SONOCHEMISTRY

ELSEVIER Ultrasonics Sonochemistry 5 (1998) 7 12

Ultrasound assisted PTC catalyzed saponification of

vegetable oils using aqueous alkali
B.S. Bhatkhande, S.D. Samant *
Organic Chemistry Laboratory, Chemistry Division, UniversityDepartment of Chemical Technology, N.M. Parikh Marg, Matunga,
Mumbai-400019, India
Received 1 May 1997; received in revised form 16 September 1997

Abstract

A few vegetable oils were saponified using aqueous KOH and different PTCs at room temperature in the presence of ultrasound.
The extent of saponification was studied using the saponification value as a reference. Optimizations of various parameters such
as time, selection of PTC, quantity of PTC, quantity of KOH and quantity of water were carried out using soyabean oil as a
sample oil under sonication with stirring. To study the effect of ultrasound, the saponification was also carried out at 35_+2C
under different conditions, namely stirring, sonication, stirring and sonication, and heating at 100C. It was found that the
heterogeneous liquid-liquid phase saponification of different vegetable oils using aq. KOH/CTAB was remarkably accelerated at
35 +2C in the presence of ultrasound along with stirring. 1998 Elsevier Science B.V. All rights reserved.

Keywords: Vegetable oils; Phase transfer catalyst; Alkaline saponification; Ultrasound

1. Introduction cation of ultrasound in the hydrolysis of oils and fats.

To our knowledge, there are only two references on the
Saponification of oils and fats is a commercially use of ultrasound in this area. Both of these references
important heterogeneous unit process which is not only describe the use of aqueous ethanolic alkali and phase
used for the preparation of soaps, but also for the transfer catalyst ( P T C ) for the hydrolysis of wool wax
preparation of commercially important fatty acid salts. and oils [7]. As wool wax or oil forms a homogeneous
In recent years we have witnessed the development of solution in 50% ethanol, the reaction becomes a homo-
novel synthetic methodologies to circumvent the prob- geneous reaction in which the exact role of PTC in
lems associated with classical heterogeneous thermal conjunction with ultrasound seems to be complex.
reactions. Among these techniques are turbulence- This paper is a part of our study in the area of
induced saponification of ethyl palmitate [1], enzyme sonochemical liquid-liquid ( L - L ) heterogeneous reac-
catalyzed hydrolysis of animal fats [2], high pressure tions [8]. Here, we would like to report our observations
hydrolysis of fats [3], superheated steam hydrolysis of on the saponification of a few commercially important
fats [4] and the hydrolysis of oils using hydrodynamic vegetable oils in aqueous alkaline solution using phase
cavitation [5]. transfer catalysts (PTCs) in the presence of ultrasound,
The use of ultrasound in organic synthesis has distinct wherein we would like to describe the specific importance
advantages, such as reduction in steps of the synthesis of the PTC and ultrasound.
facilitating one pot synthesis, reduction in time of the Soyabean oil was taken as a model oil and its saponi-
reaction, allowing use of laboratory grade reactants and fication was studied in detail. Optimizations of various
reagents, and the reduction in the reaction temperature. parameters, such as selection and quantity of PTC,
Excellent reviews are available on the use of this versatile quantity of KOH, and quantity of water were carried
technique in Synthetic Organic Chemistry [6]. With this out. The PTCs used were polyethylene glycol-200
background one may anticipate the success of the appli- (PEG-200), polyethylene glycol-400 (PEG-400), sodium
lauryl sulfate (SLS), cetyl trimethyl ammonium bromide
* Corresponding author. Tel: 91 22 414 56 16; fax: 91 22 414 56 14; (CTAB), tetrabutyl ammonium bromide (TBAB). The
e-mail: [email protected] effect of stirring and heating at 100C was compared

1350-4177/98/$19.00 1998 Elsevier Science B.V. All rights reserved.

PII: S 1350-4177 (97) 00044-8
8 B.S. Bhatkhande, S.D. Samant/Ultras'onics Sonochemistrv 5 (1998) 7 12

with that of mere sonication, and sonication with ( 1.0 g) and CTAB (0.30 g) were added and the reaction
stirring. mixture was stirred with an overhead stirrer (150 rpm)
and sonicated for 3 h.
For the nonsonicated reaction, the above reaction
2. Experimental mixture was only stirred at the desired temperature.

