Catalysis Today xxx (xxxx) xxx–xxx

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Catalysis Today
journal homepage: www.elsevier.com/locate/cattod

Biphasic reaction of glycerol and oleic acid: Byproducts formation and phase
transfer autocatalytic effect
Mariana de S. Gomesa, Mariana R.D. Santosa, Adriana B. Salvianoa, Fernanda G. Mendonçaa,
Izadora R.S. Menezesa, Marina Jurischa, Guilherme D. Rodriguesa, Rodinei Augustia,
⁎
Paulo S. Martinsb, Rochel M. Lagoa,
a
Chemistry Department, Universidade Federal de Minas Gerais, MG, Belo Horizonte, CEP31270-901, Brazil
b
Fiat Chrysler Automobiles, MG, Betim, CEP 32669-185, Brazil

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

Keywords: This work investigates two new aspects of the biphasic esterification reaction of glycerol (G) and oleic acid (A),
Glycerol i.e. the formation of several oxidation/dehydration co-products and the effect of the ester products as phase
Oleic acid transfer agents to accelerate the reaction. Potentiometric titration, FTIR, TG and especially paper electrospray
Oleate ester mass spectrometry (PS-MS) were employed to analyze the products. Reactions with different G:A molar ratios
Biphasic
(1:0.5, 1:1 and 1:2) without catalyst at 140, 160 and 180 °C showed oleic acid conversions of 50–80% to form the
Phase transfer
mono, di and triesters with several other by co-products due to dehydrogenation/oxidation of the oleic chain and
dehydration of the glycerol moiety identified by PS-MS. The phase transfer autocatalytic effect was investigated
by the addition of the oleate esters (2, 4 and 10 wt%) to the reaction. It was observed a strong acceleration of at
the initial stage of the process indicating an autocatalysis likely due to a phase transfer effect. The reaction is
discussed in terms of three stages. In the initial biphasic Stage 1, oleic acid suffers some dehydrogenation/
oxidation and the esterification reaction takes place slowly at the glycerol-oleic acid interface to form mainly the
monooleate ester which is an amphiphilic/tensoactive molecule. In the Stage 2, the amphiphilic ester products
act as phase transfer agents taking glycerol molecules to the oleic acid phase for the formation of mono and
mainly dioleate ester. At the Stage 3 in the presence of relatively high concentration of the tensoactive ester
products the reaction becomes homogeneous/monophasic.

1. Introduction considerable interest. Several works investigated the reaction of gly-

Conversion of glycerol byproduct of biodiesel to different products,
such as hydrogen [1,2], ethanol [3], methanol [4], allylic alcohol [5],
dust suppressant [6], 1,2-propanediol [7,8], trehalose and propanoic
acid [9], has been intensively investigated in the last years [10–12].
Catalytic glycerol esterification with different acids such as acetic
[13,14], lauric [15,16], and valeric [17] has been proposed as a pro-
mising route to obtain value-added products. Glycerol esterification
with fatty acids in the presence of different catalysts has been reported
to form mixtures of mono, di and triacyl glycerides [11,18]. These
products show promising applications as additives in polymeric films
[19], formulations with antibacterial activity [20,21], food emulsifiers
[22,23], and as well as in pharmaceutical and cosmetic formulations
[24]. Therefore, these glycerol esterification reactions have attracted
cerol with fatty acids using solvents, e.g., t-butanol, in the presence of
tin-organic framework and montmorillonite clays as catalysts [25,26].
On the other hand, the majority of the works have focused on solvent-
free esterification in the presence of different catalysts such as ionic
liquids [27,28], methane sulfonic acid under microwave-heating [29],
modified natural zeolites [30], layered double hydroxide [18] and
immobilized lipases [31,32]. It is interesting to observe that although
the reaction of glycerol and fatty acid, e.g. oleic acid, is biphasic, most
of the published work did not mention nor considered diffusion lim-
itations in the process. The reaction of glycerol with oleic acid in the
presence of modified clinoptilolite indicated the importance of an am-
phiphilic catalyst to interact with the polar glycerol phase and the
hydrophobic oleic acid [30]. The location of the lipase immobilized on
poly(methylmethacrylate-co-divinylbenzene) [31] at the interface

