Deodorization - W. de Greyt and M. Kellens

8
Deodorization
W. De Greyt and M. Kellens
De Smet Technologies & Services
Brussels, Belgium
1. INTRODUCTION
All crude oils and fats, obtained after rendering, crushing, or solvent extraction,
inevitably contain variable amounts of nonacylglycerol constituents such as free
fatty acids, sterols, tocopherols, hydrocarbons, pigments (gossypol, chlorophyls),
vitamins, contaminants (pesticides, polycyclic aromatic hydrocarbons, etc.), heavy
metals, glycolipids, protein fragments, as well as resinous and mucilaginous mate-
rials.
The objective of the refining process is to remove the unwanted constituents
from the oil with the least possible negative effect on triacylglycerols and minimal
loss of the desirable constituents. To be able to meet the ever-increasing quality
requirements (mainly regarding the nutritional quality) and to further reduce the
processing costs, equipment manufacturers are obliged to continuously improve
their technology. Industrial deodorization technology and operating conditions
have been adapted to meet the required organoleptic and nutritional quality stan-
dards.
Two major processing alternatives exist for the processing of edible oils and fats,
known as ‘‘chemical’’ and ‘‘physical’’ refining (Figure 1). As the term ‘‘refining’’ is
sometimes used for different processes and in a different context, it seems useful to
introduce some definitions for the terms used further in this chapter.
Bailey’s Industrial Oil and Fat Products, Sixth Edition, Six Volume Set.
Edited by Fereidoon Shahidi. Copyright # 2005 John Wiley & Sons, Inc.
341
342 DEODORIZATION
Crude Oil
Ph
ing ys
refin ica
l l re
ica fin
h em ing
C
Degumming GUMS Degumming
Neutralisation SOAPS Bleaching

SPLITTING
Bleaching Steam Refining-

FFA
Deodorisation
Deodorisation
Refined Oil
Figure 1. General overview of a physical and chemical refining line.
Chemical refining: Sequence of process stages, which definitively includes alkali

refining (also referred to as caustic refining or neutralization) to remove most of
the FFA and, in most cases, also deodorization in the last stage.
Physical refining: Sequence of process stages that starts with a degumming process,
may include a bleaching stage, and definitively includes a steam-refining stage.
Deodorization: Vacuum-stripping process in which neutral oil is treated to remove
malodorous compounds to obtain fully refined oil.
Steam refining: Vacuum-stripping process in which acid oil is treated to remove
both free fatty acids and malodorous compounds to obtain fully refined oil.
In literature, the distinction between deodorization and steam refining is rarely
and certainly not consistently made. As the process is best known as deodorization,
it is used as general term in this chapter as well.
The physical refining route can offer important advantages to the refiner, includ-
ing a higher overall yield, the use of fewer chemicals (e.g., phosphoric acid, sulfuric
acid, or caustic soda) and, above all, a much lower effluent (byproduct) production.
This last advantage has become very important because of the increasingly stringent
limits on the quality and quantity of waste water discharged from the refineries.
Physical refining, however, is a delicate process that is less adapted than chemical
refining to crude oils of low quality. Most undesirable constituents are more easily
removed by an alkali treatment than by an advanced degumming.
Some oils, like cottonseed oil, cannot be physically refined, as it requires an
alkali treatment to remove the gossypol. For lauric oils and palm oil, on the other
hand, physical refining is preferred in terms of both operating cost and refining loss.
In the case of soybean and rapeseed oils, physical refining is suitable only for crude
oils of a high quality, i.e., with a low degree of oxidation and a sufficiently low
DEODORIZATION PRINCIPLE 343
phosphatide content after degumming (<15 ppm). If not, chemical refining will
yield better results.
Another important factor is the free fatty acid content of the crude oil. In general,
physical refining only becomes advantageous when the acidity of the crude oil is
sufficiently high. For relatively cheap oils, like soybean oil, the higher oil yield
with the physical refining is less important than the higher bleaching earth con-
sumption, making chemical refining more attractive. For other unsaturated oils
with a higher value, such as peanut oil and sunflower seed oil, physical refining
will be more attractive.
2. DEODORIZATION PRINCIPLE
Although the process is commonly named deodorization, it is actually a combina-

tion of three different effects on the oil: (1) stripping: Stripping of volatile compo-
nents (free fatty acids, odorous compounds, tocopherols, sterols, and contaminants
such as pesticides and light polycyclic aromatic hydrocarbons, etc.), (2) actual
deodorization: Removal of different off-flavors, and (3) temperature effect:
Thermal destruction of pigments and unwanted side reactions such as cis-trans-iso-
merization, polymerization, conjugation, and so on.
Optimal stripping parameters (temperature, time, operating pressure, and
amount of stripping gas) are governed by the properties of the ingoing product,
the specifications of the outgoing product, equipment limitations, and the need to
minimize costs. In Table 1, some typical deodorization conditions for edible oils are
given. As observed, steam refining applied during physical refining requires more
severe conditions than deodorization in case of chemical refining. This is mainly
because of the removal of FFA by distillation, which is more significant in physical
refining, as the initial FFA levels are considerably higher.
To obtain the required final FFA content of 0.03–0.05% by physical refining, it is
necessary to adjust the operating conditions. The easiest way is to increase the
TABLE 1. Typical Operating Conditions for Deodorization of Vegetable Oils.
Chemical
————————————————
————— Physical
Conditions U.S. Europe Europe
Temperature ( C) 250–260 220–240 230–250

Pressure (mbar) 3–4 2–3 2
Sparge steam (%) 0.5–2(a) 0.5–1.5 1–2
Deodorization time (min) 20 –40 40–60 60–90
Final acidity (% FFA) 0.03–0.05 !
Trans fatty acids (%) 0.5–1 !
Tocopherol loss (%)(b) up to 60 max 25 max 25
a
To remove tocopherols, a higher amount of steam is required.
b
For example, for soybean oil in the United States, the minimum is 500 ppm; in Europe, it is 900 ppm.
344 DEODORIZATION
TABLE 2. Effect of Pressure and Temperature on Sparge

Steam Volume.a
Pressure Volume in m3/kg Steam

(mbar) 230 C 240 C 250 C
4 581 592 604

3 774 790 805
2 1162 1185 1208
a
Volume steam (m3/kg) ¼ (4.6189 * (273.15 þ X))/Y (from equation
PV ¼ nRT), where X ¼ Temperature ( C) and Y ¼ Pressure (mbar).
steam refining temperature. A high temperature is beneficial for a good stripping of

FFA and heat bleaching, but it also results in a higher trans-fatty acid content as
well as a higher loss of tocopherols. Alternatively, the deodorizer pressure can be
lowered or the amount of stripping steam increased, but this, in turn, raises the over-
all cost of production. Shortening the overall residence time can be considered for
heat sensitive oils (e.g., fish oils, cocoa butter, high PUFA oils, etc.). However,
experience has shown that certain reactions within the oil, unrelated to FFA
removal, are necessary to obtain a stable oil. These reactions, as well as heat
bleaching, are time-and temperature-dependent. To allow these reactions to occur,
commercial deodorizers have to provide a certain holding period at the deodoriza-
tion temperature.
Today, most deodorizers operate at a temperature between 230 C and 260 C, a
pressure of 3 mbar or lower, and with a stripping steam consumption of around
10 kg per ton of processed oil. All of these parameters have a direct impact on
the design of the vacuum unit. For a given amount of stripping steam, the volume
of the gas phase to be removed by the vacuum production unit increases consider-
ably when the system pressure is reduced (Table 2). The gas volume also increases
with increasing temperature, but the effect is less considerable. In a conventional
vacuum production unit with steam-jet ejectors (boosters), more motive steam
per kilogram stripping steam is therefore required to remove the gas phase
(Table 3). Consequently, steam refining is more expensive than deodorization.
TABLE 3. Effect of Deodorizer Pressure on Steam and Fuel Consumption.a
Pressure Stripping Steam Booster Steam Fuel

