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98 Eur. J. Lipid Sci. Technol. 104 (2002) 98109
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1 Introduction
1.1 Aim of this study
The bleaching stage of the refining process of edible oils,
which consists of bringing the oil into contact with an ad-
sorbent mineral clay, is regarded as the most important
step to achieve and to guarantee an excellent quality of
the final product. It is performed at temperatures of about
100 C and removes different undesired substances by
adsorption and catalytic reaction. Since these substances
are primarily pigments like carotenoids and chlorophylls,
the oil is lightened up giving this process step its name.
Beside pigments the clay also removes other impurities
such as soap, trace metals and phosphatides and re-
duces the oxidation levels by catalysing the breakdown of
hydroperoxide primary oxidation-products. As a conse-
quence, the quality of the oil is stabilised by bleaching,
since precursors and catalysts of autoxidation are re-
moved. The position of the bleaching step in the refining
process depends on the kind of deacidification used. In
case of chemical refining bleaching is placed after the
chemical neutralisation and in case of physical refining
before the distillative deacidification.
The intention of this study is to optimise the bleaching
process, focussing on the enhancement of mass transfer
and to reduce the running costs of the oil refineries.
During bleaching different impurities are removed simul-
taneously by different, partly interfering mechanisms. Ac-
cordingly the bleaching step is quite complex and difficult
to optimise, since many parameters and components
have to be taken into consideration and several threshold
values have to be reached [1, 2]. Furthermore the waver-
ing quality of the crude oil complicates optimisation, which
is usually performed empirically in the oil mills. Generally,
the goal of optimisation is to achieve a defined stability
and transparency of the oil in a minimum of reaction time
using as few clay as possible. The latter is desired since
the clay effects the processing costs in manifold ways, in-
cluding the costs of the clay itself, the costs for disposal of
spent clay, the running costs of filtration, and the clay in-
duced oil loss from the process. This is based on the fact
that spent bleaching clay contains about 30 wt-% of oil,
which can only be recovered as oil of deteriorated quality.
To optimise the bleaching of vegetable oils several strate-
gies are followed. One strategy is the optimisation of the
clay itself, (capacity, pore structure, acidity, particle size)
which is followed by the manufacturers of the clay. The
strategy of the oil mills is to improve the use of the capac-
ity of the clay by countercurrent bleaching or the empirical
enhancement of mass transfer between particle and oil.
For economic reasons the process is not run until steady
state is reached in the reactor, since the closer the system
gets to the equilibrium, the smaller becomes the driving
force, and consequently the slower the kinetics. The resi-
dence time in the reactor is shortened by using more clay
than necessary from the equilibrium point of view and by
making use of the so-called post bleach effect taking
place during the sequencing filtration [3]. This strategy
Thies Langmaack,
Rudolf Eggers
Technische Universitt
Hamburg-Harburg,
Verfahrenstechnik II,
Wrme- und Stofftransport,
Hamburg, Germany
On the bleaching kinetics of vegetable oils
experimental study and mass transfer-based
interpretation
This study focuses on the systematic investigation of the parameters involved in ad-
sorptive vegetable oil bleaching. These parameters range from the quality of oil and
bleaching conditions chosen (e.g. amount and activity of clay, initial water content,
temperature, pressure) to the effects of the different reactor systems used (agitated
vessel, bubble column) on the kinetics. The study of the latter aims to optimise the type
and intensity of power input. The most efficient process was shown to take place in the
bubble column reactor. The findings result in a kinetic model for the transport phenom-
ena of the pigments from the oil phase into the clay. The model splits the effects in phe-
nomena due to mass transfer resistances inside and outside of the clay particle. By do-
ing so it is possible to describe the bleaching kinetics in dependence of the amount of
clay added and on the size of the external mass transfer resistance, which is influ-
enced by the power input into the reactor. Thus a on model-based analysis of the ef-
fects as well as the optimisation of the bleaching reactor are made possible.
Keywords: Bleaching, rapeseed oil, adsorption, refining, reactor design.
Correspondence: Rudolf Eggers, Technische Universitt Ham-
burg-Harburg, Verfahrenstechnik II, Wrme- und Stofftransport,
Eisendorfer Strasse 38, 21073 Hamburg, Germany. Phone: +49-
40-42-878-3191, Fax: +49-40-42-878-2859; e-mail: r.eggers@
tu-harburg.de
could be optimised further by enhancing the external
mass transfer particle-pigment resulting in a reduced
need of clay or time. By enhancing the external mass
transfer the clay is loaded more effectively. Thus in the
same time the same reduction in pigment in the oil can be
obtained by using less clay. To enhance the rate of exter-
nal mass transfer the key tool is the operating mode of the
reactor to maintain a high slip velocity between particle
and liquid. These flow conditions around the particle de-
termine the thickness of the boundary layer around the
particle representing the external mass transfer resis-
tance to the particle. They depend on the agitation system
and the power input used. Therefore it should be possible
to reduce the amount of clay and the residence time to
save running costs by optimising the amount and manner
of power input.
To calculate an economic optimum for this proceeding the
dominating factors influencing the kinetics have to be
known, ranging from the effect of the external mass trans-
fer rate to the effect of parameters like amount of clay
used. To separate these interfering effects modelling work
was performed on one hand to describe the whole
process of adsorptive bleaching in a proper way and on
the other hand to compare the influence of the external
mass transfer on the kinetics with the internal mass trans-
fer in the clay particle.
1.2 Theoretical background
Although the pigments of the oil are removed by several
interfering reactions and mechanisms beside adsorption,
the removal of pigments during bleaching can be de-
scribed as an adsorptive equilibrium process following the
Freundlich isotherm [2]. The final colour of the oil, respec-
tively content of pigments, depends mainly on the amount
of clay added.
The kinetics of bleaching have been investigated by sev-
eral authors. The fundamental work was published by
Brimberg [4, 5]. She described the kinetics of pigment re-
duction in a linearised form when plotting the concentra-
tion of remaining pigments against the square root of
bleaching time:
(1)
Accordingly the reduction of pigments takes place in three
phases, characterised by the kinetic constants k
1
, k
2
and
k
3
, whereof the first step lasts the longest and reduces
most of the pigments. In further investigations Brimberg
varied the parameters activity of clay (natural or activated
clay), amount of clay, size of clay particles and amount of
ln
*
*
*
.
C
C
k t t t
k t t t t
k t t t
withk k k
0
1 1
2 1 2
3 2
1 2 3
0