1. Chemicals
2.7. The extent of sapon(fication
The following commercial grade vegetable oils were
For the determination of the extent of saponification,
used: soyabean oil (saponification value, 190), castor oil
blank experiments were carried out simultaneously,
(saponification value, 189), sesame oil (saponification
keeping all the other quantities except oil the same. The
value, 192), sunflower oil (saponification value, 190),
reaction mixture as well as a blank mixture were titrated
linseed oil (saponification value, 190). K O H and PTCs
against 0.05 N HC1 using phenolphthalein indicator.
used were of analytical grade. Saponification values o f
The extent of saponification was determined as follows
the above oils were determined by the standard AOCS
method [9].
Blank titration reading= A ml of 0.05 N aqueous HC1
Main titration reading = B ml of 0.05 N aqueous HCl
2.2. Sonication Normality of H C 1 - 0.05 N
Equivalent wt. of KOH = 56.10
For the sonication, a circular ultrasonic cleaner bath Weight of oil = Wg

was used. It was well characterized with respect to Saponification value found X
out by classical method [9] =
pressure intensity profiles developed, when filled with
Extent of saponification (%)= ( A - B ) x 0.05 x 56.10 x 100
appropriate amount of water, using a pressure pulse
WX X
intensity measurement probe (PPIMP) developed in our
laboratory [10]. The bath (circular cross section with
diameter of 14.3 cm and height 20 cm) having frequency
35 +_3 kHz and power 120 W (Model Dakshin D2 (120),
from M/s Dakshin, Mumbai, India) was used. 3. Results

2.3. Temperature control In the present study, soyabean oil was used as a
model oil and all the reaction parameters were optimized
It is known that the maximum cavitation in water with respect to this oil.
takes place at 3 5 C [ l 1]. Hence, the temperature of the
water in the ultrasonic cleaner was maintained at
3.1. PTC
35 2 C by adding crushed ice to the bath from time
to time and the water level inside the bath was kept
The hydrolysis of soyabean oil was carried out using
constant.
different PTCs, cationic, anionic and nonionic, in aque-
ous alkaline solution (3% K O H ) . The reaction mixture
2.4. Reaction vessel
was sonicated at 35 +2C with stirring for 180 min and
the extent of saponification was measured.
It is known that a flat bottom vessel is useful for
1.3 mmol of each PTC was used for 1.00 g of the oil
sonochemical reactions [12]. A flat bottom Erlenmeyer
(Table 1). To establish the necessity of the PTC, the
flask of 250 ml capacity with a long neck was used for
results of the saponification without PTC under the
the reactions.
same experimental conditions were compared. The reac-
tion was greatly accelerated in the presence of CTAB.
2.5. Saponification of vegetable oil

Saponification of vegetable oils was carried at 35 ___2C 3.2. Time

under stirring, sonication, and sonication and stirring.
Also it was carried out separately at 100C. The saponification of soyabean oil was carried out in
an aqueous K O H solution (3%, 50 ml) using CTAB,
2.6. General proeedure of sonoehemical saponification of under sonication and stirring at 35 + 2C. The extent of
vegetable oil saponification was continuously monitored at 30 min
intervals (Fig. 1 ). It was observed that after 180 min the
To the aqueous KOH solution (50 ml, 3%) taken in saponification was complete. Hence, for all the experi-
a flat bottom Erlenmeyer flask (250 ml), a vegetable oil ments, saponification was carried out for 180 min.
 B.S. Bhatkhande, S.D. Samant / Ultrasonics Sonochemistry 5 (1998) 7 12

Table 1
Saponification of soyabean oil a in presence of different PTCs

Sr.No. PTC b Extent of saponification(%)c

Stirring Sonication Sonication and stirring Thermal

I. No PTC 5 18 27 30
2. PEG-200 25 20 37 59
3. PEG-400 35 21 40 65
4. SLS 28 20 38 65
5. TBAB 36 22 42 76
6. CTAB 53 70 99 98

"Soyabean oil 1.00 g and aqueous K O H (3%, 50 mt ).

b| .3 mmol PTC per g oil.
CTime for each reaction (3 h).
dReaction temperature (100'C).

100

80

,-- 60
o

e--
g 4o
~q

20

0 I 1 I I I I
0 30 60 90 120 150 180 210
Time (rain)

Fig. 1. Optimization of time of the sonochemical saponification of soyabean oil using aq. K O H - C T A B system.