Booster Deodorizer (kg/ton oil) (kg/ton oil) (kg)
(Chemical refining)
2.5 3 mbar 10 45 4.23
(Physical refining) l
1.5 2 mbar 15 93 8.31
a
Conditions: Barometric condenser water inlet temperature: 24 C; outlet temperature: 30 C; assumed total
pressure drop of 0.5 mbar in fatty acid scrubber; assumed fuel consumption of 1 kg for each 13 kg of steam
produced.
2.1. Theoretical Considerations of Stripping

2.1.1. Vapor Pressure The volatility of a given component is expressed by
its vapor pressure, which increases with increasing temperature (Figure 2). The
lower the vapor pressure, the lower the volatility and, thus, the more diffi-
cult to remove the component from the oil. For each specific component, the
vapor pressure-temperature relationship can be expressed by the Equation of
Antoine:
B
ln P0i ¼ A ; ð1Þ
TþC
with P0i -vapor pressure of a given component i, T-absolute temperature (K), and
A,B,C-chemical constants, typical for each component.
For fatty acids, the vapor pressure-temperature relationship can also be calcu-
lated according to the empirical formula of LEDERER (1):
l0 g
ln P0i ¼ þ 1:75 ln T T þ C; ð2Þ
R:T R
with P0i ¼ vapor pressure (mbar) of a given fatty acid i at a given absolute tempera-
ture T (K), l0 ¼ molar heat of vaporization at absolute zero (kJ/mol), R ¼ 8:314,
gas-constant (kJ/mol
K), g ¼ temperature coefficient of the difference between the
specific heat in the liquid and vapor phase (kJ/mol
K), and C ¼ so-called ‘‘conven-
tional chemical constant.’’
10
260ºC
Tocopherols
Free Fatty Acids
Sterols
Vapor Pressure (mm Hg)
Component Mol. Weight Relat. volatility

1
Fatty acid 280 2.5
Squalene 411 5
Tocopherol 415 1
Sterol-Esters
Sterol 410 0.6
0.1
Sterol ester 675 0.04
Oil 885 <small>
Soybean
Oil
0.01
100 150 200 250 300 350
Temperature (C)
Figure 2. Vapor pressure-temperature relationship for different components in edible oils.

346 DEODORIZATION
TABLE 4. Values of l0, g, and C for Different Fatty Acids According to LEDERER (1).
Fatty Acid l0 g C
Caprylic acid 96240 0.1398 26.33

Lauric acid 98750 0.1461 26.54
Myristic acid 104480 0.1398 27.33
Palmitic acid 109050 0.1365 26.91
Stearic acid 114200 0.1315 27.00
Oleic acid 111600 0.1275 26.40
Erucic acid 122692 0.1105 26.67
The values of l0, g, and C are available for different fatty acids (Table 4). These
constants allow one to calculate the vapor pressure or the boiling point of a fatty
acid over a given temperature interval.
2.1.2. Activity Coefficient a The efficient removal of volatile substances during

edible oil deodorization depends not only on their vapor pressure but also on their
concentration in the oil. The theoretical principle of the deodorization process has
already been described in many publications (2– 4). All calculations start from the
basic laws of Raoult and Dalton, which are valid for ideal mixtures. However, in
practice, the mixture of a fatty acid and a vegetable oil has a ‘‘nonideal’’ behavior.
Consequently, a so-called activity coefficient a was introduced and Raoult’s law
may be written as follows:
PL;i ¼ a
xi
P0i ; ð3Þ
with PL,i ¼ partial pressure of a given fatty acid in the liquid phase, a ¼ activity
coefficient, xi ¼ molar fraction of the same fatty acid in the liquid phase, and
P0i ¼ vapor pressure of the same fatty acid.
Activity coefficients were determined for solutions of stearic acid in peanut oil
(5). At low FFA concentration (<1%), positive deviations from theory resulting in
activity coefficients around 1.5 were observed. At FFA concentration > 30%, the
activity coefficients are close to one. This observation was explained by the pre-
sence of an association in the form of a fatty acid/triacylglycerol complex that is
in equilibrium with the free fatty acids and the triacylglycerol molecules. A low
fatty acid concentration favors this equilibrium to shift toward dissociation, which
means that higher vapor pressures are measured at lower fatty acid concentrations.
2.1.3. Vaporization Efficiency E According to Dalton’s law,
PV;i ¼ yi
Pt ; ð4Þ
in this, PV,i ¼ partial pressure of the volatile component in the gas phase, Pt ¼ total
pressure of the gas phase, and yi ¼ molar fraction of the volatile component in the
gas phase.
In the case of an ideal mixing between the stripping steam and the oil, PL,i ¼ PV,i.
However, in practice, an ideal mixing cannot be achieved and therefore:
PV;i ¼ E
PL;i ; ð5Þ
with E ¼ vaporization efficiency.

The vaporization efficiency E has to be considered a measure of the complete-
ness with which the steam bubbles become saturated with volatile substances dur-
ing their passage through the oil (2).
Mathematically,
dPV;i
¼ k
A
ðPL;i PV;i Þ; ð6Þ
dt
where, t ¼ contact time between the steam bubble and the oil, A ¼ surface area of
the steam bubble, and k ¼ gas-diffusion coefficient.
From Equation 5 and integration of Equation 6, Equation 7 can be deduced:
PL;i 1
A
k
t ¼ ln ¼ ln ; ð7Þ
ðPL;i PV;i Þ ð1 EÞ
and as a consequence,
E ¼ 1 eAkt : ð8Þ
From Equation 8, it can be derived that the vaporization efficiency increases with an
extension of the total surface area and with the time of contact between steam bub-
ble and oil. In practice, the vaporization efficiency can be influenced by the depth of
the oil layer and the steam injection geometry. The shallower the oil layer, the high-
er the risk that the steam leaves the oil surface without being saturated. At the other
extreme, for deep oil layers, the contact time is longer but then problems can occur
with the agitation, leading to an insufficient renewal of the upper oil layer and a
nonuniformly treated oil mass.
Lab-scale trials indicated that elimination of reflux and radiation losses com-
bined with an optimization of the steam distributor could reduce the necessary
steam consumption significantly (6). As a result, a final overall vaporization effi-
ciency of 0.93 could be achieved (7). Industrial deodorizers, however, have a lower
efficiency, as they usually operate under conditions that are less ideal than those of a
laboratory deodorizer.
2.1.4. Principles of Deodorization/Steam Refining The stripping medium

requirements during deodorization/steam refining are described by the following
mathematical equation:

Pt Va Pt
S¼
ln þ 1 ðVa V0 Þ; ð9Þ
E
P0i V0 E
P0i
348 DEODORIZATION
where S ¼ total moles of steam or any other stripping agent, Pt ¼ total pressure of
the gas phase, Poi ¼ vapor pressure of a given fatty acid i, E ¼ vaporization effi-
ciency, Va ¼ initial molar concentration of the volatile component in the oil, and
V0 ¼ final molar concentration of the volatile component in the oil.
When the initial FFA content is low, as in the case of a classical deodorization,
(Va V0) becomes so small that Equation 9 can be simplified to:
Pt Va
S¼ 0

ln : ð10Þ
E
pi V 0
In case of steam refining, the partial pressure of the fatty acids must be taken into
account and omitting the term (Va V0) would lead to a considerable overestima-
tion of the stripping medium requirements.
The simplified Equation 10 is also known as the ‘‘Bailey Equation.’’ It states that
the amount of steam required for deodorization or steam refining is directly propor-
tional to the amount of oil and the absolute pressure in the deodorizer and inversely
proportional to the vapor pressure of the pure volatile component at the process
temperature and the overall vaporization efficiency E.
The last factor in Equation 10 (ln Va/ V0) indicates that it is impossible to elim-
inate all volatile components from the oil, as this would require an infinite amount
of stripping medium. This factor also indicates that, e.g., halving the concentration
of a given volatile requires the same amount of stripping medium irrespective of its
absolute level.
2.2. Actual Deodorization