_
,

< <
< <
<

'

> >
Eur. J. Lipid Sci. Technol. 104 (2002) 98109 Kinetics of vegetable oil bleaching 99
initial water and showed how these parameters influence
the constants k
i
. k
i
was found to increase nearly propor-
tionally with the amount of bleaching clay added; it
increased with decreasing particle diameter, increasing
activity of clay and in a certain area even with increasing
initial amounts of water when bleaching with minor acti-
vated clays. Summarising the kinetics can be described
as a function of bleaching time with this model. The draw-
backs of this approach are the impossibility to predict the
duration of the bleaching phases t
1
and t
2
and to explain
the size of the kinetic constants with a physical model.
To circumvent this drawback, a different approach was
developed by Brat et al. [6]. They determined the kinetics
of bleaching in dependence of the amount of bleaching
clay a and successfully correlated the kinetics using the
following approach
(2)
where the constants p
1
, p
2
, p
3
and p
4
are found by fitting
the measured data. The advantage of this approach is
that an algebraic solution for the whole reaction time is
given and that the effect of the amount of clay used can
be calculated directly using this equation. Although the ki-
netics can be described as function of time and amount of
clay with this model, it has some drawbacks. These are
that this approach is based on empirical fitting of the pa-
rameters p
i
, a direct physical background of the parame-
ters used is missing and an estimation or extrapolation of
these parameters is not possible.
In this work a further generalisation is achieved yielding
the expression of kinetics as function of time, amount of
clay and mass transfer between particle and pigment
based on a physical model describing bleaching as ad-
sorptive removal of pigments from oil by clay. This model
is based on the basic considerations on pure adsorption
on porous particles in liquid batch systems. In these sys-
tems the mass transfer takes place in several steps:
diffusive transfer of pigment from the bulk of the liquid
through the boundary layer to the surface of the parti-
cle,
diffusive transfer of the pigments into the particle by
surface diffusion,
adsorption of the pigments on the active sites at the
surface of the particle.
Hereof the last step has been shown to happen very
rapidly, thus the transfer to and in the particle being the
rate limiting steps. These different consecutive transport
mechanisms can be combined to differential equations
and boundary conditions and solved numerically. These
equations are similar to those equations describing the
batch treatment of water with powdered activated carbon

