Fuel 115 (2014) 625–628

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Measurements of surface acidity of solid catalysts for free fatty acids

esterification in Jatropha curcas crude oil for biodiesel production
Grisel Corro ⇑, Fortino Bañuelos, Esmeralda Vidal, Surinam Cebada
Instituto de Ciencias, Benemerita Universidad Autonoma de Puebla, 4 sur 104, Puebla, Puebla 72000, Mexico

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Free fatty acids in Jatropha curcas An easy and inexpensive method for measuring the acid sites of the solid catalysts enabled the determi-
crude oil were esterified by an acid nation of a logarithmic relation between acid sites on heterogeneous catalysts and its activity for free
heterogeneous catalytic process. fatty acids esterification.
 SiO2HF and ZnO/SiO2 were used as
solid catalysts for free fatty acids
100
esterification. SiO2HF (500°C)
 Acid sites on the solid catalysts were
measured by the aqueous method. 80
FFA Conversion / %

 Logarithmic relation between catalyst

ZnO/SiO2 (500°C)
activity and acid sites is found. 60

 This method is an inexpensive way of

SiO2 (500°C)
selecting a catalyst to improve 40
biodiesel production.
ZnO/SiO2 (700°C)
20

0 ZnO/SiO2 (1000°C)

13 14 15 16 17 18 19 20
Log (number acid sites/ g catalyst)

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

Article history: The high content of free fatty acids (FFA) present in non-edible oils and in waste cooking oil for biodiesel
Received 9 June 2011 production can be esterified with solid acid catalysts. The rate of the esterification reaction is related to
Received in revised form 16 July 2013 the catalyst surface acidity. Thus a fast and accurate method for determining the solids acidity is neces-
Accepted 17 July 2013
sary to prevent low FFA esterification yields. In this paper, the acid sites on the solid catalysts (SiO2HF
Available online 1 August 2013
and ZnO/SiO2) have been measured by the aqueous method using NaOH as titrating agent. A straight rela-
tion between the catalyst esterification and the acid sites measured by this method is found. This method
Keywords:
is fast and easy to perform in almost all research laboratories and can provide an inexpensive way of
Esterification solid catalysts
Biodiesel production
selecting a catalyst for improved yield in the FFA esterification process.
Surface acidity measurement Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction
Biodiesel has been produced from a variety of vegetable oil
sources such as soybean [1], sunflower [2], cottonseed [3], and ra-
peseed [4]. However, the use of these edible oils increases substan-
tially the production costs of biodiesel. There are several non-
⇑ Corresponding author. Tel.: +52 2222480246.
E-mail address: griselda.corro@correo.buap.mx (G. Corro).
edible oil seed species which could be utilized as a source for oil
production. Among these, Jatropha curcas is a multipurpose spe-
cies with considerable potential.
The most common way to produce biodiesel is by transesterifi-
cation which refers to a catalyzed chemical reaction involving veg-
etable oil and an alcohol (e.g., methanol) to yield fatty acid alkyl
esters (biodiesel) and glycerol (Fig. 1, Reaction 2). Triglycerides,
as the main component of vegetable oil, consist of three long chain
fatty acids esterified to a glycerol structure. When triglycerides re-