⁎
Corresponding author.
E-mail addresses: mariana.ufmg@hotmail.com (M. de S. Gomes), marianards@ufmg.br (M.R.D. Santos), adrianasalviano@colab.ead.ufmg.br (A.B. Salviano),
nandagm@ufmg.br (F.G. Mendonça), izadora.rhaynna.s.m@gmail.com (I.R.S. Menezes), marina.jurisch@gmail.com (M. Jurisch),
guilhermedr@ufmg.br (G.D. Rodrigues), augusti@ufmg.br (R. Augusti), paulosergio.martins@fcagroup.com (P.S. Martins), rochel@ufmg.br (R.M. Lago).

https://doi.org/10.1016/j.cattod.2019.02.011
Received 1 May 2018; Received in revised form 16 December 2018; Accepted 10 February 2019
0920-5861/ © 2019 Published by Elsevier B.V.

Please cite this article as: Mariana de S. Gomes, et al., Catalysis Today, https://doi.org/10.1016/j.cattod.2019.02.011
M. de S. Gomes, et al. Catalysis Today xxx (xxxx) xxx–xxx

glycerol-oleic acid was also mentioned as an important factor for the

esterification. Up to date, no detailed study on the reaction dynamics
and diffusion limitations of the biphasic system glycerol-oleic acid has
been published in the literature. Moreover, despite the relatively high
temperatures used for the esterifications, no attention has been paid to
collateral reactions, such as oxidation and dehydration commonly ob-
served for fatty acids and glycerol.
In this work, it was studied the reaction between glycerol and oleic
acid looking at the potential effect of the tensoactive reaction products,
i.e. oleate esters of glycerol, as phase transfer agents in an autocatalytic
reaction. Although several examples of different reactions are reported
to be accelerated by phase transfer catalysts [33–35], molecules such as
glycerol oleate esters have never been reported to have this effect.
Moreover, the paper spray mass spectrometry (PS-MS) was used to in-
vestigate the formation of coproduct by products related to oxidation
and dehydration processes.

2. Materials and methods

The reaction of glycerol (G) with oleic acid (A) was studied in dif- Fig. 1. Conversion of oleic acid during the reaction with glycerol at different
ferent molar proportions (1:0.5, 1:1 and 1:2) at 140, 160 and 180 °C. temperatures 140, 160 and 180 °C.
These reactions are named hereon according to the molar ratio and
temperature, e.g. G1:A1160 (glycerol : oleic acid molar ratio 1:1 at oleic acid takes place in the glycerol phase. The titrations of the oleic
160 °C). acid phase were used to calculate the acid conversion. The effect of
The reaction was carried out in a beaker containing glycerol and temperature on the oleic acid conversion is shown in Fig. 1.
oleic acid in an oil bath under stirring for 5 h. The reaction was mon- It can be observed at 140 °C no significant oleic acid conversion up
itored by titration with sodium hydroxide (0.5 mol L−1). to 1 h of reaction. During the second hour, however, reaction a strong
Infrared spectra (FTIR) were obtained on a Perkin Elmer conversion was observed. After 3 h the oleic acid conversion increased
Spectrophotometer Frontier Single Range, by the Attenuated Total linearly reaching 49% at 6 h. A similar behavior was observed for the
Reflectance (ATR) technique and registered in the region of 4000 - reaction carried out at 160 °C which reached oleic acid conversions ca.
550 cm−1, resolution of 4 cm−1 and 16 scans per sample. 66%. It was interesting to observe that the biphasic reactions gradually
The thermal stability of the obtained product was studied by TG/ become yellow/brown in color and at near 2.5 h changed to mono-
DTG (TG DTG Shimatzu-60 H) instrument under N2 dynamic atmo- phasic.
sphere, with a heating rate of 10 °C min−1 at 900 °C. On the other hand, the reaction at 180 °C showed a more important
The reactions were monitored using the paper spray mass spectro- oleic acid conversion of 21% already in the first hour and reached ca.
metry (PS-MS) technique. Under the optimized conditions, the ester- 85% after 6 h. Moreover, it was observed a mixing and homogenization
ification reaction reached equilibrium after approximately 5 h. All PS- of the biphasic mixture at near 2 h reaction.
MS experiments were performed using a LCQ Fleet (Thermo Scientific, The reaction at 160 °C at different times was analyzed by FTIR and
San Jose, CA, USA) mass spectrometer operating in the positive ion TG. The FTIR spectra showed a gradual disappearance of the band near
mode. The instrumental conditions were as follows: voltage applied to 1710 cm−1, related to COOH (C]O stretching) of oleic acid [36,37],
the paper, 4 kV; capillary temperature, 275 °C; capillary voltage, 35 V; and the appearance of the band near 1737 cm−1, characteristic of the
tube lens voltage, 65 V. Full scan mass spectra were recorded for all ester C]O stretching [38,39] (Fig. 2).
analyzes over a 100–1000 m/z range. For the PS-MS experiments, small
pieces of a chromatographic paper (grade 1, purchased from Whatman
International Ltd., Maidstone, Kent, England) were cut in a triangular
format (10 mm height and 5 mm base width). The paper was then po-
sitioned approximately 5 mm away from the mass spectrometer inlet,
using a metal clip fixed to a platform with three-dimensional move-
ment. An optimized high voltage (4.0 kV) was applied to the paper base
through the metal clip whereas sample (5 μL) and HPLC grade methanol
(5 μL) were added at the central portion of the triangle. To avoid
memory effects, each analysis was performed on a new paper.
For the autocatalysis study, the reactions were carried out with the
addition of the product of t = 5 h of the reaction G1: A1 - 160 °C at
t = 0 h of the reactions in the concentrations of 2, 4 and 10 wt% in the
reaction system G1:A1 – 160 °C at t = 0 h.