dc
dt
p a c
p p a
p
1
2 3
4
( )
,
[7, 8]. To apply these models on bleaching systems some
of the parameters as diffusion and mass transfer coeffi-
cients for the system carotene-oil-small clay particles had
to be determined, since they are not known from litera-
ture. This was done in this study using matching calcula-
tion, where calculated kinetic curves are fitted to mea-
sured kinetics curves by matching the internal diffusion
coefficients and external mass transfer coefficients.
2 Materials and methods
2.1 Oil
Rapeseed oil was used for all experiments. The main part
of the experiments was performed using chemical neu-
tralised rapeseed oil (Thywissen, Neuss, Germany;
0.065 wt-% free fatty acids, 4.9 ppm phosphor, 0.082 ppm
iron, 55 ppm carotene, 3.5 ppm chlorophyll) in this study
indicated as oil A. Since many oil mills are changing
their refinery towards physical refining, some experiments
were done using a degummed rapeseed oil B prepared
for physical deacidification (Broekelmann, Hamm Ger-
many; 0.64 wt-% free fatty acids, 50 ppm carotene,
3.6 ppm chlorophyll). For some experiments a complete-
ly refined rapeseed oil C (Broekelmann) enriched with
synthetic carotene (BASF, Ludwigshafen, Germany) was
used. In some cases this oil was further enriched with
lecithin (Lucas Meyer, Hamburg, Germany).
2.2 Clay
In nearly all experiments the highly activated clay Tonsil
Optimum 210 FF (Suedchemie, Munich, Germany) was
used. Its particle size ranged from 1 to 180 m. The latter
was determined for the coarse fraction by sieve analysis
and for the fine fraction by laser diffraction analysis. The
Sauter mean diameter calculated from this analysis was
found to be 16 m.
For the examination of the effect of the initial content of
water in the oil on the kinetics in dependency on the ac-
tivity of the clay used, the natural clay Terrana D (Sued-
chemie) and the medium activated clay Tonsil Standard
FF (Suedchemie) were used.
2.3 Reactor systems
As reactor systems a stirred vessel and a bubble column
reactor were used and run at various conditions. A sketch
of these reactor systems is given in Fig. 1.
The bubble column reactor was made from glass, with an
inner diameter of 0.06 m, a height of 1.6 m and a porous
or perforated plate as bottom. It was heated electrically
and was run using nitrogen, carbon dioxide or superheat-
ed steam. The gasflux was controlled, so that the superfi-
cial velocity could be varied between 0 and 0.19 m/s and
thus the reactor could be operated either with homoge-
neous bubble flow (< 0.02 m/s), heterogeneous flow
(< 0.1 m/s) or slug flow. The specific power input P
(W/kg
oil
) in this reactor was calculated using equation 3
[9] as directly proportional to the superficial gas velocity
u
0
(m/s):
P = g u
0
(3)
100 Langmaack et al. Eur. J. Lipid Sci. Technol. 104 (2002) 98109
Fig. 1. Sketch of the reactors
used. The table imbedded
gives some characterising da-
ta of the impeller (Newton
number at 144 and 730 rpm in
100 C hot oil). The pitched-
blade-stirrer is abbreviated as
PBS.
The power input into the bubble column was varied be-
tween 0 and 1.9 W/kg
oil
. The gas holdup was determined
by measuring the increase of the dispersed bed and well
predicted using the relation by Bach and Pilhofer [9] for
oily systems. The liquid phase dispersion was followed
using the steady-state method proposed by Deckwer [9]
using carotene as tracer.
The cylindrical stirred vessel reactor was made from
stainless steel, having an inner diameter of 0.13 m, a
height of 0.38 m and was heated electrically. The impeller
speed could be varied between 144 to 730 rpm. The
following impeller systems have been used: a Rushton
turbine (0.038 m), an anchor stirrer (0.0965 m) and a
shaft equipped with one to three 2-45 pitched blade
stirrers (0.08 m). The power input of these systems in the
reactor in dependency of the impeller speed was deter-
mined using the test station of TU Braunschweig [10] de-
tecting the torsion of the impeller shaft. The power input
achieved increases with the speed of rotation, with the di-
ameter of the stirrer and the number of stirrers used on
the shaft. From these measurements the Newton-num-
bers characterizing the power input of the impeller in
100 C hot oil were calculated using equation 4:
(4)
with the specific power input P (W/kg
oil
) into the mass of
liquid m
l
(kg) with the density
l
(kg/m
3
) and the impeller
with diameter d (m) rotating at a speed n (1/s). The New-
ton numbers obtained are given in Fig. 1. By varying the
type of impeller and the rotational speed a broad range of
power input/turbulence was investigated, ranging from
0.001 to 6,5 W/kg
oil
. In some cases the vessel was baffled
to avoid the formation of a vortex at the shaft.
2.4 Methods
Batches of 2.7 kg oil were used per bleaching experi-
ment. To perform a bleaching experiment the oil was
heated up and simultaneously degassed and dried under
vacuum. When the bleaching temperature of 98 C was
reached, water (0.25 wt-%) and citric acid (0.06 wt-%)
were added. The latter is necessary in order to complex
and precipitate trace metals, water has been shown to
enhance the kinetics additionally. Subsequently the
bleaching was started by adding powderous clay (0.2 to
1.0 wt-%). To avoid any contact of the clay-oil-system with
oxygen and to maintain the water in the system the reac-
tor was kept under an inert gas blanket at a constant pres-
sure of 1 bar for the first five minutes after the addition of
the clay. In the stirred tank reactor the pressure was then
reduced to a vacuum of 52 mbar, in contrast to the bubble
column reactor, where it was kept constant at 1 bar. From
Ne
Pm
n d
l

