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98 Eur. J. Lipid Sci. Technol.

104 (2002) 98–109

Thies Langmaack, On the bleaching kinetics of vegetable oils –


Rudolf Eggers
experimental study and mass transfer-based
interpretation
Technische Universität
Hamburg-Harburg, This study focuses on the systematic investigation of the parameters involved in ad-
Verfahrenstechnik II, sorptive vegetable oil bleaching. These parameters range from the quality of oil and
Wärme- und Stofftransport, bleaching conditions chosen (e.g. amount and activity of clay, initial water content,
Hamburg, Germany
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.

1 Introduction During bleaching different impurities are removed simul-


taneously by different, partly interfering mechanisms. Ac-
1.1 Aim of this study cordingly the bleaching step is quite complex and difficult
to optimise, since many parameters and components
The bleaching stage of the refining process of edible oils,
have to be taken into consideration and several threshold
which consists of bringing the oil into contact with an ad-
values have to be reached [1, 2]. Furthermore the waver-
sorbent mineral clay, is regarded as the most important
ing quality of the crude oil complicates optimisation, which
step to achieve and to guarantee an excellent quality of
is usually performed empirically in the oil mills. Generally,
the final product. It is performed at temperatures of about
the goal of optimisation is to achieve a defined stability
100 °C and removes different undesired substances by
and transparency of the oil in a minimum of reaction time
adsorption and catalytic reaction. Since these substances
using as few clay as possible. The latter is desired since
are primarily pigments like carotenoids and chlorophylls,
Research Paper

the clay effects the processing costs in manifold ways, in-


the oil is lightened up – giving this process step its name.
cluding the costs of the clay itself, the costs for disposal of
Beside pigments the clay also removes other impurities
spent clay, the running costs of filtration, and the clay in-
such as soap, trace metals and phosphatides and re-
duced oil loss from the process. This is based on the fact
duces the oxidation levels by catalysing the breakdown of
that spent bleaching clay contains about 30 wt-% of oil,
hydroperoxide primary oxidation-products. As a conse-
which can only be recovered as oil of deteriorated quality.
quence, the quality of the oil is stabilised by bleaching,
since precursors and catalysts of autoxidation are re-
To optimise the bleaching of vegetable oils several strate-
moved. The position of the bleaching step in the refining
gies are followed. One strategy is the optimisation of the
process depends on the kind of deacidification used. In
clay itself, (capacity, pore structure, acidity, particle size)
case of chemical refining bleaching is placed after the
which is followed by the manufacturers of the clay. The
chemical neutralisation and in case of physical refining
strategy of the oil mills is to improve the use of the capac-
before the distillative deacidification.
ity of the clay by countercurrent bleaching or the empirical
The intention of this study is to optimise the bleaching enhancement of mass transfer between particle and oil.
process, focussing on the enhancement of mass transfer For economic reasons the process is not run until steady
and to reduce the running costs of the oil refineries. 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-
Correspondence: Rudolf Eggers, Technische Universität Ham- dence time in the reactor is shortened by using more clay
burg-Harburg, Verfahrenstechnik II, Wärme- und Stofftransport,
Eisendorfer Strasse 38, 21073 Hamburg, Germany. Phone: +49-
than necessary from the equilibrium point of view and by
40-42-878-3191, Fax: +49-40-42-878-2859; e-mail: r.eggers@ making use of the so-called ’post bleach effect’ taking
tu-harburg.de place during the sequencing filtration [3]. This strategy

© WILEY-VCH Verlag GmbH, 69451 Weinheim, 2002 0931-5985/2002/0202-0098 $17.50+.50/0


