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Catalysis
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1. Introduction
Myristic acid is a saturated fatty acid (n-tetradecanoic acid,
C14H28O2) naturally occurring in nutmeg Myristica fragrans.
It is also found in palm kernel oil, coconut oil, butter fat and
animal fats, which are used to produce fatty acid alkyl esters
(FAAEs), used as biodiesel.1 It increases low density lipoprotein
cholesterol making it one of the most hypercholesterolemic of
the saturated fatty acids.2 Alkyl myristate of short chain
alcohols namely methanol, ethanol, propanol and butanol
are used in perfumes, avors, cosmetics, personal care
products, food additives, detergents, soaps, lubricants for
textiles, plasticizers etc.3 Besides, methyl myristate has been
approved as a new active constituent in veterinary chemical
products by Australian pesticides and veterinary medicines
authority4 and ethyl myristate is used as a marker of excessive
ethanol consumption that can be isolated from the hair of an
alcoholic individual.5
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Conventionally, FAAEs have been prepared by homogeneous acid catalyzed esterication of the corresponding acid
with an alcohol or homogeneous base catalyzed transesterication of oils and fats. Industrial esterication processes are
carried out in the presence of homogeneous Bronsted acid
catalysts such as sulfuric, p-toluene sulfonic or phosphoric
acid.6 To overcome the disadvantages associated with homogeneous catalysts, a number of solid acid catalysts such as
inorganic metal oxides, heteropoly acids and sulfonic acid
based resins etc. are being studied to produce FAAEs via
esterication of fatty acids (FAs) or transesterication of oil
with alcohols.6,7 Among metal oxide based solid acid catalysts,
sulfated zirconia (SZ) has exhibited signicant activity in both
the reactions.613 Kiss et al.9 have screened various solid acids
including zeolites, ion exchange resins and metal oxides for the
esterication of lauric acid with dierent alcohols and found
SZ as the most active solid acid catalyst; zeolites were not
suitable due to their microporous nature having diusion
limitations of large fatty acid molecules, whereas, ion
exchange resins have low thermal stability. SZ is a potential
solid acid catalyst for alkane isomerization at mild temperature14
and many other commercially important organic transformations due to its strong acid properties.1517
Few studies have been reported for the esterication of
myristic acid using SZ18,19 and niobia20 metal oxide catalysts.
Zeolites21 and acidic ion exchange resins namely Amberlyst-15
and silica based resin having sulfonic acid groups22 were not
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Catalyst characterization
NH3-TPD
11
15
2.6
1.04
75
74
0.12
0.09
6.5
5.7
91
87
SZ-700
16
0.87
54
0.08
7.1
85
719
116
564
112
400
627
793
2.50
0.80
0.19
0.38
0.07
0.14
0.08
2.5
0.99
3690
2939
2.07
1.66
0.67
2738
1.21
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was not sharp, which reected that the pores have varied pore
size distribution (Fig. 2).
IR-spectra of the catalysts showed the presence of sulfate
groups in the range of 1245900 cm 1 (Fig. S4, ESIw). SZ-600
showed the presence of a broad intense peak showing
shoulders at 1230, 1138, 1040 and 990 cm 1, however, highly
crystalline SZ-650 and SZ-700 clearly exhibited the peaks at
12301245, 11361142, 10471056 and 988 cm 1, which are
assigned to asymmetric and symmetric stretching frequencies
of S]O and SO bonds and are characteristic of inorganic
chelating bidentate sulfate. The partially ionic nature of the
S]O bond is responsible for the Bronsted acid sites in sulfated
zirconia.28 The intensity of the sulfate peaks was reduced in
SZ-700 due to loss of sulfate species at higher calcination
temperature.
The dehydration of cyclohexanol over SZ-600 showed 91%
conversion of cyclohexanol with selective formation of cyclohexene indicating the presence of higher Bronsted acidity in
SZ-600, which slightly decreased in SZ-650 and SZ-700
(Table 1). Similarly, the total surface acidity analyzed
by NH3-TPD showed the highest number of acid sites
(2.5 mmol g 1) in SZ-600, which decreased ominously in
SZ-650 and SZ-700 (Table 1). The acidity in sulfated zirconia
is attributed to the presence of sulfate groups; as SZ-600 has
the highest sulfur content, it showed the highest number of
acid sites, the decrease in sulfur content with increasing
calcination temperature resulted in a decrease in acidity.
Furthermore, NH3 desorption occurred at relatively higher
temperature in the SZ-600, indicating the presence of only
strong acid sites (719 1C), whereas SZ-650 and SZ-700 showed
the presence of weak (112116 1C), moderate (400500 1C) to
strong (4600 1C) acid sites (Table 1).