3 5

l
the start of the bleaching period, samples were withdrawn
from the reactor in intervals of 0.5 min for 25 min. To avoid
any contact of the hot oil/clay system with air and to stop
the bleaching process, the clay was separated immedi-
ately from the oil by filtration when taking the sample via a
vacuum-filter system.
2.5 Analysis
The concentrations of chlorophyll and carotene were de-
termined photometrically according to the method of
Brimberg [4] using 1-cm cuvettes and a spectrophoto-
meter (Shimadzu UV-120-02, Shimadzu, Kyoto, Japan).
Chlorophyll was detected at a wavelength of 660 nm,
carotene at 445 nm. At high carotene concentrations the
sample was diluted in ratio 1:10 (w/w) with isooctanol to
remain in the reliable detection range of the spectropho-
tometer. The colour according to the Lovibond chart was
additionally determined for several samples in 1 and in
5.25-cells using a Lovibond Tintometer-PFX 990 (Tin-
tometer, Dortmund, Germany). Additionally some sam-
ples were deodorised in lab scale equipment (150 ml)
and thereafter the colour according to the Lovibond chart
was determined. The Rancimat stability was determined
at 100 C and an air flow of 20 l/h.
3 Results and discussion
The dependency of the bleaching kinetics on bleaching
temperature, pressure, quality of feed material, amount of
water, amount of clay and conditions in the reactor sys-
tems (type and speed of stirrer and type and velocity of
gas in the bubble column reactor) were determined. In
this study the pigments of the oil were chosen as key
components, since it was shown, that when these pig-
ments were removed from the oil, the other impurities had
been removed properly as well. In this case quality and
stability of the oil after deodorisation were excellent.
3.1 Adsorption isotherms
The adsorption isotherms of carotene and chlorophyll cal-
culated from values measured at steady state were found
to follow the Freundlich form as frequently mentioned in
literature [2].
3.2 Particle size
To evaluate the effect of the process conditions on the
particle size of the clay, the size of the particles was de-
termined using a photosedimeter. With this apparatus the
sedimentation of the particles in oil at ambient conditions
was observed. This method was chosen, as it allows
the particles to remain in the original medium and thus
adulteration of samples is avoided. Even intensive power
Eur. J. Lipid Sci. Technol. 104 (2002) 98109 Kinetics of vegetable oil bleaching 101
input by intensive stirring showed no significant effect
on the size distribution. So neither conglomeration of the
particles nor destruction by abrasion seemed to have
occurred during bleaching.
3.3 Wettability
The wettability of the clay by oil was determined in order
to estimate flotation effects in the bubble column reactor
and to characterise the immersion behaviour of the clay in
oil. The Washburn method for powders [11] was used de-
tecting the velocity of liquid penetration induced by capil-
lary forces into a sample of powder. By comparing the ve-
locity detected for oil with the velocity detected for com-
pletely wetting hexane, the wetting angle can be calculat-
ed. The oil was found to wet the clay well at 98 C, the
wetting angle was calculated to be 34. Because of this
good wettability flotation effects are unlikely to occur in
the bubble column reactor, and in consequence the im-
mersion takes place very fast.
3.4 Kinetics
In the following the findings concerning the kinetics of
bleaching are discussed. It was shown that the carotene
removal follows nearly the same kinetics as the removal
of chlorophyll. This effect also was stated by Brimberg [4].
Therefore only the data found for carotene are presented
here. To minimise the amount of data and graphs in this
publication these effects are summarised by discussing
the effect on the kinetic constant k
1
when plotting the ki-
netic curve of carotene removal according the approach
of Brimberg vs. the square root of contact time. This
analysis is demonstrated in Fig. 2 showing the influence
of the amount of clay on the kinetics. The kinetic data
gained by the kind of analysis discussed here are listed in
Tab. 1.
When comparing the data across the sections of Tab. 1
has to consider the kind of oil that has been bleached.
Especially when bleaching the model oil C (refined oil
enriched with synthetic carotene), the kinetic constants
obtained are higher than those obtained with the normal
oils A and B at the same conditions.
3.4.1 Effect of oil quality
3.4.1.1 Physical refinement
Deacidified oil is easier to bleach than not deacidified oil.
The Lovibond colours after deodorisation were lower
when using the same amount of clay.
The removal rate of chlorophyll is not affected. The re-
moval of carotene seems to be faster in deacidified oil.
3.4.1.2 FFA addition
The variation of the initial free fatty acid (FFA) content of
the oil by adding oleic acid showed neither a significant
effect on the Lovibond colour after deodorisation nor the
decolourisation rate. The FFA content in the oil remained
nearly constant during bleaching, thus the FFA were not
adsorbed by the clay and are not competing for active
sites with the pigments.
3.4.1.3 Lecithin addition
The amount of lecithin present in the oil affects the
bleaching rate. The more lecithin is present the slower the
rate. Since the lecithin content decreases during bleach-
ing, it is likely that the lecithin is adsorbed by the clay and
might compete for active sites with the pigments. The de-
gree of lecithin removal is influenced by the amount of
water present in the system. If the amount of water is
risen from 0.02 to 0.25 wt-%, the removal of lecithin is en-
hanced whereas the rate of decolourisation is not influ-
enced significantly. The water might support the formation
of micelles of lecithin which are removed from the oil dur-
ing filtration.
3.4.2 The effect of the initial amount of water
Brimberg found that an enhanced initial amount of water
present in the system accelerates significantly the kinet-
ics when bleaching rapeseed oil with Tonsil Standard FF,
a medium activated clay [4]. When bleaching palm oil with
Tonsil Optimum FF, a highly activated clay, she could not
find an equivalent effect [5]. The same was found in this
study. When bleaching rapeseed oil in the stirred tank re-
actor with Tonsil Optimum FF and varying the initial water
content from 0 to 0.5 wt-% no significant effect of water on
the kinetics was found, the kinetics remained nearly con-
stant.
102 Langmaack et al. Eur. J. Lipid Sci. Technol. 104 (2002) 98109
Fig. 2. Analysis of kinetic data for batch bleaching as sug-
gested by Brimberg; results from bleaching deacidifed oil
with Tonsil Optimum FF in a bubble column reactor.
In contrast when bleaching rapeseed oil in the bubble col-
umn reactor using the less activated clay Tonsil Standard
or the natural clay Terrana D the presence of water in-
creased the rate in the magnitude of factor 1.2 to 1.5.
Thus the effect of initial water seems to be related recip-
rocal to the degree of activation of the clay.
Generally an accelerating effect of water on the bleaching
