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J Sol-Gel Sci Technol (2012) 62:1317

DOI 10.1007/s10971-011-2671-9

ORIGINAL PAPER

Esterification of caprylic acid with alcohol over nano-crystalline


sulfated zirconia
K. Saravanan Beena Tyagi H. C. Bajaj

Received: 8 November 2011 / Accepted: 27 December 2011 / Published online: 6 January 2012
Springer Science+Business Media, LLC 2012

Abstract The catalytic activity of nano-crystalline sulfated zirconia catalyst, prepared by solgel method and
characterized by various analytical tools, was evaluated for
the esterification of caprylic acid with different short chain
alcohols. The lower concentration of catalyst (0.5 wt%)
exhibited 9698% conversion of caprylic acid with methanol and 100% selectivity for methyl caprylate at 60 C.
The conversion was decreased with increasing carbon
chain of alcohols namely with ethanol, n-propanol and
n-butanol at 60 C but increased significantly (9198%)
at higher reaction temperature. The selectivity for respective alkyl caprylate was observed to be 100% irrespective
of the alcohol used. The activity of the catalyst was slightly
decreased with successive five reaction cycles due to the
water formed during the reaction.
Keywords Caprylic acid  Esterification  Fatty acid
methyl ester  Sulfated zirconia  Solid acid catalyst

1 Introduction
Alkyl esters have important industrial applications in a
variety of products, e.g., emulsifying agents for foods,
cosmetics; lubricants for plastics, paint and ink; perfumery
and flavor chemicals; pharmaceuticals, textile and in agricultural industry, etc. [1]. Conventionally, alkyl esters have
been prepared by the esterification of corresponding acid

K. Saravanan  B. Tyagi (&)  H. C. Bajaj


Discipline of Inorganic Materials and Catalysis, Central Salt
and Marine Chemicals Research Institute, Council of Scientific
and Industrial Research (CSIR), G B Marg,
Bhavnagar 364 002, Gujarat, India
e-mail: btyagi@csmcri.org

with an alcohol in presence of homogenous acid catalyst.


Caprylic acid (n-octanoic acid, C8H16O2) is a saturated
fatty acid and one of the constituents of coconut and palm
kernel oil [2], which are used to produce biodiesel by
transesterification in presence of base catalyst. Alkyl caprylates are also used in perfumery and in the manufacture
of dyes [3].
Industrial esterification processes are carried out in
presence of conventional Bronsted acid catalysts such as
sulfuric, p-toluene sulfonic or phosphoric acid [4]. There is
a strong global demand to replace these homogenous catalysts with eco-friendly solid catalysts, which are active
under mild conditions, can be easily recovered and reused.
Kiss et al. [5] have screened various solid acids including
zeolites, ion exchange resin and metal oxides for the
esterification of lauric acid (C12H24O2) with different
alcohols at 130180 C and found sulfated zirconia (SZ) as
the most active solid acid catalyst. SZ is well known for its
strong acidity, which is attributed to sulfate ions [6]. Few
studies have been reported for the esterification of caprylic
acid with various short chain alcohols using metal oxides
such as SZ, TiZ, WZ, AlZ [710], niobia [11], nafion/silica
composite [12] and sulfonated carbon [13] catalysts.
Besides, enzymatic catalyzed esterification of the same has
also been studied [14]. However, most of these studies
have been done at high temperature (75200 C) [710] or
in presence of higher concentration of catalyst (115 wt%)
[5, 10, 11] or longer reaction time (24 h) [12] is required to
achieve maximum conversion of fatty acid. Furuta et al. [7]
have found high activity of SZ for esterification of caprylic
acid under continuous flow reactor at higher temperature
([150 C), however remarkably low activity was observed
at \120 C.
The present study reports the esterification of caprylic
acid with methanol at 60 C to methyl caprylate in

123

14

presence of small concentration of SZ solid acid catalyst.


The study also reports the influence of reaction temperature
on the conversion of acid to respective alkyl caprylate with
other short chain alcohols such as ethanol, n-propanol and
n-butanol.

2 Experimental
2.1 Materials
Zirconium n-propoxide, Zr(OPr)4 was procured from
Sigma-Aldrich, Germany; concentrated sulfuric acid
(98%), n-propanol (99%) and n-butanol (98%) were procured from s.d. Fine chemicals, India; aqueous ammonia
solution (25%) from Rankem, India; Caprylic acid (99.5%)
and ethanol (99.9%) were purchased from Spectrochem
Pvt. Ltd., India.