The DRIFT spectra of pyridine adsorbed SZ catalysts
exhibited the characteristic peaks of pyridinium ions (Bronsted
acid sites) at 1540 cm1 and of covalently bonded pyridine
(Lewis acid sites) at 1441 cm1 (Fig. 3) along with peaks at
1616 cm1 and 1488 cm1 representing the Bronsted and total
acid sites respectively.25e,29 Both acid sites were observed to be
strong enough as they were present even after heating at 450 1C;
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though the intensity of the peaks was decreased after successive heating (Fig. S5, ESIw). SZ-600 and SZ-650 showed
intense peaks for Bronsted acid sites, whereas, in SZ-700 the
peak for the Lewis acid site was intense. The Bronsted acid site
concentration and B/L ratio, calculated from the characteristic
peak area at 150 1C, were in the descending order from SZ-600
to SZ-700 (Table 1).
2.2 Catalytic activity
Initially, esterication of myristic acid was studied with
methanol over the SZ-600 catalyst to optimize acid to alcohol
ratio, catalyst concentration and temperature to achieve the
maximum conversion of myristic acid and selectivity for
methyl myristate.
2.2.1 Eect of acid to alcohol ratio and catalyst concentration. The reaction was scrutinized using an acid to methanol
molar ratio of 1 : 5 to 1 : 20 over catalyst concentration in the
range of 0.1250.5 wt% to acid. The varying concentration of
the catalyst (0.1250.5 wt%) resulted in 98100% conversion
of myristic acid having 100% selectivity for methyl myristate
using an acid to methanol molar ratio of 1 : 20 at 60 1C after
7 h (Table 2). By decreasing the acid to methanol molar ratio
to 1 : 10, the catalyst showed 47% conversion with 0.125 wt%
of catalyst, which enhanced upon increasing the catalyst
concentration. By further decreasing the acid to methanol
ratio to 1 : 5, 82% conversion was observed with 0.5 wt%
catalyst concentration. The results indicated the requirement
Table 2 Esterication of myristic acid with methanol over varied
concentrations of SZ catalystsa
Conversion (wt%)
Catalyst (wt%)
0.5
0.25
0.125
498 (82*)
74
47
498
498
498
100
100
100
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2.2.3 Eect of calcination temperature. To study the inuence of calcination temperature on the activity of SZ catalysts,
all three samples that calcined in the range of 600700 1C have
been evaluated under both the reaction variables as stated
above (Table 4). SZ-600 and SZ-650 catalysts resulted in
similar conversion under (A) reaction variables, however,
SZ-700 showed a signicant decrease in the conversion
(61%). The acidity of SZ catalysts is ascribed to the presence
of sulfate species which undergo thermal decomposition during the calcination and therefore the loss of sulfate species with
increasing calcination temperature resulted in the decrease in
the acidity and thus the activity of the catalyst. Though SZ650 has lower sulfur content, Bronsted acidity, total surface
acidity and weak to moderate acid sites as compared to SZ-600
(Table 1); its catalytic activity for the studied reaction was not
aected. It may be due to the presence of minimum required
Conversion (wt%)
Conversion (wt%)
Temperature (1C)
Catalyst
32
40
50
55
60
69
71
498
498
498
81
87
91
498
SZ-600
SZ-650
SZ-700
Zr-400
Zr-600
498
498
61
28
23
498
80
58
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acidity for the studied reaction along with the highly crystalline nature, higher BET surface area and pore volume of
SZ-650 (Table 1), which may play a signicant role by making
the reaction facile and active.
Under (B) reaction variables, decrease in conversion was
observed over both SZ-650 and SZ-700 catalysts (Table 4).
Though, the SZ-650 catalyst showed similar conversion to
SZ-600 under (A) reaction conditions, it reduced to 80%
under (B) reaction conditions. Because, its lower acidity and
Bronsted acid site concentration (compared to SZ-600) were
sucient to achieve 498% conversion when its concentration
was higher in reaction (A), however, with lower concentration
along with higher amount of methanol in reaction (B), the
number of acid sites available was insucient to interact with
the reactant molecules and thus to obtain complete conversion
of acid. The decreasing catalytic activities of SZ catalysts were
in good agreement with their decreasing Bronsted acid site
concentration as well as B/L ratio and total surface acidity
with an increase in calcination temperature (Table 1). These
results clearly revealed that the acidity and activity of a SZ
catalyst are strongly inuenced by the temperature at which it
has been calcined before undergoing the reaction along with
the reaction parameters. The pure ZrO2 sample, calcined at
400600 1C, showed only 2328% conversion of myristic acid
(Table 4) thus conrming the enhanced catalytic activity of SZ
catalysts.
2.2.4 Eect of alcohols. The reaction was carried out with
dierent short chain alcohols namely ethanol, n-propanol and
n-butanol over SZ-600 at (A) reaction parameters. Methanol
and ethanol having smaller carbon number resulted in similar
conversion (98%) at 60 1C after 7 h, however the conversion
was decreased successively with propanol (71%) and butanol
(69%) due to the inductive eect of increased carbon chain of
alcohol (Fig. 5).
A similar trend was found with caprylic acid26b and also has
been reported for SZ catalyzed transesterication of triglycerides10
and esterication of carboxylic acids of dierent chain lengths
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Fig. 7 IR spectra of (i) fresh and (ii) re-activated (after 5 cycles) (a)
SZ-600 and (b) SZ-650 catalysts.
Deactivation of SZ catalysts
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Fig. 10 Esterication of myristic acid with fresh methanol (a) conversion/concentration of myristic acid with time (b) apparent induction period.
