Characterization and catalytic performance of basaltic dust as an efficient catalyst in the liquid-phase esterification of acetic acid with n-butanol

Article abstract of DOI:10.1002/jccs.201800397

Three natural basaltic samples were collected and used as efficient catalysts for the liquid-phase synthesis of n-butyl acetate. The samples were characterized by X-ray fluorescence analysis (XRF), X-ray diffraction (XRD), thermogravimetry (TG), differential thermal analysis (DTA), Fourier transform infrared (FT-IR), scanning electron microscopy (SEM), and N₂ sorption. The acidity of the samples was determined using isopropanol dehydration, and the strength of the acid sites was measured using chemisorption of basic probes. The catalytic activity of the samples towards the esterification of acetic acid with n-butanol was extensively examined. The influence of different parameters, such as the reaction refluxing time, molar ratio, catalyst loading, reusability, and calcination temperature, on the esterification reaction was studied in detail. The results revealed that all samples had high catalytic activity with a selectivity of 100% to n-butyl acetate formation. In addition, the sample obtained from the top hill of Volcano had the highest activity with a 80% yield of n-butyl acetate. Moreover, the significant catalytic performances were well correlated with the acidity of the samples and to the reaction rate constants.

Full text of DOI:10.1002/jccs.201800397

Received: 25 October 2018
DOI: 10.1002/jccs.201800397
Revised: 5 January 2019
Accepted: 6 January 2019
A R T I C L E
Characterization and catalytic performance of basaltic dust
as an efficient catalyst in the liquid-phase esterification of acetic
acid with n-butanol
Abd El-Aziz A. Said1 | Mohamed Th. S. Heikal2 | Mohamed N. Goda1
1Chemistry Department, Faculty of Science, Assiut
Three natural basaltic samples were collected and used as efficient catalysts for the
University, Assiut, Egypt
2Geology Department, Faculty of Science, Tanta
University, Tanta, Egypt
liquid-phase synthesis of n-butyl acetate. The samples were characterized by X-ray
fluorescence analysis (XRF), X-ray diffraction (XRD), thermogravimetry (TG),
differential thermal analysis (DTA), Fourier transform infrared (FT-IR), scanning
electron microscopy (SEM), and N2 sorption. The acidity of the samples was deter-
mined using isopropanol dehydration, and the strength of the acid sites was mea-
sured using chemisorption of basic probes. The catalytic activity of the samples
towards the esterification of acetic acid with n-butanol was extensively examined.
The influence of different parameters, such as the reaction refluxing time, molar
ratio, catalyst loading, reusability, and calcination temperature, on the esterification
reaction was studied in detail. The results revealed that all samples had high cata-
lytic activity with a selectivity of 100% to n-butyl acetate formation. In addition,
the sample obtained from the top hill of Volcano had the highest activity with a
80% yield of n-butyl acetate. Moreover, the significant catalytic performances were
well correlated with the acidity of the samples and to the reaction rate constants.
Correspondence
Abd El-Aziz A. Said, Chemistry Department,
Faculty of Science, Assiut University, Assiut,
Egypt.
Email: a.a.said@aun.edu.eg
Mohamed N. Goda, Chemistry Department,
Faculty of Science, Assiut University, Egypt.
Email: mohamed_nady@aun.edu.eg
KEYWORDS
acidity, basalt, n-butyl acetate, XRD, XRF
of undesirable side products.[4] In addition, the excess
amounts of the acids should to be counterbalanced after the
1
| INTRODUCTION
Esters are important intermediates and have many applica-
tions in both the laboratory and industry.[1] Esters can be
obtained through different routes from the combination of a
variety of carboxylic acids and alcohols. Esterification of
acetic acid with n-butyl alcohol is commercially important
because n-butyl acetate finds many uses such as in the pro-
duction of artificial perfumes, flavoring extracts, safety
glass, graphic films, pharmaceuticals, dehydrating agents,
etc.[2,3] In industry, esterification reactions are widely cata-
lyzed using sulfuric, hydrochloric, hydrofluoric, phosphoric,
phosphonic, and chlorophosphonic acids.[2,3] The use of
such acids, however, has some disadvantages including cor-
rosion, environmental problems, catalyst loss, and formation
reaction, leaving a large amount of salts to be disposed of
into the environment. So, to minimize the use of these harm-
ful and contaminating homogeneous catalysts, efforts have
been made to advance green, heterogeneous, solid-acid cata-
lysts for establishing cleaner technology.[5,6] Adopting het-
erogeneous, solid-acid catalysts in esterification reactions
has many advantages including ease of handling, safety,
good selectivity, good thermal stability, easy and inexpen-
sive removal from the reaction medium by decantation or
centrifugation, and insolubilty in organic solvents. In this
context, numerous acidic solid catalysts have been described
in the literature.[7–18] These catalysts include resins,[7]
zeolites,[8,9] superacids like sulfated zirconia,[10] Keggin-type
© 2019 The Chemical Society Located in Taipei & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
J Chin Chem Soc. 2019;1–9.