3. Results and discussion

The reactions of glycerol with oleic acid were performed with gly-
cerol:oleic acid molar ratio 1:1 (G1:A1) at 140, 160 and 180 °C without
catalyst.
The reaction was initially biphasic and the oleic acid consumption
was monitored by FTIR and NaOH titration of both phases, i.e. glycerol
and oleic acid. The analyses showed no significant chemical modifica- Fig. 2. FTIR spectra of the reaction G1:A1160 at different times and glycerol
tion of the glycerol phase. The results also showed that no dissolution of conversion into mono, di and trioleate ester.

2
M. de S. Gomes, et al.
Fig. 3. DTG analyses of the reactions G1: A1140, G1: A1160, G1: A1180, glycerol,
oleic acid and soybean oil.
TG analyses of the reactions G1:A1140, G1:A1160 and G1:A1160 after
6 h of reaction showed broad weight losses centered at ca. 250, 320,
380 °C. DTG analyses of pure oleic acid, glycerol and the tri-oleic ester
of glycerol (see Fig. 3) indicated that the peak at 250 °C could be related
to oleic acid, whereas the weight losses centered at 320 and 380 °C can
be related to the mono and the diester, respectively.
The reaction at 160 °C at different times was also monitored by
Paper Spray ionization mass spectrometry (PS-MS). PS-MS is a recently-
developed ambient ionization method. In PS-MS, the tip of a triangular
paper is placed in front of the mass spectrometer inlet whereafter a high
voltage is applied through a metal clip connected to its base. The
sample is then added to the central part of the triangle while a solvent is
added at its base. A spray emerges from the tip and charged analytes are
attracted into the mass spectrometer to be analyzed [40–45]. Due to its
peculiar characteristics, PS-MS has shown to be a convenient approach
to monitor reactions taking place in the condensed phase. Fast re-
sponses can be achieved, thus allowing the attainment of real-time and
quite useful information regarding a given reactional process. The PS-
MS obtained are shown in Fig. 4.
The results obtained for the reaction at t = 0 h (after ca. 1 h heating
to reach 160 °C) showed no significant formation of esters. On the other
hand, the PS-MS indicated some modification of the oleic acid. The
mass spectrum showed no ion at m/z 283 related to the protonated oleic
acid molecule. However, strong signals are observed at m/z 561 and
563 likely related to the dehydrogenated oleic acid dimers, i.e. [2(OA) -
H2]H+ and [2(OA) - 2H2]H+, respectively. These results seem to in-
dicate that during the heating phase to reach 160 °C, the oleic acid
molecule lost hydrogen probably by an oxidation process according to
the simplified reaction (Eq. (1)):
C17H33COOH → C17H32COOH/C17H30COOH + [H2O]
It can also be observed two ions at signals m/z 577 and 579 which
are likely related to oxidized molecules, e.g. epoxides. Similar dehy-
drogenation and oxidation processes have been observed in previous
works on the ozonization of oleic acid [46] and thermal stress of soy
bean oil [47,48].
After 2 h, the esterification product is observed by the new ion at m/
z 357 related to the protonated form of the oleate glycerol monoester
[M+]H+]. It is interesting to observe an intense ion signal at m/z 339
likely related to the monoester dehydrated [(M)–H2O]H+, suggesting a
possible dehydration process. Although this dehydration process is not
clear, it likely takes place in the glycerol moiety forming groups such as
ketone and aldehyde (Eq. 2).
Catalysis Today xxx (xxxx) xxx–xxx
RCOOCH2CH(OH)CH2OH → RCOOCH2C = OCH3/RCOOCH = CHCHO
+ [H2O] (2)
Similar dehydration processes have been observed before during
oligomerization of glycerol [48].
The ions at m/z 603, 617 and 637 are related to the beginning of the
diesters [D] formation. The ion at m/z 617 is related to the diester after
the loss of H2, [(D)-H2]H +. The ion at m/z 637 refers to the diester with
an oxygen atom (epoxy), [(D)+O]H+. The m/z 603 corresponds to the
diester that suffered the loss of H2O, [(D)-H2O]H+. No ion related to
trioleate was observed at this stage. After 5 h reaction, howevwe, the
relative intensities of the monoester-related ions decreased and lower-
intensity ions at m/z 901 and 917 likely due to the trioleate [T]
emerged. The first ion refers to trioleate with the loss of 2 molecules of
hydrogen [(T)-2H2]H + whereas the second ion one is related to oxi-
dized trioleate, i.e. [(T)+O]H+, both resulting from oxidation of the
main reaction product (trioleate) [49,50].
Based on the MS data, a plot with the relative abundances of oleic
