Sulfated Zirconia: An e Cient Solid Acid Catalyst For Esterification of Myristic Acid With Short Chain Alcoholsw
Sulfated Zirconia: An e Cient Solid Acid Catalyst For Esterification of Myristic Acid With Short Chain Alcoholsw
Sulfated Zirconia: An e Cient Solid Acid Catalyst For Esterification of Myristic Acid With Short Chain Alcoholsw
/SO
4
2
ions in the
presence of alcohol
10,11
or water.
37
We have studied the leaching of SO
4
2
ions of the catalyst
by employing two methods. (i) In one experiment, it was tested
during the esterication reaction. After 10 min of the reaction,
the catalyst was removed from the reaction mixture; and the
reaction was continued with the remaining solution without
having any catalyst. The plot of concentration of myristic acid
with time (Fig. 9) clearly showed an insignicant decrease in
concentration of myristic acid after removal of the catalyst as
Fig. 7 IR spectra of (i) fresh and (ii) re-activated (after 5 cycles) (a)
SZ-600 and (b) SZ-650 catalysts.
Fig. 8 Eect of addition of water on the conversion of myristic acid
with methanol. Reaction conditions: acid: methanol = 1 : 10; SZ =
0.5 wt%
Fig. 9 Concentration of myristic acid (%) without catalyst,
(J) catalyst removed after 10 min and (m) with catalyst. Reaction
conditions: acid: methanol = 1 : 10; SZ = 0.5 wt%
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2518 Catal. Sci. Technol., 2012, 2, 25122520 This journal is c The Royal Society of Chemistry 2012
compared to a linear decrease in myristic acid concentration in
the presence of catalyst. The autocatalysis (a blank test in the
absence of catalyst), under the similar reaction conditions,
showed nil conversion till 45 min and increased from 2.99%
(at 60 min) to 4.87% after 120 min (19% after 7 h, not shown
in gure). The initial rate of autocatalysis was signicantly
lower (0.5 mmol min
1
) as compared to the catalytic reaction
(12.9 mmol min
1
). The rate after removal of the catalyst
(2.4 mmol min
1
) was observed to be ve times lower than
the reaction done in the presence of catalyst. These results
showed that no signicant leaching of SO
4
2
ions of SZ
catalysts occur under the experimental conditions studied.
(ii) In a second experiment, a fresh SZ-600 catalyst was
stirred in methanol and distilled water separately (25 ml of
each) and pH was measured (Toshniwal, CL54) during 24 h.
The pH of the reaction mixture was found to decrease
signicantly after 1 h of stirring both in methanol and water,
however, it was not much aected further till 24 h (Fig. S6,
ESIw). Initially, the pH of the reaction mixture was higher in
water (4.3) compared to methanol (2.7), however, the decrease
in pH was observed in a similar range (38.4% in water and
38.6% in methanol) after 1 h of stirring.
It appeared from the decrease in pH by treatment with
water or methanol that the sulfate groups may be hydrolyzed
in the presence of OH groups on the catalyst surface
9
or the
sulfate groups may be leached out during the initial rst
hour,
10
which may not be strongly bonded with the zirconia
surface; however strongly bonded sulfate groups did not leach
out till further 24 h of stirring. To further conrm this, the
SZ-700 catalyst having less sulfur content and highly crystal-
line nature was checked for the same study, which also showed
a decrease in pH from 4.74 to 3.63 during the rst hour of
stirring in water. The pure ZrO
2
sample having no sulfate
species also showed a decrease in pH from 5.76 to 4.885.04
during 12 hours of stirring in water, though it was lower
compared to SZ. Therefore, the decrease in pH (as also
reported by others) does not seem to be purely due to the
leaching of sulfate species; it may be due to the hydrolysis of
sulfate species and also due to the acidic metal oxide matrix.
2.5 Reaction rate
The kinetic prole of esterication of myristic acid with fresh
methanol (Fig. 10a) showed the continuous decrease in
concentration of myristic acid with time. The myristic acid
concentration [C
A
] was calculated by subtracting the con-
sumed concentration from the initial concentration of myristic
acid. A fast linear decrease in myristic acid concentration was
observed till 60 min. The reaction rate (n) was determined by
applying linear analysis to the plot of decreasing [C
A
] with
time by the equation, n = d[C
A
]/dt. The initial rate was
12.9 mmol min
1
. Turnover frequency (TOF, moles of fatty
acid converted per mole of acid site concentration per hour) at
100% conversion was 4.44 per hour.
The kinetic experiments with o10 min reaction time were
performed to have a view on apparent induction period of the
reaction. The kinetic prole in Fig. 10b shows the conversion
of myristic acid within 1 min of the reaction, a fast decrease in
[C
A
] between 1 and 2 min, which extended to 4 min and after
that it became slow. It is to be noted that while performing the
reaction, the catalyst was added after mixing the acid and
methanol by stirring at ambient temperature. This time was
taken as zero time. After that the reaction mixture was heated
at the desired temperature (60 1C), which was already main-
tained at 60 1C (to avoid the shooting of temperature (B45 1C)
beyond 60 1C that normally occurs during the heating of the
system). This was kept in mind because of low boiling point of
methanol (6465 1C). Thus, the apparent induction period of the
studied reaction is just the heating of the system; it will be slightly
extended during the heating of the system to the desired tem-
perature. The initial reaction rate of this period was determined
to be signicantly higher (38.8 mmol min
1
).