Another main objective of the deodorization process, besides FFA stripping, is the
removal of the odoriferous compounds. Different opinions exist about the time-
dependent character of this process.
It is important to make a distinction between odoriferous compounds already
present in the crude oil and odoriferous compounds formed by thermal degradation
of flavor precursors. Removal of the first group of compounds is similar to FFA
stripping and can be considered as nearly not time dependent (as in the ‘‘Bailey’’
equation). However, perfect deodorization is a more complex and longer process
than the stripping of volatile components. This difference is mainly because of
the presence of a wide range of ‘‘nonvolatile’’ flavor precursors. A certain deodor-
ization time is required to convert these compounds into more volatile off-flavors
that can be stripped from the oil. If this minimum time is not respected, some flavor
precursors will stay in the deodorized oil resulting in the development of off-flavors
during high-temperature usage (e.g., deep frying).
The higher the concentration of these thermally labile flavor precursors, the
longer the deodorization time to arrive at a stable fully refined oil. On the other
hand, oils with a very low content of such flavor precursors will need a much
shorter deodorization.
REFINED OIL QUALITY 349
2.3. Temperature Effect

Besides a bland odor and taste, (light) color is also a quality parameter for most
refined oils. In the chemical and physical refining process, the color components
can be removed during the bleaching process by adsorption onto a suitable bleach-
ing earth or by thermal degradation during deodorization. This latter phenomenon,
also known as ‘‘heat bleaching,’’ is well recognized but, at the same time, poorly
understood. From the few studies on heat bleaching, it can be concluded that it is a
purely time-temperature-dependent reaction, not affected by the deodorization pres-
sure (8).
Literature data on heat bleaching of palm oil indicate that the rate of carotene
breakdown doubles per 20 C increase in temperature (9). For illustration, heat
degradation of carotene takes a few hours at 210 C but only a few minutes at
270 C (10).
However, if the oil is not properly pretreated (too high residual phosphatides,
iron, other ‘‘impurities’’) or if traces of bleaching earth are still present, the oil
can become darker during deodorization. This phenomenon is also known as ‘‘color
fixation’’ because it is almost impossible to remove these color pigments once they
are formed.
Other undesired effects of high deodorization temperature (trans-fatty acid for-
mation, polymerization, etc.) will be discussed further in this chapter.
3. REFINED OIL QUALITY
The quality of a refined oil is usually evaluated by traditional quality parameters

such as a low residual FFA content, a high oxidative stability, a light color, and a
neutral odor and taste. In addition, high-quality food oils should contain low trans-
fatty acid (TFA) levels, high amounts of natural antioxidants and vitamins, low
levels of polymeric and oxidized triacylglycerols, and no contaminants (pesticides,
polycyclic aromatic hydrocarbons, dioxins and polychlorinated biphenyls, etc.)
(Tables 5 and 6).
3.1. Free Fatty Acids

The efficiency of deodorization/steam refining is usually quantified by the stripping
of free fatty acids (FFA). As a result of their relatively low volatility, an efficient
TABLE 5. Overview of the Different Minor Components in Food Oils and Fats.
Group Minor Components
Valuable minor components Tocopherols, sterols, squalene, oryzanol

Fat degradation products Trans-fatty acids, polymeric and oxidized
triacylglycerols, cyclic fatty acids
Contaminants Pesticides, polycyclic aromatic hydrocarbons,
polychlorinated biphenyls, dioxins, furans,. . . .
350 DEODORIZATION
TABLE 6. Characteristics of Fully Refined Soft Oils and Hard Fats (Target Figures).
Vegetable Oils Rape/Soybean Corn/Sun Palm Lauric Oils

a
FFA (%) max 0.05 0.05 0.05 0.05
Trans (%) max 1 0.5 0.5 /
Moisture (%) max 0.05 0.05 0.05 0.05
Impurities (%) max 0 0 0 0
POVb (meq O2/ kg) max 0.5 0.5 0.5 0.5
Phosphoros (ppm) max 1 1 1 1
Tocopherols (ppm) min 500/1000d 1000/750e / /
Total metal (ppm) max 0.1 0.1 0.1 0.1
PAHc (ppb) max 25 25 25 25
Color (51/4’’cell) max 1.5R-15Y 2.0R-20Y 2.5R-30Y 1.5R-15Y
Cold test (0 C) min 48h 48h / /
Smoke point ( C) min 220 220 220 /
a
FFA ¼ free fatty acids; bPOV ¼ Peroxide value; cPAH ¼ polycyclic-aromatic hydrocarbons; dtarget figure for
soybean oil; etarget figures valid for max. tocopherol retention.
FFA removal usually indicates good removal of other more volatile components.
Experience has shown that flavor and odor removal correlate well with the FFA
reduction. Nevertheless, some differences exist among different oils. Soybean oil,
for example, requires less steam than rapeseed oil (0.6–0.8% vs. 0.8–1.2%). This
difference is mainly because of the typical rapeseed odor, which is more difficult
to remove. In general, oils are easier to deodorize during chemical refining, not only
Effect of temperature on fatty acid Effect of pressure on fatty acid

stripping of soybean oil stripping of soybean oil
3 3
2.5 2.5
% FFA (oleic acid)
2 2
%FFA (oleic acid)
1.5 1.5
220°C 5 mbar
1 1 3 mbar
235°C
0.5 0.5
250°C 1.5 mbar

0 0
0 20 40 60 80 100 120 0 20 40 60 80 100 120
Time (min) Time (min)
Figure 3. Effect of (a) temperature and (b) pressure on FFA removal during deodorization/
steam refining of soybean oil. Conditions (a) 3 mbar, 0.5% sparge steam/h, varying temperature;
(b) 230 C, 0.5% sparge steam/h, varying pressure.
because of the lower acidity before deodorization but also because a whole range of
polar minor components, oxidation products, and pigments has already been
removed during alkali refining.
For most oils, the targeted residual FFA content is 0.03–0.05%. Figure 3 shows
the effect of pressure and temperature on FFA stripping from C18-rich oils in a
cross-flow-type deodorizer. With packed columns, stripping steam consumption
is about 20–30% lower because of the countercurrent stripping effect.
3.2. Fat Isomerization and Degradation Products

3.2.1. Trans-Fatty Acids Trans-fatty acids (TFAs) are either monounsaturated
fatty acids or polyunsaturated fatty acids with one or more double bonds in the
trans-configuration. TFAs have a shape comparable with that of saturated fatty
acids. Consequently, they have a higher melting point than the corresponding
cis-isomers.
Reported activation energy values for the thermal cis-trans-isomerization of
linoleic and linolenic acid are rather low (178 kJ/mole vs. 144–148 kJ/mole, respec-
tively) (8). This is an indication that TFAs are relatively easily formed at elevated
deodorization temperature. Different studies show that the relative isomerization
rate can be expressed as follows: C18:3 (100) C18:2 (10) C18:1 (1) (11–13). Con-
sequently, oils with a high linolenic acid content, such as soybean and rapeseed oils,
are most sensitive to cis-trans-isomerization during deodorization.
Cis-trans-isomerization during deodorization is considered to be a first-order
reaction, requiring the presence of a methylene-interrupted diene and only influ-
enced by time and temperature. Generally, trans-formation is negligible below
220 C, whereas it becomes significant between 220 C and 240 C, and exponential
above 240 C (Figure 4).
50 260 °C 4.5 260 °C

