Fuel 244 (2019) 569–579

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Full Length Article

Multifunctionality of zinc carboxylate to produce acylglycerols, free fatty T

acids and fatty acids methyl esters
Alexis M. Escorsima, Fabiane Hamerskib, Luiz P. Ramosa, Marcos L. Corazzab,
Claudiney S. Cordeiroa,
⁎

a
Research Center in Applied Chemistry (CEPESQ), Department of Chemistry, Federal University of Paraná (UFPR), PO Box 19032, CEP 81531-980 Curitiba, PR, Brazil
b
Department of Chemical Engineering, Federal University of Paraná (UFPR), PO Box 19011, CEP 81531-990 Curitiba, PR, Brazil

GRAPHICAL ABSTRACT

FFA

TAG
MeOH
TAG

+
H2O

Hydrolyzed Oil
FAME

H2O

ZS ZS

ARTICLE INFO ABSTRACT

Keywords: Hydrolysis of acid oils is an important alternative for the production of non-ionic surfactants and fatty acids that
Palm oil can be converted to fatty acid methyl esters (biodiesel) by esterification. In this work, hydrolysis of palm oil was
Hydrolysis initially carried out in subcritical water using zinc stearate as catalyst. The experiments were performed in a
Simultaneous esterification and CSTR-type reactor where the effect of temperature (140–190 °C), palm oil-to-water MR (1:10–1:53) and catalyst
transesterification
amount (2–10 wt%) were evaluated. High contents of free fatty acids (up to 60 wt%) with 35 wt% diacylgly-
Fatty acid methyl esters
cerols and 20 wt% monoacylglycerols were obtained. Also, zinc stearate maintained its catalytic activity for palm
Glycerin
oil hydrolysis for five consecutive reuse cycles but changes in the catalyst chemical composition were observed,
mostly due to the conversion of zinc stearate to zinc palmitate. However, by increasing the reaction time from 4
to 8 h at 190 °C, there was a decrease in the accumulation of free fatty acids and an increase in the accumulation
of acylglycerols and this was a strong evidence for reaction reversion. After removal of water, palm oil hy-
drolysates still containing the reaction catalyst were subjected to simultaneous esterification and transester-
ification under similar reaction conditions, reaching a final monoester content of about 90 wt%. These values are
50 wt% higher than those obtained by direct transesterification using the same catalyst. Also, the resulting crude
glycerin phase was colorless in appearance, indicating little contamination with reaction products and inter-
mediates.

⁎
Corresponding author at: Department of Chemistry, Federal University of Paraná (UFPR), P. O. Box 19032, CEP 81531-980 Curitiba, PR, Brazil.
E-mail address: claudiney@quimica.ufpr.br (C.S. Cordeiro).