http://www.jccs.wiley-vch.de
1

2
SAID ET AL.
heteropoly acids (HPA),[11] oxides of five or higher valancy
elements,[12,13] supported chlorides,[14] sulfated catalysts,[15]
and clays.[16–18] However, the most frequently used solid-acid
catalysts are very expensive or treated with acids. So, the
challenge is to find natural, active, selective, easily available,
and inexpensive solid catalysts towards ester formation with-
out requiring any acid treatment.
To our knowledge, no report exists on the catalytic activ-
ity of basaltic dust for the synthesis of n-butyl acetate. So, in
this work, we examine the activity of three basaltic samples
towards the esterification of acetic acid with n-butanol. Thus
the aim of this study was to examine a naturally available
catalyst from a new location, with low cost, reusability, and
significant catalytic properties.
2.2 | X-ray fluorescence analysis
Table 1 summarizes the results of X-ray fluorescence analy-
sis (XRF) analysis of B1, B2, and B3 samples. It is clear
from these results that typical alkaline-olivine basalt compo-
sitions are present. In addition, all basaltic catalysts contain
50–66% glass-forming oxides (i.e., SiO2 and Al2O3), which
should result in good thermal and chemical resistance. More-
over, the presence of a high percentage of MgO, MnO, CaO,
TiO2, and Fe2O3 revealed a high crystallization trend and the
formation of silicate and alumino-silicate crystalline solids.
Furthermore, the presences of high contents of both SiO2
and Al2O3 should create more acid sites such as hydroxyl
groups on the surface of the catalyst, which will play the
main role in the catalytic performance of these solids.
2
| RESULTS AND DISCUSSION
2.3 | X-ray diffraction (XRD) analysis
The X-ray diffractograms of the B1, B2, and B3 samples cal-
cined at 200ꢀC are shown in Figure 2. It shows a high
amount of amorphous crystalline phases (40–60%) of hema-
tite, olivine, plagioclase, and pyroxene. In addition, hematite
is the main crystalline phase. Moreover, in B3 sample, the
intensity of the peak corresponding to the hematite phase
(at 2θ = 29.3ꢀ) is higher than that in the other two samples,
which indicates the high crystallinity of hematite phase in
this sample. These results are similar to those reported
previously.[19,20]
2.1 | Thermal analysis
Thermogravimetry and differential thermal analysis (TG and
DTA) of the raw basaltic samples (B1, B2, and B3) were
carried out and are presented in Figure 1. For the three sam-
ples within the temperature range 25–350ꢀC, the TG curves
exhibited mass losses not exceeding 2.3–2.5%. These weight
losses are accompanied by endothermic peaks in the temper-
ature range 80–100ꢀC. Such thermal events are due to the
evolution of physically adsorbed water and some organic
materials. No other thermal events were seen in either the
TG or DTA curves upon raising the temperature to 600ꢀC,
which shows that these basaltic rocks are thermally stable.
2.4 | Fourier transform infrared spectroscopy
The Fourier transform infrared (FT-IR) spectra of B1, B2,
and B3 samples annealed at 200ꢀC are shown in Figure 3.