3.3. Quantity of CTAB the rate of saponification depended upon the concen-
tration of KOH, the amount of K O H was gradually
In order to fix the quantity of CTAB, the saponifica- increased, maintaining the ratio of (soyabean oil: water)
tion of soyabean oil was carried out in aqueous K O H as 1:50 (Fig. 4). The optimum quantity of K O H was
(3%, 50 ml ) using an increasing quantity of CTAB under found to be 1.5 g per gram of oil (3% aq. solution,
sonication and stirring at 35 _+2C (Fig. 2). It was found 50 ml ).
that the extent of saponification increased with the
amount of CTAB. The saponification was found to 3.5. Effect of sonication
increase drastically above 0.25 g of CTAB per gram of
oil. It was found to be almost complete when 0.30 g of To study the effect of sonication in the saponification
CTAB was used. of different oils, 1.00 g of an oil was suspended in
aqueous K O H (50ml, 3%) with CTAB (0.30g).The
3.4. Aqueous alkali reaction mixture was sonicated for 180 rain with stirring
( 150 rpm).
It was noted that, being a heterogeneous reaction, for To bring out the importance of sonication in compari-
the sonication to be effective, it was essential to take son with mere stirring, as well as with heating, each
the oil and water in optimum ratio. Hence, using a fixed stirred reaction (150 rpm) was carried out without soni-
quantity of K O H (1.5g), soyabean oil (1.00g) was cation at 35+2C. Similarly, the reaction was also
saponified with increasing amount of water (Fig. 3). carried out at 100C with stirring ( 150 rpm), but without
From Fig. 3, it is clear that 50 ml of water per gram of sonication.
soyabean oil was optimum for the saponification. As In the case of castor oil, sunflower oil and sesame oil,
10 B.S. Bhatkhande, S.D. Samant / Ultrasonics Sonochemistry 5 (1998) 7 12

100

80

c 60
o

~ 4o
m

20 I

0 -- L I I k I I I
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4
Quantity o f C T A B (g)

Fig. 2. Optimization of the quantity of the CTAB in the sonochemical saponification of soyabean oil using aq. KOH-CTAB system.

100

80

60
o

c
8. 4o

20

0 -- i I [ I J
o 10 20 30 40 50 60
Q u a n t i t y of w a t e r (ml)

Fig. 3. Optimization of the quantity of the water in the sonochemical saponification of soyabean oil using aq. KOH-CTAB system.

it was found that 0.3 g of CTAB was insufficient to give in the water phase was satisfactory at 2% concentration
complete saponification. By increasing the quantity of of the oil. The results of saponification were also satisfac-
the PTC to 0.4 g the saponification was found to be tory at this concentration.
complete. Using the optimized conditions, different vege- It is possible that in the presence of sonic cavitation
table oils were saponified under different conditions in an aqueous solution, the saponification may take
(Table 2). place with the water alone. However, when the quantity
of the alkali was gradually increased, we found that the
rate of saponification also increased gradually. In the
4. Discussion absence of alkali, mere sonication did not effect saponi-
fication. The optimum quantity of K O H was found to
4.1. Concentration of alkali be 1.5 g per gram of the oil used.

One of the important factors accelerating a L-L 4.2. Role of PTC

heterogeneous reaction is the thorough dispersion of the
minor phase in the major phase. For complete mixing, In the L-L heterogeneous saponification of soyabean
the ratio of the two phases should be optimum, In the oil using aqueous alkali, the presence of alkali led to
present study we found that the emulsification of an oil poor emulsion under sonication as compared to the
 B.S. Bhatkhande, S.D. Samant /' Ultrasonics Sonochemistry 5 (1998) 7 12 I1

100

8O

5o

-
~. 4o

2o

I ] [ I ]

0,25 0.5 0.75 1 1.25 1.5

Quantity of KOH (g)

Fig. 4. Optimization of the quantity of K O H in the sonochemical saponification of soyabean oil using aq. KOH-CTAB system.