https://doi.org/10.1016/j.fuel.2019.01.178
Received 27 November 2018; Received in revised form 29 January 2019; Accepted 30 January 2019
Available online 19 February 2019
0016-2361/ © 2019 Elsevier Ltd. All rights reserved.
A.M. Escorsim, et al.
1. Introduction
Oils and fats have important applications in the food and pharma-
ceutical industries as well as in the production of biofuels, especially
biodiesel. Diacylglycerols (DAG) and monoacylglycerols (MAG), often
present as biodiesel contaminants, are used as emulsifiers in food,
pharmaceuticals and cosmetic industries, and also as lubricants for
plastics and additives for paints and perfumes [1,2]. In addition, several
researchers have shown that DAG-rich oils are dietary efficient against
obesity and arteriosclerosis [1,3].
Refined vegetable oils with low water and free fatty acid (FFA)
contents are the most widely used raw materials for biodiesel produc-
tion by homogeneous alkaline transesterification. This catalytic route
presents some advantages such as low energy consumption, low pres-
sure and high reaction rates. However, the downstream processing of
fatty acid methyl esters and glycerin requires high capital costs while
the use of low grade oils and fats is prohibitive due to their high water
and FFA contents, which must be removed down to acceptable levels
prior to transesterification [4,5].
One option to reduce biodiesel production costs is the use of low
value feedstocks such as rendered materials and waste oils and fats.
However, alternative technologies must be used to overcome barriers
that are usually attached their high FFA and free water contents. In this
case, hybrid processes such as hydroesterification can be used, where
hydrolysis of triacylglycerols (TAG) is followed by esterification of FFAs
to produce fatty acid alkyl esters [5].
TAG hydrolysis occurs in three steps as shown in Equations 1, 2 and
3, where one mol of TAG produces three mols of FFA. In these reactions,
water is used in excess to shift the reaction equilibrium towards the
products formation [6,7].
C3 H5 (OOCR)3 + H2 O C3 H5 (OH). (OOCR)2 + RCOOH
TAG Water DAG FFA (1)
C3 H5 (OH). (OOCR) 2 + H2 O C3 H5 (OH)2 . (OOCR) + RCOOH
DAG Water MAG FFA (2)
C3 H5 (OH) 2 . (OOCR) + H2 O C3 H5 (OH)3 + RCOOH
Water FFA (3)
MAG GLY
From techniques already described in the literature, the Colgate-
Emery® [8] process applies subcritical water at 5 MPa and temperatures
above 250 °C without any added catalyst to obtain yields above 90 wt%
in FFA from oils and fats [2,9]. Similar results were obtained by
Kusdiana and Saka [10] using rapeseed oil at temperatures within 255
and 350 °C, oil-to-water molar ratios from 1 to 217, and pressures
ranging from 5 and 20 MPa and also by Almeida et al. [11] using re-
sidual frying oils at temperatures between 250 and 275 °C, oil-to-water
mass ratios from 1 to 4, and pressures of 3.6 and 5.6 MPa. Regarding
TAG hydrolysis, catalysts can be efficiently used to improve yields as
demonstrated by Rocha et al. [5], who carried out hydrolysis of soy-
bean oil using niobium oxide as catalyst and reached conversions above
80% in FFA after 1 h. Also, Cabral et al. [12] performed the enzymatic
hydrolysis of olive oil using Lipozyme RM IN to obtain 45% of FFA after
24 h at 55 °C. By contrast, Zanevicz et al. [13] used Lipozyme TL IN to
perform hydrolysis of soybean oil and used frying oil in an ultrasound
system (132 W power) at temperatures ranging from 40 to 60 °C and
obtained FFA yields around 60% after 2 h.
Esterification consists of a single reaction step where FFA in the
presence of a short-chain alcohol (methanol or ethanol) is converted to
monoesters and water in the presence or absence of a catalyst [14]. De
Paiva et al. [15] esterified long-chain FFAs with ethanol using zinc
laurate as catalyst and obtained 92% in ethyl esters after 90 min at
165 °C. Dos Santos et al. [16] performed the esterification of different
carboxylic acids (valeric, caprylic, lauric and oleic acids) in super-
critical ethanol and obtained yields of 90% in ethyl esters after 40 min.
Processing raw materials with high FFA content (above 4.0%) to
alkyl monoesters can be carried out by esterification in a homogeneous
acid medium (usually H2SO4), followed by transesterification in
570
Fuel 244 (2019) 569–579
alkaline medium (KOH, NaOH or their corresponding alkoxides) [4]. In
addition to homogeneous catalysts, heterogeneous catalysts can also be
used for esterification and transesterification but not too many are able
to catalyze both reactions simultaneously. Some of the catalytic mate-
rials applied in such reaction systems are zeolites, oxides and inorganic
salts, coordination compounds, ion exchange resins, double layered
hydroxides and metal carboxylates. The catalytic activity of these
compounds is due to the presence of Brönsted–Lowry and/or Lewis acid
or base sites in their chemical composition [17,18].
Metal carboxylates have been tested as catalysts for different pro-
cesses such as FFA esterification [15], TAG transesterification [19],
TAG glycerolysis [20] and simultaneous esterification and transester-
ification of acid oils [17,18]. Such variety of catalytic applications is
mainly associated with their acid-base properties, high catalytic ac-
tivity, ease of synthesis by precipitation in aqueous medium and pos-
sible recovery and reuse in several consecutive reaction cycles [18].
One metal carboxylate that can be highlighted is zinc(II) carbox-
ylate, which can be obtained from saturated-chain carboxylic acids and
are represented by the formula Zn(CnH2n+1COO)2. In these compounds,
zinc occupies the center of a regular tetrahedron, where it is co-
ordinated with two carboxylate groups in a bidentate bridge whose
hydrocarbon chains interact by weak van der Waals forces. In addition,
their all-trans (zig-zag) conformation provides an inclination angle of
27° among the hydrocarbon chains forming a bilayer structure [21].
The melting point of layered carboxylates occurs at temperatures above
135 °C; therefore, it presents a behavior similar to that of ionic liquids.
This causes a derangement of the organic chains and a partial change in
the coordination between zinc and carboxylate anions, moving it from a
bidentate to a monodentate bridge in which the catalytic active sites are
more exposed. Such features unveil a variety of different applications
for this catalytic material [17,18,22].
Although many works related to hydroesterification use catalysts
capable of performing esterification and transesterification, only few
studies report on the use of the same catalytic system for TAG hydro-
lysis. In general, TAG hydrolysis is performed without a catalyst in
subcritical or supercritical water using relatively high temperatures
compared to the use of catalysts such as oxides or enzymes [5,9,23].
Niobium oxide [5,24,25] and enzymes [23,26] performed well in these
three reaction steps but these catalysts introduce high costs and lim-
itations to their practical application in industrial processes. On the
other hand, catalytic systems for the conversion of low-cost feedstocks
into fatty acid methyl esters, with advanced properties such as multi-
functionality (active in hydrolysis, esterification and transesterifica-
tion), stability (including reduced leaching of catalytic species), low
energy requirements, ease for recovery and reuse, facile chemical
synthesis and good availability at low cost, are still in great industrial
demand. Besides, advanced catalytic systems should also facilitate
glycerin recovery and produce a glycerin phase with less contamination
and high glycerol contents.
The main objective of this work was to study the hydrolysis, ester-
ification and transesterification of palm oil using zinc stearate as cat-
alyst. The variables investigated for palm oil hydrolysis were: tem-
perature, palm oil-to-distilled water molar ratio, and catalyst
concentration. The accumulation of MAG and DAG were also assessed,
as well as the characterization of the catalyst before and after use. In
addition, the catalytic effect was demonstrated by comparing its per-
formance with hydrolysis in the absence of the catalyst.
2. Experimental
Palm oil and commercial zinc stearate (ZS) were supplied by
Agropalma S/A (Belém, PA, Brazil) and Sim Estearina (Araucária, PR,
Brazil) as courtesy, respectively. Ethanol (99.8% purity) and hexane
(analytical grade) were purchased from Neon® (São Paulo, SP, Brazil)
and used without further purification.
Palm oil was characterized in terms of its free fatty acid content
A.M. Escorsim, et al.
(AOCS method Ca 5a-40), saponification index (AOCS method Cd
3–25), average molar mass (AOCS method Cd 3a-94) and fatty acid
profile by gas chromatography (see below for details).
2.1. Zinc carboxylate characterization
X-ray diffraction (XRD) of ZS was carried out in a Shimadzu DRX-
7000 X-ray powder diffractometer using Cu Kα radiation
(λ = 1.5406 Å, 40 kV and 30 mA) in the range of 3 to 60° of 2θ and a
step size of 0.02°. The basal spacings were obtained according to the
Bragg’s Law.
Fourier transform infrared (FTIR) spectroscopy of ZS was obtained
from a Bomem MB 1000 spectrometer at room temperature in the range
of 4000–400 cm−1, using a resolution of 4 cm−1 and 32 scans. The
sample pellets were prepared by mixing the ground material with
spectroscopic grade KBr (Vetec) in 1:100 mass ratio.
Thermogravimetry (TG) and differential scanning calorimetry (DSC)
were carried out in a Mettler-Toledo TG/DTA model 851 under the
oxygen flow of 50 mL min−1 and a heating rate of 10 °C min−1. Samples
were placed in platinum crucibles and heated from 30 to 1000 °C.
Scanning electron microscopy (SEM; Tescan VEGA3 LMU, Czech
Republic) of the catalyst was carried out before and after TAG hydro-
lysis. Prior to analysis and to improve the material conductivity, sam-
ples were gold plated in a SCD 030 flow exfoliant (Oerlikon Balzers,
Liechtenstein). Different areas of the sample particles were analyzed.
Surface analyses were performed under vacuum using an acceleration
voltage of 15.0 kV.
The catalytic efficiency was measured by the turnover number
(TON) (Equation 4), which represents the number of cycles that a cat-
alyst is able to perform before being deactivated, and by the turnover
frequency (TOF) (Equation 5), which represents how frequent the ob-
served catalytic activity was [18,27,28].
TON = (mol of FFA/mol of catalyst) (4)
TOF = (TON /time) (5)
The effect of heating and cooling on the phase behavior of the re-
action system was visualized and registered using a variable volume
high pressure equilibrium cell coupled to a MicroZoom 10-200× USB
camera. TAG hydrolysis images were obtained at temperatures ranging
from 25 to 140 °C to demonstrate the processes of catalyst melting and
clustering. The reaction mixture was confined into the closed cell and
the camera was mounted next to the frontal inspection window. The
system was continuously stirred using a magnetic stirrer. The tem-
perature set point (140 °C) was maintained constant using a resistive
electric heater with a PID controller. Temperatures above 140 °C were
not applied due to limitations of the equipment set up. More
details about this experimental procedure can be obtained from
Escorsim et al [29].
2.2. Quantification of TAG, DAG, MAG, FFA, GLY, FAME and water
Reactants and products were analyzed by gas chromatography after
extraction with hexane to remove water and free glycerol. Initially,
0.2 g of the reaction mixture was weighed in an Eppendorf tube and
1 mL of hexane was added. The Eppendorf tube was shaken vigorously
and centrifuged at 10,000 rpm for 10 min using an Eppendorf
Centrifuge (Marshal Scientific Model 5415C). The upper phase con-
taining TAG, DAG, MAG and FFA was collected, the organic solvent was
evaporated, and the sample was saved for analysis.
FFA and acylglycerols (MAG, DAG and TAG) were analyzed by gas
chromatography in a Shimadzu 2010 Plus chromatograph equipped
with an autosampler, a split/splitless injector at 1:10 split ratio and a
flame ionization detector (FID). Analyses were performed in an Agilent
Select Biodiesel for Glycerides capillary column (15 m × 0.32 mm;
0.10 μm). The injection and detector temperatures were 380 and
571
Fuel 244 (2019) 569–579
400 °C, respectively. Helium was the carrier gas at 29.2 mL min−1 and
the injected volume was 1.0 μL. The column temperature began at 50 °C
and was immediately heated to 180 °C at 15 °C min−1, then heated to
230 °C at 7 °C min−1, and finally to 380 °C at 10 °C min−1, where it
remained isothermally for 6 min. The quantification of reaction pro-
ducts (MAG, DAG and TAG) followed the EN 14105 method [30] using
tricaprin (1,2,3-tricaprinoylglycerol) and lauric acid (dodecanoic acid)
(FFA) as the internal standards IS1 and IS2, respectively (Sigma-Al-
drich).
For the fatty acid profiles of palm oil and ZS, an esterification
procedure was carried out according to Menezes et al. [31]. Analyses of
the resulting fatty acid methyl esters (FAME) were performed in a
Shimadzu® 2010 Plus gas chromatograph using a Shimadzu SH-Rtx-
Wax (30 m × 0.32 mm; 0.25 μm) capillary column at a split ratio of
1:10. The injector and detector temperatures were set at 250 and
260 °C, respectively. Helium was used as carried gas at a flow rate of
50 mL min−1 and the injection volume was 1.0 μL. The column was
programmed to start at 60 °C with a holding time of 2 min, followed by
a heating rate of 10 °C min−1 to 180 °C, which was held for 1 min, and a
heating rate of 5 °C min−1 to 230 °C with a final holding time of 5 min.
The identification of each compound was performed by comparing their
retention times with those of FAME standards in the range of C4 to C24
(Supelco™ 37 Component FAME Mix). Quantification was performed by
internal calibration according to the EN 14103 method [30] using
methyl nonadecanoate (C19:0, Sigma-Aldrich) as the reference stan-
dard.
Free glycerol (GLY) released after hydrolysis was quantified as de-
scribed by Bondioli et al. [32] using a UV 1100 spectrophotometer. The
presence of free water (moisture) was determined according to the
AOCS Ca 2e-84 method using Karl Fischer automatic coulometric ti-
trators (model MKC-610).
Zinc leaching to the reaction products was analyzed by inductively
coupled plasma optical emission spectrometry (ICP OES). Sample
opening was performed according to the methodology described by
Dugo et al. [33]. The analyzes were performed as described by Dos
Anjos et al. [34] using a Thermo Scientific ICAP 6500 spectrometer.
2.3. Reaction procedure
Hydrolyses were performed in a 50 mL stainless-steel Parr batch
reactor model 4597. The reagents used in ZS-catalyzed hydrolysis ex-
periments were palm oil and distilled water. The volume occupied was
always around 2/3 of the total volume of the reactor vessel. Palm oil,
water and catalyst were fed into the reactor and the system was heated
to the reaction temperature set point. The heating time was around
15 min and the reaction time was computed from the moment at which
the temperature set point was reached. All reactions were carried out at
500 rpm.
Initially, a central rotatable composite design based on a 23 factorial
experimental design with three replicates at the center point was used
to evaluate the effects of the following variables: palm oil-to-distilled
water molar ratio (MR), temperature (T) and catalyst concentration
(CAT) in relation to the total amount of oil fed into the reactor chamber
(Table 1). After performing the assays and analyzing the reaction pro-
ducts, some additional trials were performed (experiments H9 to H17 in
Table 1) under more restricted experimental conditions. The kinetic
data of both auto-catalysed and ZS-catalyzed reactions were determined
to investigate the effect of the catalyst on reaction performance. The
reaction time for all experiments was 240 min. The Statistica 7.0 soft-
ware was used to evaluate the effect of the process variables (MR, T and
CAT) on palm oil hydrolysis.
2.4. Simultaneous esterification and transesterification
The simultaneous esterification and transesterification of partially
hydrolyzed palm oil and its direct transesterification using ZS as
A.M. Escorsim, et al. Fuel 244 (2019) 569–579