45
4
C18:3trans/C18:3total (%)
C18:2trans/C18:2total (%)
40
3.5
35 245 °C 3
30
2.5
25
245 °C
20 2
15 1.5
230 °C
10 1 230 °C
215 °C
5 0.5 215 °C
0 0
0 20 40 60 80 100 120 140 160 180 0 20 40 60 80 100 120 140 160 180
Time (min)
Time (min)
relative trans-isomerisation of relative trans-isomerisation of
C18:3 C18:2
Figure 4. Effect of temperature and time on trans-isomerization of linolenic acid (C18:3) and
linoleic acid (C18:2) (10).
352 DEODORIZATION
TABLE 7. Trans-Fatty Acid and Dimeric Triacylglycerols in Commer-

cial Fully Refined Vegetable Oil Samples (10).
Oil Type Trans-Fatty Acids (%) Dimeric Triacylglycerols (%)
Soybean oil 0.9–3.5 0.6–1.3

Sunflower seed oil 0.3–1.3 0.7–1.2
Rapeseed oil 0.9–1.5 1.2–1.5
Corn oil 0.6–4.1 1.0–1.5
Groundnut oil 0.1–0.3 0.5–1.3
Used Deep frying oil / > 10
Today, trans-fatty acid levels below 1% for rapeseed and soybean oils and below
0.5% for other liquid oils (e.g., sunflower seed oil and corn oil) are required.
3.2.2. Polymeric and Oxidized Triacylglycerols Other substances, such as

polymeric and oxidized triacylglycerols, are also formed during deodorization.
The increasing evidence that these compounds may be detrimental to health implies
that their presence needs to be restricted to the lowest possible levels (Table 7) (14).
Polymerization and, more specifically, dimerization may be of thermal or oxida-
tive origin. Contrary to cis-trans-isomerization, polymerization already takes place
during storage and crushing of the oilseeds and pretreatment of the crude oil.
Oxidized triacylglycerols act hereby as catalysts (15). The level of oxidized
triacylglycerols should, therefore, be kept to a minimum by limiting the oil-oxygen
contact as much as possible in the different refining stages.
3.3. Tocopherols and Sterols

3.3.1. Tocopherols Tocopherols are widely distributed in nearly all vegetable
oils but not in animal fats. Their basic structure consists of the hypothetic tocol
molecule, a chromanol structure with a farnesyl side chain, substituted by one,
two, or three methyl groups in the positions 5, 7, or 8. (Figure 5). A homologous
R1
5 4
HO 6 3 CH3 CH3 CH3
7 2
R2 O 4′ 8′ 12′ CH3
8
1 CH3
R3
Trivial name Chemical name R1 R2 R3

α-Tocopherol 5,7,8-Trimethyltocol CH3 CH3 CH3
β-Tocopherol 5,8-Dimethyltocol CH3 H CH3
γ-Tocopherol 7,8-Dimethyltocol H CH3 CH3
δ-Tocopherol 8-Methyltocol H H CH3
Figure 5. Structure formula and nomenclature for the different tocopherols.

TABLE 8. Tocopherol Content and Composition of Some Oils and Fats.
% of Total Tocopherols
Total Tocopherols ———————————————————————— -
Oil (ppm) a-T b-T g-T d-T
Cocoa butter 275–290 6 — 91 3

Coconut1 30–80 7 — 29 —
Corn 900–1600 16 1 80 3
Cottonseed 250–900 54 — 46 —
Olive 45–215 93 — 7 —
Palm2 360–560 18 2 — 2
Peanut 250–500 56 1 42 1
Rapeseed 550–900 35 — 63 2
Soybean 900–1400 10 1 65 24
Sunflower 500–900 96 2 2 —
1
64% a-Tocotrienol.
2
33% a-Tocotrienol, 36% g-Tocotrienol, 9% d-Tocotrienol.
series of tocotrienols is also known (e.g., in palm oil), which differs only in the pre-
sence of three double bonds in the side chain (in positions 30 -40 , 70 -80 , and 110 -120 )
(Figure 5).
Tocopherols and tocotrienols are important compounds of the unsaponifiable
fraction of vegetable oils (Table 8). The tocopherol composition is specific for every
type of oil and is therefore sometimes used for their identification.
g-Tocopherol is the most abundant homologue in nearly all vegetable oils, with
relative percentages up to 65% in soybean oil and 80% in corn oil. The tocopherol
fraction of sunflower seed oil consists almost exclusively of a-tocopherol (96%).
The detection of d-tocopherol is usually an indication of the presence of soybean
oil, whereas b-tocopherol is rarely found in vegetable oils (Table 8).
Tocopherols are the most important natural antioxidants of a phenolic nature,
present in vegetable oils. Different studies have shown that the least substituted
isomers form stable radicals more easily and are thus the most potent antioxidants
(16, 17).
Recent research has shown unequivocally that tocopherols are always present in
vegetable oils in the free form and not as tocopheryl esters (18). From a biochem-
ical point of view, this could be expected because only tocopherols with a free (and
not esterified) hydroxyl group can act as an antioxidant.
Aside from their antioxidant activity, tocopherols also have an important Vita-
min E activity, generally expressed as:
Vitamin E ¼ a-toco þ 0:25 b=g-toco þ 0:01 d-toco: ð11Þ
Consequently, oils rich in a-tocopherol (sunflower seed, cottonseed oil) in particu-

lar have a high Vitamin E content.
During deodorization, some of the tocopherols are lost during stripping and
thermal and oxidative degradation. The major factors affecting stripping losses
354 DEODORIZATION
P = 2 mbar P = 4 mbar
2.5 2.5
30
15 40
25
2.0 35 2.0 50
Steam (%)
Steam (%)
45 60
1.5 1.5 70
55
65 80
1.0 1.0
90
75
0.5 0.5
230 240 250 260 230 240 250 260
Temperature (°C) Temperature (°C)
Figure 6. Relative total tocopherol retention during the deodorization of soybean oil (10).
are deodorization temperature, pressure, and stripping steam. In general, more toco-
pherols will be stripped from the oil with decreasing pressure and increasing sparge
steam and temperature. The specific effect of the different process parameters on
tocopherol retention during deodorization of soybean oil is shown in Figure 6
(12). The established mathematical models allow an accurate selection of the deo-
dorization parameters resulting in a controlled stripping of tocopherols and, hence,
the desired tocopherol level in the deodorized oil (12).
Tocopherol stripping or retention during deodorization is approached differently
in Europe and the United States. In the United States, most soft oils are chemically
refined and tocopherol stripping during deodorization is maximized. A level of
500 ppm for soybean oil, for example, is considered sufficient to protect the oil
from oxidation. The excess tocopherols are collected in the deodorizer distillate
(FAD), which is valorized as a high-value-added byproduct. Tocopherol levels in
the FAD may range from a few percent to up to 20%.
Especially for soybean oil deodorizer distillate, prices are primarily determined
by the tocopherol concentration: The higher the level, the higher the price per kilo-
gram of tocopherol.
In Europe, where physical refining is more widespread, tocopherol retention in
the refined oil is maximized. A good quality deodorized corn oil should have a toco-
pherol content of at least 800 ppm, and preferably 1000 ppm.
When drawing up the tocopherol balance during deodorization, it seems that a
certain amount is lost. Some factors that are involved in this tocopherol loss are
incomplete vapor condensation and thermal and oxidative degradation. Pure ther-
mal degradation depends on time and temperature and only becomes significant
at elevated temperatures (>260 C). Tocopherol degradation in vegetable oils
mainly occurs due to oxidation because of small, inevitable air leakages in indus-
trial deodorizers. It is generally accepted that tocopherols, while protecting the
oil, are first oxidized to quinones and tocopherol dimers (16). More specifically,
R C2H5
HO HO
R = H, Cholesterol Stigmasterol
R = CH3, Campesterol
R = C2H5, Sitosterol
Figure 7. Overview of the most common phytosterols.
4a, 5-epoxy-a-tocopherolquinone, 7,8-epoxy-a-tocopherolquinone, and a-tocopherol

quinone were identified as the most important oxidation products (18).
3.3.2. Sterols Sterols are quantitatively the most important components of the
unsaponifiable fraction of vegetable oils and animal fats (Figure 7).
Animal fats, such as milkfat, tallow, and fish oils, are characterized by the exclu-
sive presence of cholesterol, whereas the sterol fraction in vegetable oils consist of a
wide group of compounds also known as phytosterols.
The majority of the crude oils contain 1000–5000 ppm sterols. Exceptions are
corn and rice bran oil that may contain up to 1–2% of phytosterols (Table 9).
b-Sitosterol is quantitatively the most important phytosterol, followed by cam-
pesterol and stigmasterol. Other phytosterols, like 5-avenasterol, 7-avenasterol,
7-stigmasterol, and brassicasterol, are only present in minor concentrations or in
specific oils (e.g., brassicasterol in rapeseed oil).
Contrary to tocopherols, sterols can be partially present in the esterified form.
Esterified phytosterols are a heterogenous group of components in which the
TABLE 9. Sterol Content and Composition of Some Oils and Fats.
Sterol Composition (%)