kinetics can be explained by the fact that the presence of
water supports the removal of soaps and phospholipids
which would block pores of the clay otherwise. But since
the soap and lecithin content of the oils used in these ex-
periments was negligible a different effect has to be con-
Eur. J. Lipid Sci. Technol. 104 (2002) 98109 Kinetics of vegetable oil bleaching 103
Tab. 1. Results of parameter analysis during bleaching, given as the kinetic constant k
1
when analysing the kinetic data as
proposed by Brimberg.
Parameter varied Experimental conditions Kinetic constant k
1
for carotene
Lecithin Bubble column reactor, oil C, Lecithin content [ppm]
70 ppm carotene 0.6 wt-% clay initial final
water content varied: < 25 <25 / <25 1.02 / 1.04
0,02 wt-% / 0,25 wt % 910 155 / <25 0.81 / 0,85
6000 682 / 270 0.64 / 0.59
FFA Bubble column reactor, oil B FFA content [wt-%]
0.6 wt-% clay initial final
0.6 0.6 0.44
2.0 2.0 0.40
5.1 4.9 0.46
Water at different Stirred tank reactor, oil A Initial water [wt-%]
clay activities 0.6 wt-% T. Optimum FF 0.02 0.55
0.10 0.46
0.25 0.52
0.40 0.50
0.50 0.51
Bubble column reactor, oil C, 0.02 0.70
53 ppm carotene 0.25 0.83
0.6 wt-% T. Standard 0.50 0.69
Bubble column reactor, oil C, 0.02 0.054
53 ppm carotene 0.25 0.081
1.0 wt-% Terrana D 0.50 0.040
Pressure Stirred tank reactor, 0.6 wt-% clay, [rpm] [rpm] [rpm]
various impeller speeds 144 244 500
54 mbar 0.54 0.52 0.56
2 bar 0.48 0.55 0.53
Bubble column reactor, [wt-%] [wt-%] [wt-%]
various amount of clay 0.2 0.4 0.6
500 mbar 0.16 0.32 0.55
1 bar 0.16 0.37 0.62
Temperature Bubble column reactor, oil B, [C]
0.8 wt-% clay 100 0.65
83 0.60
60 0.42
Amount of clay Bubble column reactor, oil A [wt-%]
0.2 0.16
0.4 0.37
0.6 0.62
0.8 0.80
1.0 0.96
State of refining Bubble column reactor, [wt-%]
different amounts of clay 0.2 0.4 0.6 0.8 1.0
Oil A 0.16 0.37 0.62 0.8 0.96
Oil B 0.14 0.29 0.44 0.65 0.81
sidered. The different effect of initial water might be due to
a different wetting of the less and highly activated clay by
water, which has to be further investigated.
From the experiments done in the bubble column reactor
at ambient pressure even an upper limit for the supporting
amount of water can be shown. If this level is exceeded,
the removal of pigments is disturbed. When adding 0.5
wt-% of water, the hot oil is no longer a single phase but
droplets of free water are formed. In these visible droplets
a part of the clay is trapped, separated from the oil and
thus not removing pigments. Accordingly the rate of re-
moval decreases. In the end the colour of the filter cake is
grey instead of black due to the white clay particles not
having adsorbed pigments. The fact that this limit of
0.5 wt-% of water was not observed in case of using Ton-
sil Optimum FF should be due to the fact that this experi-
ment was performed at vacuum conditions.
3.4.3 Effect of pressure
There was no effect of the pressure (54 mbar or 2 bar) to
be seen on the kinetics when using Tonsil Optimum FF
clay in the stirred tank reactor. This might be connected
with the fact that no effect of initial water amount could be
seen when using this highly activated clay. However, it the
main prerequesite seems to be that contact of the oil with
oxygen is avoided, irrespective whether this is achieved
by the application of vacuum or a protective layer of inert
gas.
3.4.4 Effect of temperature
Bleaching at lower temperatures (tested for 83 C and
60 C) decreases the rate of decolourisation. This reduc-
tion correlates well with the enhancement of oil viscosity
with decreasing temperature (being 8.5 cP at 100 C,
11.6 cP at 83 C, 21.5 cP at 60 C [12]) and thus the slow-
down of transport mechanisms due to decreasing diffu-
sion rates. The final value obtained at steady state itself
was not found to be influenced significantly by the varia-
tion of temperature in this range.
3.4.5 Amount of clay
Besides the final content of pigment in the oil the amount
of clay influences the kinetics of bleaching. A duplication
in amount of clay yields a duplication in bleaching rate
and thus the effect on the kinetics is higher than on the fi-
nal content.
3.4.6 Effect of time
While the removal of pigments continues in an exponen-
tial way till the equilibrium value is reached, the sum pa-
rameters as Lovibond colour and stability of the oil after
deodorisation remain constant much earlier as can be
seen from Tab. 2. Therefore it is not necessary to contin-
ue bleaching until equilibrium and to remove as much pig-
ment as possible to gain a certain Lovibond colour of the
completely refined oil.
3.4.7 Effect of reactor system
To show the effect of the running conditions of the reactor
on the kinetics of bleaching, Fig. 3 summarizes some ki-
netic curves obtained in the stirred tank reactor system
with different stirrers and impeller speeds and a kinetic
curve gained in the bubble column reactor, using 0.6 wt-%
of Tonsil Optimum clay in all cases. The same carotene
content is reached at the end, but the way how fast it is
achieved differs significantly. The bubble column reactor
shows the fastest kinetics. When running the latter no sig-
nificant difference in kinetics was found neither when
varying the kind of bottom (perforated or porous plate nor
when varying the gaseous phase (carbon dioxide, nitro-
gen, superheated steam).
If the desired pigment concentration to be obtained by ad-
sorptive bleaching is set to be 20% of the initial value
(which is the case for the oil used in this study, since such
oils lead after deodorisation to a good Lovibond colour
and stability) the goal is reached in the best case within
7 min and in the worst case within more than 20 min using
the same amount of bleaching clay. So the operation
mode of the reactor has a significant influence. This effect
is mainly due to the degree of suspension of the particles
and to the intensity of mass transfer between suspended
particle and surrounding liquid. In the case of poor kinet-
ics at low power input the particles seem to be not sus-
pended properly or not distributed homogeneously. If the
power input exceeds a certain limit the kinetics decline.
104 Langmaack et al. Eur. J. Lipid Sci. Technol. 104 (2002) 98109
Fig. 3. Bleaching oil A in the stirred vessel reactor using
0.6 wt-% of Tonsil Optimum clay: Kinetics obtained when
varying kind, size and rotation speed of impeller and thus
the power input. For comparison one curve obtained in
the bubble column reactor is added.
This is due to the formation of a vortex in the reactor and
the resulting inhomogeneous distribution of particles is
slowing down the kinetics. When successfully avoiding
the formation of a vortex by baffling the reactor the kinet-
ics did not decrease with increasing power input.
To investigate the influence of the operating mode on the
kinetics the following model-based analysis was per-
formed, interpreting the process as adsorptive process
and splitting the mass transfer of pigments from the bulk
of the oil into the clay in internal and external mass trans-
fer phenomena.
3.5 External mass transfer
The external mass flux of pigments from the bulk of the
liquid to the surface of the clay particle n