acid and esters was built, as shown in Fig. 5.
It can be observed that the relative intensity of the oleic acid signal
rapidly decreased up to 2 h reaction. In this period, the relative in-
tensities of the signals for the mono and specially diester increased.
After 2 h the monoester relative signal intensity decreased whereas the
diester went on increasing. This result seems to suggest that both mono
but specially diester are formed at the beginning of the reaction. After
2 h, part of the monoester is apparently converted to the diester. The
relative signal intensity concentration of triester remains low
throughout the reaction.
The Paper ESI-MSPS-MS relative intensity data for the mono, di and
triester was also used to investigate the effect of temperature on the
reactions G1:A1140, G1:A1160 and G1:A1180 (Fig. 6).
It can be observed that at 140 °C the main product is the diester with
a relative abundance of ca. 54% and the monoester with 40%. As the
temperature increased to 160 °C the diester increased to 65% and the
monoester decreased to 28%. At 180 °C the diester reached ca. 70% and
the monoester further decreased to 22%.
It is interesting to consider based on the PS-MS and TG results that
no free glycerol was observed after 5 h reactions. As the amount of
glycerol used in the reaction was enough to produce the monoester,
these results suggest that glycerol is lost during the reaction by eva-
poration.
The effect of the glycerol:oleic acid molar ratio was also in-
vestigated at 160 °C by the reactions G1:A0,5160, G1:A1160 and G1:
A2160. The ESI-MS spectra PS-MS data were used to estimate the
abundance ratio of the mono, di and triesteres (Fig. 7).
It can be observed for G1:A0,5160 (a high glycerol:oleic acid molar
ratio) that the main product is the diester with 66% relative abundance.
As the concentration of oleic acid increased the relative formation of
the diester increased as expected, reaching a relative concentration of
ca. 70%.
It was also investigated a possible phase transfer catalysis effect by
adding the dioleate glycerol ester to the biphasic reaction at propor-
(1) tions equal to 2, 4 and 10 wt%. It was observed that upon the addition,
the diester was located at the glycerol-oleic acid interface. After vig-
orous stirring, the diester was mixed to the oleic acid phase. No sig-
nificant diester concentration was detected by FTIR in the glycerol
phase.
Upon heating of the biphasic mixtures glycerol-oleic acid
(G1:A1160) containing 2, 4 and 10 wt% of the diester, the conversion of
oleic acid was monitored as shown in the curves presented in Fig. 8.
It can be observed for the reaction G1:A1160 that the oleic acid
conversion increases slowly only after 1.5 h reaction. In the presence of
2 and 4 wt% diester, oleic acid conversion is already observed at 1 h
reaction. On the other hand, with 10 wt% diester the conversion
reached ca. 45% at near 1 h reaction. These results clearly indicate that
3
M. de S. Gomes, et al.
Fig. 4. PS(+)-MS of the aliquots of the reaction 1G:A1160 collected after 0, 2 and 5 h.
the ester products accelerated the reaction. The ester products have a
tensoactive nature, where the glycerol moiety is more polar/hydro-
philic whereas the oleate moiety is strongly hydrophobic and interacts
with the oleic acid phase. Therefore, the mono and diester products are
likely acting as phase transfer catalyst carrying glycerol molecules to
the oleic acid phase.
Considering these results, the reaction can be discussed in terms of
three different stages. At Stage 1 (Fig. 9) glycerol and oleic acid do not
mix and the reaction takes place at the interface. The monoester formed
is an amphiphilic molecule, with the polar glycerol moiety and the
hydrophobic oleate ramification and it will likely be located mainly at
4
Catalysis Today xxx (xxxx) xxx–xxx
the interface.
At the second stage (Fig. 10), the amphiphilic ester product acts as a
phase transfer catalyst and carry glycerol molecules to the oleic acid
phase and the esterification is accelerated. As the oleic acid is present in
high concentration, the second esterification takes place to form pre-
ferentially the diester. Likely, the esterification to form the triester does
not occur significantly due to sterical hindrance.
In Stage 3, the amphiphilic molecules are formed in quantities en-
ough to promote the homogeneous mixture of the two phases, i.e.
glycerol and oleic acid.
M. de S. Gomes, et al. Catalysis Today xxx (xxxx) xxx–xxx

