Ind. Eng. C h e m . R e s .

1988,27, 735-739
f = fat phase
g = glycerol
m = monoglyceride
t = triglyceride
w = water
0 = initial condition
= measured value at room conditions

Literature Cited
Astarita, G. Mass Transfer with Chemical Reaction; Elsevier: Amsterdam, 1967.
Basu, P. K. Chem. Age India 1976,27(10), 871.
Burrows, K. Trans. Znst. Chem. Eng. 1953,31(10), 250.
Butala, D. N. M.Tech. Dissertation, Department of Chemical Engineering, Indian Institute of Technology, Bombay, India, 1984.
Desai, S. M.; Raghunathan, T. S.; Shankar, H. S. Frontiers in
Chemical Reaction Engineering;Wiley Eastern: New York, 1984;
Vol. 1, p 253.

735

Donders, A. J. M.; Wijffels, J. B.; Reitema, K. Proceedings of the

Fourth European Symposium on Chemical Reaction Engineering,
Brussels, Sept 9-11, 1968.
Hilder, M. H. J. Am. Oil Chem. SOC.1968,45 703.
Jeffreys, G. V.; Jenson, V. G.; Miles, P. R. Trans. Znst. Chem. Eng.
1961, 39, 389.
Lascaray, L. Znd. Eng. Chem. 1949, 47, 486.
Lascaray, L. J. Am. Oil Chem. SOC.1952,29, 362.
Mehlenbacher, V. L. Analysis of Fats and Oils; Gerrad: Chapaign,
IL, 1960.
Mills, V.; McClain, H. K. Znd. Eng. Chem. 1949, 47, 1982.
Mueller, H. H.; Holt, E. K. J. Am. Oil Chem. SOC.1948, 25, 305.
Perry, R. H.; Chilton, C.H. Chemical Engineers Handbook, 4th ed.;
McGraw-Hill: Kogakusha, Tokyo, 1973; p 3.87.
Sarkar, S.; Mumford, C. J.; Phillips, C. R. Znd. Eng. Chem. Process
Des. Dev. 1980, 19, 672.
Sturzenegger, A.; Sturm, H. Znd. Eng. Chem. 1951, 43(2), 510.

Received for review November 19, 1985

Revised manuscript received August 14, 1987
Accepted November 30, 1987

Thermal Hydrolysis of Vegetable Oils and Fats. 2. Hydrolysis in

Continuous Stirred Tank Reactor
T. A. Patil, T. S. Raghunathan, and H. S. Shankar*
Department of Chemical Engineering, Indian Institute of Technology, Bombay 400 076, India

The liquid-liquid thermal hydrolysis of coconut oil is studied experimentally on a laboratory-scale

continuous stirred tank reador over the range 225 O C , 3000 kPa to 260 O C , 5500 kPa. Good agreement
is indicated between the model prediction and data.
Hydrolysis as a liquid-liquid reaction has been practiced
commercially for a long time. Batch autoclaves are commonly used in small-scale operations, while continuous
countercurrent columns are employed in large-scale operations. Batch operation involves high specific energy
consumption and idle time. The continuous countercurrent spray towers require very high initial investment. In
India both batch and continuous countercurrent operations
are in use.
The hydrolysis can be brought about over a batch of oil
by a spray of high-pressure water. This scheme could have
somewhat poor productivity in relation to continuous
countercurrent operations. No work on semicontinuous
hydrolysis has been reported so far.
The reaction can also be conducted in a continuous
stirred tank reactor. This scheme offers advantages with
respect to energy integration and productivity in addition
to cost advantages in terms of investment. In this scheme,
a mixture of water and oil is pumped to a reactor. In this
paper, we examine the behavior of this configuration
theoretically by using the model developed earlier (Patil
et al., 1988). The model predictions are then tested experimentally.