Table 1
Experimental conditions for zinc stearate-catalysed palm oil hydrolysis, ar-
A
ranged as a central rotatable composite design that was developed from a 23
factorial design with three replicates at the center point.
Experiment Conditionsa

T (°C) CAT (%) Palm oil-to-water MR B

H1 140 2 1:10
H2 190 2 1:10

Relative Intensity (u.a.)

H3 140 10 1:10
C
H4 190 10 1:10
H5 140 2 1:53
H6 190 2 1:53
H7 140 10 1:53
D
H8 190 10 1:53
H9b 131.2 6 1:31.5
H10 b 198.8 6 1:31.5
H11 b 165 6 2.4 E
H12 b 165 6 60.6
H13 b 165 0.6 1:31.5
H14 b 165 11.4 1:31.5 F
H15c 165 6 1:31.5
H16 c 165 6 1:31.5
H17c 165 6 1:31.5 2954
1730 1409 719
2916 2848 1538 1467
a
T, temperature; CAT, catalyst concentration; MR, molar ratio.
b
Central composite rotatable design. 4000 3500 3000 2000 1500 1000 500
c
Center point of the experimental design. -1
Wavenumber (cm )

catalyst were carried out for comparison. Reactions were performed in
a 50 mL stainless-steel Parr batch reactor model 4597. Initially, palm oil
hydrolysis was performed using a palm oil-to-water MR of 1:31.5 and
6% catalyst at 190 °C for 4 h. After this period, the reactor was cooled,
water was removed by phase separation, methanol was added at a palm
oil hydrolysate-to-methanol MR of 1:10 and the reaction was carried
out for another 2 h at 160 °C [18]. Palm oil hydrolysates and products
obtained after simultaneous esterification and transesterification were
collected for analysis after reaction completion.
2.5. Catalyst recovery from the reaction medium
Removal of the catalyst was performed by washing the reaction
products with a 1:1 (v/v) ethanol:hexane mixture followed by cen-
trifugation and subsequent filtration on qualitative filter paper with a
grammature of 80 g m−2 [35]. This procedure was repeated at least five
times. After filtration, the catalyst was dried in an air circulating oven
(Solab, model SL100) at 60 °C for 12 h and reserved for chemical
characterization and reuse. Also, the solvent was removed from the
filtrate in a rotary evaporator (Ika, model RV 10 Digital) and the pro-
ducts were analyzed by gas chromatography for FFA, MAG, DAG and
TAG quantification using the methods mentioned above.
3. Results and discussion
3.1. Palm oil characterization
The raw material (palm oil) used in this study presented a saponification
index of 195.39 ± 2.08 mg KOH g−1, an average molar masses (MM) of
859.65 ± 2.62 g mol−1 for triacylglycerols and 273.87 ± 1.12 g mol−1
for free fatty acids, and an acidity of 0.15 ± 0.02 g oleic acid 100 g−1 of
sample, which corresponds to 0.30 ± 0.03% in FFA. The FFA profile
contained 0.97 ± 0.01 wt% myristic acid (C14:0), 40.59 ± 0.03 wt%
palmitic acid (C16:0), 4.85 ± 0.03 wt% stearic acid (C18:0),
43.90 ± 0.03 wt% oleic acid (C18:1), 0.20 ± 0.03 wt% linoleic acid
(C18:2), and 9.11 ± 0.01 wt% arachidic acid (C20:0). Therefore,
palmitic and oleic acids corresponded to 84.5% of the total palm oil
fatty acid content. TAG, DAG, MAG and FFA contents in palm
oil were 98.16 ± 0.05 wt%, 1.07 ± 0.01 wt%, 0.47 ± 0.02 wt% and
0.30 ± 0.01 wt%, respectively.
Fig. 1. FTIR spectra of zinc stearate before and after palm oil hydrolysis at
different experimental condition: (A) ZS; (B) ZS in H25 after 8 h; (C) ZS in H26
after 8 h; (D) ZS in H27 after 8 h; (E) ZS in H28 after 8 h and (F) ZS in the 5th
cycle of H27 after 4 h. Conditions of each experiment are presented in Table 3.
3.2. Catalyst characterization
Fig. 1A shows the infrared spectra (FTIR) of the solid catalyst, which
contained strong bands in the 2916–2848 cm−1 region and weak bands in
the 1467–719 cm−1 region that are typically attributed to methylene
groups of fatty acid (carboxylate) hydrocarbon chains [36]. The band
centered at 2954 cm−1 is attributed to asymmetric axial deformation of
terminal methyl groups. The absence of bands in the 3500–3300 cm−1
region (axial deformation of associated hydroxyl groups) confirms that the
ZS catalyst was anhydrous. According to the literature [18,19,36], bands
assigned to the carbonyl group are: ʋa(COO) at ∼1538–1531 cm−1
(asymmetric stretching); ʋs(COO) at ∼1409–1394 cm−1 (symmetrical
stretching); ʋd(C–C)COO at ∼949–957 cm−1 (axial deformation);
ʋδ(COO) at ∼ 745–743 cm−1 (angular deformation or bending); ʋτ(COO)
at ∼580 cm−1 (out-of-plane twisting); and ʋρ(COO) at ∼550–547 cm−1
(chain oscillation).
Table 2 shows the fatty acid composition of the solid catalyst.
Stearic (50%) and palmitic (40%) acids (Table 2) corresponded to 90%
of its total fatty acid content, whose average molar mass was estimated
as 269.5 g mol−1. According to Barman and Vasudevan [22], saturated
fatty acids establish better van der Waals interactions among carbox-
ylate hydrocarbon chains resulting in solids with a better structural
stability. By contrast, when unsaturated fatty acids are present in levels
above 30%, the layered structure of metal carboxylates is weakened,
leading to less stable aggregates in which their original all-trans con-
formation is partially lost.
Fig. 2A shows the XRD for the ZS catalyst. The diffractogram was
typical of layered carboxylates with basal peaks in the 3–18° region (in
2θ) whose calculated basal spacing was 40.60 Å. The wide peaks ob-
served in the region of 18-25° of 2θ were attributed to the structural
disorder of palmitate and stearate anions that were intercalated be-
tween the lamellae.
The thermal analyses (TG/DSC) of the catalyst revealed the pre-
sence of an exothermic peak in the region of 135 °C (Fig. 3A), which
was attributed to the melting of zinc stearate caused by rearrangement

