Applied Catalysis A, General 566 (2018) 121–129

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Applied Catalysis A, General

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

Biofuels production by esterification of oleic acid with ethanol using a T

membrane assisted reactor in vapour permeation configuration
⁎
Catia Cannilla , Giuseppe Bonura, Fabio Costa, Francesco Frusteri
CNR-ITAE, Istituto di Tecnologie Avanzate per l’Energia “Nicola Giordano”, Via S. Lucia 5, 98126 Messina, Italy

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

Keywords: Biodiesel production by performing the oleic acid esterification reaction in a new reactor system, realized by
Oleic acid coupling the batch reactor with a tubular permeoselective membrane, has been investigated. Such reactor
Esterification reaction configuration was adopted to remove the water produced as by-product during the reaction thus increasing the
Biodiesel oleic acid conversion and the alkyl ester production. The activity of acid catalysts and zeolites was evaluated in
Methanol
presence of methanol and ethanol. The membrane resulted much more selective towards water separation when
Ethanol
Vapor permeation
ethanol was used, allowing to force thermodynamic equilibrium at higher conversion values. Very interesting
Membrane results in terms of oleic acid conversion were achieved with both methanol and ethanol (96% and 98% re-
spectively) in presence of a commercial Amberlyst-15 catalyst, at 80 °C, at a low membrane surface to gas
volume ratio (0.20 cm−1) and low acid/alcohol molar ratio (2/1 and 1/1 respectively). Over zeolite samples,
conversion values higher than 60% were obtained at 100 °C after 5 h in the esterification reaction performed in
vapor permeation configuration.

1. Introduction
Biodiesel is a fatty acids alkyl esters (FAAEs) mixture, derived from
renewable lipid feedstocks (vegetable oils, animal fats or waste cooking
oils), which could be considered a suitable substitute for petroleum
derivate fuels due to its environmental benefits [1]. Cetane number,
energy content, viscosity and phase changes of biodiesel are similar to
those of fossil diesel [2–4]. FAAEs are generally produced by transes-
terification reaction between the triglycerides contained into oils or fats
and an alcohol; anyhow, the moisture and the free fatty acids (FFAs)
present into the feedstock could react with the homogenous alkali
catalyst used in the industrial process, producing soaps and gels. This
reduces the FAAEs yield and deeply influences the performance and the
economics of biodiesel production [5]. So, to use low-cost feedstocks
(waste frying oils or fats and oils with high FFAs amount), a pretreat-
ment esterification step is mandatory to reduce the free acidity level
below 1% wt/wt. Therefore, the esterification reaction can be exploited
both as a pre-treatment step of a conventional transesterification pro-
cess [6,7] or as biodiesel direct production [8,9]. Methanol (MeOH),
ethanol (EtOH) and butanol (ButOH) are the most employed alcohols
[10]. Anyhow, the biological nature of EtOH and its extra-carbon atom,
which slightly increases the heat content and the esters cetane number,
make ethyl esters (EEs) more interesting than methyl esters (MEs).
Moreover, EtOH is nontoxic and has better solvent properties than
MeOH for oil solubility and EEs have cloud and pour points lower than
the MEs [10].
The esterification of oleic acid (OlAc) can represent well the bio-
diesel production, since it is present in most of oil crops [11]. With
EtOH, ethyl oleate (OleOEt) is produced and water is the by product,
according to the following equation:
C8H17CH=CH(CH2)7COOH + CH3CH2OH ⇆ C8H17CH=CH
(CH2)7COOC2H5 + H2O (1)
The industrial esterification processes carried out with strong
Brønsted acid catalysts [12–14] are not environmentally benign, since
they require special treatments as neutralization involving costly cata-
lyst separation steps from the homogeneous reaction mixtures. Het-
erogeneous catalysts could be easier separated, they show high activity
and stability and could be reused offering milder operating conditions.
Ion exchange resins [15,16], zeolites [17–19], heteropolyacids [20] and
modified zirconia [21,22] are the most used solid acid catalysts for
OlAc esterification. Besides, niobic acid [23], polymers with acid

Abbreviations: Ai, initial acidity; Af, final acidity; FAAEs, fatty acids alkyl esters; FFAs, free fatty acids; EEs, ethyl esters; MEs, methyl esters; MVol, micropore
volume; OlAc, oleic acid; OleOEt, ethyl oleate; PV, pervaporation; PVol, pore volume; SA, surface area; Sm, surface of the membrane; TPD, temperature programmed
desorption; VP, vapor permeation; Vg, volume of gas phase
⁎
Corresponding author.
E-mail address: catia.cannilla@itae.cnr.it (C. Cannilla).

