J.

of Supercritical Fluids 126 (2017) 25–36

Contents lists available at ScienceDirect

The Journal of Supercritical Fluids

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

Esterification of fatty acids with supercritical ethanol in a continuous

tubular reactor
Paulo Ricardo Schizaki dos Santos a , Fernando A. Pedersen Voll a , Luiz Pereira Ramos b ,
Marcos L. Corazza a,∗
a
Department of Chemical Engineering, Federal University of Paraná, 81531-980, Curitiba, PR, Brazil
b
CEPESQ − Research Center in Applied Chemistry, Department of Chemistry, Federal University of Paraná, Curitiba, PR, Brazil

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

Article history: This work reports on the esterification kinetics of carboxylic acids of different chain lengths (valeric,
Received 21 December 2016 caprylic, lauric and oleic acids) and an industrial mixture of distillate fatty acids (MDFA) using supercritical
Received in revised form 2 March 2017 ethanol. The kinetic experiments were performed in a continuous PFR-type reactor (22 mL) under fixed
Accepted 3 March 2017
conditions of temperature and pressure. The experimental kinetics were obtained at temperatures of 220,
Available online 6 March 2017
250 and 280 ◦ C, ethanol to fatty acid molar ratio (MR) of 6:1 and 9:1 and fixed pressure of 100 bar and
modeled considering the acid self-catalyzed approach. The kinetic behavior was similar for the different
Keywords:
carboxylic/fatty acids at supercritical conditions of ethanol. The results showed high conversions (around
Biodiesel
Esterification
90%) for all samples: valeric, caprylic, lauric, oleic and for the distillate fatty acid mixture at 280 ◦ C, MR
Supercritical ethanol of 6:1 and 100 bar.
Kinetic studies © 2017 Elsevier B.V. All rights reserved.

1. Introduction
Among all biofuel alternatives, biodiesel has received a lot of
attention because it is seen as a potential alternative to replace
partially or even totally the petroleum-derived diesel due their
similarity in terms of chemical structure and energy content [1,2].
Also, biodiesel presents many advantages when compared with
conventional diesel fuel such as renewability, biodegradability,
non-toxicity, higher combustion efficiency, high flash point, inher-
ent lubricity, higher cetane number, lower sulfur and aromatic
content and it contributes to the reduction of most regulated
exhaust emissions [3–7].
Currently, more than 95% of the biodiesel is produced from
edible sources [2,7]. Therefore, its production in large scale com-
petes with the edible oil market, raising ethical questions about
food availability and further impacts in the retailing cost of edi-
ble oils and biodiesel itself [8,9]. In order to overcome this issue,
several researches have focused on the use of cheaper and non-
edible sources as alternative feedstocks for biodiesel production
[9]. The use of low-cost and/or non-edible feedstocks such as jat-
∗ Corresponding author at: Department of Chemical Engineering, Federal Univer-
sity of Paraná, PO Box 19011, Polytechnic Center, Curitiba, 81531-980, PR, Brazil.
E-mail address: corazza@ufpr.br (M.L. Corazza).
ropha [10,11], macaúba [12], palm fatty acid distillate [13], waste
animal fats [5,14] and waste cooking oils [15] have been proposed
for this purpose, among others. In this context, transesterification
and esterification reactions with short chain alcohols at supercrit-
ical conditions have been applied to low cost feedstocks due the
technical advantages of this conversion technology.
It is well known that the conventional alkaline-catalyzed trans-
esterification methods require oils and fats that are almost free
of water and free fatty acids (FFA) due the undesirable reactions
of hydrolysis and saponification [8] while supercritical processes
are not necessarily affected by these feedstock contaminants. In
addition, the biodiesel purification process are facilitated due to
the absence of residual catalyst and soaps [16,17]. Other advan-
tages about biodiesel production at supercritical conditions are
that both esterification and transesterification reaction can be per-
formed simultaneously [18] and the possibility of introducing a
supercritical co-solvent that may reduce the energy consumption
by lowering the reaction temperature and pressure [18].
The benefits of supercritical conversion processes are based
on the effect of pressure and temperature on the thermophysical
properties of both solvent and reactants, such as, their dielectric
constant, viscosity, density and polarity improving the phase sol-
ubility, decreasing mass-transfer limitations and affording higher
reaction rates [19–21].

