While supercritical methanol and ethanol esterification studies [34,47]
obtained activation energy between 72 and 93.4 kJ.mol−1, respec-
tively. Farobie et al. [48] studied the transesterification of canola oil in
supercritical ethanol and considered the three transesterification reac-
tions in the kinetic modeling. The activation energy obtained in our
work are like the values reported in the literature, at least with same
magnitude. The activation energy of the direct and inverse reactions
were approximately the same value for the DAG conversion reaction, as
reported by Farobie et al. [48], and in our study this occurred for the
MAG reaction. However, the work of Farobie et al. [48] presented some
contradictions with the literature, as they can achieve maximum ester
yields in reactions at 400 °C and the literature has mentioned the oc-
currence of degradation reactions at lower temperatures [20,21,23].
The activation energy values obtained in this work are in agreement
with some similar studies presented in the literature. The values were
Table 2
Kinetic parameters adjusted for the acid soybean oil (trans)esterification in ethanol
(temperature range: 220–300 °C, P = 100 bar, Ac0 = 20 wt% and Et:AO = 4:1).
i ki0 [(cm3.mol−1)2.min−1]
1 8.48
−1 0.50
2 8.81
−2 1.18
3 8.77
−3 6.84
4 7.27
−4 0.40
compared in terms of magnitude due to the differences in the raw
materials, molar ratio and reactor type used in the different works.
Figs. 2 and 3 show the comparison between experimental and calcu-
lated values by the kinetic model regarding the components profiles
and ester yield at different reaction conditions of runs 2, 6, 7 and 8. For
the parameters estimation, the root mean square deviation (rmsd)
considering the experimental and calculated content values in terms of
DAG, MAG, FFA, and FAEE was 3.18 wt%. From the Figs. 2 and 3, and
the low value of rmsd obtained, it is possible to observe that the kinetic
model proposed was capable to represent the kinetic behavior con-
cerning the esterification and transesterification reactions of acid oil in
ethanol.
The effect of the temperature on the kinetic and ester yields was
evaluated at different temperatures varied from 220 to 300 °C with an
ethanol to acid oil ratio of 4:1, 100 bar and initial free fatty acid content
around 20 wt% (Figs. 2 and 3). The reaction rate increases with in-
creasing temperature. The ester yield (Fig. 3) increased from 58% to
82% in the temperature range from 200 to 300 °C. Wang et al. [49]
studied the transesterification of crude rapeseed oil in supercritical
methanol at condition of 250 °C, 100 bar and methanol to oil molar
ratio of 36:1 and they obtained 10% yield in ester in 20 min of reaction
without a catalyst. When comparing this result with the kinetics at
250 °C (our work), it can be observed an ester yield of 4 times higher
and with the use of lower molar ratio. From Fig. 2, it is possible to note
that the mass profiles that present the highest temperature effect are the
diacylglycerol and free fatty acids components. This behavior is justi-
fied by the enthalpy change of reaction for each individual reaction
assumed in the kinetic modeling, since the conversion reaction of DAG
and FFA were the reactions with higher enthalpies, as it can be ob-
served by the values presented as supplementary material (Section S2).
At both two higher temperatures (280 and 300 °C, Fig. 2c and d, re-
spectively), practically all triacylglycerol, diacylglycerol and free fatty
acid were consumed at the end of the reaction and monoacylglycerol is
in equilibrium. And, in Fig. 3 it is observed that the ester yield gain is
small as the temperature increases from 280 to 300 °C. Thus, these
conclusions indicate that the optimum operating condition is 280 °C.
Eai [kJ.mol−1] The kinetic parameters obtained using the set of experimental data
from runs 2, 6, 7 and 8 (Table 1) were used to predict the kinetic re-
94.96 actions at different conditions (Runs 1, 3, 4, 5, 9, 10 and 11 in Table 1)
62.40
97.50
to access the capability of the mathematical model in predicting the
30.75 esterification and transesterification of acid oil with ethanol. From
97.09 Figs. 4–9 can be observed that the model was also able to predict well
80.21 the kinetic profiles and the overall ester yields for different reaction
84.37
conditions than those used in the kinetic parameter estimation.
20.90
It is worth mentioning that TAG, glycerol and water contents were