All the samples show broad bands at 3,490–3,650 and
1,420 cm−1, which are attributed to the stretching and bend-
ing vibration modes, respectively, of the OH groups of water
molecules adsorbed on the samples surface.[21] A sharp band
at 1,020 cm−1 is due to the asymmetric in-plane stretching
vibrations of the Si–O–Si silicate tetrahedron.[22,23] The group
100
95
B3
90
85
80
100
TABLE 1 XRF analyses of B1, B2, and B3 samples
90
B2
wt%
B1
B2
B3
SiO2
TiO2
Al2O3
Fe2O3
MnO
MgO
CaO
48.23
2.33
17.66
9.77
0.16
7.67
7.56
4.20
1.23
0.69
0.50
100
49.37
2.05
15.77
8.28
0.13
6.78
7.37
4.60
2.42
1.28
1.85
100
46.88
2.14
16.62
8.99
0.15
6.11
6.66
6.33
3.88
1.18
1.21
100
80
100
95
B1
90
85
80
Na2O
K2O
100
200
300
400
500
600
P2O5
LOI
Temperature (oC)
Total
FIGURE 1 TG and DTA curves of B1, B2, and B3 samples

SAID ET AL.
3
isotherm of the B3 sample (Figure 4) conforms to type II of
Brunauer's classification.[25] In addition, the isotherms of the
catalysts under study are irreversible and reveal hysteresis
loops close to a low value of P/Po. These hysteresis loops
are of type H4 with a small portion of type E of de Bore
classification.[26] This illustrates principally that in this set of
adsorbents, we basically deal with slit-like pores. The spe-
cific surface area SBET was obtained by applying the BET
equation in the region of monolayer formation assuming a
cross-sectional area of nitrogen of 16.2 Å2. The calculated
values of SBET of the B1, B2, and B3 samples do not exceed
2.5 m2/g. The low values of the specific surface area may be
attributed to the high formation temperatures of these basal-
tic rocks, resulting in sintering and agglomeration of the
particles.[27]
On the other hand, the porosity of the B3 sample was
examined by adopting the Va–t plots and pore size distribu-
tion, as illustrated in Figure 4. The Va–t plot shows a down-
ward trend, indicating a microporous nature of the sample
under investigation.[26,27] The pore size distribution shows a
curve with a maximum located in the microporosity range of
<2 nm, which confirms the microporosity of these catalysts.
FIGURE 2 XRD patterns of the B1, B2, and B3 samples calcined
at 200ꢀC
of bands at 540 cm−1 and lower is due to hematite and other
M–O interactions.[24]
2.6 | Scanning electron microscopy
Scanning electron microscopy (SEM) was used to study the
surface textures of the basaltic rocks under study. Figure 5
shows the SEM micrographs of B1, B2, and B3 samples.
Examination of these micrographs revealed the presence of
some textural features that describe the surface of the basal-
tic samples, grain morphology, vesicularity, and cracks. The
types of grain morphology describe the three samples:
(a) blocky, equant grains with several well-developed planer
surfaces resulting from the breaking of brittle, quenched
lava; (b) all samples containing vesicles. In the studied size
range of particles, vesicles range from ~5 to 70 μm in
2.5 | Texture assessment
The different surface characteristics of B1, B2, and B3 sam-
ples calcined at 200ꢀC were determined from the nitrogen
sorption isotherms at –196ꢀC. Adsorption–desorption
B3
5
(1.7 nm)
1.2
1.0
0.8
0.6
0.4
0.2
0.0
4
3
2
1
0
B2
0
2
4
6
8
10
12
14
16
18
Pore diameter (nm)
B1
0 .0
0 .2
0 .4
0 .6
0 .8
1 .0
1 .2
1 .4
1 .6
1 .8
2 .0
2 .2
S ta tis tic a l th ic k n e s s [n m
]
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
P/Po
4000
3500
3000
2500
2000
1500
1000
500
Wavenumber (cm-1)
FIGURE 4 Adsorption–desorption isotherm, Va–t plot, and pore size
FIGURE 3 FT-IR spectra of B1, B2, and B3 samples calcined at 200ꢀC
distribution of B3 sample calined at 200ꢀC

4
SAID ET AL.