J Sol-Gel Sci Technol (2012) 62:1317

Vapor phase cyclohexanol dehydration to cyclohexene


in a fixed bed reactor was used to evaluate the Bronsted
acidity of the catalyst. Cyclohexanol (2 ml) was delivered
by a syringe pump injector (Cole Parmer, 74900 series)
with a flow rate of 1 ml h-1 under N2 at 175 C over the
catalyst sample (0.2 g) packed in a reactor bed. Product
samples were collected after 1 h and analyzed with a
HewlettPackard gas chromatogram (HP 6890) having FID
detector. The conversion of cyclohexanol and selectivity
for cyclohexene was calculated as follows:
Conversion of cyclohexanol (wt%
100  Initial wt%  Final wt%=Initial wt%
Selectivity for cyclohexene (wt%
100  GC peak area% of cyclohexene=
R peak area of total products
2.4 Catalytic activity for esterification of caprylic acid
with alcohol to synthesize alkyl caprylate

2.2 Catalyst synthesis


Nano-crystalline sulfated zirconia catalyst was prepared by
solgel method [15]. In a typical synthesis procedure,
Zr(OPr)4 was hydrolyzed by aqueous ammonia followed
by the treatment with H2SO4 (1 N). The sulfated powder
was oven dried at 120 C for 12 h followed by calcination
at 600 C for 4 h.
2.3 Catalyst characterization
The crystalline characterization of sulfated zirconia catalyst was done by powder X-ray diffractometer (Philips
). The crysXpert) using CuKa radiation (k = 1.5405 A
tallite size of tetragonal phase of zirconia was determined
from the characteristic peak (2h = 30.22 for the (111)
reflection) using Scherrer formula with a shape factor
(K) of 0.9 [16]. The bulk sulfur (wt%) present in catalyst
before and after calcination at 600 C was analyzed by
inductively coupled plasma (ICP) emission spectroscopy
using a Perkin-Elmer, Optima 2000 DV spectrometer.
Specific surface area and pore size of the sample were
determined from nitrogen adsorptiondesorption isotherms
at -196 C (ASAP 2010, Micromeritics, USA) using BET
equation and BJH adsorption respectively [17].
The total surface acidity of the catalyst was measured by
temperature programmed desorption (TPD) of NH3 (Micromeritics Pulse Chemisorb 2720). In a typical procedure,
a mixture of 10% NH3 and He gas was passed for 30 min at
40 C over the sample (in situ activated at 120 C for 2 h).
The excess physisorbed NH3 was flushed out for 10 min
with pure He gas flow. The sample was then heated at a
rate of 10 C min-1 up to 800 C and volume of desorbed
NH3 was measured.

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Esterification of caprylic acid with alcohol was carried out


in a liquid phase batch reactor to evaluate the catalytic
activity of sulfated zirconia sample. In a typical reaction
procedure, required amount of caprylic acid, alcohol (acid :
alcohol molar ratio = 1:10) and catalyst (0.5 wt%) were
taken in a round bottom flask and the suspension was
magnetically stirred (600 rpm) in oil bath maintaining
constant temperature (1 C) in the temperature range of
60110 C. The reaction kinetics was monitored by withdrawing small amounts of the reaction mixture at 1 h
intervals and analyzed using a gas chromatograph (HP
6890) having a DB-225 capillary column and FID detector.
The conversion of caprylic acid and selectivity for alkyl
ester was calculated by GC peak area as below:
Conversion of caprylic acid (wt%
Initial wt%  Final wt%=Initial wt%  100
Selectivity for alkyl ester(wt%

GC peak area% of alkyl ester=

R peak area of total products  100

3 Results and discussion


3.1 Catalyst characterization
Powder X-ray diffraction (PXRD) pattern of sulfated zirconia
catalyst, calcined at 600 C, showed the presence of tetragonal crystalline phase (2h = 30.21, 35.27, 50.21, 60.31)
(Fig. 1). The sample was observed to be less crystalline due to
the presence of higher sulfur content (Table 1); as higher
thermal energy is required for dehydroxylation during crystallization in the presence of sulfate groups that enhances the

J Sol-Gel Sci Technol (2012) 62:1317

15
70

b
a

60
50

40

Pore volume (cm 3/g)

Intensity (a.u)

Volume Adsorbed cm/g STP

0.008
0.006
0.004
0.002
0.000
3

30

12 15 18 21 24 27 30

Pore diameter (nm)