Experimental Apparatus
A laboratory autoclave of 1-L capacity made from 316
stainless steel mounted in a compact, electrically heated
furnace was used. The specifications of the autoclave are
given elsewhere (Patil et al., 1988). The top flange houses
a cooling coil with provision for cooling the water inlet and
outlet. A 316 stainless steel rupture disc tested at 50 000
kPa and 600 "C is also provided. The flange contains a
thermowell for temperature measurement and four ports.
One of the ports is connected to a pressure gauge for
pressure measurement. The others are connected via
0888-5885/ 8812627-0135$01.50/0

precision needle valves to sampling tubes of variable length

for sampling from inside the vessel. A magnetically driven
stirrer is housed at the center.
Schematic representation of the arrangement is shown
in Figure 1. A mixture of a predetermined quantity of
coconut oil and water is prepared in a storage tank and
fed to reactor via a dosing pump supplied by Jagdish
Engineering Works, Bombay, capable of operating up to
20000 kPa and having adjustable stroke length with a
maximum capacity of 2 L/h. The high-pressure dosing
pump and reactor are connected by 316 stainless steel tube
on which a check valve is mounted. This is provided in
addition to a built-in nonreturn valve on the pump. The
reactor outlet is connected to a cooler where cooling water
circulates followed by a 316 stainless steel back-pressure
regulating valve to maintain pressure inside the reactor
during the experiment.

Experimental Procedure
Water and oil are mixed in the desired proportion and
stirred well to obtain a uniform mixture, and this was
continuously pumped to the reactor by the high-pressure
dosing pump. It was found that no segregation of wateroil
emulsion occurred in the feed line, and also it was verified
that the back flow of the reactants was completely prevented by providing the additional nonreturn valve on the
feed line. Runs were conducted at chosen residence times
until steady state was reached, which was determined by
trial to vary between 1.5 and 2 h. Cooled product emerging
out of the reactor was collected, maintaining constant
pressure inside the vessel by prior setting of the backpressure regulating valve.
The mixing pattern inside reactor was examined; for this
purpose, a step input of a tracer solution containing freshly
prepared sodium hydroxide was used.
0 1988 American Chemical Society

736 Ind. Eng. Chem. Res., Vol. 27, No. 5, 1988

Table I. Hold-Up Measurement in CSTR
feed, L/h
temp, "C

GIL, vlv
0.83

225
240
260
260
260

1.0
1.0

1.0
0.5
1.5

water-oil

m'

0.83
0.83
0.83
0.83

total holdup, mL

fat-phase holdup, 6

Dredicted bv ea 7

920
915
900
905
902

0.54
0.55
0.55
0.55
0.55

0.547
0.547
0.547
0.547
0.547

sample

A - Feed storage tank

B- Hlgh pressure dosing Pump

C - Non return valve
D - Needle valve
E - Impeller
F Heat exchanger

300

G - Pressure regulating valve

260-

'

'

'

'

'

'

'

'

R- Reactor

220

Figure 1. Schematic diagram of CSTR.

Steady-state liquid hold-up measurements using a

mixture of water and oil over the desired range of waterto-oil ratio at 225,240, and 260 OC were made. This was
done by simultaneously closing both inlet and outlet valves
in the running condition and noting the volume of total
liquid together with its phase ratio in the reactor. In the
present work, residence time of 25-500 min was used.

Theoretical Section
Patil et al. (1988) proposed a kinetic model to describe
the thermal hydrolysis of vegetable oils/animal fats considering a three-step reaction scheme. The rate of generation of triglyceride as per the model is given as
rt = k,CaCd - k,C,C,
(1)

180AV

140 0

100

Experimental

63- /

-I

20
I

A mass balance on triglyceride gives

T = CmXl/(-rt)
where T is the fat-phase residence time. Substituting for
rt in eq 2, we get
T = PX1/(-X12 + QX1 + R )
X1 = [(Q - P/T)+ [(Q - P/T)' + 4R]"2]/2

(3)
The extents of reaction X2 and X3 can be given in terms
of XI as per the earlier paper as
x
2 = CX, - C'
X, = BX2 - B'
The quantities A , B, C, D,A', B', C', E , etc., are as defined
in Patil et al. (1988). Aqueous-phase glycerol concentration
is given by

9, = (xtJ,M&/MtG) + 9,o

(4)

Productivity of fatty acid and glycerol is given by

Pa = Lfa/VR = Pff,/T
P g

= G ~ ~ / V=RPa$g/T

(5)
(6)