100
80
60
40
20
0
(a)
B2
B1
B3
(b)
35
30
25
20
15
10
5
B3
B2
B1
0
100
125
150
175
200
225
250
Reaction temperature (oC)
FIGURE 6 (a) Catalytic dehydration of isopropyl alcohol over the surface
of basaltic samples at the reaction temperature of 225ꢀC. (b) Population of
PY and DMPY desorption with the reaction temperature from the surface of
B catalyst
FIGURE 5 SEM micrographs of (a) B1, (b) B2, and (c) B3 samples
calcined at 200ꢀC
show only 55 and 80%, conversion, respectively. The above
results reveal that B3 has the largest number of acidic sites
among the samples, which are responsible for the dehydra-
tion of IPA to propene.
diameter with the average size of 50 μm. Vesicles are more
or less of the same size within each sample. In addition, the
micrographs showed the presence of aggregates of semi-
platted shape.[28,29]
100
90
80
70
60
50
40
30
20
10
0
PY
DMPY
2.7 | Acidity measurements
It is well known that dehydration and dehydrogenation of
alcohols are very interesting processes and are commonly
used for determining the acid/base identity of the catalyst’s
surface. In particular, the conversion of isopropyl alcohol
(IPA) to propene and acetone indicates the existence of both
acid and base sites on the surface of catalysts.[21,30–33] The
catalytic dehydration reaction of IPA over B1, B2, and B3
catalysts annealed at 200ꢀC was studied at 225ꢀC, and the
results are shown in Figures 6 and 7. The results in
Figure 6a indicate that propene was the only reaction prod-
uct. This means that the active surface sites on the basaltic
sample's surface are acidic.[21,30–33] In addition, at 225ꢀC,
the B3 catalyst has 100% conversion, while both B1 and B2
(c)
(b)
(a)
0
1
2
3
4
5
6
7
8
9
10
11
12
Volume of adsorbate (μL)
FIGURE 7 Activity variation of IPA with the volume of PY and DMPY
over (a) B1, (b) B2, and (c) B3 catalysts calcined at 200ꢀC

SAID ET AL.
5
2.8.1
| Effect of refluxing time
However, the reaction of IPA over these catalysts only
provides information about the total acidity (Lewis and
Brønsted acid sites) but does not differentiate between the
nature and strength of the different acid sites. Therefore,
the chemisorption of pyridine (PY) and dimethyl pyridine
(DMPY) is a good method to distinguish between
them.[30–33] In this method, the PY molecules get chemi-
sorbed on both acid sites while DMPY is selectively che-
misorbed on the Brønsted acid sites due to the steric
hindrance of the two methyl groups. Consequently, the
poisoning of the acid sites of B1, B2, and B3 catalysts cal-
cined at 200ꢀC during the IPA reaction was carried out by
saturating the acid sites with PY or DMPY adopting the
method previously reported[30] and the results are pre-
sented in Figure 7a–c. The results show that the admission
of PY or DMPY resulted in a gradual decrease in the IPA
conversion up to 6 μL, followed by a steady state with the
further addition. It is notable from these results that there
is no difference between the number of molecules
adsorbed from both basic probes, indicating that all avail-
able sites on the catalyst surface are only Brønsted. Also,
the decrease in Brønsted acid sites (expressed as the
decrease in IPA conversion via PY and DMPY injection)
is in the following order: B3 > B2 > B1. Again, this
reflects that B3 has a larger number of active acidic sites
than B1 or B2.
Moreover, to shed a light on the strength of the acid sites
existing on the basaltic surfaces, the effect of the reaction
temperature on the dehydration of IPA over B1, B2, and B3
catalysts calcined at 200ꢀC presaturated with PY was stud-
ied, and the results are presented in Figure 6b. This figure
presents the population of desorption of PY from the surface
of the catalysts with the increase in the reaction temperature.
Examination of these results shows that the majority of PY
molecules desorb from the surface of both B2 and B3 in the
temperature range 150–175ꢀC while that of B1 occurs at
200–225ꢀC. This behavior reflects that the acid sites on the
surface of the basaltic samples are weak and of intermediate
strength[21,33,34] and that the sites over the surface of B1 cat-
alyst are stronger than those over B2 and B3. It is important
to mention here that this difference in strength of the acid
sites explains the variation in IPA activity over B1, B2, and
B3 catalysts, which also should influence the catalytic activ-
ity of these basaltic catalysts.