0016-2361/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.fuel.2013.07.060
626 G. Corro et al. / Fuel 115 (2014) 625–628
Fig. 1. Biodiesel (fatty acid methyl esters) production by: FFA esterification
catalyzed by solid catalyst (Reaction 1); triglycerides transesterification catalyzed
by NaOH (Reaction 2).
act with an alcohol, the three fatty acid chains are released from
the glycerol skeleton and combine with the methanol to yield fatty
acid methyl esters (FAME). Glycerol is produced as a by-product.
An alkali catalyzed process can achieve high purity and yield of
biodiesel product in a short time (30–60 min) [5–8]. However, it is
very sensitive to the purity of the reactants. Well refined vegetable
oils with low amounts of free fatty acids (FFA) can be used as the
reactant in this process [9].
The analysis of our non-refined JCCO revealed a high content in
free fatty acids (18.05 wt%). Therefore, for the biodiesel production,
an acid catalyzed process would have been preferred, but it would
have required more excess of methanol, high pressure (170–
180 kPa) and high cost stainless steel equipment [9–11]. It is well
known that high FFA content of crude vegetable oils leads to soap
formation and lower yield of biodiesel [6–12].
In a recent investigation [13] we applied a combined process for
biodiesel production from JCCO, similar to the process proposed by
Wang et al. [14] for the production of biodiesel from waste cooking
oil of high acid value by a two step catalysis process (Fig. 1, Reac-
tion 1). In this process, at first step, a solid acid catalyst was intro-
duced to catalyze the esterification reaction in which the FFA
reacted with methanol. The rate of the esterification reaction
may be related to the catalyst surface acidity. Therefore, measure-
ment of surface acidity of the solid catalysts is of great importance
from technological point of view because it helps to characterize
the catalyst samples and also provides a scientific method of
screening the catalysts for being used in the esterification process.
Acid sites are commonly regarded as the active centers on cer-
tain oxides to catalyze many reactions involving hydrocarbons (e.g.
catalytic cracking, isomerization, alkylation, cationic polymeriza-
tion and reforming). The proposed mechanisms of these processes
mostly involve the formation of carbenium or carbonium ions as
reactive intermediates. The acid sites on oxide surfaces are of
two types as described by Lewis and Bronsted [15]. A proton trans-
fer occurs at the Bronsted site from the solid to the adsorbed mol-
ecule as an ion is emerged and an ion dipole interaction with the
solid takes place, while Lewis acid sites accept electrons from the
adsorbed molecule and a coordinate bond with the surface is
formed. In general, an acid catalyst can be characterized for its
interaction with the adsorbed species if the number of adsorption
sites, the strength of adsorption, the nature of the interaction and
the chemical nature of the adsorbed species are ascertained. Many
methods are available for determining the surface acidity of solid
catalysts: the amine titration method [16], infrared (IR) pyridine
adsorption method [17,18], temperature programmed desorption
of ammonia method [19] and the microcalorimeter method
[20,21]. Unfortunately, all these methods are expensive and time
consuming. As will be shown in this work, the aqueous method
[22,23] can be very useful for determining comparatively the Lewis
acidity of solid catalysts used for the esterification of free fatty
acids in vegetable oils. This method is not expensive, very easy to
perform in almost all research laboratories and enables the deter-
mination of the specific total number of acid sites of the prepared
catalyst thus enables to establish in advance a selection of the sam-
ples by ruling out the low acidic ones.
In the present work, the surface Lewis acidity of a series of cat-
alyst prepared for the JCCO free fatty acids esterification reaction
has been measured by the exchange method using NaOH.
2. Materials and methods
2.1. Preparation of the catalysts
2.1.1. SiO2HF
Fused SiO2 (Aldrich 99.9%) was impregnated with the appropri-
ate amount of HF solution to obtain a 10 wt% HF in the SiO2. The
suspension was stirred at room temperature for 1 h. After drying
at 120 °C overnight the catalyst (SiO2HF) was calcined in air at
500 °C for 12 h. A reference SiO2 sample was prepared in the same
way using only water.
2.1.2. ZnO/SiO2
Fused SiO2 (Aldrich 99.9%) was impregnated with the appropri-
ate amount of a Zn(NO3)2 solution to obtain 1 wt% Zn in the SiO2.
The suspension was stirred at room temperature for 1 h. After dry-
ing at 120 °C overnight the catalysts (ZnO/SiO2) were calcined in
air at different calcinations temperatures (500 °C, 700 °C, and
1000 °C) for 12 h.
2.2. Catalyst characterization
2.2.1. Measurement of BET surface area
Adsorption measurements were performed using a Quanta-
chrome Nova-1000 sorptometer. Total surface areas (Sg) were mea-
sured by N2 physisorption at 77 K using BET analysis methods. The
samples (1 g) were degassed for 2 h in the apparatus at 400 °C prior
to performing gas physisorptions experiments. After cooling to the
desired temperature, the isotherms were performed at a pressure
range of 0–6.6 kPa. The technique of back extrapolation of the lin-
ear portion of the isotherms to zero equilibrium pressure to deter-
mine the saturation uptake value was used.
2.2.2. Measurement of Lewis acidity
The number of catalytically available Lewis acid sites of the cat-
alysts was determined according to the following process:
 A pH electrode (range of 0–14, precision of 0.01 and tempera-
ture range of 0–100 °C) was introduced in 20 ml of NaOH
0.005 M standardized solution, until no pH variations were
observed (pH = 12).
 1 g of the catalyst fresh sample was added and pH evolution as a
function of time was measured for 1 h.
2.3. FFA esterification with methanol
The esterification of the FFA present in JCCO (18.05 wt%) with
methanol was catalyzed by the acid solid catalysts prepared in this
investigation. This reaction was carried out in a laboratory scale
reactor applying the optimized conditions described in our earlier
 G. Corro et al. / Fuel 115 (2014) 625–628 627