https://doi.org/10.1016/j.apcata.2018.08.014
Received 2 May 2018; Received in revised form 2 August 2018; Accepted 16 August 2018
Available online 18 August 2018
0926-860X/ © 2018 Published by Elsevier B.V.
C. Cannilla et al.
groups [24]; ammonium salt of TPA [25], carbon material [26] were
used too. Anyhow, considering the reaction equilibrium, the water
produced and that contained into waste oils could hinder the ester-
ification, accelerating the inverse reaction. Amberlyst-15 (A-15), for
example, resulted to be a suitable catalyst for OlAc esterification with
MeOH [27], but the conversion rate increased only replacing MeOH
and catalyst with fresh one or by removing water from the reaction
mixture. For this reason, it is of great interest, from a practical point of
view, to study separation processes able to eliminate the water during
the reaction [28].
On this account, Son et al. [29] obtained high MEs yield by per-
forming the OlAc esterification in a three-phase fixed bed reactor
(80 °C–120 °C) coupled with a continuous water evaporation system.
Nijhuis et al. [30] exploited a reactive stripping operation in a mono-
lithic reactor; Lucena et al. [5] employed a reactor coupled to an ad-
sorption column filled with zeolite 3A in the OlAc esterification with
MeOH using H2SO4 as catalyst and shifted the biodiesel yield from
88.2% to 99.7% at 100 °C.
Recently, the integration of chemical reaction with the membrane
separation has received great attention: the use of a reactor equipped
with a permeoselective membrane significantly improves the process
efficiency favoring not only the chemical equilibrium shift but also a
longer catalyst lifetime [31–33]. Specifically, pervaporation (PV) and
vapor permeation (VP) technologies could be considered as clean
technologies which, because of low temperatures and pressures in-
volved, could efficiently replace conventional energy-intensive se-
paration processes [34–37]. They are based on the use of a semi-
permeable active or passive membrane which allows the separation of
one or more species of a mixture by their passage from one site to the
other one on the basis of a sorption-diffusion mechanism. Considering
that in PV, the feed is a liquid, a liquid-vapour phase change is required
involving an enthalpy of vaporization, as a function of the concentra-
tion gradient between the phases on the opposite site of the interfacial
barrier. Instead, in VP the feed is a vapour mixture. In such a case, no
phase change or no significant temperature differences across the
membrane are required, the driving force being the partial pressure of
the component in the feed. A noteworthy advantage of VP configuration
is that the membrane is not in contact with the liquid reaction mixture
rather, thus a longer membrane lifetime is assured [38].
So far, PV process has been exploited in some liquid-phase equili-
brium reactions for biofuels production, while very low papers deal
with the use of VP technique. Kita et al. [39] published one of the first
papers regarding gas separation in the carboxylic acids esterification
with alcohols, demonstrating that, by selecting suitable permeation
conditions, total conversion could be achieved. The water vapor was
removed using a polyimide hollow fiber membrane module placed on
the top of a stirred batch vessel; p-toluenesulfonic acid was the catalyst
[39,40]. Yamamoto et al. [41] and Okamoto et al. [42] exploited the
very high permeation flux, water affinity and selectivity of NaA zeolite
membrane in VP configuration to improve the esterification reaction
performance.
In this paper, the efficiency of a coupled reactor-membrane set-up
was demonstrated by performing the heterogeneous esterification of
OlAc in presence of a commercial permselective membrane in VP
configuration. In this case, two separate units, a batch reactor and an
external separation module, were employed. This set-up allows to make
clean-up or regeneration steps easier and to optimize independently
both the catalytic behavior and the separation step. Solid acid catalysts,
as A-15 resin and some zeolites, have been used in the esterification
either with MeOH or EtOH. The obtained results have been compared
with typical runs performed without the use of membrane.
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Applied Catalysis A, General 566 (2018) 121–129
2. Materials and methods
2.1. Reagents
OlAc purchased from Sigma Aldrich presented 99% oleic acid and
1% mixture of palmitoleic acid, palmitic acid and myristic acid, with an
acid value of 139.9 mg of NaOH/g. Methanol (> 99%) or anhydrous
ethanol (> 99%) were supplied from Fluka.
2.2. Catalysts
Amberlyst-15 wet ion exchange was purchased from the Dow
Chemical Company, whereas the zeolite catalysts were supplied by
Alpha Aesar. A-15 resin was used without any pretreatment. Zeolites
have been calcined for 6 h at 500 °C. Two solid acid supported catalysts
have been prepared by dry impregnation of two microspherical silica
(ES70Y and MS3030 by PQ Corporation) in an ethanolic solution with
Hyflon® Ion S4X perfluorosulphic ionomer (20 wt%) with an equivalent
weight of 730 (Solvay Solexis) [43].
2.3. Catalyst testing
OlAc esterification reaction was carried out in two stainless steel
reactors of different volumes (90 and 300 cc), with a constant stirring
rate of 1100 min−1. Experiments were performed under autogenous
pressure by maintaining the temperature in the range 65–100 °C. The
amount of catalyst, in respect to the OlAc (Rcat/OlAc) was varied from 1
to 15 wt.% and the alcohol/OlAc molar ratio (RAlcohol/OlAc) was in the
range 1–1 to 20–1. The reactants and the catalysts were loaded into the
reactor in the fixed ratio, nitrogen flux was employed for reactor
cleaning and then the reactor was heated to the desired temperature. At
the end of the reaction, the reactor was cooled down with an ice bath to
condense gaseous products. The catalyst was recovered by filtration.