f
(kg/m
2
s) is
given by
(5)
with
f
[m/s] representing the external liquid-particle mass
transfer coefficient, C [kg/m] the concentration of pigment
in the bulk of the liquid, C
s
[kg/m] the concentration of the
pigment in oil at the outer surface of the clay particle (see
Fig. 4). The external mass transfer coefficient
f
can be
interpreted as ratio of film diffusion coefficient D
f
[m
2
/s]
and thickness [m] of the boundary layer around the
particle. From this setting it can be seen directly that the
reduction of the boundary layer by proper circumflow or
reduction of the viscosity should enhance the external
mass transfer rate. For the case of bleaching vegetable
oil the latter can be reached by enhancing the temper-
( ) ( ) n C C
D
C C
f f S
f
S

Eur. J. Lipid Sci. Technol. 104 (2002) 98109 Kinetics of vegetable oil bleaching 105
Tab. 2. Effect of time of bleaching on pigment removal, Lovibond colour and Rancimat stability after deodorisation.
Bleaching oil A in a After time t After time t of bleaching
stirred tank reactor of bleaching and subsequent deodorisation
Amount of clay Time of bleaching t Chlorophyll Lovibond [5,25 cell] Rancimat stability
[wt-%] [min] [ppm] yellow/red [h]
0.2 5 2.4 17/2.1 13.8
10 1.7 14/2.0
15 1.5 15/2.0 14.2
20 1.3 15/2.0
25 1.1 15/2.0 14.9
0.4 5 1.5 14/2.2 14.1
10 0.7 13/2.0
15 0.5 11/2.7 14.9
20 0.4 12/1.7
25 0.4 13/2.0 15.2
0.6 5 0.8 12/1.7 15.7
10 0.3 12/1.7
15 0.2 11/1.6 15.7
20 0.1 11/1.6
25 0.1 11/1.6 14.5
Fig. 4 A. Surface Diffusion Model to describe adsorption
in liquids. B. Matching measured data using the Surface
Diffusion Model with setting the inner diffusion coefficient
to be constant 3.5 E-15 m
2
/s and the outer resistance to
be 10 E-6 m/s.
A
B
ature or by bleaching in the presence of supercritical car-
bon dioxide dissolved in the oil [13].
The size of the external mass transfer coefficient
f
can
be derived from experimental data by analysing the initial
kinetics if it is supposed that in this period only external
mass transfer takes place. This means that in the begin-
ning pigments are only covering the outer surface of the
completely homogeneously suspended spherical parti-
cles.
Thus in the initial period of decolourisation the effect of
the internal mass transfer resistance on the rate is ne-
glected. Therefore the external mass transfer coefficient