paper [13]. Therefore, the reaction was performed at 60 °C using 3.1. SiO2HF characterization
100 g JCCO, 10 g catalyst, and a methanol/JCCO molar ratio of 12/
1 for 2 h. Table 1 summarizes the catalysts characterization data. In this
table it can be seen that the HF pretreatment of SiO2 resulted in
a strong increase of the Lewis acid sitesg cat1 and a decrease of
2.3.1. Acid number determination the specific surface area. Results presented in Table 1 shows that
The acid number of the initial JCCO or after the FFA esterifica- the use of SiO2HF for esterification, resulted in a strong decrease
tion reaction was determined according to the ASTM D 664 inter- of the FFA content in JCCO (97% FFA conversion) related to the
national standard method. use of SiO2 calcined at 500 °C (10% FFA conversion). These results
suggest that the increase of Lewis acid sites generated during
2.3.2. Determination of the % conversion of FFA SiO2 pretreatment with HF, are responsible of the increase of FFA
The conversion of the FFA is defined as the fraction of FFA that esterification rate.
reacted during the esterification reaction with methanol. The con- The SiO2HF lower surface area, should have resulted in a lower
version of FFA (% CFFA) was determined from the acid number ratio activity for FFA esterification related to SiO2. However, this is not
using the following equation: the case. Thus, the strong increase in acid sites generated during
the high temperature treatment of SiO2 impregnated with HF,
Ai  Af may largely compensate the loss in SiO2 surface area.
% C FFA ¼  100 ð2Þ
Ai
3.2. ZnO/SiO2 characterization
where Ai is the initial acid number of the JCCO. Af is the final acid
number of the JCCO after the FFA esterification reaction.
Results obtained of the ZnO/SiO2 characterization are reported
in Table 1. In this table, we can observe the following facts:
3. Results and discussion
 Zn(NO3)2 impregnation on SiO2 and further calcination at 500 °C
resulted in a strong increase of the Lewis acid sitesg cat1
In Fig. 2 the pH evolution as a function of time has been repre-
related to SiO2 calcined at 500 °C. However, the specific surface
sented for the different catalysts prepared in this work. In this fig-
area of both catalysts remained almost the same.
ure, it can be seen that for SiO2HF and ZnO/SiO2 calcined at 500 °C,
 The specific surface area of the ZnO/SiO2 catalysts decreased as
the rate of acidity neutralization is very high. After 20 min, no sig-
the calcination temperature increased, as expected.
nificant pH changes were detected for these catalysts. However, for
 The increase of the calcination temperature resulted in a
SiO2 calcined at 500 °C and ZnO/SiO2 calcined at 700 °C and
decrease of the ZnO/SiO2 Lewis acid sitesg cat1. This result
1000 °C, the acid sites reaction with NaOH is slower. After 6 h of
suggests that during the high temperature calcinations, the sin-
reaction, pH variations were still detected.
tering of the catalyst surface caused the loss of surface acid
sites.
 The FFA % conversion values measured after the esterification
SiO2 (500°C) reaction on the different catalysts studied decreased with the
SiO2 HF (500°C) decrease in the specific surface acid sites, thus with the increase
ZnO/SiO2 (500°C) of the calcination temperature.
ZnO/SiO2 (700°C)
14
ZnO/SiO2 (1000°C) Fig. 3 shows the evolution of the FFA % conversion as a function
12 of the catalyst acid sites determined by the method proposed in
this investigation. In this figure it can be seen the linear depen-
pH

10

4 100
SiO2HF (500°C)

2
80
FFA Conversion / %

0
0 5 10 15 20 25 30 35 40 45 50
ZnO/SiO2 (500°C)
Time (min) 60

Fig. 2. pH evolution as a function of time measured on the catalysts samples (in SiO2 (500°C)
parenthesis are the calcination temperatures). 40

Table 1 ZnO/SiO2 (700°C)

20
Characterization data of the catalysts studied.

Catalyst Calcination Specific surface Acid FFA

temperature area (m2 g cat1) sitesg cat1 conversion 0 ZnO/SiO2 (1000°C)
(°C) (%)
SiO2 500 200 1.07  1015 10 13 14 15 16 17 18 19 20
SiO2HF 500 140 5.75  1019 97
1% ZnO/SiO2 500 185 4.68  1019 95
Log (number acid sites/ g catalyst)
1% ZnO/SiO2 700 86 6.02  1015 25
1% ZnO/SiO2 1000 66 5.5  1013 2 Fig. 3. FFA % conversion as a function of the logarithmic number of surface acid
sites on the different catalysts (in parentheses are the calcination temperatures).
628 G. Corro et al. / Fuel 115 (2014) 625–628
dence of the catalyst esterification activity with the logarithm of
the specific acid sites on the catalysts. This dependence may enable
to determine the optimum catalyst sample for FFA esterification,
thus for optimum production of biodiesel from non-edible oils.
4. Conclusions
This paper shows that Lewis acid surface sites on the solid cat-
alysts used for the FFA esterification present in the vegetable oils
used for biodiesel production can be measured by the aqueous
method using NaOH as the base and following the pH evolution
with a pH electrode. This method is fast and easy to perform and
can provide an inexpensive way of screening a catalyst sample
for improved yield in the FFA esterification process.
The number of Lewis surface acid sites on SiO2 increases with
the impregnation of HF or Zn(NO3)2 and further calcination in air
at 500 °C. The ZnO/SiO2 catalysts studied, showed a FFA esterifica-
tion activity which decreased with the increase in the calcination
temperature, due to the loss of acid surface sites during thermal
sintering of the samples.
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