The batch reactor and the water separation module were two dis-
tinct units and the schematic configuration of the reaction system was
shown in Fig. 1. The gas phase (mainly containing the alcohol and the
water) was recirculated through the water permselective membrane
(HybSi), provided by Pervatech BV [35,36]. The membrane
(250*10*7 mm) had an effective area of 0.005 m2, the substrate mate-
rial was a γ-alumina phase whereas the top layer was a hybrid silica
coated on inside of the support tube. It could operate at a maximum
temperature of 150 °C and a pressure of 10 bar, in the pH range of
2–8.5, showing a permeability to pure H2O of 19.66 l/m2 bar at 150 °C.
To avoid the gas phase condensation, during the reaction, the re-
circulation loop was maintained at 115 °C. The recirculation of gas
phase was maintained constant (2.8 L/min) by using a gas-pump
equipped with a variable potentiometer. At the permeate side of the
membrane, the permeate was purged with a stream of carrier gas (N2,
2 L/min) and the permeate was finally obtained in the liquid state after
condensation to be subsequently analyzed.
2.4. Biodiesel analysis
Conversion of OlAc was calculated based on the AOCS (American
Oil Chemist’s Society) official methods for acid value (Cd 3d-63) and
FFA amount (Ca 5a-40). Samples were analyzed by a standard acid-base
titration procedure for the evaluation of the free residual acidity. The
analysis repeatability has been improved by removing methanol or
ethanol in excess and water formed in a vacuum condenser, prior to
submit the samples to titration. A weighed amount of the sample was
dissolved in an ethanol/ethylic ether mixture 1/1 wt/wt and then was
titrated with a NaOH 0.5 M solution and phenolphthalein as indicator.
The volume of alkaline solution consumed was recorded and the acidity
of the sample was determined by means of the Eq. (2), referred to the
oil phase (oleic acid + ester) with an error less than 1–2% on the free
acidity
C. Cannilla et al.
Fig. 1. Schematic configuration of batch reactor coupled with the permeoselective membrane. The insert shows the ceramic tubular membrane [A] and the PVM-035
membrane housing [B].
Acidity = Vtitr(mL) * Ctitr (mol/L) * MWOlAc/(1000 * gsample) * 100 (wt.
%) (2)
The acidity was expressed as OlAc weight percent. The OlAc con-
version was calculated as the fraction of the removed acid:
OlAc conversion = (Ai − Af)/Ai * 100
where Ai and Af indicate the initial and final acidity of the solution
respectively.
2.5. Catalyst characterization
The textural properties of catalysts were determined by physical
adsorption measurements of nitrogen to its boiling point (−196.15 °C)
using a Micromeritics ASAP2020 gas adsorption device. The isotherms
were elaborated for assessment of surface area (SA) and porosity
(PVol), with the micropore volume (MVol) determined by the t-plot
approach. Surface concentration of acidic sites was determined by
temperature programmed desorption of ammonia (NH3-TPD) for zeo-
lite. Before TPD experiment, the catalyst sample (∼100 mg) was satu-
rated for 2 h at 150 °C under a gas mixture containing 5 vol.% of NH3/
He (flow rate = 25 stp mL/min). Then, the sample was purged in he-
lium flow until a constant baseline level was attained. The measure-
ment was performed in the temperature range 100–700 °C, at a rate of
10 °C/min using helium (25 stp mL/min) as the carrier flow. The
evolved gases were detected by an on-line thermal-conductivity de-
tector, calibrated by the peak area of known pulses of NH3.
Potentiometric titrations were performed to evaluate the acid capacity
(meq gcat−1) of the Hyflon-based systems according to the procedure
elsewhere described [43].
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Applied Catalysis A, General 566 (2018) 121–129
3. Results and discussion
3.1. Oleic acid esterification with MeOH
The homogenous esterification reaction of oleic acid is generally
carried out using H2SO4 as catalyst: a small amount of catalyst (0.01%
wt/wt) is enough to promote the reaction [5]. Anyhow, heterogeneous
catalysis could be more advantageous from many points of view
avoiding reactor corrosion, aqueous waste production and the need of
costly neutralization and separation steps.
The operating conditions that mainly affect the conversion of OlAc
into biodiesel are the temperature, the amount of catalyst and the al-
cohol/OlAc molar ratio. Specifically, the stoichiometry amount of
molar ratio alcohol/OlAc is 1; however, in literature, a very high al-
cohol to fatty acid molar ratio has also been reported to improve the
esterification reaction rate [14,44,45] by mitigating the inhibiting ef-
fect of the water formed which tends to reverse the reaction.
Some preliminary experiments of esterification with MeOH have
been carried out at 80 °C by using solid acid catalysts with a Rcat/OlAc
equal to 5 wt.%, lower than that usually used in literature [46]. The
results obtained are reported in Table 1 along with main chemical-
physical properties of catalysts used. Specifically, the performance of
the A-15 resin was evaluated along with HZSM-5 zeolite with a Si/Al
ratio of 23 and two Hyflon-based catalysts on spherical silica (20H730/
MS3030 and 20H730/ES70Y). High stirring rate of the mixture
(1100 rpm) was employed to avoid external mass or heat transport
limitations. After two hours, by employing a RMeOH/OlAc of 2 mol/mol,
the activity of A-15 was the highest. This result is mainly correlable
with a higher acidity of A-15 (4.50 meqH+ gcat−1) in respect of the
other systems (< 1.00 meqH+ gcat−1) and confirms the good properties
of the resin in terms of esterification efficiency already reported in
literature [46].
By considering such preliminary results, A-15 was employed for the
study finalized to optimize the reaction conditions.
First of all, the influence of the alcohol amount and the reaction
C. Cannilla et al. Applied Catalysis A, General 566 (2018) 121–129