f0
can be determined from the slope at the beginning of
the process by graphical derivation [7, 8]. This initial value
for
f0
was observed to be constant for the whole period of
bleaching, meaning that the thickness of the boundary
layer and the diffusion coefficient in the film remain con-
stant, thus it is supposed to be equal to
f
. This value
f
was determined for all batch bleaching experiments done
in this study and it is found to vary between 0.3 E-6 m/s
and 18 E-6 m/s and to be independent of the amount of
clay added. To correlate the values, they were plotted
(Fig. 5) in dependence of the power input. This kind of
plot is frequently used in literature [9] for the correlation of
solid-liquid mass transfer coefficients for suspended par-
ticles.
A certain minimum amount of power input is necessary to
suspend the particles sufficiently. If the power input falls
below this value the mass transfer coefficient is quite low.
The height of this minimum power input depends on the
type of impeller used and the flow structure close to the
bottom of the vessel. In the bubble column reactor a high-
er external mass transfer coefficient is obtained than in
the stirred tank reactor. In the state of heterogeneous
bubble flow (> 0.2 W/kg
oil
) the mass transfer coefficient
increases with increasing power input (respectivly super-
ficial velocity), in the area of slug flow (> 1.0 W/kg
oil
) it de-
creases again. The latter might be due to the pulsating
flow in the reactor causing an heterogeneous distribution
of the clay and thus resulting in a slower kinetic. In the
stirred tank reactor a certain plateau is reached when the
power input reaches 0.2 W/kg
oil
. A further increase of
power input does not enhance the external mass transfer
further since it does not result in a higher slip velocity be-
tween particle and fluid. Consequently there is no need to
run a stirred reactor with a higher power input.
To generalise these findings on the external mass transfer
the Sherwood numbers obtained in the system were cal-
culated from the
f
measured using equation 6:
(6)
with d
p
[m] as Sauter mean diameter of the particles and
D
f
(m
2
/s) as film diffusion coefficient of carotene in oil,
calculated to be about 6 E-11 m
2
/s for carotene in oil at
100 C using the Stokes-Einstein-Equation [14]. The Sh
numbers ranged between 2.0 and 5.0. These experimen-
tally obtained numbers were compared with calculated
numbers using power input-based correlations recom-
mended in literature. The best fit was obtained using the
correlation proposed by Sano et al. [10]:
(7)
in which
c
() is the Karman surface factor (being 1.0 for
a spherical particle), P (W/kg) the specific power input,
(m
2
/s) the kinematic viscosity of the oil and Sc () the
Schmidt number defined as the ratio of kinematic viscosi-
ty and film diffusion coefficient.
The experimentally based numbers determined in this
study were found to deviate in a range of 30% from the
calculated values. This might be due to the fact that the
correlations published so far are based on the transfer de-
tected between liquid and particles of a 5 to 10 times big-
ger size than the particles used in this study. In the case
of such small particles as used in this study the slip veloc-
ity between particles and liquid is close to zero at least for
the smallest particles. This is supported by the fact that
the Sherwood numbers achieved in this study are close to
2.0 representing a slip velocity of zero. This coincides
with the finding that enhancement of power input higher
than 0.2 W/kg
oil
in the stirred tank reactor does not accel-
erate the kinetics further. Due to their small size the clay
Sh
Pd
Sc
c
p
+

_
,

1
]
1
1

2 0 4
4
3
1 4
1 3
.
/
/
Sh
d
D
f p
f

106 Langmaack et al. Eur. J. Lipid Sci. Technol. 104 (2002) 98109
Fig. 5. Experimentally gained external mass transfer
coefficient in dependence on power input and reactor
system when varying kind, size and rotation speed of im-
peller resp. superficial velocity of gas using 0.6 wt-% of
clay.
particles might move with the motion of eddies or get
trapped in small eddies where viscous effects are prevail-
ing in spite of high turbulence in the bulk liquid [15].
3.6 Internal mass transfer
To rate the effect of mass transfer resistance inside the
particle the whole process was modelled and the intra-
particle diffusion coefficients were determined by match
calculations.
To do so a model approach has been developed in this
study based on the differential pigment balances around
and in the particle considering external and internal mass
transfer resistance resulting in differential equations.
A fairly good approach was obtained by describing the in-
traparticle transport by pure surface diffusion with a con-
stant diffusion coefficient. This proceeding resulted in the
2 parametric Surface Diffusion Model (SD-model) based
on the external mass transfer coefficient
f
and the intra-
particle diffusion coefficient D
S
. The results of using this
model are given here.
The principles used for this approach are depictured in
Fig. 4A, the basic equations can be found in [7].
Around the clay particle an external boundary layer of the
thickness exists, the pigment is transported through this
layer by film diffusion powered by the difference in con-
centration in oil at the surface of the particle C
S
and the
bulk concentration C (see equation 5). The concentration
C
S
is assumed to be in equilibrium with the adsorbed
amount of pigment at the surface q
S
via the adsorption-
isotherm. The adsorbed pigment is transported via sur-
face diffusion into the core of the particle powered by a
gradient of amount of pigments adsorbed.
In case of a constant surface diffusion coefficient the dif-
ferential equation describing this transfer is [7]:
(8)
with D
S
(m
2
/s) representing the intra-particle diffusion
coefficient, r (m) the radius of the particle and t (s) the
time.
The internal transfer phenomena are connected to the ex-
ternal transfer phenomena (equation 5) via the boundary
condition.
(9)
with R (m) representing the radius of the clay particle. The
differential equation obtained was solved numerically.
t r R D
q
r
C C
p S f S
> 0, : ( )