Total Sterols ———————————————————————————
Oil or Fat (ppm) Campesterol Stigmasterol b-Sitosterol Other
Soybean 2000–4000 15–21 10–24 57–72 —

Palm 2000–2500 25 14 65 —
Sunflower 2500–4500 7–12 8–12 62–75 —
Rapeseed 900–1000 30–33 <1 50–55 12–14a
Cottonseed 2700–5500 6–14 3–6 75–90 2–5b
Coconut 500–1000 6–9 18–19 69–75 13–25b
Rice Bran 10000 20–28 8–15 49–54 5–11b
Corn 8000–20000 18–24 4–8 55–67 4–8b
Olive 100 <1 <1 75–80 4–14b
a
brassicasterol; b-5 avenasterol.
356 DEODORIZATION
3-hydroxyl group of the phytosterol part is esterified to a fatty acid or a phenolic

acid. The relative proportion of free and esterified phytosterols varies widely among
different oils. Analyses of more than 90 crude and refined vegetable oils resulted in
an average esterified/free sterol ratio of 3/5 (19).
Free sterols are slightly less volatile than tocopherols (Figure 2). Deodorization
of soybean oil under varying process conditions (temperature: 220–260 C, low
pressure: 1.5 mbar and 1.5% steam) resulted in a 10–35% reduction of the total
sterol content (20). This sterol reduction is totally attributed to the free sterol
fraction because esterified sterols are not volatile under the conditions prevailing
inside the deodorizer. In case of steam refining, an increase of the steryl ester con-
tent can sometimes be observed, probably because of a heat-promoted esterification
reaction between free sterols and fatty acids (20). This phenomenon will not take
place during deodorization of chemically neutralized oil because the initial FFA
concentration is much lower in that case.
Although severe process conditions are required (low pressure: 1–2 mbar; high
temperature: up to 250 C), steam refining is the most suitable and economical pro-
cess to lower the cholesterol content of animal fats (e.g., milkfat and tallow).
The positive nutritional aspects of phytosterols have recently gained much inter-
est, especially after the succesful commercial introduction of margarines and
spreads enriched in phytosterols and phytostanols. Phytosterols can be isolated
from deodorizer distillates through a whole series of purification processes.
Depending on the type of oil, the refining technique applied (chemical vs. physical
refining), deodorization conditions, and the design of the vapor scrubber, the sterol
concentration (including sterol esters) in the deodorizer distillate can vary between
5% and 25%.
3.4. Contaminants
Most, if not all, crude food oils contain some contaminants. The most hazardous
contaminants in edible oils and fats are the so-called ‘‘persistent organic pollu-
tants’’ (POP). In 1995, the United Nations urged for immediate action on a group
of 12 POP, including 8 chlorinated pesticides, polychlorinated biphenyl (PCB),
hexachlorobenzene (HCB), polychlorinated dibenzo-p-dioxin (PCDD), and poly-
chlorinated dibenzofuran (PCDF). Polycyclic aromatic hydrocarbons (PAH) are
not on the shortlist, but their presence in edible oils is also a matter of concern.
Contaminants need to be removed during the refining process in order to achieve
residual levels that are as low as reasonably achievable (ALARA-concept). In prac-
tice, this can be achieved by selective adsorption onto a suitable adsorbens or dur-
ing the deodorization process.
3.4.1. Pesticides Many studies have been published regarding the removal of
pesticides from oils and fats (21–23). All concluded that organo-chlorine and orga-
no-phosphorus pesticides are fully removed during deodorization, provided that the
process temperature is high enough (>230 C) and the applied pressure sufficiently
low (<4 mbar). As a result of their relatively high volatility, most pesticides are
removed by stripping. Some pesticides like captan and dichlorvos are thermally
decomposed into more volatile products that are subsequently stripped from the
oil (23). When appropriate deodorization conditions are applied, the residual pesti-
cide content in refined food oils is generally below the limit of detection (10–
50 ppb) (21,22). Pesticides can present a problem in so-called ‘‘mild-refined’’
oils that are usually deodorized at a lower temperature (<220 C). Unfortunately,
‘‘mild’’ deodorization will not always guarantee a complete removal of pesticides.
3.4.2. Polycyclic Aromatic Hydrocarbons Only the light polycyclic aromatic

hydrocarbons (PAH) with four or less benzene rings in their chemical structure
(e.g., anthracene, chrysene, etc.) are volatile enough to be removed during deodo-
rization. Commonly applied deodorization conditions for coconut oil (210–235 C)
are sufficient to strip light PAH and reduce the concentration to below 20–25 ppb, a
maximum level that is frequently set in refined oil specifications. However, litera-
ture data show that light PAH can still be present in significantly higher amounts in
refined coconut oil (25). Problems seem to be mainly related to crude coconut oil
from Southeast Asia, which are heavily contaminated with PAH during the ‘‘smoke
drying’’ of the copra. Analyses of the PAH levels in ten different refined coconut oil
samples of Southeast Asian origin showed ‘‘light’’ PAH levels ranging from 220 to
420 ppb, with a mean residual contamination of 337 ppb (25).
3.4.3. Polychlorinated Biphenyls and Dioxins ‘‘Dioxin’’ is the systematic

name for organic compounds consisting of two benzene rings linked by two oxygen
atoms and with at least one chlorine atom. The 2,3,7,8-tetrachloordibenzo-p-
dioxins (2,3,7,8-TCDD) are the most important isomers. Dioxins are often linked
to the group of the polychlorinated dibenzofurans, which have similar physical,
chemical, and biological properties (Figure 8).
Dioxins Furans
9 10 1 9 1
Cl 8 O 2 Cl Cl 8 2 Cl
Cl 7 O 3 TMS Cl 7 O 3 Cl
6 4 6 4
WHO-TEF WHO-TEF
Congener (Humans) Congener (Humans)
Dioxins and Furans PCB
2,3,7,8-TCDD 1 3,3',4,4',5-PeCB (126) 0.1
1,2,3,7,8,-PeCDD 1 3,3',4,4',5,5'-HxCB (169) 0.01
1,2,3,4,7,8-HxCDD 0.1 3,4,4',5-PeCB (81) 0.0001
1,2,3,6,7,8-HxCDD 0.1 3,3',4,4',5-PeCB (77) 0.0001
1,2,3,7,8,9-HxCDD 0.1 2,3,4,4',5-PeCB (114) 0.0005
2,3,7,8-TCDF 0.1 2,3,3',4,4',5-HxCB (156) 0.0005
2,3,4,7,8-TCDF 0.5 2,3,3',4,4',5-PeCB (126) 0.0005
Figure 8. Structural formula of 2,3,7,8-TCDD (dioxins) and 2,3,7,8-TCDF (furans) and overview
of the WHO Toxicity Equivalency Factors (WHO-TEF) for humans and mammals.
358 DEODORIZATION
Polychlorinated biphenyls (PCBs) are a group of 209 discrete synthetic chemical