Eur. J. Lipid Sci. Technol. 104 (2002) 98–109 Kinetics of vegetable oil bleaching 99

could be optimised further by enhancing the external initial water and showed how these parameters influence
mass transfer particle-pigment resulting in a reduced the constants ki. ki was found to increase nearly propor-
need of clay or time. By enhancing the external mass tionally with the amount of bleaching clay added; it
transfer the clay is loaded more effectively. Thus in the increased with decreasing particle diameter, increasing
same time the same reduction in pigment in the oil can be activity of clay and in a certain area even with increasing
obtained by using less clay. To enhance the rate of exter- initial amounts of water when bleaching with minor acti-
nal mass transfer the key tool is the operating mode of the vated clays. Summarising the kinetics can be described
reactor to maintain a high slip velocity between particle as a function of bleaching time with this model. The draw-
and liquid. These flow conditions around the particle de- backs of this approach are the impossibility to predict the
termine the thickness of the boundary layer around the duration of the bleaching phases t1 and t2 and to explain
particle representing the external mass transfer resis- the size of the kinetic constants with a physical model.
tance to the particle. They depend on the agitation system
and the power input used. Therefore it should be possible To circumvent this drawback, a different approach was
to reduce the amount of clay and the residence time to developed by Brat et al. [6]. They determined the kinetics
save running costs by optimising the amount and manner of bleaching in dependence of the amount of bleaching
of power input. clay “a” and successfully correlated the kinetics using the
following approach
To calculate an economic optimum for this proceeding the dc p4
dominating factors influencing the kinetics have to be − = p1 a p 2 c ( p 3 a ) , (2)
dt
known, ranging from the effect of the external mass trans-
where the constants p1, p2, p3 and p4 are found by fitting
fer rate to the effect of parameters like amount of clay
the measured data. The advantage of this approach is
used. To separate these interfering effects modelling work
that an algebraic solution for the whole reaction time is
was performed on one hand to describe the whole
given and that the effect of the amount of clay used can
process of adsorptive bleaching in a proper way and on
be calculated directly using this equation. Although the ki-
the other hand to compare the influence of the external
netics can be described as function of time and amount of
mass transfer on the kinetics with the internal mass trans-
clay with this model, it has some drawbacks. These are
fer in the clay particle.
that this approach is based on empirical fitting of the pa-
rameters pi, a direct physical background of the parame-
1.2 Theoretical background ters used is missing and an estimation or extrapolation of
these parameters is not possible.
Although the pigments of the oil are removed by several
interfering reactions and mechanisms beside adsorption, In this work a further generalisation is achieved yielding
the removal of pigments during bleaching can be de- the expression of kinetics as function of time, amount of
scribed as an adsorptive equilibrium process following the clay and mass transfer between particle and pigment
Freundlich isotherm [2]. The final colour of the oil, respec- based on a physical model describing bleaching as ad-
tively content of pigments, depends mainly on the amount sorptive removal of pigments from oil by clay. This model
of clay added. is based on the basic considerations on pure adsorption
on porous particles in liquid batch systems. In these sys-
The kinetics of bleaching have been investigated by sev-
tems the mass transfer takes place in several steps:
eral authors. The fundamental work was published by
Brimberg [4, 5]. She described the kinetics of pigment re- – diffusive transfer of pigment from the bulk of the liquid
duction in a linearised form when plotting the concentra- through the boundary layer to the surface of the parti-
tion of remaining pigments against the square root of cle,
bleaching time: – diffusive transfer of the pigments into the particle by
surface diffusion,
 −k * t 0 < t < t 1 – adsorption of the pigments on the active sites at the
C  1
ln   =  −k 2 * t t 1 < t < t 2 with k 1 > k 2 > k 3 . (1) surface of the particle.
 C0  
−k 3 * t t 2 < t
Hereof the last step has been shown to happen very
Accordingly the reduction of pigments takes place in three rapidly, thus the transfer to and in the particle being the
phases, characterised by the kinetic constants k1, k2 and rate limiting steps. These different consecutive transport
k3, whereof the first step lasts the longest and reduces mechanisms can be combined to differential equations
most of the pigments. In further investigations Brimberg and boundary conditions and solved numerically. These
varied the parameters activity of clay (natural or activated equations are similar to those equations describing the
clay), amount of clay, size of clay particles and amount of batch treatment of water with powdered activated carbon
100 Langmaack et al. Eur. J. Lipid Sci. Technol. 104 (2002) 98–109