q
t
D
q
r
r
q
r
S
+

_
,

2
2
2
To determine the size of the intra particle diffusion coeffi-
cient D
S
this model was used to match the kinetic curves
given in Fig. 3. The external mass transfer coefficient for
every single experiment was determined by graphical dif-
ferentiation of the curves as described above, given in
Fig. 4B. Afairly good matching was obtained when setting
the intra particle diffusion coefficient D
S
to be 3.5
E-15 m
2
/s. This number can be used to predict bleaching
kinetics as can be seen from Fig. 6. Here calculated and
measured data gained from oil bleaching in a bubble col-
umn reactor, using different amounts of clay, are listed.
For the calculation the external mass transfer coefficient
was set to be 10 E-6 m/s, a value which is reasonable for
these conditions in a bubble column reactor (as can be
seen from Fig. 5).
With this approach the kinetics of bleaching can be de-
scribed similar to an adsorptive process.
Using this SD-Model the effect of the external mass trans-
fer on the total kinetics of bleaching can be investigated
doing model calculations where the size of the external
mass transfer is varied. The results of this kind of calcula-
tion are given in Fig. 6 where the size of the external
mass transfer coefficient has been varied in the range of
1.0 to 20.0 E-6 m/s when bleaching with 0.6 wt-% of clay
and using an inner diffusion coefficient of 3.5 E-15 m
2
/s
for calculation.
As can be seen from this graph the effect of the external
mass transfer coefficient influences the total kinetics in
this case only significantly if it is smaller than 8 E-6 m/s. A
higher coefficient does not enhance the total kinetics
much further compared to other experiments using the
same amount of clay. This interaction of external and in-
ternal mass transfer can be summarised when calculating
the Biot number Bi with the numerator representing the
Eur. J. Lipid Sci. Technol. 104 (2002) 98109 Kinetics of vegetable oil bleaching 107
Fig. 6. Effect of external mass transfer coefficient on
total kinetics of bleaching when bleaching with 0.6 wt-%
respectively 0.8 wt-% of clay (calculated data).
external transfer rate to the particle and the denominator
representing the internal transfer rate in the particle. For
the case of surface diffusion this number is defined as [7]:
(10)
with C
0
[kg/m] as initial pigment concentration, r
p
[m] as
the Sauter mean radius of the particle,
p
[kg/m] as the
density of the particle and q
*
0
[kg/kg] as the loading of the
particle with pigment being in equilibrium with C
0
. The
higher the Biot number is the more likely it is that the in-
ternal transfer is dominating the rate. If it exceeds 50.0
the mass transfer resistance of the film around the parti-
cle can be neglected [7]. In the graphs shown in Fig. 6 the
Biot number varies between 1.6 and 32.0.
From this figure it even can be seen that the effect of ex-
ternal mass transfer coefficient is highest during the first
minutes of bleaching. The closer the systems gets to the
equilibrium state of bleaching the effect of the internal re-
sistance of mass transfer is dominating the total kinetics.
To demonstrate the approach of saving costs by enhanc-
ing mass transfer, a curve calculated for the use of 0.8 wt-%
of bleaching clay and gained with a poor external mass
transfer of 3.0 E-6 m/s was added to this graph. Compar-
ing this curve to the curve gained with 0.6 wt-% of clay
and a proper external mass transfer coefficient of 7.5
E-6 m/s shows that a proper mass transfer allows the
saving of clay by reaching a reduction of pigment to 20%
in about the same time in the reactor for both conditions.
However, in order to get a proper external transfer coeffi-
cient a higher power input is necessary, thus increasing
the running costs again. But calculations using the pre-
sented model allow to optimise the total costs and e.g.
lead to the conclusion, that significant savings of clay are
possible when investing in better external mass transfer
either by building a bubble column reactor or by changing
the stirrer system. Thus the possible reduction in running
costs by saving clay can be balanced with the increase in
running and investment costs by investing in a better ex-
ternal mass transfer to obtain this.
An attractive compromise could be the application of a
semi-continuous bleaching reactor run as a cascade of
several reactors. Here the external mass transfer should
be highest in the first vessel obtained by an intensive mix-
ing, followed by tanks where the power input is kept just
as high as to keep the particles suspended.
4 Conclusions
The mode of running the bleaching reactor, thus deter-
mining the external mass transfer rate of the pigment to
Bi
C r
D q
f p
S p
*

0
0
the particle was shown to influence the rate of vegetable
oil bleaching significantly up to a certain amount of power
input. To evaluate this operating point a model is devel-
oped describing the bleaching kinetics as an adsorptive
process combining extra and intra particle diffusive mass
transfer phenomena. This model can be used to predict
the effects of the amount of clay and of the external mass
transfer resistance on the kinetics. From these calcula-
tions can be deduced an upper optimum for the external
transfer rate. Exceeding this optimum by enhancing the
power input to the reactor does not enhance the kinetics
much further since the intra-particle mass transfer domi-
nates the kinetics. The rate of the latter depends on clay
characteristics such as particle size and distribution of
pores.
Acknowledgements
The practical and consultative support by Dr. T. Krause
from Pilot Pflanzenoeltechnologie Magdeburg e.V., the
Suedchemie AG, the Institute of Process and Nuclear
Technology at TU Braunschweig and the Krss GmbH is
gratefully acknowledged. This research project was sup-
ported by the FEI (Forschungskreis der Ernaehrungsin-
dustrie e.V., Bonn), the AiF and the Ministry of Economics
and Technology. Project No: 11567 B.
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[Received: August 27, 2001; accepted: October 30, 2001]