By use of these equations, performance of CSTR can now

be evaluated. If the holdup of phases in the reactor is in

Results and Discussion

The experimental values of holdup are shown in column
5 of Table I. The values from eq 7 are shown in column
6 of Table I. It is observed that the holdup is around 910
mL and that the average holdup can be predicted satisfactorily from eq 7.
An F curve for the stirred tank is shown in Figure 2. It
is seen that the curve exhibits a negative slope and intercept of unity. It is clear from the linearity, slope, and
intercept of this curve that the reaction vessel used in this
work is very close to an ideal back mix reactor.
Coconut oil was used in all hydrolysis experiments. The
residence time ( 7 ) was calculated from eq 8. Results from
experiments at 225 "C, GIL = 0.9 w/w, and Qso = 0 are
shown in Figures 3,4, and 5 respectively. Model prediction
using parameters for coconut oil from Patil et al. (1988)
is also shown. Very good agreement between the experimental data and model predicted acid value against residence time, monoglyceride levels versus residence time,

Ind. Eng. Chem. Res., Vol. 27, No. 5, 1988 737

0 13

3L-A
0.010

LO

80

160

120

Residence time

200

240

280

min

Figure 4. Comparison between prediction and experimental levels

of monoglycerides for coconut oil hydrolysis in CSTR at 225 "C, GIL
= 0.9 w/w, and AVO = 3.

xE 0
0"07

i'

40

80
120 160
Residence time

, , ,

40
80 120
Residence time

160

,
200

T min

Figure 7. Comparison between model-predicted and experimental

concentrations of monoglyceride for coconut oil hydrolysis in CSTR
at 260 "C, G f L = 0.9 wfw, AVO = 3, and 9, = 0.

,I

200 2'40
T min

280

Figure 5. Comparison between experimental and model-predicted

aqueous glycerol concentration profiles for coconut oil hydrolysis in
CSTR at 225 "C, GIL = 0.9 w/w, AVO= 3, and yfl = 0.

. - 0 0 3260

Experimental

0'0511
0

- Mode'

0 03

o o l ~ ,, ,

o.ol/

J%k%%%%+
0

Residence time C min

Figure 6. Comparison between predicted and experimental acid
values for coconut oil hydrolysis in CSTR at 260 "C, GIL = 0.9 w/w,
AVO= 3, and yfl = 0.

and aqueous glycerol against residence time is indicated

in all the cases.
The results at another condition, viz. 260 "C and G / L
= 0.9 w/w, is shown in Figure 6-8. It is observed from
Figure 6 that an acid value of 242 is realized only at large
residence time; under identical conditions in a batch reactor, an equilibrium acid value of 242 is reached in about
45 min. Figures 7 and 8 show respectively the experimental and model-predicted behavior for monoglyceride

Residence time

T mln

Figure 8. Comparison between experimental and model-predicted

concentrations of aqueous-phase glycerol for coconut oil hydrolysis
in CSTR at 260 OC, G / L = 0.9 wfw, AVO = 3, and QgO = 0.

and aqueous-phase glycerol content against time. Once

again, re&onable agreement is seen between the data and
prediction.
It may also be possible to develop other approaches to
modeling the course of hydrolysis. The oil phase contains
water and fatty acids besides other components. The
hydrogen ion concentration in the oil phase could thus vary
as fatty acid accumulates. The observed course of hydrolysis could then be viewed to be a consequence of the
changes in hydrogen ion concentration in the oil phase.
These possibilities were recognized during our work;
however, no detailed study to discriminate between these
alternatives was undertaken.
Performance of batch and CSTR is compared in Figure
9 which shows acid value against batch reactor time or
residence time for G I L = 0.9 w/w, at 240 "C. It is seen
that, in the case of a batch reactor, 99% of the equilibrium
conversion is achieved in 1.5 h. The same level of conversion is attained in over a very large residence time in
CSTR; the results indicate that a rise in the acid value
beyond the residence time of 2 h is small since the shape
of the performance curve reaches plateau in slope. A value
of residence time around this region is therefore to be
preferred for CSTR practice.
Hydrolysis being a reversible and sluggish reaction, one
of the two products formed in the reaction has to be removed to push the reaction in the favorable direction.
There seem to be two possible schemes to carry out this
stagewise splitting.

738 Ind. Eng. Chem. Res., Vol. 27, No. 5, 1988

Settling tank I

Settling tank II

Figure 11. Two-stage splitting using CSTRs at 240 C and G / L =

0.7, scheme 2. Interstage separation of fatty acid.
t or

of X = 0.96 and aqueous-phase glycerol concentration of

hrs

Figure 9. Comparison between the performance of batch reactor

and that of CSTR by model prediction for coconut oil hydrolysis at
240 O C , G / L = 0.9 w/w, AVO = 3, and QgO= 0.