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A.M. Escorsim, et al. Fuel 244 (2019) 569–579

Table 2
Zinc stearate (ZS) chemical composition before and after its use in palm oil hydrolysis at different reaction conditions (see Table 3 for details).
Fatty acid Cn:ma ZS ZS after use in:

H19 after 8 h H20 after 8 h H21 after 8 h H3 after 8 h H21 after 4 h, 5th cycle

Lauric C12:0 0.03 ± 0.01 – – – – –

Myristic C14:0 1.97 ± 0.02 1.00 ± 0.01 1.06 ± 0.01 1.08 ± 0.02 0.99 ± 0.01 1.42 ± 0.01
Pentadecanoic C15:0 0.41 ± 0.01 0.33 ± 0.02 0.42 ± 0.01 0.49 ± 0.01 0.35 ± 0.01 0.21 ± 0.01
Palmitic C16:0 39.86 ± 0.12 82.24 ± 0.13 80.74 ± 0.11 76.81 ± 0.10 58.53 ± 0.12 70.54 ± 0.14
Heptadecanoic C17:0 1.28 ± 0.03 – – – 0.27 ± 0.01 –
Stearic C18:0 50.18 ± 0.21 11.85 ± 0.05 10.52 ± 0.04 10.63 ± 0.04 18.29 ± 0.05 12.44 ± 0.03
Arachidic C20:0 – – 0.60 ± 0.01 0.88 ± 0.01 1.47 ± 0.01 1.78 ± 0.02
Myristoleic C14:1 0.15 ± 0.01 – – – 0.09 ± 0.01 –
Palmitoleic C16:1 0.11 ± 0.01 0.27 ± 0.01 – – 0.26 ± 0.01 0.21 ± 0.01
Heptadecanoic C17:1 0.08 ± 0.01 – – – – –
Oleic C18:1 2.77 ± 0.03 4.30 ± 0.03 6.40 ± 0.05 6.22 ± 0.04 18.32 ± 0.06 12.62 ± 0.04
Elaidic C18:1 1.89 ± 0.02 – – 0.20 ± 0.01 1.25 ± 0.02 0.34 ± 0.01
Linolenic C18:3 0.62 ± 0.01 – 0.25 ± 0.01 – 0.13 ± 0.01 0.40 ± 0.01

a
n is the number of carbon atoms in the hydrocarbon chain and m is the number of the existing double bonds.

Relative Intensity (u.a.)

B

B
C
C
Intensity (U.A.)

D
E
D
TG F

0 100 200 300 400 500 600 700 800 900 1000
E
Temperature (°C)

B
F
Relative Intensity (u.a.)

5 10 15 20 25 30 35 40 45 50 55 60
C
Angle 2θ

Fig. 2. X-ray diffraction analysis (XRD) of zinc stearate (ZS) before and after D
palm oil hydrolysis at different experimental condition: (A) ZS; (B) ZS in H25 E
after 8 h; (C) ZS in H26 after 8 h; (D) ZS in H27 after 8 h; (E) ZS in H28 after 8 h
F
and (F) ZS in the 5th cycle of H27 after 4 h. Conditions of each experiment are
presented in Table 3.
Exo
Endo
DSC
of molecules in the liquid phase, while the presence of endothermic
peaks was associated to the burning of organic matter (fatty acid car- 0 100 200 300 400 500 600 700 800 900 1000
boxylates). Thermal analysis gave also the amount of fixed residue Temperature (°C)
(ZnO) and organic matter that were present in the ZS catalyst and these
Fig. 3. TG and DSC profile of zinc stearate before and after palm oil hydrolysis:
were 17.2% and 82.8%, respectively (Fig. 3A). Then, the amount of (A) ZS; (B) ZS in H25 after 8 h; (C) ZS in H26 after 8 h; (D) ZS in H27 after 8 h;
fixed residue was used to calculate the zinc content of ZS, which cor- (E) ZS in H28 after 8 h and (F) ZS in the 5th cycle of H27 after 4 h. Conditions of
responded to 13.8% (138 g kg−1). This value was close to that found in each experiment are presented in Table 3.
the literature for freshly synthesized ZS (13.5%) [37].

3.3. Hydrolysis
Hydrolysis of refined palm oil produced a blend of FFA, MAG, DAG,
TAG and GLY. Table 3 shows the results for reactions that were carried
out at the experimental conditions described in Table 1. The results
obtained for the thermal conversion of palm oil to its corresponding
FFA are observed in rows H18–H24 of Table 3. The highest FFA content
of 2.60% was obtained at 190 °C using a palm oil-to-water MR of 1:53,
while the smallest was 0.53% at 140 °C using a palm oil-to-water MR of
1:10. This clearly demonstrates that ZS was catalytic active in palm oil
hydrolysis. The highest FFA content were observed in experiments H6
(45.8%), H10 (47.7%), H12 (59.2%) and H15–17 (47.7%) (Table 3).
The actual gains in relation to the highest thermal conversion (Table 3,

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Table 3
Palm oil hydrolysis with and without zinc stearate (ZS) as catalyst and its corresponding catalytic efficiency (TON and TOF).
Exp. T CAT Palm oil-to-water MR Time P Component (wt%)a TONb TOFb
(°C) (%) (h) (bar) (h−1)
TAG DAG MAG FFA GLY