Table 1 water formation. In addition, the presence of water in the reaction

Main physico-chemical properties of catalysts employed in OlAc etherification medium could negatively affect the reaction rate upon adsorption on
(TR = 80 °C; RMeOH/OlAc = 2 mol/mol; Rcat/OlAc = 5 wt.%; time = 2 h). acid sites of solid catalysts, so blocking the access of the reactants
Catalyst SA (m2 g−1) PVol Acidity OlAc [17,46].
(cm3 g−1) (meqH+ gcat−1) conversion (%) Thus, in the attempt of overcoming such equilibrium restrictions a
water permeo-selective membrane was used, coupled with the batch
A-15a 45 0.40 4.50 67.0
reactor, by exploiting the VP technology. As previously reported
20H730/ 177 0.33 0.88 51.4
ES70Y [35,36], the membrane was not in direct contact with the reaction li-
20H730/ 204 0.33 0.77 32.6 quid mixture, gas phase being forced to circulate through the mem-
MS3030 brane by a pump. The “driving force” to favor the water permeation
HZSM5 498 0.20 0.30 18.3
was ensured by the pressure difference between the reactor (auto-
(23:1)
genous pressure) and the environment (permeate side). The preliminary
a
Data supplied by Rohm and Haas. SABET= Surface Area. PVol = Pore results obtained using the permselective membrane with the methanol
Volume, determined from N2 ads/des isotherms at −196.15 °C. in presence of A-15 are reported in Table 2. The removal of water po-
sitively affected the reaction favouring the acid conversion, which in-
creased from 67.0% (run 1, without the membrane) up to 80.2% (run 2,
with the membrane) after 2 h. Nevertheless, by using a higher RMeOH/
OlAc, the acid conversion followed a sort of volcano shape trend with a
maximum value for a molar ratio of 4 (83.7%).
To achieve high conversion values in a short reaction time, a fun-
damental parameter to take into consideration is the water permeation
rate. In this regard, from results reported in Table 2, it can be observed
that the amount of water collected at the same reaction time (2 h) and
the theoretical water permeation rate (evaluated on the OlAc conver-
sion values) changed with the MeOH/OlAc molar ratio, decreasing with
the methanol amount. Specifically, when the methanol amount was
high (run 4), no permeated water was trapped. This is likely because of
lower water partial pressure in the gas phase recirculated trough the
membrane when higher MeOH concentration was used. In such a case,
the water permeation capability of the membrane resulted to be lim-
ited. Anyhow, at low MeOH/OlAc molar ratio, the condensation system
resulted to be more efficient, in fact 27.6% of theoretical water was
recovered after 2 h (run 2) which increased up to 56.3% after 5 h (run
5). Naturally, when the permeation of water was more efficient, the
acid conversion achievable was higher. In fact, in run 5, the acid con-
version approached 97.3%, so confirming the benefit obtained in terms
of equilibrium shift due to water removal through the membrane.
Anyhow, by analyzing the water solution recovered during the re-
action, it has been observed that a little amount of MeOH passed
through the membrane along with the water (5 wt.%). This was much
more evident when the reactor with a lower volume (90 cc) was used. In
fact, in this case, the OlAc conversion didn’t increase, rather after 5 h,
the OlAc conversion was only 74.0% (run 6) and no water was re-
covered. This result likely suggests that the membrane performance is
not high when the water concentration in the gas phase is too low.
Another factor to consider in the configuration of membrane reactor
is the recirculation rate of gas phase containing the water vapor, which
also plays an important role. Specifically, as shown in Fig. 3, regardless
the MeOH/OlAc molar ratio used (2 or 4), higher amounts of water
Fig. 2. Esterification reaction of oleic acid with MeOH and A-15: [A] Influence permeated through the membrane and therefore higher oleic acid
of MeOH/OlAc molar ratio (TR = 80 °C; Rcat/OlAc = 5 wt.%; time = 2 h). [B] conversion values were achieved when higher recirculation rate were
Influence of reaction time (TR = 80 °C; RMeOH/OlAc = 4 mol/mol; Rcat/OlAc used. Specifically, limiting the gas phase recirculation, or rather by
= 5 wt.%). filling almost completely the reactor (Sm/Vg = 0.71 cm−1, where Sm is
the surface of the membrane and Vg is the volume of gas phase eval-
time were evaluated at 80 °C. Fig. 2A clearly shows that the reaction uated at the beginning of the reaction), the maximum oleic acid con-
rate is slightly affected by the MeOH/OlAc molar ratio considering that version reached after 2 h of reaction was about 64.2% and no water was
by increasing it from 2 up to 4, OlAc conversion increases from 67.0% collected. On the contrary, almost total conversion (96.1%) was ob-
to 72.1% then reaching a plateau (73.1% at RMeOH/OlAc = 8 mol/mol). tained along with 53.2% of theoretical water when gas phase volume
So, the use of a MeOH/OlAc molar ratio higher than 4 does not produce was higher (Sm/Vg ratio of 0.20 cm−1). It is evident that, with high
noteworthy effects. On the other hand, Fig. 2B shows that the reaction recirculation flow, the turbulence regime necessary to improve water
does not take place with high reaction rate and equilibrium conditions permeability is ensured and high conversion can be achieved.
are reached only after 6–8 h.
According to the literature evidences [5,28,46], the total OlAc 3.2. Oleic acid esterification with ethanol
conversion and the production of high esters yield are limited by the
reversibility of the reaction and the equilibrium constraints due to the In Fig. 4, a comparison of the activity of A-15 catalyst in the oleic
acid esterification with MeOH and EtOH is shown in terms of effect of