compounds, called congeners, in which one to ten chlorine atoms are attached to a
biphenyl. The empirical formula for PCB is thus C12H10-nCln, where n is one to ten.
The 209 congeners are systematically numbered from one to 209.
The toxic potential of pure dioxins and PCBs is indicated in toxic equivalence
factors (TEF) giving the relative toxicity of the relevant dioxin or PCB relative to
the toxic effect of 2,3,7,8-TCDD. TEF for different dioxins and furans vary from
0.01 to 1, whereas TEF for the different PCB congeners is much lower (0.0001–
0.01) (26, 27). (Figure 8).
Toxic equivalencies (TEQ) are calculated by multiplying the TEF by the concen-
tration of each of the different congeners present in a sample and adding them up.
The TEQ represents the relative toxicity of a dioxin/PCB mixture in terms of the
toxic effect of 2,3,7,8-TCDD.
Food contamination with dioxins and PCB seems to be comparable in terms of
TEQ and is usually below 5 ppt-TEQ ( ¼ 5 picogram-TEQ/g fat) (26, 27). A higher
degree of contamination (>10 ppt-TEQ) is commonly detected in fish and fish
products.
The vapor pressure of PCB can vary within a wide range. The more volatile
PCBs have a vapor pressure around 40–75 mbar, which is similar to the vapor pres-
sure of some organo-chlorine pesticides. Our own lab deodorization trials showed
that PCBs and dioxins can be stripped from fish oil without degradation of the o-3
fatty acids (eicosapentaenoic acid, EPA, and docosahexaenoic acid, DHA) provided
that the deodorization pressure is very low (>2 mbar) (Table 10). Other studies
showed that deodorization at 230 C and 5 mbar was insufficient to remove a
PCB heat-transfer agent from contaminated rice bran oil (28).
3.5. Deodorizer Distillate

Volatile components removed during deodorization are collected in the deodorizer
distillate. The overall composition of the deodorizer distillate depends on the
TABLE 10. PCB and Dioxin Stripping from Fish Oil.
Fish Oil
————————————–
Crude Deodorizeda
Dioxins (pptb) 5.3 1.8

Non-ortho PCB (pptb) 17.9 5.5
Mono-ortho PCB (pptb) 7.2 1.3
Free fatty acids (%) 0.66 0.11
EPAc (%) 8.7 8.6
DHAd (%) 12.7 12.6
a
Lab deodorization: 190 C-1 mbar-2% steam; bWHO-TEQ ppt;
c
Eicosapentenoic acid; dDocosahexenoic acid.
TABLE 11. Detailed Composition of Deodorizer Distillate Obtained During Chemical or Physical Refining of Different Soft Oils [Concentrations
Expressed as % (w/w)].
Soybean Corn Sunflower Seed Rapeseed

—————————————————————————————————————————————————————— ——
Chemical Physical Physical Chemical Physical Chemical
Squalene 1.3–2.1 0.6 0.2–1.0 0.7 1.0 0.1–0.4

d-Tocopherol 4.4–5.6 2.0 0.1 n.d. n.d. 0.2–0.3
b-Tocopherol 0.4–0.5 n.d. 0.1 n.d. n.d. 0.1–0.2
g-Tocopherol 10.7–11.3 5.0 1.1–2.8 0.3 0.1 2.3–2.5
a-Tocopherol 0.8 0.5 0.2–0.4 4.8 1.2 0.9–1.4
Total tocopherols 16.3–18.2 7.5 1.5–3.4 5.1 1.3 3.5–4.4
Brassicasterol n.d.3 n.d. n.d. n.d. n.d. 1.6–2.8
Campesterol 5.1–5.7 1.9 0.8–1.7 1.6 0.5 2.9–4.4
Stigmasterol 4.1–4.8 1.4 0.2–0.4 2.0 0.6 n.d.
b-Sitosterol 7.9–8.3 3.0 1.7–3.4 8.6 2.6 4.1–6.2
Other sterols1 n.d. n.d. n.d. 1.7 0.6 n.d.
Steryl esters 2.3–2.6 4.5 0.6 0.3 0.1 1.4–5.3
Total sterols2 19.4–21.4 10.8 3.3–6.1 14.2 4.4 10.0–18.7
Monoacylglycerols 1.2–1.9 1.9 0.1 0.9 n.d. 1.4–2.1
Diacylglycerols 2.7–3.8 8.1 0.5–1.3 1.9 0.7 3.8–3.9
Triacylglycerols 5.1–5.9 3.8 0.1–0.8 2.6 2.7 3.0–7.5
FFA (as C18:1) 33 73.8 77–81 39.2 70.8 39–42
1
Sum of 5-avenasterol; 7-avenasterol and 5-stigmasterol.
2
Sum of free and esterified sterols.
3
Not detectable.
360 DEODORIZATION
processed oil characteristics, the applied refining mode (chemical or physical

refining), the operating conditions during deodorization, and the design of the
scrubber. Aside from desired components (fatty acids, tocopherols, sterols, etc.),
volatile contaminants (pesticides, light PAH, etc.) will also be concentrated in
the deodorizer distillate.
Deodorizer distillates from physical refining consist mainly of free fatty acids
(>80%) (Table 11) (29). This byproduct can have some value for use in feed pro-
ducts provided that it contains (very) low levels of contaminants. Where a higher
degree of contamination exists, it can only be sold as a source of technical-grade
fatty acids.
Deodorizer distillate flow in physical refining can be 5% or more of the oil flow
to the deodorizer, depending on the initial FFA content of the oil. Consequently, the
theoretical concentration factor of the volatile contaminants in the deodorizer dis-
tillate will be around 20. Knowing that the concentration of light PAH in crude
coconut oil can be high, levels of up to 10 ppm can be expected in coconut oil deo-
dorizer distillate (Table 12).
Deodorizer distillates obtained during the deodorization of chemical refined
soybean oil usually have a significantly higher added value as a result of the
high concentration of valuable minor components such as tocopherols and sterols
(Table 11). A complex downstream processing of these deodorizer distillates, con-
sisting of a combination of chemical and physical separation processes, finally
results in the production of purified tocopherols and sterols.
Deodorizer distillate flow is much lower in the case of chemical refining (0.2–
0.5% of the oil flow to the deodorizer). Consequently, contaminant concentration in
the distillate can theoretically become 200–500 times higher than in the crude oil.
For pesticides, the observed concentration factor is significantly lower, mainly
because of thermal decomposition of some pesticides and incomplete condensation
of volatile pesticides in the vapor scrubber. The limited amount of data available in
the literature, combined with our own research figures, indicate that pesticide con-
centration in soybean, sunflower seed, and rapeseed deodorizer distillate is usually
TABLE 12. Polycyclic Aromatic Hydrocarbon Content (PAH) of Refined

Coconut Oil and the Corresponding Deodorizer Distillate (Data in ppb).
Refined Deodorizer
PAH Coconut Oil Distillate
Naphtalene 3.3 1670

Phenantrene 62.9 10,968
Pyrene 48.5 8142
Benzo(b)fluoranthene 1.5 8.9
Dibenz(a,h)anthracene 0.1 0.5
Benzo(a)pyrene 0.7 1.3
Sum of light PAH 168.9 38,690
Sum of heavy PAH 3.8 21.3
Own research data; coconut oil from Southeast Asian origin.