H1 140 2 1:10 4 1.2 64.89 21.23 4.78 8.23 0.87 39.6 9.9
H2 190 2 1:10 4 1.8 45.42 26.66 10.23 15.93 1.75 72.6 18.2
H3 140 10 1:10 4 1.2 33.35 21.41 15.37 26.94 2.93 24.5 6.1
H4 190 10 1:10 4 1.8 31.97 34.35 12.41 19.22 2.05 17.6 4.4
H5 140 2 1:53 4 3.5 37.05 30.88 15.94 14.54 1.60 64.3 16.1
H6 190 2 1:53 4 3.7 12.14 23.83 13.09 45.85 5.09 204.0 51.0
H7 140 10 1:53 4 3.5 24.03 18.88 17.06 35.92 4.11 33.5 8.4
H8 190 10 1:53 4 3.7 17.19 18.95 20.18 39.34 4.34 36.2 9.0
H9c 131.2 6 1:31.5 4 0.3 37.87 21.02 14.00 26.70 0.11 41.1 10.3
H10c 198.8 6 1:31.5 4 3.9 11.59 22.74 15.66 47.70 2.03 73.2 18.3
H11c 165 6 2.4 4 1.5 24.10 26.08 12.29 36.11 1.17 520.4 130.1
H12c 165 6 60.6 4 4.2 1.46 17.87 18.10 59.24 3.02 48.0 12.0
H13c 165 0.6 1:31.5 4 2.7 50.43 21.98 9.63 17.76 – 27.2 6.8
H14c 165 11.4 1:31.5 4 2.8 19.43 19.55 17.37 42.13 1.30 64.5 16.1
H15d 165 6 1:31.5 4 2.8 9.60 19.81 17.37 47.79 5.43 70.3 17.6
H16d 165 6 1:31.5 4 2.8 9.80 19.44 17.13 48.32 5.31 71.5 17.9
H17d 165 6 1:31.5 4 2.9 9.65 20.57 17.19 47.12 5.47 70.7 17.7
H18e 140 – 1:10 4 1.3 93.03 4.61 1.78 0.53 0.04 – –
H19e 190 – 1:10 4 1.9 91.02 5.41 1.99 1.42 0.16 – –
H20e 140 – 1:53 4 3.5 90.43 5.91 2.33 1.20 0.13 – –
H21e 190 – 1:53 4 3.8 83.63 9.24 4.20 2.60 0.32 – –
H22e 165 – 1:31.5 4 2.8 92.19 4.61 1.98 1.11 0.11 – –
H23e 165 – 1:31.5 4 2.7 92.43 4.30 2.00 1.12 0.15 – –
H24e 165 – 1:31.5 4 2.9 92.31 4.46 1.99 1.12 0.13 – –
H25f 140 6 1:31.5 8 1.5 14.83 17.80 15.70 46.48 2.57 – –
H26f 165 6 1:31.5 8 3.2 8.11 16.23 13.43 55.60 4.12 – –
H27f 190 6 1:31.5 8 4.1 2.93 29.15 16.57 46.15 1.92 – –
H28g 140 10 1:10 8 1.2 21.26 18.02 12.40 43.49 2.72 – –

a
TAG. triacylglycerol; DAG. diacylglycerol; MAG. monoacylglycerol; FFA. free fatty acids; GLY. Glycerol.
b
TON. turnover number; TOF. turnover frequency.
c
Central composite rotatable design.
d
Center point of the experimental design.
e
Experimental design without addition of the ZS catalyst.
f
Center point with temperature variation for a reaction time of 8 h.
g
H3 experiment performed by 8 h.

experiment H21) were 43.2%, 45.1%, 56.6% and 45.1% points percent, response function (FFA content) of the factorial design,
respectively.
FFA content at the center point of the experimental design had a FFA (%) = 454.0679 + 5.1629·T 0.0147· T 2 0.5432· MR
very low standard deviation of 1.12% and this demonstrated the good 0.0058·MR2 + 19.9667· CAT 0.7743· CAT 2
repeatability of the experimental procedures (Table 3). The FFA content (6)
+ 0.0079·T · MR 0.0562· T ·CAT
described in Table 3 were fitted to a quadratic model (Equation 6)
whose statistical analysis showed high linear regressions and small lack where FFA (%) is the content of free fatty acids, T is the reaction
of fit compared to Fisher F standard values at a 95% confidence level temperature (°C), MR the palm oil-to-water MR and CAT the catalyst
(Table 4). Maximum explained variances of 91% were obtained for both concentration (%) in relation to the amount of fatty material used for
palm oil hydrolysis and FFA contents and the regression factors were conversion. The linear effects of T, palm oil-to-water MR and CAT were
significant in relation to the residues. The lack of fit in relation to the statistically significant and had a positive influence on FFA content
pure error was also acceptable among the ANOVA data, with a good while the quadratic effects influenced it negatively (Eq. 6). The binary
dispersion of the residues in relation to the predicted answers, therefore interaction between T and MR had also a positive effect on FFA content,
demonstrating that the model was predictive and not biased but the interaction between T and CAT was negative. By contrast, no
(Supplementary Material – Fig. S2). significant effect was observed from the interaction between MR and
Eq. (6) describes the quadratic model that was developed to fit the CAT (Supplementary Material – Fig. S1).
The quality of the ANOVA data enabled the construction of the re-
Table 4 sponse surfaces (SDR) that are presented in Fig. 4. The non-linear aspect
Analysis of variance (ANOVA) and F-test for palm oil hydrolysis using zinc of the response surfaces (Fig. 4) confirmed the significance of the
stearate (ZS) as catalyst. second-order effects. With this, a broad region was defined to achieve
high FFA content of palm oil hydrolysis using a wide range of reaction
Source SS df MS F Ftab
conditions involving T, MR and CAT.
Regression 3555.0 8 444.4 90.4 3.44 Micic [9] studied the hydrolysis of sunflower oil under subcritical
Residual 39.4 8 4.9 conditions without the use of catalyst and observed a 1.8-fold increase
Lack of fit 38.6 6 6.4 17.8 19.33 in FFA content (35 for 63% at 200 °C) by increasing the palm oil-to-
Purr error 0.72 2 0.4
Total 3594.4 16
water MR from 1:5 to 1:25. Kusdiana and Saka [10] observed a 1.4-fold
increase in FFA content (62 to 85% at 270 °C) during hydrolysis of
SS, sum of squares; df, degree of freedom; MS, mean square; R-sq = 0.9557 and rapeseed oil under subcritical conditions without the presence of an
%Var = 0.9113. added catalyst when the rapeseed oil-to-water MR was increased from

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14.54 to 45.85% as observed in experiments H5 and H6. Micic [9],

Pinto and Lanças [38] and Moquin and Temelli [2] observed also a
significant increase in TAG conversion to FFA when T was increased
from 200 to 250 °C, with FFA contents increasing from 65 to 95%.
A possible mechanism for the catalytic activity of zinc stearate in
palm oil hydrolysis is the initial interaction of the electron pair of the
carbonyl oxygen of the fatty acids with the metal present in the car-
boxylate, leading to the adsorption of the molecule. Thus, the metal
acting as a Lewis acid increases in the positive charge density on the
carbonyl carbon atom favoring the nucleophilic attack of the electron
pair of the water oxygen, with the consequent formation of a tetra-
hedral intermediate. Therefore, hydrogen exchanges between the two
oxygen atoms loses one DAG molecule, while the FFA formed remains
on the surface of the catalyst until desorption occurs. With this, the
catalyst active site is released for another reaction cycle (see a proposal
for the reaction mechanism in Supplementary Material – Fig. S3)
[18,19,39].
The best conditions for palm oil hydrolysis were obtained in the
center point of the experimental design (165 °C, 6% ZS and a palm oil-
to-water MR of 1:31.5), where a maximum FFA (50%) and a minimum
TAG (10%) contents were observed. This reaction condition was used to
evaluate the reaction kinetics with and without the presence of ZS as
catalyst. Furthermore, the three replicates that were performed at the
center point of the experimental design (H15, H16 and H17) indicated
the good repeatability of the experiments, since the resulting FFA
contents presented a standard deviation of only 0.60%.
Fig. 5A and 5B show the kinetic profile of ZS-catalyzed palm oil
hydrolysis at 165 and 190 °C, respectively, using a palm oil-to-water
MR of 1:31.5 and a CAT of 6%. After 8 h of hydrolysis, the FFA content

Fig. 4. Response surfaces relative to FFA content after palm oil hydrolysis. (A)
temperature (T) vs. molar ratio oil: water (MR), (B) temperature (T) vs. catalyst
content (%CAT) and (C) palm oil-to-water molar ratio (MR) vs. catalyst con-
centration (CAT).