The influence of the refluxing time on the esterification reac-
tion of acetic acid with n-butyl alcohol over 1 g each of B1,
B2, and B3 catalysts calcined at 200ꢀC was studied for dif-
ferent times up to 10 hr while the alcohol:acid molar ratio
was kept constant at 1:2 and at the boiling point of the mix-
ture (120ꢀC). The obtained results are shown in
Figure 8a. Form these results, the following conclusions can
be drawn: (a) the percentage conversion of n-butanol and the
percentage yield of n-butyl acetate monotonically increase
with increasing refluxing time up to 5 hr. Beyond this time,
no significant increase in the catalytic activity is observed.
Thus, the results suggest that 5 hr of reflux is sufficient to
achieve the optimum conversion and selectivity. (b) The
selectivity of catalysts towards n-butyl acetate formation was
100%. (c) The variation in activity of the three catalysts fol-
lows the order B3 > B2 > B1. This order is well correlated
with the variation in acidity among the catalysts under
investigation.
2.8.2
| Effect of acid/alcohol molar ratio
The influence of the molar ratio of acetic acid to n-butyl
alcohol on their reaction over B1, B2, and B3 catalysts cal-
cined at 200ꢀC was studied over 1 g of catalyst at the boiling
point of the mixture and after a refluxing time of 5 hr, and
the data are presented in Figure 8b. As can be seen, the con-
version and yield of n-butyl acetate increase upon increasing
the molar ratio of acetic acid, reaching a maximum at the
ratio of 1:2 (alcohol/acetic acid). On exceeding this ratio,
that is, 1:3, no significant improvement was noted in the cat-
alytic activity. Such behavior may be due to the saturation of
the catalyst surface with the reactant molecules or to the
prevention of nucleophilic attack by shielding the protonated
n-butyl alcohol by excess acid. In addition, the variation in
activity of the three catalysts is in the following order: B3 >
B2 > B1. The significant difference in the catalytic activities
among the three catalysts is due to the difference in the num-
ber of Brønsted acidic sites and the reaction rate constant
(as discussed later).
2.8.3
| Effect of catalyst weight
The influence of the catalyst load on the reaction of acetic
acid with n-butanol was studied on samples calcined at
200ꢀC under the ratio of alcohol/acid of 1:2 and the reflux-
ing time of 5 hr. The obtained results are shown in
Figure 8c. It shows an increase in the conversion of
n-butanol and yield of n-butyl ester on increasing the cata-
lyst weight up to 0.5 g. An increase in the catalyst load up
to 1 g resulted in only a slight enhancement in the yield of
n-butyl acetate, while on the further increase of the catalyst
load up to 2.0 g, the yield remained almost constant, the
same as that obtained at 1 g.
2.8 | Catalytic activity
The liquid-phase esterification of acetic acid with n-butanol
was carried out to study the effects of various parameters on
the catalytic activity of the basaltic samples. These parame-
ters are the refluxing time, molar ratio of reactants, catalyst
loading, calcination temperature, and reusability. The results
are given below.

6
SAID ET AL.
90
80
70
60
50
40
30
20
10
0
90
80
70
60
50
40
30
20
10
0
(a)
(a)
B3
B2
B1
B3
B2
B1
0
100
200
300
400
500
600
700
Original
1
2
3
4
5
6
7
8
9
10
Calcination temperature (oC)
Reluxing time (h)
90
80
(b)
(b)
80
70
60
50
40
30
20
10
0
B3
B2
B1
70
60
50
40
30
20
10
0
B3
B2
B1
a
b
c
1:2
d
1:1.5
Molar ratio (Alcoho:Acid)
1:1
1:3
C1
C2
C3
Cycles
(c)
-2.8
-3.0
-3.2
-3.4
-3.6
-3.8
-4.0
-4.2
-4.4
-4.6
80
70
60
50
40
30
20
10
0
B3
(c)
B2
B1
B3
B2
B1
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
1
2
3
4
5
6
7
Catalyst Weight (g)
Time (h)
FIGURE 8 Effect of (a) reflux time, (b) alcohol : acid molar ratio, and
(c) catalyst weight on the catalytic performance of B1, B2, and B3 catalysts
towards the liquid-phase esterification of acetic acid with n-butanol
FIGURE 9 Effect of calcination temperature on the catalytic performance
of B1, B2, and B3 catalysts towards the esterification of (a) acetic acid with
n-butanol and (b) n-butanol using recovered catalysts. (c) Graphical
representation of the first-order model over B1, B2, and B3 catalysts
2.8.4
| Effect of annealing temperature
had almost the same activity and selectivity. Upon raising
the annealing temperature above 200ꢀC, a continuous
decrease in the yield of the n-butyl ester was observed. This
is due to the sintering process, which leads to a decrease in
the number of active Bronsted sites responsible for the ester
formation.[31]
Effect of heat treatment on the catalytic performance of
basaltic samples towards the reaction of acetic acid with
n-butanol was studied keeping the molar ratio of alcohol/
acid constant at1: 2, with refluxing time of 5 hr and 1 g of
catalyst. The obtained results, which are shown in Figure 9a,
revealed that the original sample and that calcined at 200ꢀC

SAID ET AL.