2.6 Comparison of catalytic performance with other acids
Based on literature reports
9,1113,36
we have focused on SZ in the
present study. However, we have also carried out the reaction
with concentrated H
2
SO
4
and heterogeneous ion exchange resin
Amberlyst-15 to have a comparable view on the catalytic activity.
The results (Fig. S7, ESIw) showed the activity in the order of
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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This journal is c The Royal Society of Chemistry 2012 Catal. Sci. Technol., 2012, 2, 25122520 2519
H
2
SO
4
4 SZ 4 Amberlyst-15. Concentrated H
2
SO
4
, used as a
benchmark catalyst, is not eco-friendly and cannot be readily
re-cycled. To overcome the disadvantages associated with
liquid acid catalysts, heterogeneous catalysts are the sustain-
able alternatives, though having lower catalytic performance.
The initial rate of esterication reaction was slow with SZ
catalysts (12.9 mmol min
1
) as compared to conc. H
2
SO
4
(1415 mmol min
1
), the nal conversion after 2 h was in a
comparable range. These results clearly showed the potential
of SZ solid acid catalyst near to the benchmark catalyst.
Amberlyst-15 showed signicantly lower activity (56 mmol min
1
)
under the reaction conditions studied and was comparable with
esterication of oleic acid with methanol at 80 1C.
38
A comparison of catalytic activity of SZ used in the present
study with reported studies of SZ or other solid acid catalysts
gave fairly good performance (716 mmol min
1
g
1
) as com-
pared to reported SZ (125 mmol min
1
g
1
) and SZ incorpo-
rated on SBA-15 (175 mmol min
1
g
1
) for methyl palmate
and laurate formation at 68 1C.
39
TOF of the present reaction
was also found to be higher (4.44 per hour) as compared to
SZ (1.92.5 per hour) and SZ incorporated on SBA-15
(2.63.4 per hour) for methyl palmate and laurate (calculated
from data given in ref. 39). Similarly, the activity was observed
to be higher (716 mmol min
1
g
1
) as compared to other SZ
(150 mmol min
1
g
1
) and sugar catalyst (478 mmol min
1
g
1
)
for methyl oleate formation at 80 1C.
38
The conversion rates
were also observed in a similar range for esterication of lauric
acid with 2-ethyl hexanol by the SZ (SSZr-1) catalyst, studied
at 170 1C with 10 wt% of catalyst.
8
The authors reported
similar results for esterication of lauric and myristic acids
with iso-propanol. TOF values of the reported reactions may
be higher. A high reaction rate for esterication of myristic
acid with methanol was observed over SZ
18
(7585% conver-
sion in 5 min) at 22 bar in a Parr reactor at 120170 1C. The
high temperature and pressure are important factors to signi-
cantly enhance the reaction rates besides the catalyst properties.
Therefore, a proper comparison of catalytic activity, though
normalized with acid site concentration, can only be viable
when the reactions have been performed at comparable reaction
parameters such as temperature, catalyst amount and acid to
alcohol ratio
9,18,40,41
along with the carbon chain length of
alcohol
8,20,41
and carboxylic
33
/fatty acid.
19,20
2.7 Structureactivity co-relation
The co-relation between acidic features in terms of total
surface acidity, Bro nsted acidity, Bro nsted acid site concen-
tration, B/L ratio and the activity of all three SZ catalysts
reveals that esterication of myristic acid with short chain
alcohols is mainly Bro nsted acid catalyzed reaction. The
activity decreases with a decrease in Bro nsted acidity in either
terms. Furthermore, a SZ catalyst with lower number of weak
and moderate acid sites is also able to demonstrate the
esterication activity similar to a SZ catalyst having compara-
tively higher number of strong acid sites; however, the latter is
requisite to retain the original activity of re-used SZ catalysts
along with a higher B/L ratio. The dierence in the activity of
re-used catalysts clearly revealed that re-usability of SZ cata-
lysts strongly depends on the acidity of the catalysts.
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 H
2
SO
4
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 = W
b
W
s
; W
b
is the broadened prole width of the
experimental sample and W
s
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.
NH
3
-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 Bro nsted acidity of
the catalysts.
26b
Diuse Reectance FT-IR spectroscopy
(DRIFT) was used to dierentiate between Bro nsted 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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2520 Catal. Sci. Technol., 2012, 2, 25122520 This journal is c The Royal Society of Chemistry 2012
were performed in duplicate with 2% variations in conver-
sion. 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 Bro nsted 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 require-
ment of more number of Bro nsted 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 conver-
sion 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. H
2
SO
4
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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