Reaction conditions: acid : methanol = 1 : 10; SZ = 0.5 wt%
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Structureactivity co-relation
3. Experimental
3.1 Materials
Zirconium n-propoxide (70 wt% in n-propanol) was procured
from Sigma-Aldrich, Germany; n-propanol (99.5%), n-butanol
(99.5%), aqueous ammonia solution (25%) and concentrated
sulfuric acid (98%) were procured from s.d. Fine chemicals,
India. Methanol (99%) was purchased from Ranbaxy, India
and Merck, India. Myristic acid (99.5%) and ethanol (99.9%)
were procured from Spectrochem Pvt. Ltd., India.
3.2 Catalyst synthesis and characterization
A sulfated zirconia catalyst was prepared using a two-step
sol-gel technique as described previously.26a In a typical
synthesis procedure, Zr(OPr)4 was hydrolyzed by aqueous
ammonia and the obtained gel was treated with H2SO4 after
oven drying at 120 1C for 12 h. The sulfated powder was
calcined at 600700 1C for 4 h and designated SZ-T, where T
represents the calcination temperature.
PXRD patterns were obtained using a Philips Xpert
diractometer. The crystallite size was determined from the
characteristic peak of tetragonal phase (2y = 30.22) using the
Scherrer equation,42 crystallite size = Kl/W cos y, where K is
the Scherrer constant (0.9), l = 1.5406 A (CuKa radiation),
W = Wb
Ws; Wb is the broadened prole width of the
experimental sample and Ws is the standard prole width of
the reference silicon sample and y is the angle of diraction.
TEM micrographs were obtained using a JEOL JEM 2100
transmission electron microscope by dispersing the catalyst
sample in ethanol by sonication and deposited on a Cu grid
coated with carbon lm. IR spectra were recorded on a Perkin
Elmer GX spectrophotometer. The bulk sulfur present before
and after calcination at dierent temperatures was analyzed by
ICP emission spectroscopy using Perkin-Elmer, Optima 2000
DV. BET surface area, pore volume and pore diameter were
calculated from nitrogen sorption isotherms after pre-activation
at 120 1C for 4 h at 196 1C on ASAP 2010, Micromeritics.
NH3-TPD was used to estimate the total surface acidity, i.e.
strength and number of acid sites present in the catalysts using
Micromeritics Pulse Chemisorb 2720 as described earlier.26a
Vapor phase cyclohexanol dehydration in a xed bed reactor
was used as a model reaction to assess the Bronsted acidity of
the catalysts.26b Diuse Reectance FT-IR spectroscopy
(DRIFT) was used to dierentiate between Bronsted and
Lewis acidity of pyridine adsorbed SZ samples using Perkin
Elmer GX equipped with DRIFT Selector accessory (Graseby
Specac, P/N 19900 series).25e The spectra were recorded at
room temperature (B27 1C) to 450 1C after holding at each
temperature for 10 min, thus allowing sucient time for
pyridine desorption.
3.3 Catalytic activity
Esterication of myristic acid was carried out in a liquid phase
batch reactor.26b In a typical reaction procedure, required
amounts of acid, alcohol, and catalyst were taken in a round
bottom ask and the suspension was magnetically stirred
(600 rpm) in an oil bath maintained at constant temperature
(1 1C) in the temperature range of 4060 1C. The reactions
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were performed in duplicate with 2% variations in conversion. The samples were withdrawn at regular intervals and the
reaction product was analyzed using a gas chromatograph (HP
6890) having a DB-225 capillary column (20 m length, 100 mm
diameter and 0.10 mm lm thickness) and a FID detector.
4. Conclusions
The acidity and activity of a SZ catalyst for esterication of
myristic acid with methanol and other short chain alcohols are
strongly inuenced by its calcination temperature along with
the reaction parameters mainly acid to alcohol ratio, catalyst
concentration and reaction temperature. Among the structural,
textural and acidic properties of the catalyst, the acidic
features play a major role in its activity and re-usability
behaviour for the studied reaction.
The present study reveals a very remarkable result that the
SZ-catalyst having higher number of Bronsted acid sites could
be re-used for ve reaction cycles without signicant loss in
activity for myristic acid esterication, whereas the SZ-catalyst
having less number of acid sites showed decrease in activity
after ve reaction cycles. This explicitly conrms the requirement of more number of Bronsted acid sites for better
re-usability of SZ catalysts for esterication of myristic acid.
The present study concludes that the requirement of a very
small concentration of the catalyst yielding maximum conversion and selective formation of the ester at lower temperature
within reasonable reaction time makes SZ an appealing
catalyst for the synthesis of FAAEs. In addition, eco-friendly,
recyclable SZ catalysts may nd wide applications in reactions
where conc. H2SO4 is currently being used as a catalyst.
Acknowledgements
The authors are thankful to CSIR Network Programme on
Inorganic Materials for Diverse Application and to Analytical
Science discipline for catalyst characterization analysis. The
authors are also thankful to Dr Ram S. Shukla for helping in
initial reaction rate determination.
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