Separation tank I

Figure 10. Two-stage splitting using CSTRs at 240 C and G / L =

0.7, scheme 1. Interstage removal of aqueous glycerol.
Table 11. Performance Comparison of Schemes 1 and 2 for
Two-Stage Splitting Using CSTRs
obiective function
scheme 1 scheme 2
0.945
0.96
overall conversion, R
aq phase glycerol content, Yg
0.188
0.16
fatty acid productivity, Pa,kg/(m3.h)
218
370.0
glycerol productivity, Pg,kg/(m3.h)
49
49.4

Scheme 1as shown in Figure 10 uses two CSTRs where

lean glycerol and fresh oil enter the first reactor and the
product coming out is allowed for phase separation,
thereby removing aqueous glycerol. The fat phase containing fatty acid, unsplit oil, diglyceride, and monoglyceride along with fresh water is fed to the next CSTR.
The lean glycerol solution produced is used in the first
stage, and fatty matter of high conversion is attained.
Scheme 2 as shown in Figure 11employs the interstage
distillation of fatty acid. The product of the first stage
is allowed for phase separation. The fat phase is led to
the distillation unit to separate fatty acid. The residue
mainly containing intermediates and unsplit oil is pumped
to the second reactor together with fresh water.
In both schemes mentioned above, hydrolysis of coconut
oil at 240 C, flow ratio G / L = 0.7 w/w, and 7 = 120 min
is considered as an example. Table I1 summarizes the
performance comparison of scheme 1 and 2. Scheme 1
consisting of interstage separation of aqueous glycerol uses
two equal sized CSTRs, while scheme 2 involving interstage fatty acid removal requires two unequal sized vessels.
Performance comparison of schemes 1 and 2 can be conveniently examined from the aqueous-phase glycerol content Qg,and productivity of fatty acid and glycerol, Pa and
Pg,respectively. Table I1 summarizes these results.
Scheme 1 yields an overall conversion of X = 0.945
where 8 = (2,- fa0)/xa and aqueous-phase glycerol concentration 9, = 0.188. In comparison, an overall conversion

Q, = 0.16 are obtained in scheme 2. Productivities of fatty

acid (Pa)in schemes 1and 2, respectively, are 218 and 370
kg/ (m3.h) while the productivity for glycerol in both
schemes is Pg= 49 kg/(m3.h).
The above calculations show the usefulness of the proposed model in evaluating process alternatives. Of course,
the economic viability of such alternative approaches depends on many factors.

Conclusions
1. The CSTR experimental data on thermal hydrolysis
are shown to be consistent with the model of Patil et al.
(1988),thus providing additional support to the proposed
model.
2. Several design alternatives for carrying out liquidliquid hydrolysis exist. The continuous stirred tank reactor
is one such approach, the feasibility of which is experimentally demonstrated in the present work.
Nomenclature

A = 1/(1 m G / L )
A = ( x ~+. y@G/L)M,/[M (1 + mG/L)I
AV = acid value, mg of K H/g of fat

gt0

B = K&/(A + K382)
B = (A - K3&$mo/Cto)/(A + K362)
C = K&/(1 + K362 - B )
C = [B + (Cmo/Cto) - K382Cdo/Ctol/(l + K382 - B )
C, = concentration of species i, kmol/m3
D = 1+BC + c
D= (Ca0/Cto) - (C+ BC+ B)
E=1-C
G = mass flow rate of aqueous phase, kg/h
K , = equilibrium constant for ith reaction step, i = 1-3
k, = specific reaction rate constant in fat phase, m3/
(kmol-min)
L = mass flow rate of fat phase, kg/h
M , = molecular weight of species i
m = equilibrium distribution coefficient for glycerol, w/w
n = 1, 3, or 5 for forward reactions and 2,4, or 6 for reverse
reactions
Pi = productivity of species i, kg/(m3-h)
P = 1/(k1Cto82[D- 81/62 + DE/(KI~,)I)
Q = [ D - 2(61/62) - Cao/Cto- (C~O/C~O)(E/(K~~,))I/[D
- 61/62
+ DE/(Ki&Jl
R = [6,/& + c a ~ / C t ~ l / [-D61/82 + DE/(K182)1
SV = saponification value, mg of KOH/g of fat
T = temperature, OC
X = overall conversion
xi = mass fraction of species i in fat phase
y , = mass fraction of species i in aqueous phase

Greek Symbols
6, = proportion of water in fat phase
82 = proportion of water in fatty acid
pr = density of fat phase, kg/m3

I n d . E n g . C h e m . Res. 1988,27, 739-743

7

739

w = water
0 = initial condition
= measured value

= residence time, min

= fat phase holdup ratio in reactor

Subscripts a n d Superscripts
a = fatty acid

Literature Cited

d = diglycerides
e = equilibrium state
f = fat phase
g = glycerol
m = monoglyceride
t = triglyceride

Patil, T. A.; Butala, D. N.; Raghunathan, T. S.; Shankar, H. S. Ind.