Fig. 5. Relative abundances of oleic acid, mono, di and trioleate esters of gly- Fig. 7. Relative abundance of mono, di and triglycerides after 5 h reactions in
cerol for the reaction G1:A1160 obtained acquired from the PS-MS data. the molar ratios of G1:A0,5160, G1:A1160 and G1:A2160.

Fig. 8. Autocatalysis study of the esterification reaction with the addition of 2,

Fig. 6. Selectivity of mono, di and triesters after 5 h G1:A1 reactions at 140 and 4 and 10 wt% of the product G1: A1160 at the beginning of the reaction, com-
160 °C. pared to the reaction without the addition of the diester.

4. Conclusions

The biphasic esterification reaction of glycerol (G) and oleic acid (A)
has been reported in many recent works but several aspects of this re-
action have been neglected. The use of paper spray MS mass spectro-
metry showed that at temperatures 140–180 °C, besides the esterifica-
tion reaction, several collateral processes take place, such as the oleic
acid chain oxidation/dehydrogenation and glycerol moiety dehydra-
tion. Moreover, the esterification reaction is limited by diffusion pro-
cesses. As the reaction initiates, the amphiphilic/tensoactive oleate
ester derivatives are likely acting as phase transfer agents and carry
glycerol molecules to the oleic acid phase where the esterification re-
action takes place to form the mono but mainly the dioleate ester. As Fig. 9. Schematic representation of ester formation at the glycerol-oleic acid
the concentration of the oleate esters increase the reaction become interface (Stage 1).
homogeneous/monophasic.

Acknowledgements

The authors gratefully acknowledge the financial support of Fiat

Chrysler Automobiles group for the financial assistance of the fluid

5
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Fig. 10. Schematic representation of the phase transfer of glycerol to oleic acid followed by the esterifications to form the mono and diester (Stage 2).

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