20
10

10

20

30

40

50

60

70

80
0.0

2 Theta (degree)

0.2

0.4

0.6

0.8

1.0

Relative Pressure (P/Po)

crystallization temperature of the sample [18]. The sample


was found to have nano-crystallite size of 11 nm (Table 1).
The bulk sulfur present in sulfated zirconia sample was
3.7 wt% before calcination, which decreased to 2.6 wt%
after calcination at 600 C (Table 1).
N2 adsorption isotherm (Fig. 2) of the sample was found
to be of type IV, which is characteristic of mesoporous
solids [17], having the narrow pore size distribution
(Fig. 2) and average pore diameter of 7.6 nm (Table 1).
The sample was found to have low BET surface area
(28 m2/g) and pore volume (0.05 cm3/g).
NH3-TPD results showed that NH3 desorption occurred
at 719 C indicating the presence of stronger acid sites.
The total number of acid sites was found to be 2.5 mmol/g
(Table 1). The vapor phase dehydration of cyclohexanol to
cyclohexene resulted into 91% conversion of cyclohexanol
with 100% selectivity for cyclohexene. It indicated the
presence of higher Bronsted acidity in the prepared sulfated
zirconia catalyst (Table 1).
3.2 Esterification of caprylic acid
The esterification of caprylic acid with methanol was carried out in presence of sulfated zirconia catalyst in a liquid
phase batch reactor at 60 C (b.p. methanol *65 C). GC
analysis of the reaction mixture showed the selective formation (100%) of methyl caprylate.

Fig. 2 N2 adsorptiondesorption isotherm, (inset) Pore size distribution of nano-crystalline sulfated zirconia

100
90

Conversion (wt.%)

Fig. 1 Powder X-ray diffraction pattern of nano-crystalline sulfated


zirconia (a) before and (b) after calcination at 600 C

80
70
60
50
40
30
0

100

200

300

400

500

600

Time (min)
Fig. 3 Esterification of caprylic acid with methano1 over sulfated
zirconia. Reaction conditions: caprylic acid: methano1 molar
ratio = l:10; catalyst: 0.5 wt%, temperature: 60 C

The reaction kinetic study showed an exponential


increase in the conversion of caprylic acid from 10 min
(37%) to 4 h (90%) followed by a linear increase till 7 h
and remained steady afterwards (Fig. 3). The maximum
conversion of caprylic acid was 9698% after 7 h. The
earlier studies reported in the literature showed the higher
conversion of caprylic acid either at higher temperature or
using higher amount of the catalyst or after longer reaction

Table 1 Characterization of nano-crystalline sulfated zirconia catalyst


Crystallite
size (nm)

BET surface
area (m2/g)

Average pore
volume (cm3/g)

Average pore
diameter (nm)

Sulfur
(wt%)

Acid sites
(mmol/g)

Cyclohexanol
conversion (%)

11

28

0.05

7.6

2.60

2.5

91

123

16

J Sol-Gel Sci Technol (2012) 62:1317

Table 2 Esterification of caprylic acid with alcohol using different


solid acid catalysts
Catalyst
amount

Temp (C),
Time (h)

Max.
conversion
(%)

Reference

SZ, Nafion,
Amberlyst

13 wt%

120180,
15

*80

[5]

SZ, SSn

4g

150, 20

*100

[6]

WZA, SZA,
STO

4g

200, 20

*100

[7]

TiZ, AlZ

4g

175, 20

*100

[8]

SZ, WZ, TiZ

8 wt%

75, 4

*1060

[9]

Niobia
Nafion/silica

15 wt%
2.42 wt%

65, 3
60, 24

*98
*60

[10]
[11]

Sulfonated
carbon

2.5 wt%

60, 1

*20

[12]

SZ

0.5 wt%

60, 7

98

Present
results

time [Table 2]. Besides caprylic acid, higher conversion of


other fatty acids has also been reported using 275 wt% of
different solid acid catalysts [19].
The difference in the activity of various catalysts occurs
due to the variation in their structural, textural and acidic
features, which strongly depends on the preparation methods.
Different reaction parameters also lead to different catalytic
behaviour. To the best of our knowledge, this is the first report
of using minimum concentration (0.5 wt%) of sulfated zirconia catalyst resulting 98% conversion of caprylic acid
within reasonable reaction time period (7 h) at 60 C.
3.2.1 Effect of alcohols
The esterification of caprylic acid with various alcohols
namely ethanol, n-propanol and n-butanol showed the successive decrease in the conversion values (8867%) with
increasing carbon chain of alcohols (Fig. 4). This is due to the
inductive effect of increased carbon chain of alcohol. The
electron donating ability of alkyl group towards the hydroxyl
group increases with increasing the alkyl chain of alcohol thus
lowers the hydroxylation and limiting the electrophilic attack
by the acid. When the reaction was studied at higher temperature in reflux conditions, near to the boiling point temperature of respective alcohol (75110 C), the conversion
was found to increase significantly (9198%) (Fig. 4). The
selectivity for respective alkyl caprylate was observed to be
100% irrespective of the alcohol used.
3.2.2 Reusability of SZ catalyst
To study the reusability of SZ catalyst, the used catalyst
was recovered from the reaction mixture, washed with