[7, 8]. To apply these models on bleaching systems some used. Its particle size ranged from 1 to 180 µm. The latter
of the parameters as diffusion and mass transfer coeffi- was determined for the coarse fraction by sieve analysis
cients for the system carotene-oil-small clay particles had and for the fine fraction by laser diffraction analysis. The
to be determined, since they are not known from litera- Sauter mean diameter calculated from this analysis was
ture. This was done in this study using matching calcula- found to be 16 µm.
tion, where calculated kinetic curves are fitted to mea-
sured kinetics curves by matching the internal diffusion For the examination of the effect of the initial content of
coefficients and external mass transfer coefficients. 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
2 Materials and methods
FF (Suedchemie) were used.
2.1 Oil
Rapeseed oil was used for all experiments. The main part 2.3 Reactor systems
of the experiments was performed using chemical neu-
tralised rapeseed oil (Thywissen, Neuss, Germany; As reactor systems a stirred vessel and a bubble column
0.065 wt-% free fatty acids, 4.9 ppm phosphor, 0.082 ppm reactor were used and run at various conditions. A sketch
iron, 55 ppm carotene, 3.5 ppm chlorophyll) in this study of these reactor systems is given in Fig. 1.
indicated as oil “A”. Since many oil mills are changing
their refinery towards physical refining, some experiments The bubble column reactor was made from glass, with an
were done using a degummed rapeseed oil “B” prepared inner diameter of 0.06 m, a height of 1.6 m and a porous
for physical deacidification (Broekelmann, Hamm Ger- or perforated plate as bottom. It was heated electrically
many; 0.64 wt-% free fatty acids, 50 ppm carotene, and was run using nitrogen, carbon dioxide or superheat-
3.6 ppm chlorophyll). For some experiments a complete- ed steam. The gasflux was controlled, so that the superfi-
ly refined rapeseed oil “C” (Broekelmann) enriched with cial velocity could be varied between 0 and 0.19 m/s and
synthetic carotene (BASF, Ludwigshafen, Germany) was thus the reactor could be operated either with homoge-
used. In some cases this oil was further enriched with neous bubble flow (< 0.02 m/s), heterogeneous flow
lecithin (Lucas Meyer, Hamburg, Germany). (< 0.1 m/s) or slug flow. The specific power input P
(W/kgoil) in this reactor was calculated using equation 3
[9] as directly proportional to the superficial gas velocity
2.2 Clay u0 (m/s):
In nearly all experiments the highly activated clay Tonsil
Optimum 210 FF (Suedchemie, Munich, Germany) was P = g u0 (3)

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.
Eur. J. Lipid Sci. Technol. 104 (2002) 98–109 Kinetics of vegetable oil bleaching 101

The power input into the bubble column was varied be- the start of the bleaching period, samples were withdrawn
tween 0 and 1.9 W/kgoil. The gas holdup was determined from the reactor in intervals of 0.5 min for 25 min. To avoid
by measuring the increase of the dispersed bed and well any contact of the hot oil/clay system with air and to stop
predicted using the relation by Bach and Pilhofer [9] for the bleaching process, the clay was separated immedi-
oily systems. The liquid phase dispersion was followed ately from the oil by filtration when taking the sample via a
using the steady-state method proposed by Deckwer [9] vacuum-filter system.
using carotene as tracer.
2.5 Analysis
The cylindrical stirred vessel reactor was made from
stainless steel, having an inner diameter of 0.13 m, a The concentrations of chlorophyll and carotene were de-
height of 0.38 m and was heated electrically. The impeller termined photometrically according to the method of
speed could be varied between 144 to 730 rpm. The Brimberg [4] using 1-cm cuvettes and a spectrophoto-
following impeller systems have been used: a Rushton meter (Shimadzu UV-120-02, Shimadzu, Kyoto, Japan).
turbine (0.038 m), an anchor stirrer (0.0965 m) and a Chlorophyll was detected at a wavelength of 660 nm,
shaft equipped with one to three 2-45° pitched blade carotene at 445 nm. At high carotene concentrations the
stirrers (0.08 m). The power input of these systems in the sample was diluted in ratio 1:10 (w/w) with isooctanol to
reactor in dependency of the impeller speed was deter- remain in the reliable detection range of the spectropho-
mined using the test station of TU Braunschweig [10] de- tometer. The colour according to the Lovibond chart was
tecting the torsion of the impeller shaft. The power input additionally determined for several samples in 1” and in
achieved increases with the speed of rotation, with the di- 5.25”-cells using a Lovibond Tintometer-PFX 990 (Tin-
ameter of the stirrer and the number of stirrers used on tometer, Dortmund, Germany). Additionally some sam-
the shaft. From these measurements the Newton-num- ples were deodorised in lab scale equipment (150 ml)
bers characterizing the power input of the impeller in and thereafter the colour according to the Lovibond chart
100 °C hot oil were calculated using equation 4: was determined. The Rancimat stability was determined
at 100 °C and an air flow of 20 l/h.
P ml
Ne = (4)
n d 5 ρl
3
3 Results and discussion
with the specific power input P (W/kgoil) into the mass of The dependency of the bleaching kinetics on bleaching
liquid ml (kg) with the density ρl (kg/m3) and the impeller temperature, pressure, quality of feed material, amount of
with diameter d (m) rotating at a speed n (1/s). The New- water, amount of clay and conditions in the reactor sys-
ton numbers obtained are given in Fig. 1. By varying the tems (type and speed of stirrer and type and velocity of
type of impeller and the rotational speed a broad range of gas in the bubble column reactor) were determined. In
power input/turbulence was investigated, ranging from this study the pigments of the oil were chosen as key
0.001 to 6,5 W/kgoil. In some cases the vessel was baffled components, since it was shown, that when these pig-
to avoid the formation of a vortex at the shaft. ments were removed from the oil, the other impurities had
been removed properly as well. In this case quality and
2.4 Methods stability of the oil after deodorisation were excellent.