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Table 2
OlAc esterification reaction in presence of MeOH with and without the membrane (TR = 80 °C; Rcat/OlAc = 5 wt.%).
Run RMeOH/OlAc (mol/mol) Time (h) OlAc conversion (%) Sm/Vg (cm−1)a H2Oteor. (g)b H2Oteor. (g)c H2OColl (%)d H2O permeation rate (h−1)e

1f 2 2 67.0
2 2 2 80.2 0.27 5.10 4.09 27.6 0.066
3 4 2 83.7 0.27 4.33 3.63 20.1 0.032
4 8 2 79.8 0.27 3.25 2.60 – 0.014
5 2 5 97.3 0.32 6.37 6.04 56.3 0.038
6g 2 5 74.0 0.72 0.96 0.71 –

a
Sm = surface of the membrane; Vg = volume of gas phase evaluated at the beginning of the reaction.
b
Water amount evaluated by theoretical total OlAc conversion.
c
Theoretical water amount evaluated by measured OlAc conversion.
d
Percentage of water collected as a function of theoretical water (b).
e
Value obtained considering the theoretical water amount produced by measured OlAc conversion.
f
Run carried out without membrane.
g
Run carried out by using a 90 cc reactor.

Fig. 3. Influence of Sm/Vg ratio on the esterification reaction of oleic acid with
MeOH in presence of membrane (catalyst: A-15; TR = 80 °C; RMeOH/
OlAc = 2 mol/mol; Rcat/OlAc = 5 wt.%; time = 2 h). Triangle symbols are re-
ferred to the run with RMeOH/OlAc = 4 mol/mol.

reaction temperature on OlAc conversion and activation energy is

shown. Esterification with methanol resulted to be more endothermic
than with ethanol [45] and a pseudo first order dependence for fatty
acid esterification emerged. From the conversion data obtained at dif-
ferent temperatures, the apparent activation energy was determined by
Arrhenius plot. The activation energies found were 31.5 kJ/mol and
28.0 kJ/mol for methanol and ethanol respectively, values lower than
that reported by other authors on solid catalysts [20,45] although in the
range of the existing results [12,14,47]. In a prevailing kinetic regime,
the esterification reaction with ethanol (1.16 * 10−5 molEEgcat−1 s−1)
takes place with a lower rate than in presence of methanol
(8.03 * 10−6 molMEgcat−1 s−1). This result is confirmed in literature for
palmitic acid esterification, the order of effectiveness being methanol Fig. 4. Esterification reaction of oleic acid with MeOH and EtOH: [A] Influence
of reaction temperature (Rcat/OlAc = 1 wt.%; time = 1 h; RAlc/OlAc = 5 mol/
> ethanol, due to the different reactivity of the carbon chains of each
mol). [B] Arrhenius plot.
alcohol [42].
In Table 3 the comparative results of the esterification reaction of
OlAc with EtOH carried out in the two batch reactors of different vo- ethanol is the reactant. In fact, after 5 h of reaction, by using the small
lume (90 and 300 cc) with and without the membrane, are reported. reactor, the OlAc conversion was almost total (run 5, 98.1%) unlike the
First of all, it is possible to observe that, after 2 h at 80 °C, the OlAc reaction with MeOH (74.0%, see Table 2, run 6). This evidence in-
conversion, with membrane by-passed, was 50.0% and 57.8% de- dicates that the membrane has a higher selectivity towards the water
pending on the reactor capacity (runs 1–7), lower than that obtained permeation when ethanol is employed instead of methanol.
with methanol (67.0%, see Table 2) as expected on the basis of the Anyhow, by using the reactor at a capacity as low as 90 cc, the water
kinetic results. By using the membrane coupled with the reactor of permeated during reaction was not recovered due to its low con-
smaller volume, the conversion increased up to 63.2% (run 2). Also in centration; for this reason it was preferred to operate with a larger
this case, with a higher alcohol/oleic acid molar ratio, 8 mol/mo (run batch reactor (300 cc). In this case, with a REtOH/OlAc of 2 mol/mol, the
4), OlAc conversion slightly decreased to 52.2%, likely due to a lower oleic acid conversion increased from 57.8% (run 7) without membrane
concentration of water vapour in the gas phase. It is interesting to up to 78.6% after 2 h (run 9) with the VP system (under the same
highlight the better efficiency obtained with the membrane when the amount of reactants) but unfortunately only about 10% of theoretical