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Conversion (wt.%)

Catalyst

100

60 C
75 C

110 C

90 C

80

60

40

20

0
MeOH

EtOH

n-PrOH

n-BuOH

Fig. 4 Esterification of caprylic acid with various alcohols at


different temperatures over sulfated zirconia. Reaction conditions:
caprylic acid: methano1 molar ratio = l:10; catalyst: 0.5 wt%

Table 3 Conversion (%) of caprylic acid over re-generated sulfated


zirconia catalyst
Cycles

Conversion (%)

98

89

88

84

81

Reaction conditions: caprylic acid: methano1 molar ratio = l:10;


catalyst: 0.5 wt%, temperature: 60 C, time: 7 h

methanol, dried and activated at 450 C for 2 h before its


re-use for further reaction cycle. The activity of SZ catalyst
was found to slightly decrease with successive reaction
cycles and the conversion of caprylic acid was 81% after
five cycles (Table 3). The decrease in the activity may be
due to the deactivation of the catalyst by the presence of
water, a co-product formed during the esterification reaction. Water having the higher dielectric constant (80 at
20 C) than methanol (33 at 20 C) has higher affinity to
interact with the active acid sites and thus lowers the
interaction of methanol with active sites resulting into a
decrease in conversion of acid.
3.2.3 Mechanism
Esterification of acid with alcohol may be catalyzed by
both Bronsted and Lewis acids. SZ catalyst has both
Bronsted (H?) and Lewis acid sites (Zr?) as shown in
Scheme 1, therefore, both acid sites may take part in the
reaction. As the catalyst was having higher Bronsted
acidity, the studied esterification is supposed to be mainly

J Sol-Gel Sci Technol (2012) 62:1317

17

O
Brnsted
HO-H

SZ

Zr
O

O
S
O

Lewis
Zr+

Zr
O

O
H

H+
SZ

C7H15-C-OH
O

Caprylic acid

C7H15-C-OH

ROH

OH

C7H15-C-OH

SZ

OH
SZ

OR

C7H15-COOR
Alkyl caprylate

C7H15-C

OR

-H2O

decrease with successive five reaction cycles, which may


be due to the water molecules formed during the esterification reaction as a co-product. The higher sulfur content,
Bronsted and total acidity of sulfated zirconia seems to be
responsible for its high activity for the studied reaction.
The detailed study for varied reaction parameters, effect
of calcination on the crystallinity, acidity and activity of
the catalyst, deactivation of sulfated zirconia catalyst in
presence of water and esterification of higher carbon chain
fatty acids are the subject of ongoing investigations in our
laboratory.

C7H15-C-OH2

O H

OH

SZ

SZ

Scheme 1 Plausible structure of SZ catalyst and mechanistic representation of esterification of caprylic acid with alcohol to synthesize
alkyl caprylate using Bronsted acid sites of SZ

Bronsted acid catalyzed reaction, wherein H? transfers


from the Bronsted acid sites of catalyst to carbonyl oxygen
of the acid, which is nucleophillic attacked by oxygen of
alcohol; subsequent deprotonation and loss of water forms
the ester product (Scheme 1).

4 Conclusions
Sulfated zirconia catalyst, prepared by solgel method, was
found to have nano-crystalline size of 11 nm. It showed the
presence of higher Bronsted and total surface acidity;
though the crystallinity and BET surface area was low. The
small concentration of the catalyst showed encouraging
activity for esterification of caprylic acid with different
alcohols. With methanol 9698% conversion of caprylic
acid and 100% selectivity for methyl caprylate was
observed at 60 C in presence of 0.5 wt% catalyst concentration. The conversion was found to decrease
(8867%) with increasing carbon chain of alcohols, i.e.,
ethanol, n-propanol and n-butanol without affecting
the selectivity for respective alkyl caprylate. However, the
conversion was increased (9198%) by increasing the
reaction temperature near to the boiling point of the alcohol. The activity of the catalyst was found to slightly

Acknowledgments Authors are thankful to CSIR Network Programme on Inorganic material for diverse application and to Analytical science discipline for catalyst characterization analysis.

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