Batches of 2.7 kg oil were used per bleaching experi-


ment. To perform a bleaching experiment the oil was 3.1 Adsorption isotherms
heated up and simultaneously degassed and dried under The adsorption isotherms of carotene and chlorophyll cal-
vacuum. When the bleaching temperature of 98 °C was culated from values measured at steady state were found
reached, water (0.25 wt-%) and citric acid (0.06 wt-%) to follow the Freundlich form as frequently mentioned in
were added. The latter is necessary in order to complex literature [2].
and precipitate trace metals, water has been shown to
enhance the kinetics additionally. Subsequently the
3.2 Particle size
bleaching was started by adding powderous clay (0.2 to
1.0 wt-%). To avoid any contact of the clay-oil-system with To evaluate the effect of the process conditions on the
oxygen and to maintain the water in the system the reac- particle size of the clay, the size of the particles was de-
tor was kept under an inert gas blanket at a constant pres- termined using a photosedimeter. With this apparatus the
sure of 1 bar for the first five minutes after the addition of sedimentation of the particles in oil at ambient conditions
the clay. In the stirred tank reactor the pressure was then was observed. This method was chosen, as it allows
reduced to a vacuum of 52 mbar, in contrast to the bubble the particles to remain in the original medium and thus
column reactor, where it was kept constant at 1 bar. From adulteration of samples is avoided. Even intensive power
102 Langmaack et al. Eur. J. Lipid Sci. Technol. 104 (2002) 98–109

input by intensive stirring showed no significant effect When comparing the data across the sections of Tab. 1
on the size distribution. So neither conglomeration of the has to consider the kind of oil that has been bleached.
particles nor destruction by abrasion seemed to have Especially when bleaching the model oil C (refined oil
occurred during bleaching. enriched with synthetic carotene), the kinetic constants
obtained are higher than those obtained with the ’normal’
3.3 Wettability oils A and B at the same conditions.