1:13 to 1:54. Rocha [5] used castor oil and soybean oil and observed an
1.5-fold increase in FFA content (49 for 75% at 300 °C) with an increase
in the oil-to-water MR from 1:5 to 1:20 using 20% of niobium oxide as
catalyst. Hence, increased water concentrations in the reaction mixture
shift the reaction equilibrium towards products formation. In our study,
changes in the palm oil-to-water MR from 1:10 to 1:53 provided the
highest recovery of FFA (15.93 for 45.85% in experiments H2 and H6 of
Table 3) giving a 2.9-fold increase in FFA content. Fig. 5. Kinetics of palm oil hydrolysis catalyzed by zinc stearate under the
An increase in reaction temperature provides higher solubilities of following reaction conditions: (A) 165 °C, palm oil-to-water molar ratio of
both non-polar (oil) and polar (water) reactants due to the decrease of 1:31.5 and 6% catalyst, (B) 190 °C, palm oil-to-water molar ratio of 1:31.5 and
the dielectric constant of the latter, generating an increase in the re- 6% catalyst. Diamonds for free fatty acids (FFA), squares for monoacylglycerols
action rate [9]. Indeed, Table 3 shows that by increasing the tem- (MAG), asterisks for diacylglycerols (DAG), triangles for triacylglycerols (TAG)
perature from 140 to 190 °C, the FFA content was also increased from and circles for glycerol (GLY).