493
K.C. dos Santos et al. Fuel 224 (2018) 489–498

Fig. 2. Comparison between experimental data (symbols) and kinetic model (lines) of TAG (□, ), DAG (+, ), MAG (○, ), FFA ( , ), FAEE ( ,
) and GLY ( , ) for the (trans)esterification of acid oil with Et:AO = 4:1 (A) 221 °C, 100 bar, Ac0 = 22 wt% (Run 6 in Table 1), (B) 249 °C, 100 bar, Ac0 = 20 wt%
(Run 7 in Table 1), (C) 278 °C, 103 bar, Ac0 = 22 wt% (Run 2 in Table 1) and (D) 299 °C, 102 bar, Ac0 = 20 wt% (Run 8 in Table 1).

no considered in the kinetic parameters estimation. All results re-

garding these compounds are merely predictions from the mathema-
tical model and its comparison with the experimental values measured
for this compounds. In the kinetic modeling, hydrolysis of TAG, DAG
and MAG were not considered due to the low free water content of
reactants. When evaluating the water content profile along the reac-
tions in the tables presented in the supplementary material (Tables
S1–S14), it is observed that the water amount produced is low and its
content during the reaction did not reduce, i.e., water is not consumed
as a reagent for the hydrolysis reactions. Another hypothesis assumed in
kinetic modeling is that the reaction is catalyzed by the free fatty acid
[34]. All these hypotheses contributed to the good performance and
predictions obtained from the kinetic model proposed.
The literature [22] have mentioned that the fatty acids for this
system have two functions: reactant of the esterification reaction and
the catalyst of the transesterification reaction. This duality of fatty acids
is observed by the results presented in Figs. 2c, 4 and 5. These figures
depict the high influence of the initial free fatty acid content in the
Fig. 3. Comparison between experimental data (symbols) and kinetic model (lines) ester
reactant over the (trans)esterification reactions at conditions around
(FAEE) yield for the (trans)esterification of acid oil with ethanol at different tempera- 280 °C, 100 bar and Et:AO of 4:1. Fig. 5 shows that ester yields of up to
tures: 220 °C (□, ); 250 °C ( , ); 280 °C ( , ) and 300 °C (△, 90% can be achieved with 35 wt% of free fatty acid present in the oil.
) (Run 2, 6, 7 and 8 in Table 1). The increase in the free fatty acid content of the raw material increased
the reaction rate, being able to consume all triacylglycerol up to around