http://dx.doi.org/10.1016/j.supflu.2017.03.002
0896-8446/© 2017 Elsevier B.V. All rights reserved.
26 P.R.S. dos Santos et al. / J. of Supercritical Fluids 126 (2017) 25–36
The supercritical route related to biodiesel production has
been widely studied in batch mode for both transesterification
[19,22] and esterification [13,23,24]. Continuous transesterifica-
tion [14,18,25] has been also studied but the use of low cost raw
materials has not been explored inasmuch depth.
Minami and Saka [26] produced methyl esters in a two-step
supercritical process. First, rapeseed oil was treated in subcritical
water for the hydrolysis of triacylglycerols (TAG) to produce FFAs.
These authors carried out the hydrolysis of TAG and the methyl
esterification of oleic acid separately, where oleic acid was used to
represent the mixture of fatty acids that was obtained by hydrolysis
of rapeseed oil. Oleic acid was mixed with methanol and esterified
under supercritical conditions at 290 ◦ C and 200 bar, resulting in a
yield of 90% in FAME in 15 min. It is worth mentioning that both
reactions were carried out independently. As mentioned by the
authors, the two step process can be carried out at mild conditions,
needing less methanol excess than classical esterification methods
and consequently reducing the energy consumption for unreacted
alcohol recovery after the reaction conversion. Moreover, Minami
and Saka [26] also introduced the concept of auto-catalytic esterifi-
cation, in which the fatty acids were found to act as an acid catalyst.
Lokman et al. [13] studied the catalytic esterification of a dis-
tillate of palm fatty acids at sub and supercritical conditions using
methanol in a batch reactor and a carbohydrate-derived solid acid
catalyst. These authors obtained high yields (above 95%) of fatty
acid methyl esters (FAME) at 290 ◦ C using a methanol to distillate
of palm fatty acids molar ratio of 6:1, 1 wt% catalyst and 5 min of
reaction time. Alenezi et al. [23] reported the esterification of FFA
(mostly oleic acid) with supercritical methanol in a batch reactor
at 250–320 ◦ C and 10 MPa. A systematic study was presented about
the influence of temperature, stirring speed and methanol to FFA
molar ratio in the production of FAMEs. Fast reaction rates were
reported at 290 and 320 ◦ C, where the equilibrium conversion was
reached in only 5 min. A kinetic study including kinetic modeling
and was also reported by these authors.
Marchetti and Errazu [27] compared, from both technical and
economic point of view, four industrial plants for the continuous
production of FAMEs from 36,036 ton/yr of acid oils containing 5%
FFA that were based on the following conversion technologies: i)
homogeneous alkaline catalysis with pre-esterification, ii) homo-
geneous acid catalysis, iii) heterogeneous solid catalysis and iv)
supercritical technology. The supercritical process required higher
alcohol to oil molar ratios (42:1) and higher temperatures (about
350 ◦ C) than those of the other three systems but the obtained
FFA conversions (about 98%) were also much higher. By comparing
these technologies, it can be verified that the supercritical route
was technically suitable but not economically viable because of its
higher capital and operating costs. On the other hand, this route was
more environmentally friendly because it produced less effluent
compared to the other conventional processes.
Although the fundamentals of esterification at supercritical con-
ditions are well known, from our best knowledge and also as
mentioned by Alenezi et al. [23], there is a lack of information about
the kinetics of esterification using supercritical ethanol systems.
In this context, the main goal of this work was to investigate the
kinetics of different carboxylic/fatty acids (C5–C18) with supercrit-
ical ethanol in a bench-scale continuous reactor. These studies are
important to understand the technical advantages and/or limita-
tions of this biodiesel production route and to seek the optimal
process conditions to achieve higher ethyl ester yields, such as
the reaction temperature, pressure and ethanol to acid molar
ratio. Additionally, the supercritical technology was applied to
obtain ethyl esters from a residual feedstock whose low cost may
equalize the economics of both supercritical and conventional
routes.
2. Materials and methods
2.1. Experimental section
The esterification reactions of valeric acid (pentanoic acid,
C5 H10 O2, C5:0, ≥99%, Sigma-Aldrich), caprylic acid (octanoic acid,
C8 H16 O2 , C8:0, ≥99.5%, Vetec), lauric acid (C12 H24 O2 , C12:0, ≥98%,
Sigma-Aldrich), oleic acid (C18 H34 O2 , C18:1, technical grade 90%,
Sigma-Aldrich) and the mixture of the distillate fatty acids (MDFA),
kindly provided by Potencial Biodiesel S/A (Lapa, Paraná, Brazil),
containing a FFA profile of C14:0, C16:0, C18:0 and C18:1, were
performed with ethanol (99.8% vol., Neon) using a tubular contin-
uous reactor. The reactor consisted of a stainless steel column (316
1/8 OD x 0.91, Swagelok) with 22 ± 1 cm3 capacity (free-volume)
that was inserted into an electrical furnace (maximum operat-
ing temperature of 420 ◦ C) (Sanchis Fornos Industriais, Brazil).
The reaction mixture was pumped into the heated reactor by
an HPLC pump (Shimadzu, model LC-20AT) at a fixed volumet-
ric flow (uncertainty of flow rate within 0.01, maximum flow rate
of 10 cm3 min−1 ). The pressure was adjusted by using two micro-
metric needle valves (fine-tuning). The temperature profile and
the pressure inside the reactor were monitored by four K-type
thermocouples (uncertainty within 1 ◦ C) and one pressure trans-
ducer (Huba Control, uncertainty within 0.025 MPa), respectively.
A schematic diagram for the reaction set-up is presented in Fig. 1.
Samples were collected at the reactor outlet after the steady
state condition had been reached at each volumetric flow. The
steady-state was considered after an operating time at least twice
of the residence time of the reaction.
The free acid content in the collected samples (in terms of
valeric, caprylic, lauric, oleic and distilled fatty acid mixture) were
measured according to the American Oil Chemist’s Society (AOCS)
official method Ca-5a-40, which presents a satisfactory correlation
with the Nuclear Magnetic Resonance analytical method [28,29].
The molar mass of oleic acid was used as the representative com-
ponent for the industrial MDFA used in this work.
The conversion of valeric, caprilic, lauric and oleic acids as well
as the mixture of distilled fatty acids (MDFA) to ethyl esters was
defined as:
InitialAcidity − FinalAcidity
Conversion(%) = 100x (1)
InitialAcidity
In Eq. (1), initial and final acidities correspond to prepared solution
of fatty acid and ethanol (at different MR condition) and mixture
collected at the reactor outlet after the residence time, respectively.
2.2. Experimental kinetics and modeling
Kinetics data were obtained at subcritical (220 ◦ C and 100 bar)
and supercritical conditions of the ethanol (100 bar, 250 and 280 ◦ C;
ethanol: Tc = 240.75 ◦ C and Pc = 61.48 bar). The experiments were
performed using one carboxylic acid (valeric acid) and different
fatty acids (caprylic, lauric and oleic acids) plus the MDFA mix-
ture. The volumetric flow rates varied from 0.2 to 10.0 mL min−1 ,
in which different reaction residence times were defined. For sim-
plification, all acids used in this study are mentioned as fatty acids
in the following descriptions.
The kinetics of fatty acid esterification with ethanol at high tem-
perature and pressure conditions were modeled considering that
these esterification reactions are self-catalyzed by the free fatty
acids. The following equation was used (2):
k1
→
A + A + Et E+W +A (2)
←−
k2
 P.R.S. dos Santos et al. / J. of Supercritical Fluids 126 (2017) 25–36 27