575
A.M. Escorsim, et al.
reached 55% at 165 °C and by increasing the reaction temperature from
165 to 190 °C, the same FFA content was already reached at 4 h,
therefore reducing the reaction time by half. Also, in Fig. 5B, a decrease
in the FFA content from 60 to 50% was observed between 4 and 8 h,
along with a slight increase in the acylglycerol contents (MAG, DAG and
TAG). According to Macierzanka and Szelag [20], this is due to the
esterification of glycerol (also demonstrated by the drop in GLY con-
centration in the reaction media), which is favored at temperatures
above 150 °C in the presence of the ZS catalyst. In addition, glycerol
acylation may have occurred after 1 h (Fig. 5A and 5B) as suggested by
the observed decrease in GLY with the concomitant increase in DAG.
Gomes and Cordeiro [40] demonstrated that ZS exhibits good catalytic
activity in the breakdown of TAG by glycerol, however, this reaction
was not observed at the conditions applied in this study for palm oil
hydrolysis.
The hydrolysis kinetic data were used to validate the mathematical
model presented in Equation 6. Two independent experimental proce-
dures were carried out for this purpose. The model prediction for
165 °C, palm oil-to-water MR of 1:31.5 and CAT of 6% after 4 h were
51.5 ± 2.9% while the FFA content obtained experimentally was
48.6%. Also, the model predicted an FFA content of 47.4 ± 2.9% for
reactions carried out at 190 °C with a palm oil-to-water MR of 1:31.5
and 6% of CAT after 4 h, while the result obtained in a confirmatory
experiment was 53.2 ± 1.3% (Fig. 5A and 5B). These data demon-
strated the validity of the proposed mathematical model for predicting
FFA contents derived from ZS-catalysed palm oil hydrolysis.
The catalytic effect was assessed by performing palm oil hydrolysis
at the same conditions in the absence (thermal conversion) and pre-
sence of the ZS catalyst. Low FFA, GLY, MAG and DAG contents where
obtained by thermal conversion (Supplementary Material – Fig. S4),
compared to the results of the catalytic reaction (Fig. 5). Also, the
significant decrease in TAG after 8 h of thermal conversion was asso-
ciated to auto-hydrolysis because the first FFA molecules released in the
medium were able to act as an acid catalyst [7].
Another observation from the experiments performed in this work
refers to the pressure reached in the reaction media, which remained
low at values around the vapor pressure of water. Also, the efficiency of
the ZS catalyst was demonstrated by the poor reaction performance in
its absence using otherwise identical reaction conditions.
3.4. Catalyst reuse assays
Table 5 shows the catalyst recovery and reuse based on a single
batch of ZS using reaction conditions in which the best FFA contents
were achieved (190 °C, 1: 31.5 palm oil-to-water MR and 6% catalyst
for 4 h). Despite the already mentioned conversion of zinc stearate to
zinc palmitate, the solids maintained the same catalytic efficiency in
five consecutive reaction cycles. Also, even with an increase in lamellar
disorganization (characterized by XRD) and changes in its melting point
(noted by DSC), no segregation of any crystalline impurity was ob-
served.
Table 5
Catalyst reuse at 190 °C for 4 h using 6% zinc stearate and a palm oil-to-water molar ratio of 1:31.5 (experiment H21).
Exp. Component (wt%)*
TAG DAG
Initial reaction 2.05 ± 0.01 23.97 ± 0.13
1st reuse 2.13 ± 0.06 23.97 ± 0.05
2nd reuse 2.16 ± 0.10 24.43 ± 0.08
3rd reuse 2.75 ± 0.19 23.73 ± 0.84
4th reuse 2.12 ± 0.14 22.76 ± 0.21
5th reuse 2.51 ± 0.20 23.13 ± 0.24
* TAG, triacylglycerol; DAG, diacylglycerol; MAG, monoacylglycerol; FFA, free fatty acids; GLY, glycerol.
576
Fuel 244 (2019) 569–579
3.5. Simultaneous esterification and transesterification
Table 6 shows the results for simultaneous esterification and
transesterification of partially hydrolyzed palm oil and its direct
transesterification using ZS as catalyst. As observed, there was a 99%
reduction in TAG, 92% in DAG, 85% in MAG and 89% in the FFA
content of pre-hydrolyzed palm oil for a total ester content of 89%.
Direct transesterification of refined palm oil was also performed under
the same conditions used for its acid hydrolysis and the results in-
dicated 85% TAG conversion for a product with a total ester content of
60%. Therefore, hydrolysis followed by simultaneous esterification and
transesterification improved the total ester content from palm oil by
48% compared to its direct transesterification. Kusdiana and Saka [10]
reported similar trends for the transesterification of rapeseed oil and the
esterification of hydrolyzed rapeseed oil in supercritical methanol,
whose FAME yields were 60 and 98%, respectively. However, reactions
were carried out for 20 min at 270 °C and 17 MPa with an oil-to-me-
thanol MR of 1:42.
The moisture content of the resulting FAMEs was 0.30 ± 0.03%
after hydrolysis and 1.47 ± 0.05% after simultaneous esterification
and transesterification. Such increase in water content is associated
with the esterification of FFA, where water is obtained as co-product.
The presence of water causes TAG hydrolysis, leading to the release of
FFAs that are rapidly converted to FAMEs. This observation was also
confirmed by Kusdiana and Saka [41] as a result of the transester-
ification of rapeseed oil in the presence of water using supercritical
methanol.
The crude glycerin phase from experiment H27 was analyzed for the
quantification of glycerol using the procedure described by Bondioli
et al. [32]. Samples were obtained from hydrolysis of palm oil followed
by simultaneous esterification and transesterification of palm oil hy-
drolysate, as well as from the direct transesterification of palm oil. In
both situations, analyses were carried out after removal of water and
methanol by evaporation under low pressure. The total mass recovery
of glycerol after hydrolysis followed by simultaneous esterification and
transesterification was 77.0 ± 3.1% (47.4 and 29.6%, respectively),
whereas for direct transesterification, this value reached 90.8 ± 4.5%.
Glycerol losses were observed in both situations because phase se-
paration and washing stages were not optimized for its highest re-
covery. However, the FTIR spectra of these crude glycerin phases were
practically identical to the results obtained from pure glycerol, there-
fore evidencing the absence of symmetrical and asymmetric axial de-
formations of carboxylate anions (Supplementary Material – Fig. S5). A
crude glycerin phase with high glycerol content (around 86%) was also
obtained by Ramos et al. [18] after transesterification of palm oil with
methanol using zinc carboxylates (zinc laurate) as a catalyst.
In general, zinc stearate showed good FFA contents in palm oil
hydrolysis. Also, high FAME contents were obtained by hydrolysis fol-
lowed by simultaneous esterification and transesterification. These re-
sults demonstrate the potential and flexibility of zinc carboxylates for
biodiesel production because, by applying this multifunctional catalytic
system, hydrolysis, esterification and transesterification would be
MAG FFA GLY
18.82 ± 0.06 58.44 ± 0.48 6.63 ± 0.08
15.98 ± 0.28 57.69 ± 0.74 6.48 ± 0.07
16.24 ± 0.49 57.46 ± 0.30 6.41 ± 0.10
17.25 ± 0.28 56.73 ± 0.30 6.30 ± 0.02
18.06 ± 0.38 57.19 ± 0.37 6.23 ± 0.15
17.86 ± 0.35 58.02 ± 0.34 6.42 ± 0.02
A.M. Escorsim, et al.
Table 6
Palm oil conversion by hydrolysis, hydrolysis followed by simultaneous esterification and transesterification, and direct transesterification of palm oil.
Experiment Components (wt%)1
TAG
2
Hydrolysis 1.98 ± 0.06
Hydrolysis followed by esterification and transesterification3 0.01 ± 0.00
Transesterification4 13.94 ± 0.27
1
TAG, triacylglycerol; DAG, diacylglycerol; MAG, monoacylglycerol; FFA, free fatty acids; GLY, glycerol.
2
Hydrolysis at 190 °C for 4 h using 6% zinc stearate and an oil-to-water molar ratio of 1:31.5 (experiment H21).
3
Simultaneous esterification and transesterification of palm oil hydrolysates (experiment 21) at 160 °C for 4 h using 6% zinc stearate and an oil-to-methanol molar
ratio of 1:10.
4
Direct transesterification of palm oil at 160 °C for 4 h using 6% zinc stearate and an oil-to-methanol molar ratio of 1:10.
eventually feasible in three relatively simple reaction steps (hydrolysis,
water withdrawal and simultaneous esterification and transesterifica-
tion). Also, the employment of zinc stearate allows the processing of
much more complex feedstocks composed by different levels of FFAs,
MAGs, DAGs, TAGs and H2O, combining the use of low cost raw ma-
terials with the good reuse capacity of a cheap and commercially
available catalytic system. In addition, the reactions occur at the vapor
pressure of the solvents, enabling the use of hydroesterification reaction
systems without a significant change in the reactor design.
3.6. Characterization of the catalyst after the hydrolysis of palm oil
The solids were characterized by FTIR and XRD after the hydrolysis
of palm oil. Fig. 1B to 1F show the FTIR spectra of the solid catalysts
that were recovered after hydrolysis of refined palm oil. In general,
these FTIR spectra were identical to that of the original structure
(Fig. 1A) except for the 1730 cm−1 band which, according to Taylor
and Ellis [36], are attributed to the presence of FFA (hydrolysis pro-
ducts) between the structural lamellae.
Table 2 shows the fatty acid composition of the ZS catalyst after
hydrolysis. Changes in the chemical composition of the solid catalyst
were observed mainly in relation to the presence of saturated FFA. The
concentration of stearic and palmitic acids, initially at 40:50 in ZS,
changed to 12:82, 11:81, 11:77 and 18:59 after experiments H25, H26,
H27 and H28, respectively, and to 12:71 after five complete reuse cy-
cles (experiment H27). These changes in chemical composition are re-
lated to the rearrangement of the zinc carboxylate anions during hy-
drolysis. This is explained by the ZS melting at 135 °C (see DSC profile
in Fig. 3A), leading to a structural derangement that led to a shift in the
coordination between carboxylate anions and zinc atoms, moving from
a bidentate to a monodentate bridge. With cooling, the solid catalyst
reorganizes, and the bidentate bridge is restored while palmitic acid
becomes the predominant fatty acid in the solid catalyst chemical
composition.
The reorganization and reconstitution of the zinc carboxylate
layered structure does not follow a specific rule. However, saturated
fatty acids build more stable metal carboxylates due to their chain