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Table 3
Oleic acid esterification reaction in presence of EtOH, with and without the permeoselective membrane (TR = 80 °C; Rcat/OlAc = 5 wt.%).
Run REtOH/OlAc (mol/mol) Time (h) OlAcConversion (%) Sm/Vg (cm−1)a H2O (g) H2Oteor. (g)b H2Oteor. (g)c H2OColl (%)d

Autoclave 90 cc
1e 2 2 50.0
2 2 2 63.2 0.74 – 0.96 0.60 –
3 4 2 60.0 0.72 – 0.67 0.40 –
4 8 2 52.2 0.71 – 0.45 0.23 –
5 2 5 98.1 0.74 – 0.96 0.94 –

Autoclave 300 cc
6e 1 2 59.0
7e 2 2 57.8
8 1 2 85.0 0.20 1.07 2.74 2.32 46.01
9 2 2 78.6 0.20 0.19 2.35 1.83 10.47
10 1 5 98.2 0.20 1.80 2.74 2.69 66.90
11 1 2 77.6 0.28 2.48 5.87 4.55 54.60
12 2 2 73.8 0.28 1.14 5.10 3.76 30.28

a
Sm = surface of the membrane; Vg = volume of gas phase evaluated at the beginning of the reaction.
b
Water amount evaluated by theoretical total OlAc conversion.
c
Theoretical water amount evaluated by measured OlAc conversion.
d
Percentage of water collected as a function of theoretical water (b).
e
Runs carried out without membrane.

water was collected. Instead, by employing a REtOH/OlAc of 1 mol/mol,
OlAc conversion value increased of about 30% thanks to the membrane
effect (run 6, 59.0%; run 8, 85.0%) and the percentage of the collected
water was higher (46,01%). The gas chromatographic analysis of the
liquid mixture collected showed a very low amount of EtOH (< 0.1 wt.
%) permeated through the membrane and thus confirmed a higher se-
lectivity towards ethanol/water separation (than methanol/water). By
further increasing the reaction time, it was possible to achieve almost
complete OlAc conversion (i.e. 98.2%) by maintaining mild reaction
conditions (run 10). As already seen with MeOH, even in this case, the
Sm/Vg ratio influences the performance of the membrane; in fact by
increasing this value from 0.20 cm−1 up to 0.28 cm−1, the conversion
decreased from 85.0 to 77.6% with a REtOH/OlAc of 1 mol/mol and from
78.6% to 73.8% with a REtOH/OlAc of 2 mol/mol. These very interesting
results show a significant improvement in the esterification rate with
EtOH under milder reaction conditions if compared with recent litera-
ture data [16,48].
3.3. Oleic acid esterification with EtOH using zeolites
In the attempt to find more resistant solid acid catalysts for this
reaction, a series of zeolites have been investigated. Such zeolites were
characterized from a structural and morphological point of view and
main results are reported in Table 4.
As regards textural properties, Y zeolite exhibited the highest
surface area value (1027 m2 g−1), followed by BEA zeolite (∼800 m2/
g); others investigated zeolite samples showed similar values, with an
average surface exposure of about 500 m2/g. The determined surface
area values reflect the micropores volume resulting higher for Y and
BEA zeolites (0.27 cm3 g−1 and 0.21 cm3 g−1 respectively). Surface acid
properties are also reported in Table 4 in terms of quantitative data
obtained by NH3-TPD measurements (desorption profiles are shown in
Fig. S1 of Supplementary data). As expected, for all samples, total
acidity was lower than that of Amberlyst-15. Two main peaks char-
acteristic of the interaction of ammonia with weak and strong acid sites
at low (150–250 °C) and high temperature (350–450 °C), were ob-
served. As well known, by NH3-TPD profiles it is not possible to dis-
criminate between Brønsted and Lewis acidity, anyhow it is generally
accepted that the peak at lower temperature is associated both to the
presence of Lewis sites on zeolite framework or to extra-framework
aluminum oxide/hydroxide species. Instead, the peak at higher tem-
perature is generally ascribable to the presence of Brønsted acid sites
due to the framework Al ions [49]. On this account, the Y zeolite
showed the highest total acidity (1211 μmol g−1), whereas in the
HZSM-5 samples acidity decreased by increasing the SiO2/Al2O3 ratio.
Preliminary experiments carried out with EtOH at 80 °C revealed
that, at this temperature, all zeolites investigated were not so active as
A-15 catalyst, therefore, using a molar REtOH/OlAc of 2/1, the reaction
temperature was increased at 100 °C. Without the use of the membrane,
the higher OlAc conversion achieved was around 23%, and the

Table 4
Textural properties and quantitative data of NH3-TPD measurements and acid sites distribution of the investigated zeolites samples.
Sample SiO2/Al2O3 (mol/mol) Textural properties Surface acidic properties