The wettability of the clay by oil was determined in order


to estimate flotation effects in the bubble column reactor 3.4.1 Effect of oil quality
and to characterise the immersion behaviour of the clay in 3.4.1.1 Physical refinement
oil. The Washburn method for powders [11] was used de-
Deacidified oil is easier to bleach than not deacidified oil.
tecting the velocity of liquid penetration induced by capil-
The Lovibond colours after deodorisation were lower
lary forces into a sample of powder. By comparing the ve-
when using the same amount of clay.
locity detected for oil with the velocity detected for com-
pletely wetting hexane, the wetting angle can be calculat- The removal rate of chlorophyll is not affected. The re-
ed. The oil was found to wet the clay well at 98 °C, the moval of carotene seems to be faster in deacidified oil.
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- 3.4.1.2 FFA addition
mersion takes place very fast. The variation of the initial free fatty acid (FFA) content of
the oil by adding oleic acid showed neither a significant
3.4 Kinetics effect on the Lovibond colour after deodorisation nor the
decolourisation rate. The FFA content in the oil remained
In the following the findings concerning the kinetics of
nearly constant during bleaching, thus the FFA were not
bleaching are discussed. It was shown that the carotene
adsorbed by the clay and are not competing for active
removal follows nearly the same kinetics as the removal
sites with the pigments.
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 3.4.1.3 Lecithin addition
publication these effects are summarised by discussing The amount of lecithin present in the oil affects the
the effect on the kinetic constant k1 when plotting the ki- bleaching rate. The more lecithin is present the slower the
netic curve of carotene removal according the approach rate. Since the lecithin content decreases during bleach-
of Brimberg vs. the square root of contact time. This ing, it is likely that the lecithin is adsorbed by the clay and
analysis is demonstrated in Fig. 2 showing the influence might compete for active sites with the pigments. The de-
of the amount of clay on the kinetics. The kinetic data gree of lecithin removal is influenced by the amount of
gained by the kind of analysis discussed here are listed in water present in the system. If the amount of water is
Tab. 1. 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
Fig. 2. Analysis of kinetic data for batch bleaching as sug- content from 0 to 0.5 wt-% no significant effect of water on
gested by Brimberg; results from bleaching deacidifed oil the kinetics was found, the kinetics remained nearly con-
with Tonsil Optimum FF in a bubble column reactor. stant.
Eur. J. Lipid Sci. Technol. 104 (2002) 98–109 Kinetics of vegetable oil bleaching 103

Tab. 1. Results of parameter analysis during bleaching, given as the kinetic constant k1 when analysing the kinetic data as
proposed by Brimberg.
Parameter varied Experimental conditions Kinetic constant k1 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

In contrast when bleaching rapeseed oil in the bubble col- Generally an accelerating effect of water on the bleaching
umn reactor using the less activated clay Tonsil Standard kinetics can be explained by the fact that the presence of
or the natural clay Terrana D the presence of water in- water supports the removal of soaps and phospholipids
creased the rate in the magnitude of factor 1.2 to 1.5. which would block pores of the clay otherwise. But since
Thus the effect of initial water seems to be related recip- the soap and lecithin content of the oils used in these ex-
rocal to the degree of activation of the clay. periments was negligible a different effect has to be con-
104 Langmaack et al. Eur. J. Lipid Sci. Technol. 104 (2002) 98–109