linearity and greater association by Van der Waals interactions. On the
basis of their corresponding fatty acid profile, the average molar mass
of the recovered solid catalysts were in the range of 260–266 g mol−1
(261.9 g mol−1 for H19, 260.9 g mol−1 for H20 and H21,
266.0 g mol−1 for H22 and 262.4 g mol−1 for H21-4 h), compared to
269.5 g mol−1 for the starting material (ZS).
Fig. 2B to F shows the XRD for the ZS catalyst after palm oil hy-
drolysis. The diffractograms were all typical of layered carboxylates
with basal peaks in the 3–18° region (in 2θ) and with the following
calculated basal spacing: 38.67, 38.62, 38.63, 39.12 and 38.77 Å for
experiments H19, H20, H21, H3 and H21, respectively.
The observed peaks in the region of 18-25° of 2θ were attributed to
the structural disorder of palmitate and stearate anions that were in-
tercalated in-between the lamellae, in addition to some X-ray
Fuel 244 (2019) 569–579
DAG MAG FFA GLY FAME
22.12 ± 1.25 13.25 ± 0.28 56.01 ± 1.43 6.64 ± 0.09 –
1.75 ± 0.17 1.93 ± 0.03 6.13 ± 0.48 3.38 ± 0.23 88.95 ± 0.70
9.23 ± 0.37 13.61 ± 0.27 0.49 ± 0.02 6.05 ± 0.20 57.04 ± 0.11
scattering. After hydrolysis, the catalyst assumed an intermediate basal
spacing between zinc palmitate (38.36 Å) and zinc stearate (42.67 Å)
and this variation was associated to its restructuring process [36].
Hence, the slight migration to higher values of 2θ corresponded to a
decrease in basal spacing that is associated to the replacement of
stearate anions by shorter chain length anions such as palmitate. As
mentioned above and also demonstrated in the literature, palmitic acid
is the main component of palm oil and its acid hydrolysate [18,36].
After palm oil hydrolysis, the TG/DSC profiles of the recovered
solids (Fig. 3B to 3F) were also identical to the profile of the original
structure (Fig. 3A). The TG/DSC data also provided the amount of fixed
residue (ZnO) and organic matter that were present in the recovered
solids and these values were 18.9 and 81.1% (Fig. 3B), 15.2 and 84.8%
(Fig. 3C), 16.1 and 83.9% (Fig. 3D). 12.8 and 87.2% (Fig. 3E) and 11.6
and 88.4% (Fig. 3F), respectively. Then, the amount of fixed residue
was used to calculate the zinc content of these materials, which cor-
responded to 13.8% for ZS and 15.2%, 12.2%, 12.9%, 10.3% and 9.3%
for experiments H25, H26, H27, H28 and H27 (after five reuse cycles),
respectively. These values were close to those found in the literature,
which are 9.9% and 13.5% for zinc palmitate and zinc stearate, re-
spectively [37,42]. The values found for recovered solids averaged
12%, which are lower than the theoretical values reported by Gönen
et al. [37]. This decrease, according Taylor and Ellis [36], is due to
differences in the composition of the carboxylate hydrocarbon chains
(Table 2) and also to the presence of FFAs in-between the zinc car-
boxylate lamellae, which was confirmed by the appearance of C]O
axial deformations in the FTIR spectra of Fig. 1B to 1F. As mentioned
above, this trend increased the organic matter and reduced the zinc
content of the recovered solids. In addition to the presence of FFA, mass
losses of solid catalyst may have occurred during water washing and
some of the material may have remained adhered to the filter paper
after filtration.
The contribution of unsaturated fatty acids (mainly oleic and lino-
leic acids) increased in the ZS composition after palm oil hydrolysis,
reaching more than 15% of its dry mass (Table 2). This result led to a
small reduction of the layered carboxylate melting point as observed by
DSC in Fig. 3E and 3F. This reduction in melting point is caused by a
distortion of the all-trans (zig-zag) conformation of zinc carboxylates,
which is due to the stereochemical arrangement of the double bonds. In
general, layered carboxylates melt when approximately 30% of their
all-trans conformation is lost [36]. Thus, the presence of unsaturated
fatty acids during restructuration changes the linearity of the carbox-
ylate chains that are coordinated to the zinc atoms, resulting in a lower
crystallinity and a lower aggregate stability [22].
Fig. 6 shows the beginning of palm oil hydrolysis at 25 °C, when
water, palm oil and ZS phases are observed in the system. Melting of the
ZS catalyst started at 135 °C with its complete fusion at 140 °C. There-
fore, zinc carboxylates behaved as a homogeneous catalyst during TAG
hydrolysis; consequently, their catalytic activity is independent of the
surface area of ZS solids originally added to the reaction mixture.
Cooling of the reaction mixture from 130 to 110 °C led to the formation
577
A.M. Escorsim, et al.
Fig. 6. Representative photographs of zinc stearate-catalyzed palm oil hydrolysis starting at 25 °C until the complete melting of the ZS catalyst at 140 °C, followed by
cooling after hydrolysis for 2 h to observe the gradual restructuration (clustering) of ZS.
of zinc carboxylate clusters from the border to the center (mist) of the
equilibrium cell. With this, the layered structure of zinc carboxylates
was restored as already observed by other authors [17–19,35] during
the esterification of lauric acid using different metal laurates as cata-
lysts.
The crystal morphology of a ZS sample before and after palm oil
hydrolysis (Supplementary Material – Fig. S6). ZS exhibited crystals in
the form of randomly arranged plates and/or sheets. After melting,
there was a change in crystal morphology in relation to starting ma-
terial. Larger aggregates in which the lamellae were better organized
and neatly packed. According to Gönem et al. [37], melting was better
than precipitation for the synthesis of ZS solids.
Tests of zinc leaching were carried out after the ZS-catalyzed con-
version of palm oil to FAMEs. The zinc content in palm oil hydrolysates
varied from 38 to 60 mg kg−1, which corresponded to 0.04% of the
total zinc content of the ZS catalyst. Lower zinc contents of 13 and
15 mg kg−1 were obtained after simultaneous esterification and trans-
esterification of palm oil hydrolysates and after transesterification of
refined palm oil, respectively, corresponding to less than 0.01% of the
total zinc content of the ZS catalyst. Therefore, zinc leaching to the
reaction products was low, ranging from 0.01 to 0.04% in all cases.
There is no regulation for zinc content in biodiesel. However, the
maximum content of alkaline (sodium or potassium) and alkaline earth
metals (calcium and magnesium) is 5.0 mg kg−1 each. Hence, if these
values were extended to zinc, further washing steps would be required
to reach the current specifications for alkaline and alkaline earth metals
of internationally accepted biodiesel standards such as EN 14214 and
ASTM 6751.
3.7. Catalytic efficiency in palm oil hydrolysis
The ZS catalyst presented high TON values (Table 3) and such be-
havior demonstrates the good regeneration capacity of these carbox-
ylates, with no evidence of structural alterations after the first stage of
restructuration. Also, TON values increased with an increase in the
reaction temperature, therefore enhancing the ability of the catalyst to
convert more TAG molecules to FFA. However, at the same tempera-
ture, TON values decreased by increasing the percentage of catalyst in
the reaction system because less interactions were expected to occur
between reactants and a single catalytic site. By contrast, with an in-
crease in the oil-to-water MR while keeping the other reaction para-
meters unchanged, a slight positive influence in TON values was
578
Fuel 244 (2019) 569–579
observed, but not as much as that observed for an increase in the re-
action temperature. The molar masses adopted for these calculations
were 604.4 g mol−1 for ZS and 273.9 g mol−1 for palm oil FFAs.
TOF values indicate the number of reaction cycles at one single
catalytically active center per unit of time (Table 3). TOF calculations
for ZS indicated an excellent activity and fast regeneration of the cat-
alytic site. In general, both TON and TOF values exhibited the same
reaction behavior, that is, more catalytic cycles were observed with an
increase in temperature and oil-to-water MR and a decrease in catalyst
concentration.
The TON and TOF values for the simultaneous esterification and
transesterification reactions of the palm oil hydrolysate were 85.1 and
42.5 h−1, respectively. The values of TON and TOF determined for the
transesterification of palm oil were 60.1 and 30.3 h−1, respectively. The
molar masses adopted for these calculations were 604.4 g mol−1 for ZS,
344.6 g mol−1 for palm oil hydrolysate and 859.7 g mol−1 for palm oil.
As noted, the ZS presented high TON values and such behavior de-
monstrates the good regeneration capacity of these carboxylates in si-
multaneous esterification and transesterification as well as in transes-
terification reactions. The high TOF values indicate excellent activity
and rapid regeneration of the catalytic site.
4. Conclusions
The potential of ZS as catalyst for producing MAG, DAG and FFA
from palm oil was demonstrated. Hydrolysis occurred under subcritical
water, short reaction times and low pressures while its selectivity for
acylglycerols (DAG and MAG) or FFA could be adjusted by changes in
process variables such as temperature, palm oil-to-water MR and catalyst
concentration. The lamellar structure of the catalyst remained after its
use but its fatty acid composition changed by intercalation of a higher
percentage of saturated fatty acids. In addition, the high turnover fre-
quency of the system proved its great stability and capability to maintain
its catalytic performance in several consecutive reaction cycles.
Hydrolysis followed by simultaneous esterification and transester-
ification without removal of the catalyst afforded a 48% increase in
FAME content compared to direct transesterification using the same
catalytic system. Thus, zinc carboxylates had an effective performance
in hydrolysis as well as in both esterification and transesterification of
palm oil. In addition to the multiple applications demonstrated herein,
zinc carboxylates are inert, relatively inexpensive, safe and commer-
cially available solid catalysts.
A.M. Escorsim, et al.
Acknowledgments
The authors are grateful to CNPq (Grants 306920/2013-1, 558836/
2010-0 and 406737/2013-4) for the financial support to carry out this
study. This work was also financed in part by the Coordenação de
Aperfeiçoamento de Pessoal de Nível Superior – Brasil (CAPES) –
Finance Code 001.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.fuel.2019.01.178.
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