494
K.C. dos Santos et al.
Fig. 4. Comparison between experimental data (symbols) and kinetic model (lines) profile of TAG (□,
) and GLY ( , ) for the (trans)esterification of acid oil with Et:AO = 4:1 (A) 280 °C, 100 bar, Ac0 = 5 wt% (Run 10 in Table 1) and (B) 280 °C, 102 bar,
Ac0 = 35 wt% (Run 11 in Table 1).
Fig. 5. Comparison between experimental data (symbols) and kinetic model (lines) ester
(FAEE) yield for the (trans)esterification of acid oil with ethanol at different initial free
fatty acid contents (Ac0) in the reactant oil: 5 wt% (□, ); 20 wt% ( ,
and 35 wt% ( , ) (Run 2, 10 and 11 in Table 1).
60 min (Fig. 4). It is also possible to observe that the kinetic model can
predict well the ester yields for systems with a wide range of initial free
fatty acid content.
The ethanol to oil molar ratio is the parameter that presents the
greatest differences in the literature, where its optimum conditions vary
from 12:1 to 45:1 [22,24,28,35,50,51]. The effect of ethanol to acid oil
molar ratio in the mass profile and ester yield are accessed by com-
paring the results in Figs. 2c, 6 and 7. For the lowest molar ratio tested
(Et:AO = 2:1) the lowest yield was obtained. However, for Et:AO of
20:1 the initial reaction rate was the lowest, but at the end of the re-
action the ester yield was close to that obtained for molar ratios of
4:1–8:1. From Fig. 7, it is possible to note a similarity in the kinetics of
the intermediate molar ratios. Therefore, the ethanol to acid oil molar
ratio of 4:1 is found to be an optimized condition to achieve the best
possible ester yield. In the study of supercritical (trans)esterification
reaction of soybean fried oil, performed by Gonzalez et al. [7], 75%
ester yield was obtained for a methanol to oil molar ratio of 40:1. In the
present study, we have reported ester yield of 80% with ethanol to acid
oil molar ratio ten times smaller (Fig. 7). This result proves the
Fuel 224 (2018) 489–498
), DAG (+, ), MAG (○, ), FFA ( , ), FAEE ( ,
efficiency of the transesterification and esterification reactions carried
out with low proportions of alcohol.
Figs. 2c, 8 and 9 present the effect of pressure on the (trans)ester-
ification reaction of acid oil in ethanol. It can be noted that pressure has
no significant effects on ester yield varying this factor from 100 bar to
200 bar because the compressibility of the system is low due to the high
concentration of free fatty acid and oil in ethanol. In systems with
higher alcohol to oil, e.g. 40:1, the effect of the pressure is much more
pronounced [7,52]. In addition, in the systems with high alcohol con-
centration, the density variation of the mixture is determined by the
properties of the alcohol. Even though using an approximate and
completely predictive approach for the density of the mixture (PC-SAFT
equation of state [34,44] used to estimate the density of pure soybean
oil, represented by the triolein molecule as a model, and pure oleic acid,
and ethanol density was estimated by the accurate equation of state of
Dillon and Penoncello [45] and thus the mixture density was calculated
assuming an ideal solution) the model proposed was capable to predict
the kinetic behavior at 200 bar of pressure (Fig. 8). Fig. 9 indicates that
the increase in pressure positively influences the initial reaction rate,
but the ester yield reached at the end of the reaction is practically the
) same for both pressures. The small gain of the ester yield does not
compensate for double the pressure.
3.1. Thermal degradation
A matter of concern in these reactions at supercritical conditions for
alkyl ester production is the degradation that both the raw material and
products. As mentioned earlier in this paper, some authors [20,21,23]
have presented different results about the ethyl ester yield and de-
gradation at temperatures above 300 °C. In general, they agreed that it
is unstable between 275 and 325 °C. Polyunsaturated esters, a higher
percentage of fatty acids in soybean oil, undergo thermal decomposi-
tion at 300 °C, while monounsaturated FAMEs are relatively stable at
this temperature [53]. However, some studies point out supercritical
transesterification reactions in temperatures above 300 °C and with
high yields. For example, Palacios-Nereo et al. [26] reached 90% of
ester yield at 320 °C in the soybean oil supercritical transesterification
reaction. At temperatures above 320 °C, they also noticed the de-
gradation. Fig. 10 depicts the ester yield profile along the (trans)es-
terification reaction of acid oil conducted at different temperatures
(220–350 °C) in the presented study. As expected, the temperature has a
positive influence on the yield up to 300 °C, however at temperatures
495
K.C. dos Santos et al. Fuel 224 (2018) 489–498

Fig. 6. Comparison between experimental data (symbols) and kinetic model (lines) profile of TAG (□, ), DAG (+, ), MAG (○, ), FFA ( , ), FAEE ( ,
) and GLY ( , ) for the (trans)esterification of acid oil with ethanol (A) 283 °C, 102 bar, Ac0 = 20 wt%, Et:AO = 2:1 (Run 1 in Table 1), (B) 283 °C, 102 bar,
Ac0 = 20 wt%, Et:AO = 5:1 (Run 3 in Table 1), (C) 280 °C, 100 bar, Ac0 = 22 wt%, Et:AO = 8:1 (Run 4 in Table 1) and (D) 280 °C, 101 bar, Ac0 = 20 wt%, Et:AO = 20:1 (Run 5 in
Table 1).