SALang (m2/g) PVola (cm3/g) MVolb (cm3/g) Total sites (μmol g−1) w-m sitesc m-s sitesd TM1e (°C) TM2f (°C)

Y 12 1027 0.52 0.27 1211 0.65 0.35 219 376

FER 20 449 0.21 0.14 527 0.62 0.38 206 439
HZSM5 23 498 0.20 0.13 542 0.34 0.66 223 407
BEA 38 781 0.34 0.21 871 0.35 0.65 194 413
HZSM5 50 539 0.25 0.11 303 0.56 0.44 212 396
HZSM5 80 574 0.29 0.11 73 0.66 0.34 216 377

a
Cumulative Pore Volume, evaluated in the range 5–600 Å (micro and mesopores).
b
Micropores Volume evaluated by t-Plot.
c
Weak-medium acid site fraction with temperature of maximum desorption of NH3 in the range 100–300 °C.
d
Medium-strong acid site fraction with temperature of maximum desorption of NH3 above 300 °C.
e
Temperature of maximum desorption of NH3 in the range 100–300 °C.
f
Temperature of maximum desorption of NH3 above 300 °C.

126
C. Cannilla et al.
Fig. 5. [A] Experimental results for catalytic screening in OlAc esterification
reaction as a function of SiO2/Al2O3 (TR = 100 °C; REtOH/OlAc = 2 mol/mol;
Rcat/OlAc = 5 wt.%, time = 2 h). [B] Total acid sites and weak-medium acid site
fraction vs. SiO2/Al2O3 ratio.
reactivity of different zeolites was the following:
HZSM5 (80:1) > Y > FER > HZSM5 (50:1) > BEA > HZSM5
(23:1)
From the results reported in Fig. 5A it was not possible to establish a
clear correlation between the catalytic activity and zeolite properties
(see Table 4), however, it was observed that an optimum bulk Si/Al
molar ratio maximizes the catalytic behavior. This evidence could be
correlated to the hydrophobic character of zeolite surface. In fact, as
reported in literature, to a lower Si/Al ratio, it is associated a higher
capability to coordinate water molecules, with consequent covering of
the solid surface which limits the adsorption of organic substrates [50].
Specifically, this was the trend observed for HZSM-5 zeolites, for which
a higher Si/Al molar ratio that could be correlated to a higher hydro-
phobicity also reflected in a lower acid site availability along with a
higher amount of weak/medium acid site fraction (Fig. 5B). Anyhow,
the fitting reported in Fig. 5A was obtained without considering the Y
zeolite which was characterized by a high OlAc conversion of 21.22%,
but, at the same time, by a Si/Al ratio of 12. This catalytic result was
likely ascribable to the synergic role played by both the acid surface
properties and the textural properties. Specifically, the catalyst porosity
generally represents a key factor for biodiesel production since it
strictly influences the active sites accessibility of big molecules involved
in the esterification reaction [3].
Considering the high activity of HZSM-5 with a Si/Al ratio of 80, it
was further employed for new experiments in the attempt at optimizing
the reaction conditions.
Using such a zeolite as catalyst, it was considered important to ex-
clude the occurrence of mass transfer phenomena during the reaction.
In fact, as well known, in a liquid phase reaction, two types of mass
transfer resistances should be considered: the external mass transfer
resistance, which takes place across the solid-liquid interface and the
internal mass transfer resistance, associated with the difference in
particle size distribution of the catalyst [7]. Considering the high
127
Applied Catalysis A, General 566 (2018) 121–129
Fig. 6. OlAc esterification reaction with ethanol. [A] Influence of EtOH/OlAc
molar ratio (catalyst: 5 wt.% referred to the OlAc amount; TR = 100 °C,
time = 2 h). [B] Influence of catalyst amount (TR = 100 °C; REtOH/OlAc = 2 mol/
mol; time = 14 h; * indicates REtOH/OlAc = 20 mol/mol).
stirring speed utilized in the experiments, the first one could be over-
looked, whereas bigger attention should be paid on the internal mass
transfer resistances. For this reason, a set of experiments were con-
ducted using the HZSM5-80 catalyst particle size in the 16–70 μm
range. The results summarized in Fig. S2 showed no effect of the par-
ticle size on the OlAc conversion suggesting that there was no intra-
particle diffusion control.
The effect of the ethanol/OlAc molar ratio was investigated in the
range 1–20 mol/mol. The results reported in Fig. 6A show a volcano-
type trend indicating that the suitable molar ratio was comprised be-
tween 2 and 4. This result partially fits with data obtained by Marchetti
et al. [17] which observed that, under their reaction conditions (60 °C
and 20 wt.% of catalyst), the 1:1 ethanol/oleic acid molar ratio gave the
highest reaction rate. This evidence was justified by considering that
the reaction was not at the equilibrium level but still in an initial stage.
However, it should be also considered that, when an excess of ethanol
was used, it could be preferentially adsorbed onto the acid sites thus
decreasing their availability. Furthermore an excessive dilution of so-
lution could cause a decrease in acid sites concentration with negative
effect on reaction kinetics [51].
Such findings suggested to optimize the reaction conditions by
employing a higher zeolite amount for a longer reaction time.
Specifically, as shown in Fig. 6B, with a Rcat/OlAc of 15 wt.%, OlAc
conversion values of 62.2% and 70.1% were achieved for a EtOH/
OleOH molar ratio of 2 and 20 respectively, after 14 h of reaction.
At this point, the VP module was coupled to the batch reactor and
different reaction conditions were studied in presence of the HZSM5-80
C. Cannilla et al. Applied Catalysis A, General 566 (2018) 121–129