Fig. 1. Schematic diagram of the experimental apparatus. FE − reactional mixture; P − HPLC pump; F – electrical furnace; R – tubular reactor; T1–furnace thermocouple; T2,
T3, T5–thermocouples; T4–on line thermocouple; CS – cooling system; PT – pressure transducer; V1–needle valve; V2–micrometric valve; DA – data acquisition system; PR
– products.

where A, Et, E and W represent the fatty acid, ethanol, ester and An Arrhenius-type equation was used to calculate the kinetic
water mole number, and k1 and k2 are the forward and backward constants considering both direct and reversible self-catalyzed
kinetic rate constants. reactions, as indicated in Eq. (8):
Considering the mass-balance in the continuous tubular reactor
and the elementary mechanism presented in Eq. (2), the kinetic  
−Eaj
model of the self-catalyzed acid esterification with ethanol was kj = 10k0,j exp (j = 1, 2) (8)
RT
modeled according to the following Eqs. (3)–(11):
dXA 1
= (−rA ) (3) Therefore, the parameters to be adjusted are the pre-
d CA0
exponential (or frequency) factors k0,1 , k0,2 , and the activation
where XA is the conversion of the fatty acid, CA0 is the acid concen- Ea Ea
energies R1 , R2 .
tration at the inlet of the reactor (at T and P of the reaction), ␶ is the The objective function (OF) (Eq. (9)) was minimized using the
reaction residence time and rA is the net reaction rate that is define stochastic Particle Swarm Optimization (PSO) algorithm [29] for
by the following equation: pre-estimating the parameters k0,1 , k0,2 , Ea1 ⁄R and Ea2 ⁄R. Then, the
 