Fig. 7. Comparison between experimental data (symbols) and kinetic model (lines) ester Fig. 8. Comparison between experimental data (symbols) and kinetic model (lines)
(FAEE) yield for the (trans)esterification of acid oil with ethanol at different ethanol to profile of TAG (□, ), DAG (+, ), MAG (○, ), FFA ( , ),
acid oil molar ratios of 2:1 (□, ); 4:1 ( , ); 5:1 (△, ); 8:1 ( ,
FAEE ( , ) and GLY ( , ) for the (trans)esterification of acid oil
) and 20:1 ( , ) (Run 1–5 in Table 1). with Et:AO = 4:1 at 279 °C, 202 bar, Ac0 = 20 wt% (Run 9 in Table 1).

496
K.C. dos Santos et al. Fuel 224 (2018) 489–498

higher than that the ester degradation is evidenced by the decrease in

the overall ester yield measured, corroborating the results presented in
the literature. And the degradation is much more pronounced at 350 °C
than at 320 °C.
The experimental reproducibility was evaluated for the condition of
320 °C, 100 bar, 20 wt% of oleic acid in the oil (Ac0) and ethanol to acid
oil molar ratio (Et:AO) of 4:1 (Run 12 and 13 in Table 1) and the results
are showed in Fig. 11 as the average and standard deviation for the
ester yield and the residence time (different flow rates into the reactor).
The low deviations confirm the good experimental reproducibility. On
the other hand, the residence time presented a large deviation only for
the last experimental point, where the pump operates at a low feed rate.
Calculation of the reaction time uses the mass flow rate at the reactor
outlet, in which the sample is collected in one minute timed.
When evaluating the experimental results, it was verified that the
best condition for the supercritical esterification/transesterification
reaction of acid oil (20 wt% free fatty acid) in ethanol is the condition
of 280 °C, 100 bar and ethanol to acid oil of 4:1, in which an ester yield
Fig. 9. Comparison between experimental data (symbols) and kinetic model (lines) ester
around 85% was achieved in 60 min of reaction (Fig. 7). This condition
(FAEE) yield for the (trans)esterification of acid oil with ethanol at different pressures: shows the viability of using lower ethanol to the acid oil molar ratios
100 bar ( , ) and 200 bar (×, ) (Runs 2 and 9 in Table 1). those presented in the literature to reach high fatty acid ethyl ester
content from acid oils (waste materials) that can be mandatory to the
economic biodiesel production.

4. Conclusions

The esterification and transesterification reactions of acid oil with

ethanol was investigated in a continuous tubular reactor. The tem-
perature was the parameter that most influenced the reaction yield. The
acid content in the raw material increased the reaction rate varying the
raw material acidity within 5–35 wt% and reaching yields of 50–90% in
about 60 min of reaction time conducted at 280 °C, 100 bar and ethanol
to acid oil molar ratio of 4:1. This work brings two possibilities of
economics in the process of biodiesel production from the use of re-
sidual oils and low amounts of ethanol for the reaction. The kinetic data
were correlated satisfactorily with the model proposed. In addition, the
model was capable to predict satisfactorily different reactions condi-
tions than those used for the parameters adjustment. Applying this
technique (tubular reactor operating at supercritical conditions) for
producing alkyl ester from raw materials with different free fatty acid
content is a promising alternative to reduce costs and intensification of
Fig. 10. Effect of temperature on the (trans)esterification of acid oil with ethanol at
the process.
100 bar, Ac0 = 20 wt% and Et:AO = 4: 220 °C ( ), 250 °C ( ), 280 °C
( ), 300 °C ( ), 320 °C ( ) and 350 °C ( ) (Run 2, 6, 7, 8, mean
Acknowledgments
of 12 and 13 and 14 in Table 1).

The authors want to thank the Brazilian funding agencies (CNPq –

grants 406737/2013-4 and 305393/2016-2, CAPES and Fundação
Araucária) for financial support and scholarships.

Appendix A. Supplementary data

The supplementary material presents the experimental condition for

the (trans)esterification of acid oil (soybean oil with oleic acid) with
ethanol for each experimental condition presented in Table 1 (Table
S1–S14), the mean and standard deviation of the experimental condi-
tions of the runs 12 and 13 in Table 1 (Table S15) and the calculation of
the enthalpy change of reaction involved in kinetic modeling.
Supplementary data associated with this article can be found, in the
online version, at http://dx.doi.org/10.1016/j.fuel.2018.03.102.

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