below 1 ppm. Only in very exceptional cases, when the degree of contamination in
the crude oil is unacceptably high (>1 ppm), the pesticide concentration in the cor-
responding deodorizer distillate can increase to 50 ppm.
Although contaminants can be removed from the deodorizer distillate during the
downstream processing, their presence is certainly unwanted and may affect the
commercial value of the distillate in a negative way. For this reason, edible oil refi-
ners are becoming more and more interested in (new) technologies that can either
remove the contaminants from the deodorizer distillate prior to sales or avoid their
presence in (part of) the distillate. The first option seems to be the most straightfor-
ward choice because known technology, either adsorption or stripping, can be used.
The overall volatility of the contaminants will be higher in the deodorizer distillate
as a result of the higher initial concentration (cfr. Law of Raoult). Therefore, con-
taminants can be removed to a certain extent from the deodorizer distillate by strip-
ping under appropriate processing conditions. Process technology and conditions
have to be optimized to maximize the amount of the low-contaminant distillate
stream. On the other hand, this process will always result in a certain contaminated
residue fraction that has to be considered as a waste stream with no value. Alterna-
tively, improved design of the scrubber (e.g., dual condensation) offers the possibi-
lity of collecting two different distillate fractions, one enriched in FFA and the other
in unsaponifiable components (sterols, tocopherols, etc.).
3.6. Oil Loss During Deodorization

Aside from volatile components (e.g., free fatty acids, secondary oxidation pro-
ducts, tocopherols, sterols, etc.), the deodorizer distillate also contains some neutral
oil (tri-, di-, and mono-acylglycerols). With the exception of the more volatile
monoacylglycerols, this neutral oil is present mainly as a result of mechanical
entrainment by the stripping steam and is therefore considered as a direct refining
loss.
Neutral oil loss (NOL) mainly depends on the deodorization conditions. In gene-
ral, NOL increases with higher deodorization temperature, lower pressure, and a
larger amount of stripping steam. At the same time, NOL during steam refining
is higher than during deodorization. This is because mechanical entrainment causes
NOL to be proportional to the distillate flow or the amount of stripping steam,
which are both higher in the case of steam refining.
Improvement of the deodorizer design by the installation of baffles and demis-
ters in the vapor chimneys has significantly reduced entrainment losses to 0.1–0.2%
in chemical refining. For steam refining, an additional loss directly proportional
to the FFA content has to be taken into account. For most oils (soybean oil,
palm oil, etc.), NOL is exclusively due to mechanical carry-over. However, in lauric
oils, part of the NOL is a consequence of effective evaporation of volatile short-
chain mono- and diacylglycerols (30). (Table 13). This distillation loss of NOL
is inherently due to the deodorization conditions, but is not affected by the deodor-
izer design.
362 DEODORIZATION
TABLE 13. Melting and Boiling Points of Some Fatty Acids and Glyceridic Components.
Component Fatty Acid Monoacylglycerol Diacylglycerol Triacylglycerol

Chain Length Melting Point ( C)
C6 3.4 19.4 / 25

C8 16.7 / / 8.3
C10 31.6 53 44.5 31.5
C12 44.2 63 57.8 46.4
C14 54.4 70.5 66.8 57.0
C16 62.9 77 76.3 63.5
C18 69.6 81.5 79.4 73.1
C18:1 16.3 35.2 21.5 5.5
Component Fatty Acid Monoacylglycerol Diacylglycerol Triacylglycerol

Chain Length Boiling Point ( C) at 1 mm Hg 0.05 mm Hg
C6 61.7 / / 135
C8 87.5 / / 179
C10 110.3 175 / 213
C12 130.2 186 / 244
C14 149.2 199 / 275
C16 167.4 211 / 298
C18 183.6 190a 313
C18:1 / 186a 308b
a
At 0.2 mm Hg; bolive oil.
Expected NOL can be estimated from the initial and final FFA content of the oil and
the FFA content of the deodorizer distillate (FAD) by the following formulas:
NOLð%Þ ¼ FAD flow ð100-FFAFAD -UnsapsFAD Þ=100; ð12Þ

FADð%Þ ¼ ðFFAOIL IN -FFAOIL OUT Þ=ðFFAFAD -FFAOIL OUT Þ 100: ð13Þ
In practice, NOL can be slightly higher as a result of hydrolysis of the refined oil
during deodorization. Our own research showed that short-chain oils (e.g., coconut
oil) are more prone to hydrolysis than long-chain oils (e.g., soybean oil). Hydrolysis
during deodorization of coconut oil resulted in the production of 0.01– 0.03% addi-
tional FFA (30).
3.7. Handling and Storage of Deodorized Oil

Deodorized oils require particular handling and storage conditions to avoid oxida-
tion or other degradation reactions that may affect the quality. Flavor deterioration,
in particular, and color reversion, to a lesser extent, may occur if the oil is not pro-
perly protected. Saturation of the oil with nitrogen after deodorization and low-tem-
perature storage in stainless steel tanks protect the oil against oxidation when stored
in bulk for a longer time. Modern processing plants are usually equipped with an
inert gas blanketing system through the different refining stages. All parts in contact
DEODORIZER TECHNOLOGY 363
with the oil are made best of stainless steel (minimum SS 304) to avoid migration of
Fe ions into the oil. Furthermore, the storage temperature is best kept as low as pos-
sible as the autoxidation rate increases as the temperature rises. For example, the
rate of oxidation doubles with each 10 C increase in temperature.
It has become common practice to add a small amount of citric acid (20–50 ppm)
to the oil after deodorization, because it improves the flavor stability and, at the
same time, acts as a metal chelator. Some refiners even add natural antioxidants
(e.g., tocopherols), although it seems more logical to prevent the oil from losing
too many natural antioxidants during deodorization by using less-severe
conditions.
In a modern refining operation, end-product storage is minimized. Refined oil is
shipped in bulk or bottled as soon as possible. Furthermore, there is an increasing
tendency to integrate the refinery with the finishing lines in the crushing plant as
this strongly reduces intermediate and final oil storage. Despite careful measures
taken during bulk handlling and shipment to industrial customers, a large part of
the refined oil is redeodorized prior to its final use. This ‘‘brush’’ deodorization
serves to remove small amounts of off-flavors formed during transport and storage.
Redeodorization normally requires less-severe process conditions.
4. DEODORIZER TECHNOLOGY
Deodorization is a multi-step process comprising de-aeration, heating, deodoriza-

tion-deacidification, and cooling of the oil (Figure 9).
Figure 9. General overview of the different stages in deodorization.

364 DEODORIZATION
4.1. De-Aeration
As a first step, the oil is de-aerated prior to heating in order to avoid excessive oxi-
dation and, hence, risk of polymerization.
Information of solubility of gases in oils is rather limited. Vegetable oils readily
dissolve between 4% and 10% of their own volume of air and other gases at ambi-
ent temperature. All gases, with exception of carbon dioxide, increase in solubility
with increasing temperature. The relation between solubility (S) and temperature (t)
can be expressed by following linear equations (30):
For Nitrogen SðN2 Þ ¼ ½0:0590 þ 0:000400 t 100; ð14Þ

For Oxygen SðO2 Þ ¼ ½0:1157 þ 0:000443 t 100: ð15Þ
With S: Solubility, gas in oil (% v/v) at atmospheric pressure; t: Temperature ( C).

To achieve a proper de-aeration, the bleached oil is sprayed into a vessel under
reduced pressure, before entering the heating section. The lower the pressure
applied, the lower the residual oxygen level in the oil. Usually, the oil is heated
to at least 80 C and sprayed in a tank, which is kept at a pressure below 50 mbar.
Some refiners even use the low pressure of the deodorizer or add some sparge steam
in the spraying vessel to improve de-aeration.
4.2. Heating and Cooling

The subsequent heating of the oil is usually accomplished in two stages. In the first
stage, the incoming oil is heated countercurrently in an oil-oil heat exchanger
(economizer), with the finished oil leaving the deodorizer. Finally, the oil is heated
under reduced pressure to the final deodorization temperature with a high-temperature
source. Nowadays, nearly all deodorizers operate with high-pressure steam boilers
(Figure 10) (Table 14). Thermal oil heaters were quite commonly used in the past to
Figure 10. High-pressure steam boiler used in deodorization (Geka).