Table 2
Saponification of different vegetable oils under different experimental conditions

Sr. No. Oil ~ Extent of saponification (%)b

Stirring Sonication Stirring and sonication Thermal ~

1. Soybean a 53 70 99 98
2. Linseed d 38 60 98 98
3. Sesame c 33 50 83 85
4. Castor 51 80 98 98
5. Sunfloweff 40 71 97 98

a1.00 g oil and aqueous K O H ( 3%,50 ml ).

bTime for each reaction (3 h).
CReaction temperature (100"C).
d0.8 mmol of CTAB per g of oil.
el .0 mmol of CTAB per g of oil.
Note: In case of sesame oil, castor oil and sunflower oil when 0.8 mmol of CTAB per g of oil was used under sonication and stirring: the extent
of saponification was found to be 67, 73 and 83%, respectively.

emulsion of oil in water under sonication. This may be than TBAB. Thus, under sonication also CTAB served
due to the increased difference in the density of oil and as a best catalyst. It is interesting to note that the
the aqueous alkaline solution, resulting in poor mass optimum concentration of CTAB was approximately six
transfer. The O H - anion is of relatively low polarizabil- fold excess of the critical micellar concentration ( C M C )
ity (a hard anion) and is difficult to extract into a non- of the CTAB which is 1 mmol.
polar medium. Thus, the presence of a PTC is of prime In a liquid-solid nonaqueous heterogeneous reaction
importance in this reaction. involving hydroxide ion transfer, PEGs are excellent
When different PTCs were compared for the saponifi- catalysts. In the present reaction PEGs did not serve as
cation reaction, we found that only CTAB could effect effective PTCs. Moreover, SLS was also found to be
the saponification satisfactory. Though TBAB was poor in the same reaction. In each case, though the
slightly better than the remaining PTCs, it was much reaction using a PTC showed a betterment over the
inferior to CTAB. In the present reaction the main reaction in the absence of a PTC, in the presence of
function of the PTC was to transport O H - ions into sonication, the reactivity profile of these PTCs, other
organic phase. Obviously cationic surfactants are best than CTAB, did not change much. This indicated that
suited for this purpose. It is known that for the transport PEG-200, PEG-400, SLS, and TBAB more or less acted
of O H - ions, TBAB is inferior to CTAB in a nonsoni- as surfactants rather than as phase transfer catalysts.
cated reaction due to steric crowding at the quaternary From Table 2, it can be seen that the other vegetable
nitrogen atom in the TBAB [13]. Moreover, for an oil oils more or less followed the same trend as followed
having linear hydrocarbon chains, CTAB is better suited by soyabean oil. In all cases, sonication with stirring
12 B.S. Bhatkhande, S.D. Samant / Ultrasonics Sonochemistry 5 (1998) 7-12

was found to be much superior as compared to any one cary, M. Llama, J. Serra, L. Landeta, M. deRenobales, Enzyme
Microb. Technol. 16 (1994) 61.
of them alone. Individually also, sonication was found
[3] X. Huang, Riyong Huaxue Gongye 5 (1992) 260.
to be better than stirring. Using a combination of PTC [4] M. Deibert, Energy Res. Abstr. 18 (1993) Abstr. 3541 (C.A, 121:
and ultrasound, saponification comparable to thermal 2079300.
saponification (at 100C) was observed, but at a con- [5] A. Pandit, J. Joshi, Chemical Engineering Science 48 (1993) 3442.
siderably lower temperature (35 _+2C). [6] T.J. Mason, J.P. Lorimer, Sonochemistry: Theory, Applications
and Uses of Ultrasound in Chemistry, Ellis Horwood, UK, 1988.
[7] (a) R. Davidson, A. Safdar, J. Spencer, B. Robinson, Ultrasonics
25 (1987) $35; (b) B. Robinson, A. Safdar, R. Davidson, Saponi-
fication of Fats, UK Patent Application No. 8602316, 1986.
Acknowledgements [8] S.R. Soudagar, S.D. Samant, Ultrasonic Sonochemistry 2 (1)
(1995) S15.
One of the authors (BSB) is grateful to the University [9] Official and tentative methods of the American Oil Chemist's Soci-
Grant Commission, New Delhi, India for the award of ety, Method No. Cd-3-25.
a Research Fellowship. [I0] S.R. Soudagar, S.D. Samant, Ultrasonic Sonochemistry 2 (I)
(1995) $49.
[11] T.J. Mason, Practical Sonochemistry: Users Guide to Applica-
tions in Chemistry and Chemical Engineering, Ellis Horwood,
UK, 1990, p. 57.
References [12] B. N iemczewski, Ultrasonics 18 (1980) 107.
[13] C.M. Starks, C.L. Liotta, M. Halpern, Phase-transfer Catalysis,
[1] J. Fang, P. Joos, Colloids Surf. A 83 (1994) 63. Fundamental Applications an Industrial Perspectives, Chapman
[2] M. Virto, I. Agud, S. Montero, A. Blanw, R. Solozabal, J. Las- and Hall, USA, 1994, p. 129.