7
CH3(CH2)CH2+ + CH3COOH
2.8.5
| Recycling of the catalysts
! CH3(CH2)CH2–O+(H)–COCH3
To investigate whether the basaltic catalysts lose their activ-
ity after the esterification reaction, B1, B2, and B3 catalysts
were recovered and reused after the esterification reaction.
The recovery process was done as follows: After the first
catalytic run, the solid catalyst was filtered off, washed sev-
eral times with double-distilled water, dried at 110ꢀC, and
then used in a fresh reaction mixture in the esterification
reaction. The same procedures as mentioned above were
repeated in a third reaction test, and the results are presented
in Figure 9b. It shows that after three cycles the yield of n-
butyl ester slightly decreases by 5%, while the selectivity to
the ester still remains at 100%. This comparison shows that
these basaltic rock catalysts are structurally very stable with
great improvement in the leaching-resistance property.
3. The formed intermediate dissociates to form n-butyl
ester and loses the proton of the Brønsted acid site.
CH3(CH2)CH2-O+(H)–COCH3
! CH3(CH2)CH2–OCOCH3 + H+(catalyst)
Finally, comparison of this work with those previously
reported in the literature revealed that the obtained yield of
n-butyl acetate in this work is higher than that obtained
in Refs [1,16,34,37,38] and comparable to that reported in
Refs [36,39,40].
3
| EXPERIMENTAL
2.8.6
| Determination of reaction rate constant
3.1 | Materials
It is well known that the esterification of acetic acid with
n-butanol is an electrophilic substitution reaction.[1] It is
slow without activation either by elevated temperature or by
an active catalyst. So, an attempt was made to study the
reaction kinetics and obtain the reaction rate constants for
the esterification reaction of acetic acid and n-butanol
catalyzed by B1, B2, and B3 catalysts, and the results are
presented in Figure 9c.It shows a straight line plot between
(−ln (1–conversion)) and time. This indicates that the esteri-
fication reaction over the three catalysts proceeds according
to a rate equation that is first order with respect to acetic acid
and zeroth order for n-butanol.[1,16,17,35] The specific rate
constants that were calculated from the slopes of the straight
lines are 475, 763, and 889 s−1 over B1, B2, and B3 cata-
lysts, respectively. Examination of these data shows that the
rate constants follow the order B3 > B2 > B3. These results
correlate well with those of acidity reported above.
The basaltic samples B1, B2, and B3 were obtained from
basaltic flows of the Jabal Isbil Volcano, Yemen, from the
foothill, middle, and top of the volcano, respectively. The
obtained samples were well ground and sieved to less than
0.125 mm. Glacial acetic acid (99.99%), n-butyl alcohol
(99.99%), IPA (99.98%), PY (99.3%), and DMPY (99.3%)
were supplied by Aldrich and were used without further
purification. The basaltic samples were calcined at 200, 300,
400, and 600ꢀC in a static atmosphere for 3 hr.
3.2 | Characterization
X-ray fluorescence (XRF) analysis was conducted for the
basaltic catalysts using a Philips X-ay fluorescence instru-
ment (model PW/2404) equipped with Rh radiation and
eight analyzing crystals. One crystal (LIF-200) was used for
estimating calcium, iron, potassium, titanium, and manga-
nese, while another crystal (TIAP, PX-1) was used for deter-
mining magnesium and sodium. A Ge crystal was used for
estimating phosphorous, and another crystal (PET) for deter-
mining silicon and aluminum.