no membrane membrane Fig. 7. OlAc esterification reaction with EtOH. Comparison of

data with and without membrane at 100 °C.
Sm/Vg = 0.74 cm-1 Sm/Vg = 0.20 cm-1 A) Rcat/OlAc = 5 wt.%; REtOH/OlAc = 2/1 mol/mol; t = 2 h; Sm/
Vg = 0.74 cm−1.
Rcat/OlAc = 5 wt%
90 REtOH/OlAc = 2/1 mol/mol B) Rcat/OlAc = 15 wt.%; REtOH/OlAc = 20/1 mol/mol; t = 14 h;
Sm/Vg = 0.74 cm−1.
Rcat/OlAc = 15 wt% C) Rcat/OlAc = 5 wt.%; REtOH/OlAc = 2/1 mol/mol; t = 2 h; Sm/
80 REtOH/OlAc = 20/1 mol/mol Vg = 0.20 cm−1.
time = 14 h D) Rcat/OlAc = 5 wt.%; REtOH/OlAc = 2/1 mol/mol; t = 5 h; Sm/
Vg = 0.20 cm−1.
70
time = 5 h
60

50

time = 2 h
40
Rcat/OlAc = 5 wt%
REtOH/OlAc = 2/1 mol/mol
30 time = 2 h

20

10

catalyst. The results reported in Fig. 7 show that by using a Sm/Vg of

0.74 cm−1, at 100 °C, with a REtOH/OleOH of 2 mol/mol (A condition),
the oleic acid conversion value didn’t increase using the membrane. The
membrane effect was not so evident by performing the etherification
reaction under the optimized reaction conditions previously found
without the use membrane (see Fig. 6), that is for a long reaction time
(14 h), high ethanol/OlAc molar ratio (20/1 mol/mol) and 15 wt.% of
catalyst (B condition). Anyhow, a very interesting result was obtained
when the recirculation rate of gas phase was increased by employing
the optimized value of Sm/Vg ratio equal to 0.20 cm−1. In this case, in
fact, at 100 °C, the OlAc conversions were doubled as evidenced by
looking at C and D conditions, so achieving a value of 35.4% after 2 h
and 62.1% after 5 h of reaction, at low EtOH/OlAc molar ratio (2 mol/
mol) and with 5 wt.% of catalyst.
In Fig. 8, three reproducibility tests with HZSM5-80, in presence of
membrane, are reported. The runs were carried out at 100 °C, REtOH/
OlAc = 2 mol/mol and 5 wt.% of catalyst. As it is possible to observe,
after three experiments, the OlAc conversion remained almost constant.
After each experiment, the catalyst was washed by hot distilled water
and filtered prior to drying at 110 °C and the calcination at 500 °C for
3 h. Therefore, the obtained results suggest that, before a new run,
zeolite samples need a simple regeneration step to restore their initial
surface features and so ensuring a complete reproducibility of catalytic
activity upon reusing.
In any case, irrespective of the catalytic system employed, the po-
tential of the tandem reactor-membrane setup for biofuels production
by equilibrium-limited esterification reaction was fully demonstrated.
Specifically, the optimization of the catalytic process-membrane system
allowed obtaining higher conversion rate of the substrate at relatively Fig. 8. Catalyst stability (TR = 100 °C; Rcat/OlAc = 5 wt.%; REtOH/OlAc = 2/
1 mol/mol; time = 5 h; Sm/Vg = 0.20 cm−1).
short reaction time, by employing low alcohol-to-FFA molar ratios, with
consequent several economic and ecological advantages.
using a batch reactor coupled with a membrane separation system in VP
4. Conclusions configuration to drive the esterification reaction of oleic acid have been
clearly demonstrated. By optimizing the reaction setup, a total oleic
The catalytic and technological benefits that can be obtained by acid conversion can be achieved by continuously subtracting the water

128
C. Cannilla et al.
formed from the reaction medium. A higher selectivity of the mem-
brane towards ethanol rather than methanol favours an enhanced es-
terification rate. An efficient water permeation through the membrane
is ensured by a recirculation rate of the gas phase in turbulent flow
regime. From the catalytic point of view, a higher catalyst acidity of A-
15 favours the conversion in relatively mild reaction conditions
(TR = 80 °C, REtOH/OlAc = 1 mol/mol; Rcat/OlAc = 5 wt%) although a
slight increase of the temperature is beneficial if zeolite samples are
used.
Funding sources
Part of this work was supported by the Bilateral Agreement of
Scientific and Technological Cooperation CNR-MTA/HAS (Hungarian
Academy of Science).
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.apcata.2018.08.014.
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