sidered. The different effect of initial water might be due to deodorisation remain constant much earlier as can be
a different wetting of the less and highly activated clay by seen from Tab. 2. Therefore it is not necessary to contin-
water, which has to be further investigated. ue bleaching until equilibrium and to remove as much pig-
ment as possible to gain a certain Lovibond colour of the
From the experiments done in the bubble column reactor completely refined oil.
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
3.4.7 Effect of reactor system
wt-% of water, the hot oil is no longer a single phase but To show the effect of the running conditions of the reactor
droplets of free water are formed. In these visible droplets on the kinetics of bleaching, Fig. 3 summarizes some ki-
a part of the clay is trapped, separated from the oil and netic curves obtained in the stirred tank reactor system
thus not removing pigments. Accordingly the rate of re- with different stirrers and impeller speeds and a kinetic
moval decreases. In the end the colour of the filter cake is curve gained in the bubble column reactor, using 0.6 wt-%
grey instead of black due to the white clay particles not of Tonsil Optimum clay in all cases. The same carotene
having adsorbed pigments. The fact that this limit of content is reached at the end, but the way how fast it is
0.5 wt-% of water was not observed in case of using Ton- achieved differs significantly. The bubble column reactor
sil Optimum FF should be due to the fact that this experi- shows the fastest kinetics. When running the latter no sig-
ment was performed at vacuum conditions. nificant difference in kinetics was found neither when
varying the kind of bottom (perforated or porous plate nor
3.4.3 Effect of pressure when varying the gaseous phase (carbon dioxide, nitro-
gen, superheated steam).
There was no effect of the pressure (54 mbar or 2 bar) to
be seen on the kinetics when using Tonsil Optimum FF If the desired pigment concentration to be obtained by ad-
clay in the stirred tank reactor. This might be connected sorptive bleaching is set to be 20% of the initial value
with the fact that no effect of initial water amount could be (which is the case for the oil used in this study, since such
seen when using this highly activated clay. However, it the oils lead after deodorisation to a good Lovibond colour
main prerequesite seems to be that contact of the oil with and stability) the goal is reached in the best case within
oxygen is avoided, irrespective whether this is achieved 7 min and in the worst case within more than 20 min using
by the application of vacuum or a protective layer of inert the same amount of bleaching clay. So the operation
gas. 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
3.4.4 Effect of temperature
particle and surrounding liquid. In the case of poor kinet-
Bleaching at lower temperatures (tested for 83 °C and ics at low power input the particles seem to be not sus-
60 °C) decreases the rate of decolourisation. This reduc- pended properly or not distributed homogeneously. If the
tion correlates well with the enhancement of oil viscosity power input exceeds a certain limit the kinetics decline.
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 Fig. 3. Bleaching oil A in the stirred vessel reactor using
0.6 wt-% of Tonsil Optimum clay: Kinetics obtained when
While the removal of pigments continues in an exponen- varying kind, size and rotation speed of impeller and thus
tial way till the equilibrium value is reached, the sum pa- the power input. For comparison one curve obtained in
rameters as Lovibond colour and stability of the oil after the bubble column reactor is added.
Eur. J. Lipid Sci. Technol. 104 (2002) 98–109 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

This is due to the formation of a vortex in the reactor and A


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 B


The external mass flux of pigments from the bulk of the
liquid to the surface of the clay particle n· f (kg/m2 s) is
given by
Df
n˙f = βf (C − CS ) = (C − CS ) (5)
δ
with βf [m/s] representing the external liquid-particle mass
transfer coefficient, C [kg/m] the concentration of pigment
in the bulk of the liquid, Cs [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 βf can be
interpreted as ratio of film diffusion coefficient Df [m2/s]
and thickness δ [m] of the boundary layer around the
particle. From this setting it can be seen directly that the Fig. 4 A. Surface Diffusion Model to describe adsorption
reduction of the boundary layer by proper circumflow or in liquids. B. Matching measured data using the Surface
reduction of the viscosity should enhance the external Diffusion Model with setting the inner diffusion coefficient
mass transfer rate. For the case of bleaching vegetable to be constant 3.5 E-15 m2/s and the outer resistance to
oil the latter can be reached by enhancing the temper- be 10 E-6 m/s.
106 Langmaack et al. Eur. J. Lipid Sci. Technol. 104 (2002) 98–109