(rA ) = k1 CA CEt − CE CW ⁄Ke CA (4) parameter values obtained from PSO optimization were used as
initial guesses for the kinetic parameters, which were optimized
With, using the fminsearch subroutine from Matlab .
®

k1
Ke = (5)
k2 Nj
 2

M 
Exp Calc
and, FO = XA,ji − XA,ji (9)
CEt = CEt0 − XA CA0 j i

CE = CE0 + XA CA0 (6) Exp Calc are the experimental and calculated conver-
where XA,ji and XA,ji
CW = CW 0 + XA CA0 sion values (%) of each experimental point “i” for each kinetic curve
The initial concentrations of water (CW 0 ) and esters (CE0 ) were “j” used in this study, M is the number of kinetic curves and Nj is the
considered equal to zero, and the molar concentration of ethanol number of experimental data for each kinetic curve. Furthermore,
and fatty acid were given by: the root mean square deviation (rmsd) was used to evaluate the
  correlation between the model predictions and the experimental
¯ mix,R data.
CA0 = xA0
xA0 MMA + xEt MMEt
  (7)

M Nj
¯ mix,R
 2
CEt0 = xEt0
Exp
xA0 MMA + xEt MMEt
Calc
XA,ji − XA,ji

j i=1
where xA0 and xEt0 are the acid and ethanol mole fractions, respec- rmsd(%) = 100 (10)
tively (obtained from the ethanol to fatty acid molar ration that NOBS
was fed into the reactor), ¯ mix,R is the density of the reactant mix-
ture (in g cm−3 ) at the inlet condition of the reactor (under selected where NOBS is the number of total experimental runs (MxNj ). It is
temperature and pressure condition), and MMA and MMEt are the worth to mention that the kinetic parameters were obtained from
acid and ethanol molar masses, respectively. Details about the TR a global estimation by correlating the kinetics data taking account
and PR parameters are given below. all isotherms pertaining to each fatty acid esterification system.
28 P.R.S. dos Santos et al. / J. of Supercritical Fluids 126 (2017) 25–36

0.9

0.8

0.7

Lauric Acid Con version (MR: 3:1)

0.6 (0%)
Density (g.cm-3)

(100%)

0.5
Lauric Acid Con version (MR: 6:1)
(0%)
0.4 (100 %)

Lauric Acid Con version (MR: 9:1)

0.3 (0%)
(100 %)

0.2 Lauric Acid Conversion (MR: 12:1)

(0%)
(100%)
0.1
0 50 10 0 15 0 20 0 25 0 30 0 35 0
Tempe rature (oC)

Fig. 2. Density-temperature diagram for the quaternary system lauric acid + ethanol + ethyl laurate + water at different ethanol to lauric acid molar ratios (MR) and extent of
reaction (lauric acid conversion). Pressure was fixed at 100 bar.

3. Results and discussion ␧/k = 233.02 K) and ethyl octanoate (m = 5.4672, ␴ = 3.6689 A,
␧/k = 244.29 K).
3.1. Residence time Fig. 2 depicts a density-temperature diagram of different
mixtures of ethanol + lauric acid + ethyl laurate + water systems
In this work, the residence time (␶, min) in the tubular reactor considering 0% and 100% of lauric acid conversion at different
was calculated by Eqs. (11) and (12): ethanol to lauric acid molar ratios. As estimated by the PC-SAFT
EoS, the density of the mixture is almost the same throughout the
VR reaction course. Thus, density values considered as a function of
= (11)
v0 TR and PR to calculate the reaction residence times of the reaction.
Table 1 presents the density values of the reaction mixture that
with,
were estimated using the PC-SAFT EoS as mentioned above.
q̇ v 
v0 = = in in (12)
¯ mix,R ¯ mix,R Table 1
Density values calculated using the PC-SAFT EoS for different ethanol + fatty acid
reaction mixtures.
where VR is the free-volume in the tubular reactor (22 cm3 ), v0
is the volumetric flow rate (cm3 .min−1 ) of the reactant mixture P (bar) T (◦ C) Ethanol to fatty Density
(ethanol plus acid solutions) at the inlet reaction conditions (TR and acid molar ratio (g cm−3 )