The TG-DTA investigaions of the catalysts were carried
out on a thermal analyzer (TA 60H, Shimadzu Japan). The
samples were placed in a platinum crucible under a flow of
air at the rate of 30 mL/min and a heating rate of 10ꢀC/min.
X-ray studies of the samples were carried out using a dif-
fractometer (Philips model PW 2103, λ = 1.5418 Å; 35 kV
and 20 mA) using Cu Kα1 radiation (Ni-filtered).
2.8.7
| Possible reaction mechanism
As mentioned previously, the esterification reaction is an
electrophilic substitution reaction activated by Brønsted acid
sites.[1] In addition, the obtained linear fit of the first-order
reaction suggests that this reaction follows the Eley–Rideal
mechanism.[36] The proposed mechanism can be as follows:
1. A stable carbonium ion is formed via the chemisorption
of n-butanol molecules on the H+ of the hydroxyl group
of the Brønsted acid site.
SBET, Va–t plots, and pore volume distribution were
determined using a Nova 3200 instrument (Quantachrom,
USA). The basaltic catalysts were methodically outgassed
for 3 hr at 200ꢀC before measuring the adsorption
isotherms.
CH3(CH2)2CH2OH + H+(catalyst)
+
! CH3(CH2)CH2 + H2O
2. The formed carbonium ion attacks the nucleophilic cen-
ter of acetic acid, leading to the formation of an unstable
intermediate.
FT-IR spectra of the original and the calcined samples
were recorded in the range 4,000–400 cm−1 using a Nicolet
6700 spectrophotometer.

8
SAID ET AL.
SEM images were obtained using a JEOL electron
microscope (model JSM-5400 LV, Tokyo, Japan).
• The catalytic performance of the basaltic samples corre-
lates well with the acid site population on the catalyst
surface and the reaction rate constants.
Acidity measurements of the catalysts were carried out
by studying the conversion of IPA and the chemisorption of
basic molecules such as PY and DMPY, as previously
described by Said et al.[21,31–33] In this method, 0.3 g of the
basaltic sample (sandwiched between two plugs of glass
wool) was placed in a tubular electric furnace whose temper-
ature was adjusted and controlled by a K-type thermocouple
projecting under the charged catalyst. Nitrogen containing
4.5% IPA at the flow rate of 50 mL/min was allowed to pass
through the reactor. The analysis of the outlet feed was done
by a flame ionization detector (FID) on a proGC Unicam
instrument using a glass column of PEG (2 m). The amount
of pyridine desorption was calculated as follows: the catalyst
under investigation was presaturated with pyridine vapor for
7 days. This presaturated catalyst was then tested for IPA
dehydration at different reaction temperatures. The values of
the obtained conversions were then derived with respect to
the reaction temperature, and the derivative (ΔC/ΔT,
C being the conversion and T the reaction temperature) was
then plotted against the reaction temperature.
The liquid-phase esterification of CH3COOH and
CH3(CH2)2CH2OH was carried out in a round-bottom glass
flask (250 mL) connected with a water-cooled condenser, as
previously described.[18,41] The reaction temperature was
controlled using a thermostated heating mantle. Experiments
were carried out by varying the refluxing time, acid: alcohol
molar ratio, catalyst weight, and calcination temperature.
The reaction products were detected by an FID on the
proGC Unicam instrument using a glass column of 10%
APL (2 m). In the absence of the basaltic catalyst, blank
mixtures were also tested. The results showed that the only
product formed was n-butyl acetate. The percentage conver-
sion was estimated based on gas chromatographic analyses
using the method previously described by Kirumakki
et al.[41]
• The basaltic Isbil Volcano dust can be used as natu-
rally available and cheap catalyst for esterification
reactions.
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B3 is the most active catalyst with 80% yield and 100%
selectivity.

SAID ET AL.
9
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Goda MN. Characterization and catalytic performance
of basaltic dust as an efficient catalyst in the liquid-
phase esterification of acetic acid with n-butanol.
J Chin Chem Soc. 2019;1–9. https://doi.org/10.1002/
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