ature or by bleaching in the presence of supercritical car- er external mass transfer coefficient is obtained than in
bon dioxide dissolved in the oil [13]. the stirred tank reactor. In the state of heterogeneous
bubble flow (> 0.2 W/kgoil) the mass transfer coefficient
The size of the external mass transfer coefficient βf can increases with increasing power input (respectivly super-
be derived from experimental data by analysing the initial ficial velocity), in the area of slug flow (> 1.0 W/kgoil) it de-
kinetics if it is supposed that in this period only external creases again. The latter might be due to the pulsating
mass transfer takes place. This means that in the begin- flow in the reactor causing an heterogeneous distribution
ning pigments are only covering the outer surface of the of the clay and thus resulting in a slower kinetic. In the
completely homogeneously suspended spherical parti- stirred tank reactor a certain plateau is reached when the
cles. power input reaches 0.2 W/kgoil. A further increase of
power input does not enhance the external mass transfer
Thus in the initial period of decolourisation the effect of
further since it does not result in a higher slip velocity be-
the internal mass transfer resistance on the rate is ne-
tween particle and fluid. Consequently there is no need to
glected. Therefore the external mass transfer coefficient
run a stirred reactor with a higher power input.
βf0 can be determined from the slope at the beginning of
the process by graphical derivation [7, 8]. This initial value To generalise these findings on the external mass transfer
for βf0 was observed to be constant for the whole period of the Sherwood numbers obtained in the system were cal-
bleaching, meaning that the thickness of the boundary culated from the βf measured using equation 6:
layer and the diffusion coefficient in the film remain con- βf d p
stant, thus it is supposed to be equal to βf. This value βf Sh = (6)
Df
was determined for all batch bleaching experiments done
in this study and it is found to vary between 0.3 E-6 m/s with dp [m] as Sauter mean diameter of the particles and
and 18 E-6 m/s and to be independent of the amount of Df (m2/s) as film diffusion coefficient of carotene in oil,
clay added. To correlate the values, they were plotted calculated to be about 6 E-11 m2/s for carotene in oil at
(Fig. 5) in dependence of the power input. This kind of 100 °C using the Stokes-Einstein-Equation [14]. The Sh
plot is frequently used in literature [9] for the correlation of numbers ranged between 2.0 and 5.0. These experimen-
solid-liquid mass transfer coefficients for suspended par- tally obtained numbers were compared with calculated
ticles. numbers using power input-based correlations recom-
mended in literature. The best fit was obtained using the
A certain minimum amount of power input is necessary to correlation proposed by Sano et al. [10]:
suspend the particles sufficiently. If the power input falls
below this value the mass transfer coefficient is quite low.   P d p4 
1/ 4 
The height of this minimum power input depends on the Sh = ϕ c 2 + 0.4 3  Sc 1/ 3  (7)
  ν  
type of impeller used and the flow structure close to the  
bottom of the vessel. In the bubble column reactor a high-
in which ϕ c (–) is the Karman surface factor (being 1.0 for
a spherical particle), P (W/kg) the specific power input, ν
(m2/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
Fig. 5. Experimentally gained external mass transfer the Sherwood numbers achieved in this study are close to
coefficient in dependence on power input and reactor 2.0 representing a slip velocity of zero. This coincides
system when varying kind, size and rotation speed of im- with the finding that enhancement of power input higher
peller resp. superficial velocity of gas using 0.6 wt-% of than 0.2 W/kgoil in the stirred tank reactor does not accel-
clay. erate the kinetics further. Due to their small size the clay
Eur. J. Lipid Sci. Technol. 104 (2002) 98–109 Kinetics of vegetable oil bleaching 107

particles might move with the motion of eddies or get To determine the size of the intra particle diffusion coeffi-
trapped in small eddies where viscous effects are prevail- cient DS this model was used to match the kinetic curves
ing in spite of high turbulence in the bulk liquid [15]. given in Fig. 3. The external mass transfer coefficient for
every single experiment was determined by graphical dif-
3.6 Internal mass transfer ferentiation of the curves as described above, given in
Fig. 4B. A fairly good matching was obtained when setting
To rate the effect of mass transfer resistance inside the the intra particle diffusion coefficient DS to be 3.5
particle the whole process was modelled and the intra- E-15 m2/s. This number can be used to predict bleaching
particle diffusion coefficients were determined by match kinetics as can be seen from Fig. 6. Here calculated and
calculations. measured data gained from oil bleaching in a bubble col-
umn reactor, using different amounts of clay, are listed.
To do so a model approach has been developed in this
For the calculation the external mass transfer coefficient
study based on the differential pigment balances around
was set to be 10 E-6 m/s, a value which is reasonable for
and in the particle considering external and internal mass
these conditions in a bubble column reactor (as can be
transfer resistance resulting in differential equations.
seen from Fig. 5).
A fairly good approach was obtained by describing the in-
With this approach the kinetics of bleaching can be de-
traparticle transport by pure surface diffusion with a con-
scribed similar to an adsorptive process.
stant diffusion coefficient. This proceeding resulted in the
2 parametric Surface Diffusion Model (SD-model) based
Using this SD-Model the effect of the external mass trans-
on the external mass transfer coefficient βf and the intra-
fer on the total kinetics of bleaching can be investigated
particle diffusion coefficient DS. The results of using this
doing model calculations where the size of the external
model are given here.
mass transfer is varied. The results of this kind of calcula-
The principles used for this approach are depictured in tion are given in Fig. 6 where the size of the external
Fig. 4A, the basic equations can be found in [7]. 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
Around the clay particle an external boundary layer of the and using an inner diffusion coefficient of 3.5 E-15 m2/s
thickness δ exists, the pigment is transported through this for calculation.
layer by film diffusion powered by the difference in con-
centration in oil at the surface of the particle CS and the As can be seen from this graph the effect of the external
bulk concentration C (see equation 5). The concentration mass transfer coefficient influences the total kinetics in
CS is assumed to be in equilibrium with the adsorbed this case only significantly if it is smaller than 8 E-6 m/s. A
amount of pigment at the surface qS via the adsorption- higher coefficient does not enhance the total kinetics
isotherm. The adsorbed pigment is transported via sur- much further compared to other experiments using the
face diffusion into the core of the particle powered by a same amount of clay. This interaction of external and in-
gradient of amount of pigments adsorbed. ternal mass transfer can be summarised when calculating
the Biot number Bi with the numerator representing the
In case of a constant surface diffusion coefficient the dif-
ferential equation describing this transfer is [7]:

∂q  ∂ 2q 2 ∂q 
= DS  2 +
r ∂r 
(8)
∂t  ∂r

with DS (m2/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.
∂q
t > 0, r = R : ρ p DS = βf (C − CS ) (9)
∂r
Fig. 6. Effect of external mass transfer coefficient on
with R (m) representing the radius of the clay particle. The total kinetics of bleaching when bleaching with 0.6 wt-%
differential equation obtained was solved numerically. respectively 0.8 wt-% of clay (calculated data).
108 Langmaack et al. Eur. J. Lipid Sci. Technol. 104 (2002) 98–109

external transfer rate to the particle and the denominator the particle was shown to influence the rate of vegetable
representing the internal transfer rate in the particle. For oil bleaching significantly up to a certain amount of power
the case of surface diffusion this number is defined as [7]: input. To evaluate this operating point a model is devel-
βf C 0 r p oped describing the bleaching kinetics as an adsorptive
Bi = (10) process combining extra and intra particle diffusive mass
DS ρ p q *0 transfer phenomena. This model can be used to predict
the effects of the amount of clay and of the external mass
with C0 [kg/m] as initial pigment concentration, rp [m] as transfer resistance on the kinetics. From these calcula-
the Sauter mean radius of the particle, ρp [kg/m] as the tions can be deduced an upper optimum for the external
density of the particle and q*0 [kg/kg] as the loading of the transfer rate. Exceeding this optimum by enhancing the
particle with pigment being in equilibrium with C0. The power input to the reactor does not enhance the kinetics
higher the Biot number is the more likely it is that the in- much further since the intra-particle mass transfer domi-
ternal transfer is dominating the rate. If it exceeds 50.0 nates the kinetics. The rate of the latter depends on clay
the mass transfer resistance of the film around the parti- characteristics such as particle size and distribution of
cle can be neglected [7]. In the graphs shown in Fig. 6 the pores.
Biot number varies between 1.6 and 32.0.

From this figure it even can be seen that the effect of ex- Acknowledgements
ternal mass transfer coefficient is highest during the first
minutes of bleaching. The closer the systems gets to the The practical and consultative support by Dr. T. Krause
equilibrium state of bleaching the effect of the internal re- from Pilot Pflanzenoeltechnologie Magdeburg e.V., the
sistance of mass transfer is dominating the total kinetics. Suedchemie AG, the Institute of Process and Nuclear
Technology at TU Braunschweig and the Krüss GmbH is
To demonstrate the approach of saving costs by enhanc- gratefully acknowledged. This research project was sup-
ing mass transfer, a curve calculated for the use of 0.8 wt-% ported by the FEI (Forschungskreis der Ernaehrungsin-
of bleaching clay and gained with a poor external mass dustrie e.V., Bonn), the AiF and the Ministry of Economics
transfer of 3.0 E-6 m/s was added to this graph. Compar- and Technology. Project No: 11567 B.
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
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