PR ), q̇ is the total mass flow rate (g min−1 ) of the feed containing Ethanol + lauric acid esterification system
the reaction mixture, vin is the volumetric flow rate (cm3 min−1 ) 100 25 6:1 0.8301
180 0.6867
of the reaction mixture at the pump conditions (around 25 ◦ C and
220 0.6308
PR ), in is the density of the reactant mixture (g cm−3 ) at inlet 250 0.5783
pump conditions and ¯ mix,R is the density of the mixture (g cm−3 ) 280 0.5091
at reaction conditions (TR and PR ). The density of the reaction 100 250 9:1 0.4716
mixture at both conditions, in and ¯ mix,R , were calculated using Ethanol + oleic acid esterification system
the PC-SAFT equation of state [30–32]. PC-SAFT parameters of 100 25 6:1 0.8318
pure ethanol, ethyl laurate and ethyl oleate were taken from the 220 0.6452
250 0.5996
literature [31,32] and water parameters were taken from Gross and
280 0.5434
Sadowski [30]. PC-SAFT parameters of other compounds were fit-
ted using vapor pressure and density experimental data, where the Ethanol + pentanoic esterification system
100 25 6:1 0.8199
absolute deviations were all less than 2% for both vapor pressure
220 0.6000
and density: valeric acid (pentanoic acid) (m = 4.1544, ␴ = 3.3280 A, 250 0.5272
␧/k = 246.81 K, ␬HB = 0.07434 and ␧HB /k = 2126.91 K), octanoic 280 0.3908
acid (m = 6.1103, ␴ = 3.6766 A, ␧/k = 231.75 K, ␬HB = 0.033495 Ethanol + octanoic esterification system
and ␧HB /k = 2467.77 K), lauric acid (m = 9.4996, ␴ = 3.1715 A, 100 25 6:1 0.8315
␧/k = 229.11 K, ␬HB = 0.051364 and ␧HB /k = 833.88 K), oleic acid 220 0.6305
(m = 8.7192, ␴ = 3.7118 A, ␧/k = 254.78 K, ␬HB = 0.018312 and 250 0.5743
280 0.4969
␧HB /k = 810.92 K), ethyl pentanoate (m = 4.6589, ␴ = 3.4868 A,
 P.R.S. dos Santos et al. / J. of Supercritical Fluids 126 (2017) 25–36 29

16

14

12

10
Acidity (%)

0
0 20 40 60 80 100 120 140

Time (min)
Fig. 3. Acidity profile during 120 min of lauric acid esterification at the constant volumetric flow rate of 0.5 mL min−1 , using an ethanol to lauric acid molar ratio of 6:1,
100 bar and different temperatures: 220 ◦ C (), 250 ◦ C (䊐) and 280 ◦ C (䊉). Lines are provided just to improve visualization.

Several experimental runs were carried out to assess changes in
the acidity profile of the reaction mixture. Initially, the reactor was
fed with pure ethanol until the desired temperature and pressure
were reached. Thus, it was fed with the reaction mixture contain-
ing an ethanol to lauric acid molar ratio of 6:1, all conditions at
P = 100 bar. The reaction was carried out at 220, 250 and 280 ◦ C
and the time was counted from the moment that the reaction mix-
ture was injected with the HPLC pump at an adjusted volumetric
flow rate of 0.5 mL min−1 . Fig. 3 shows that from time zero until
about 40 min the acidity values are close to zero because the mix-
ture inside the reactor consisted of pure ethanol. Beyond 40 min,
the acidity values increased sharply until the steady state condition

85

80

75
Conversion (%)

70

65

60

55
70 85 100 125 150

Pressure (bar)
Fig. 4. Effect of pressure on the conversion of lauric acid to ethyl laurate at 250 (䊏) and 280 ◦ C (䊐), ethanol to acid molar ratio of 6:1 and volumetric flow rate of 1 cm3 min−1 .
The experimental runs were carried out in duplicate and maximum standard uncertainty U(Conversion%) was 3.03, with 95% confidence. Lines are straight-line fittings.
30 P.R.S. dos Santos et al. / J. of Supercritical Fluids 126 (2017) 25–36

Table 2
Kinetic parameters adjusted for the self-catalyzed esterification of fatty acids with ethanol at supercritical conditions.