Eng. Chem. Res. 1988, preceding paper in this issue.

Received for review May 8, 1986

Revised manuscript received May 19, 1987
Accepted June 18, 1987

Thermal Hydrolysis of Vegetable Oils and Fats. 3. An Analysis of

Design Alternatives
P. D. Namdev, T. A. P a t i l , T. S. Raghunathan, and H. S. S h a n k a r *
Department of Chemical Engineering, Indian Institute of Technology, Bombay 400 076, India

An analysis of the oil hydrolysis reactor design alternatives is performed. A model reaction t ==
g for oil hydrolysis is used to simulate the performance of several reactor configurations. The
continuous countercurrent spray column is shown t o be superior t o others in terms of productivity
and conversion. A tubular plug-flow reactor module is shown t o have promising features.
1. Introduction
A number of reactor configurations can be considered
for oil hydrolysis. These include batch, semicontinuous,
and continuous reactors. However, commercial operations
employ either batch autoclaves or continuous countercurrent spray columns. Batch operations have considerable operational flexibility but involve low productivity.
The countercurrent columns have higher productivity but
lower operational flexibility, thus the need for evaluation
of existing as well as possible design alternatives.
A three-step kinetic model for the oil hydrolysis reaction
is given by Patil et al. (1988a). It is possible to simulate
the performance of different reactor configurations by
using this model. Since the kinetic model is nonlinear,
numerical procedures are required for the solutions of
resulting ordinary differential equations. Namdev (1987)
has simulated the performance of a continuous countercurrent spray column by using this model.
In this paper, the elementary reaction t g is used to
model the oil hydrolysis reaction. The single-step kinetic
model is fitted to the experimental data of Sturzenneger
and Sturm (1951) to estimate the parameters. Analytical
solutions of the performance equations for batch, semicontinuous, and continuous hydrolyzers are given. The
procedure thus provides a quick method of understanding
the performance aspects of different design alternatives
and would therefore be valuable for design and operating
personnel.
2. The Model Reaction

Consider the model liquid-liquid reaction

k

t&g
k2

(1)

under the following assumptions to be equivalent to the

fat/oil hydrolysis reaction described earlier by Patil et al.
(1988a,b).
(a) Component t is present in phase 1, where reaction
1 occurs, while product g distributes between phases 1and
2 such that the following equation applies:
y g = mxg
(2)

(b) Component t has no solubility in phase 2, and phases

1 and 2 are immiscible.
(c) The mass and density of each phase remain constant
during the reaction.
(d) Reaction 1 belongs to a very slow reaction regime.
The model reaction and oil hydrolysis are equivalent.
Thus, t may be assumed to represent the triglycerides or
oil and g to represent glycerol. The initial level of t in
phase 1 (xto)is therefore to be adjusted to correspond to
the glycerol content of feed oils. Also, for this model reaction, the ratio of molecular weights M J M , is obviously
unity. The extent of reaction, X , can be related to the
measured acid and saponification values as
- AVO
x = AV
-SV - AVO

(3)

Also for every mole of glycerol produced, 3 mol of fatty

acids is produced. Hence, the fatty acid productivity, Pa,
can be determined from the g productivity by the following
relationship:

Pa = fpg

(4)

where f is 3 times the ratio of molecular weights of fatty

acid to glycerol.
The objective functions (X)and Pg will depend upon
reactor configurations and operating conditions used. We
examine a number of reactor alternatives to bring out these
features in the following sections.
3. Batch Reactor
The balance for component't giyes
dC,/dt, = rt = kzCg- k;C, _._

(5)

The overall balance of component g in both phases'gives

(Lxto/MJX + (Lxg0/Mg)+ (Gygo/Mg)=
( L x g / M g )+ ( G y g / M g )

Using eq 2 for y g gives

xg = ( A / D ) X

1988 American Chemical Society

+B

(6)