Acid k0,1 k0,2 Ea1 /R Ea2 /R rmsd (%)

(cm3 mol−1 )2 min−1 (cm3 mol−1 )2 min−1 (K−1 ) (K−1 )

Pentanoic (Valeric) 13.15 12.94 10802.58 10802.57 3.51

Octanoic (Caprylic) 13.25 12.93 10939.88 10939.88 4.41
Lauric 15.50 15.16 13261.45 13261.44 3.77
Oleic 13.89 13.29 11231.49 10834.55 3.41
MDFA 12.69 10.31 9896.06 6957.92 6.43

was reached. Higher temperatures resulted in higher fatty acid con-
versions. At 220 ◦ C, the transition of acidity around 40 min is less
pronounced than 250 ◦ C and 280 ◦ C because the density of the mix-
ture decreased as the temperature was increased and consequently
the residence time is lower at higher temperatures.
3.2. Effect of pressure
To assess the effect of pressure on the esterification reaction at
ethanol supercritical condition in the continuous reactor, various
experiments were carried out under at a same ethanol to lauric acid
molar ratio (6:1) and fixed volumetric flow rate of (1 cm3 .min−1) .
The pressure at 250 and 280 ◦ C was varied from 70 to 150 bar
and the reactions were carried out in duplicates. The experimen-
tal points as well as their corresponding error bars (one unit of
standard deviation) are presented in Fig. 4.
The conversion of lauric acid to ethyl laurate presented a small
increase with an increase in the reaction pressure. A difference of
about 10% in fatty acid conversion was observed by varying the
pressure from 70 to 150 bar at the same temperature condition.
Therefore, the operating pressure of 100 bar was selected to study
the esterification kinetics of the different fatty acid systems with
ethanol.
3.3. Kinetic study
The adjusted kinetic parameters for the esterification of dif-
ferent carboxylic and/or fatty acids with ethanol at supercritical
conditions are presented in Table 2. Low rmsd values were obtained
even for kinetic esterification of MDFA, in which the oleic acid was
used as the model component to represent the unknown and com-
plex mixture of fatty acids. Therefore, the kinetic model proposed
was capable of correlating the experimental kinetics obtained for
all studied systems.
Fig. 5 shows the kinetic data for the esterification of lauric acid
with ethanol. The kinetic parameters were fitted using an ethanol
to acid (MR) of 6:1, 100 bar and the temperatures of 220, 250 and
280 ◦ C (Table 2). The kinetic parameters obtained using these data
were used to predict the kinetics at 180 ◦ C and 310 ◦ C with an
ethanol to acid molar ratio of 6:1, at 250 ◦ C with an ethanol to acid
molar ratio of 9:1, all experiments at 100 bar. The kinetic model
was capable to predict the kinetics of lauric acid esterification with
ethanol at the different temperatures and reactant molar ratios that
ones used to fit the kinetic parameters. It is also noticed that the
kinetic at 310 ◦ C is almost overlapped on 280 ◦ C showing a small
increase in the equilibrium conversion. Thus we adopted 280 ◦ C as
the maximum temperature in this study. The effect of tempera-

Fig. 5. Experimental (symbols) and calculated (kinetic model lines) conversions of lauric acid to ethyl laurate at different temperatures (180–310 ◦ C) and ethanol to acid
molar ratio (RM of 6:1 and 9:1) and fixed pressure of 100 bar.
 P.R.S. dos Santos et al. / J. of Supercritical Fluids 126 (2017) 25–36 31

Fig. 6. Experimental (symbols) and calculated (kinetic model lines) conversions of (A) oleic acid to ethyl oleate, (B) caprylic acid to ethyl caproate, (C) valeric acid to ethyl
valerate at different temperatures (220–280 ◦ C), at ethanol to acid molar ratio of 6:1 and 100 bar.
32 P.R.S. dos Santos et al. / J. of Supercritical Fluids 126 (2017) 25–36
Fig. 6. (Continued)
ture on reaction conversion was also assessed for all other acids
used in this work using an ethanol to acid molar ratio at 6:1 and
100 bar. Reactions were carried out at 220, 250 and 280 ◦ C and the
results are shown in Fig. 6(A)–(C), where the experimental results
and the calculated values using the proposed kinetic model are
compared. As expected, a rise in temperature led the systems to
higher conversions and increased initial reaction rates. At 280 ◦ C,
conversions around 80% were obtained for all compounds at rel-
atively short residence times of around 10 min, which might be
seen as an advantage of the proposed reactor design and operat-
ing conditions. Unquestionably, these are important points for the
economic viability of this route, since supercritical technologies
require equipment with a high mechanical resistance.
Variations in the chain length (C5:0, C8:0, C12:0 and C18:1)
resulted in small differences not only in the reaction rates but also
in the overall kinetics of acid esterification with ethanol at least
for the three temperatures tested in this study. In addition, the
kinetic curves of Figs. 5 and 6 reached almost the same reaction
conversion at residence times around 100 min, regardless of the
properties of the starting material. By contrast, slightly differences
in reaction conversion were observed at shorter residence times for
the different organic acids involved in this study.
The kinetic results obtained in this work presented a simi-
lar behavior when compared to esterification with methanol at
supercritical conditions. However, the equilibrium conversions for
esterification with ethanol are lower than methanol. Tsai et al. [18]
performed oleic acid esterification with supercritical methanol in
a similar continuous system using a methanol to fatty acid molar
ratio of 5:1, temperatures of 220, 240 and 260 ◦ C and at 100 bar.
The authors reached equilibrium conversions over 95% in reaction
times around 20 min at these three temperatures. Alenezi et al. [23]
studied the supercritical esterification of a mixture of fatty acids
(mainly oleic acid, 88 wt%) with methanol at 270 ◦ C, 100 bar and an
alcohol to molar fatty acids molar ratio of 7:1 in a batch reactor sys-
tem. The authors reached conversion about 90% in 30 min, whereas
we reached 85% in 30 min of reaction time for the ethyl esterifica-
tion of oleic acid at 280 ◦ C. The differences observed in the kinetic
behavior of fatty acids esterification with methanol and ethanol
can be attributed to lower reactivity of ethanol when compared to
methanol.
The kinetics of MDFA esterification with ethanol was investi-
gated at 220, 250 and 280 ◦ C using a fixed ethanol to MDFA molar
ratio of 8.77:1 to improve the miscibility of MDFA with ethanol at
room temperature. In Fig. 7, the experimental kinetic data of MDFA
esterification are compared to the calculated values provided by the
kinetic model, in which the molar mass and the PC-SAFT parame-
ters of oleic acid and the ethyl oleate were used to represent the
MDFA and the mixture of ethyl esters of MDFA, respectively. It is
observed that this approach was useful and capable of representing
the esterification kinetics of a complex mixture of free fatty acids.
In a general way, following the similarity observed in the kinetic
behavior of four pure carboxylic/fatty acids (Figs. 5 and 6) with dif-
ferent chain length and properties it is observed that the oleic acid
can be used to represent the kinetic behavior of complex mixtures
of fatty acids in terms of kinetic modeling and reactor design.
The proposed kinetic approach adjusted well to the time course
data that were obtained for the MDFA mixture, as it can be seen
in Fig. 7, particularly if the complexity of that fatty acid mixture
is considered. In addition, relatively high conversion values were
achieved in short residence time, even using this complex fatty
acids mixture as feedstock. Since the cost of the raw material is
the most important component of the biodiesel production cost,
the use of this industrial residue may represent an important argu-
ment for demonstrating the economic viability of the supercritical
route because it may compensate its otherwise higher capital and
operating costs.
 P.R.S. dos Santos et al. / J. of Supercritical Fluids 126 (2017) 25–36 33

Fig. 7. Experimental (symbols) and calculated (kinetic model lines) conversions of MDFA at different temperatures (220–280 ◦ C), at ethanol to acid molar ratio of 9:1 and
100 bar.

Fig. 8. Pressure-temperature diagram for different carboxylic/fatty acids(1) + ethanol(2) at overall molar composition of x1 = 0.1429 and x2 = 0.8571 (simulating ethanol to
acid molar ratio of 6:1 and 0% of reaction conversion). Continues and dashed lines represent the bubble and dew point lines respectively.
34 P.R.S. dos Santos et al. / J. of Supercritical Fluids 126 (2017) 25–36
Fig. 9. Pressure-temperature diagrams for carboxylic/fatty acids(1) + ethanol(2) + carboxylic/fatty acid ethyl esters(3) + water(4) at an overall molar compositions at 0%
conversion (x1 = 0.1429, x2 = 0.8571, x3 = 0 and x4 = 0) and 100% conversion (x1 = 0, x2 = 0.7143, x3 = 0.1429 and x4 = 0.1429) (ethanol to carboxylic/fatty acid of 6:1). Continues
and dashed lines represent the bubble and dew point lines respectively.
3.4. Phase behavior analysis
Following the approach presented by Osmieri et al. [33], we
performed a phase behavior analyses of the supercritical esterifica-
tion system. As mentioned by those authors, the phase equilibrium
diagram is an important tool to understand and assure that the reac-
tion is placed in a homogeneous-phase region, where the presence
of a single phase increases the reaction kinetics [33]. Figs. 8 and 9
depict the pressure-temperature diagrams of the systems related
to the esterification of different carboxylic/fatty acids with ethanol
evaluated in this work. PC-SAFT equation of stated was used to per-
form this phase behavior analysis considering all binary interaction
parameters equal to zero (kij = 0). All simulations were performed
using the Aspen Plus V8.4 (30.0.033) software.
In Fig. 8, the pressure-temperature diagram for carboxylic/fatty
acids + ethanol systems (0% conversion) are presented. The vapor-
liquid region decreases as the carbon chain length is decreased,
showing that the system valeric acid + ethanol is much more soluble
than the system oleic acid + ethanol. Fig. 9(A–D) present the phase
behavior for the systems considering the mixture at 0 and 100% of
conversion for the different acids used in this work. Although the
water is produced during the reaction, it can be observed that as
the reaction (esterification) takes place the vapor-liquid envelops
decrease (system becomes more soluble) due to the ethyl ester
to ethanol and water to ethanol interactions into the system. In
addition, the liquid saturation points (bubble point lines) occur at
slightly higher pressure for shorter chain length acids, showing that
the shorter ethyl esters (octanoate and valerate) are more volatile
than long chain esters. From Figs. 8 and 9 it can also be noticed
that the critical point of the binary fatty/carboxylic acid + ethanol
decrease as the acid carbon chain decreases and the critical point
of the mixtures (acids, ethanol, ethyl esters and water) are slightly
changed following the reaction course (0–100% of conversion).
These behaviors indicate that all kinetic conditions evaluated in
our work were placed in a one-phase region without transition
occurrence during the reaction.
As an additional analysis, in Fig. 10 the phase behavior of lau-
ric acid + ethanol was simulated varying the ethanol to lauric acid
molar ratio from 1:1 to 30:1. It can be observed that due to the
high affinity and association between ethanol and carboxyl/fatty
acid the phase equilibrium of such components follows a Type I
phase behavior, according to the Konynenburg and Scott classifi-
cation [34,35]. Even using high molar ratio of ethanol to acids, the
phase behavior diagram of systems related to the carboxylic or fatty
acids with ethanol must be carefully considered to assure that the
reaction is place at homogeneous phase conditions.
4. Conclusions
Ethylic esterification of valeric, caprylic, lauric, oleic acids and
mixture of distillate fatty acids (MDFA) were investigated at sub
and supercritical conditions in a continuous micro tubular reactor.
Considering the temperature range investigated in this work, a sim-
ilar kinetic behavior was observed among four pure carboxylic/fatty
 P.R.S. dos Santos et al. / J. of Supercritical Fluids 126 (2017) 25–36
Fig. 10. Pressure-temperature diagram for the lauric acid(1) + ethanol(2) system at different ethanol to lauric acid of molar ratios.
acids suggesting that the differences in chain length did not influ-
ence significantly the kinetic behavior, and it can be confirmed by
the kinetic of the mixture of distillate fatty acids used in this study.
This raw material represents a more complex matrix than pure fatty
acids, however the kinetics behavior was very similar to the simpler
feedstocks and it can be represented by pure fatty acids.
The proposed kinetic model is in good agreement with the
experimental measured values of ethyl esters conversions and rmsd
values have varied between 3.41% and 6.43% (considering the pre-
dictions of MDFA esterification) in terms of ethyl esters conversion.
The model used to represent the systems as well as the kinet-
ics parameters adjusted can be useful to better understanding of
FFA esterification kinetics at supercritical conditions in a continu-
ous reactor, using a real and complex material as feedstock. This
residual material represents an important, promising and cheaper
feedstock.
The temperature was an important factor to improve ethyl
esters conversion, and this fact can be observed by faster kinet-
ics at 280 ◦ C, in which high conversions (about 90% for all fatty
acids) can be achieved in shorter time (10 min) for all pure fatty
acids as well as MDFA. Aiming the biodiesel production from waste
fatty material, these results can represent a significant advantage
in terms of reactor design considering the esterification of fatty
acids at ethanol supercritical conditions. Additionally, the similar-
ity among the results of pure fatty acids and MDFA kinetics can
represent an important point for the biodiesel process modeling
and optimization trough supercritical process.
Acknowledgments
The authors are grateful to CNPq (Grant 406737/2013-4) and to
Fundação Araucária (Brazilian Agencies) for providing both finan-
cial support and scholarships to carry out this study.
35
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