TABLE 14. Correlation Among Steam Pressure, Temperature, Latent Heat, and Specific
Volume
Pressure Steam Temperature Latent Heat Specific Volume

(bar) ( C) (kJ/kg) (m3/kg)
1 99.6 2258 1.694

2 120.2 2202 0.8853
3 133.5 2163 0.6056
5 151.8 2108 0.3747
7 164.9 2065 0.2762
10 179.9 2014 0.1943
15 198.3 1945 0.1316
20 212.4 1889 0.09952
30 233.8 1794 0.06663
40 250.3 1713 0.04975
50 263.9 1640 0.03943
heat edible oils, but, due to the potential risk of contamination, the use of thermal
heating fluids has mostly been abandoned. The use of diphenyl/diphenyloxide (e.g.,
Downtherm1 A from Dow Chemical Co.) is still allowed, but only in exceptional
cases and if no other alternative is available. In that case, a control and loss-detec-
tion system has to be installed and the deodorized oil needs a certificate of noncon-
tamination.
The net heating energy required for a deodorization system can be calculated as:
H ¼ ½O
c
ðT2 T1 Þ
f L
f R ; ð16Þ
where O is the amount of oil (kg), T1/T2 is the incoming and final temperature of
the oil ( C), c is the average specific heat capacity of vegetable oils (typically 2.2–
2.4 kJ/kg C), fL is the heat loss factor from radiation (typically 1.05–1.15), and fR is
the heat recovery factor [1-(%heat recovery/100)].
In industrial practice, heat recovery has become an important factor because it
minimizes the cost of additional heating of the oil to the deodorization temperature.
In recent years, there has been a very fast evolution in the manufacture of heat
exchangers for heat recovery. Generally speaking, they can be divided into external
and internal heat exchangers (Figure 11).
External heat exchangers usually result in high recovery and provide easier
access for cleaning. On the other hand, internal heat exchangers allow energy
recovery under vacuum and ensure less cross-contamination and less risk of foul-
ing. The final choice for a heat-exchange system is based not only on its thermal
performance but also on other criteria such as easy maintenance, low risk of
fouling, low level of cross-contamination, and an acceptable installation cost com-
pared with the expected energy recovery.
Heat recovery can be achieved directly by exchange of heat between two oil
streams at different temperatures (e.g., bleached vs. deodorized oil), flowing in a
countercurrent direction through the exchangers, or indirectly by steam production.
366 DEODORIZATION
oil-steam heat exchanger
plate spiral Internal heat exchangers
shell & tube oil-oil heat exchanger
External heat
exchanger
Figure 11. Examples of external and internal heat exchangers used in edible oil deodorization
(Alfa Laval, Ciat, De Smet).
Direct heat recovery is the most efficient, with up to 85% of the heat recoverable. It
is usually applied in continuous deodorizers, whereas the indirect heat recovery sys-
tem is used preferentially in semi-continuous deodorizers with frequent feedstock
changes. The efficiency of the indirect heat recovery depends largely on the type
and design of the system (Figure 12).
A special indirect heat-recovery device is the themosiphon system. The steam
produced in the oil cooling section is sent in a closed loop to the oil heating
section. The steam will condense there, and the water is returned to the cooling
section.
Final cooling of the oil is usually conducted under reduced pressure to prevent
the possible production of degradation byproducts. The necessity of conducting
cooling under vacuum while maintaining steam injection has always been a
matter of discussion. As a result of the technological complexity and for cost
reasons, cooling under vacuum is usually applied only in a large capacity deodor-
izer. Small capacity plants often make use of external oil–oil heat-exchanging
devices.
4.3. Steam Stripping

The necessary amount of stripping agent is directly proportional to its molecular
weight. Therefore, stripping agents with the lowest possible molecular weights
are selected. For economic reasons, steam is generally used, but the use of nitrogen
has been studied extensively. Nitrogen has the advantage of being an inert and
L.P. Steam
Heating
H.P. Steam H.P.
Steam H.P. Steam
Heating
Heating Heating
L.P. Steam
Generation
Water
Cooling
L.P. Steam Generation & Double Thermosyphon Single Thermosyphon

Thermosyphon Heat Recovery 67% Heat Recovery 45%
Heat Recovery 75%
Figure 12. Indirect heat recovery systems used in semicontinuous deodorizers (thermosiphon
systems) (De Smet). LP: low-pressure steam ; HP: high-pressure steam.
noncondensable gas. Theoretically, its use will result in lower loss (no hydrolysis)
and a more pure deodorizer distillate. Although it is possible to work with nitrogen
under the commonly applied process conditions, experiments have shown that
the profitability is very uncertain, depending on the existing installations in the
factory and the nitrogen supply (31, 33). Further studies have indicated that color,
residual FFA, oxidative stability, as well as the formation of trans-fatty acids and
the stripping of tocopherols are not affected by the nature of the stripping agent
(34, 35).
In any case, the stripping agent must be ‘‘dry’’ and free of oxygen. Superheating
will ensure that the stripping agent is ‘‘dry’’ and that no cooling of the oil occurs.
Apart from the stripping agent, different deodorizer designs attempt to provide
the best contact between the gas phase and the oil phase by creating a large contact
surface, together with an optimal sparge steam distribution. In this way, a maximum
vaporization efficiency can be reached.
Deodorization only occurs at the vapor-liquid contact zone where the lowest
operating pressure exists. It is therefore essential to expose all parts of the oil to
surface conditions. In most deodorizers, the stripping agent is introduced into the
oil through special sparge coils with very fine holes (with a diameter between 0.5
and 2.5 mm) or by steam lift pumps. However, the main function of steam lift
pumps is to improve agitation and enhance overall deodorization efficiency by
continuously refreshing the oil in the top layer (Figure 13). A minimum oil layer
height (more than 0.8 m) is required to allow good operation of a steam lift pump.
368 DEODORIZATION
Figure 13. Sparge steam injection systems used in deodorizers (De Smet, Tirtiaux).
Another way to improve the stripping is to increase the contact surface between
steam and oil. In edible oil deodorization, this is accomplished in so-called packed
columns that can be filled with various types of surface-extending devices. Packed
columns have already been applied in edible oil deodorization for decades. A very
good contact between the vapor and the oil at low pressure is created by a conti-
nuous thin film of oil flowing over the packing material. Both random and
structured packings are used, but the structured packing is most preferred for its
lower pressure drop and higher vaporization efficiency. As a result of the fact
Figure 14. Principle of countercurrent and cross-flow stripping.

TABLE 15. Calculation of the Residual Free Fatty Acid Content in a C-18 Oil Under Ideal
Conditions (Efficiency E ¼ 1).
Conditions Cross Flow Deodorizer Packed Column
Theoretical trays 5 5
Steam (kg/ton) 6 6
FFA-in (%) 0.3 0.3
Temperature 230 245 260 230 245 260
Pressure (mbar) 3 3–4
FFA-out (%) 0.14 0.08 0.032 0.09 0.023 0.003
———————————————
Pressure (mbar) 2
FFA-out (%) 0.097 0.043 0.014
———————————————
Pressure (mbar) 1.5
FFA-out (%) 0.07 0.026 0.008
that stripping steam is introduced into the column in a countercurrent way, packed
columns require less steam than tray deodorizers, which work according to the
cross- flow principle (4) (Figure 14). For chemically refined oils, for example, a
stripping steam consumption of 0.5–0.7% is reported as being sufficient for packed
columns, compared with 1.0–1.2% for tray deodorizers. However, modern tray deo-
dorizers today operate with even less steam, as low as 0.7–0.9%.
The stripping efficiency of a deodorizer can be improved either by incorporating
a packed column or by reducing the operating pressure of the deodorizer (Table 15).
The best solution, of course, is a combination of both, but this results in an expen-
sive deodorization technology.
A convenient way of controlling the stripping steam flow through the steam dis-
tributors is to maintain a fixed pressure upstream of an orifice plate of known size.
As the pressure always falls to a low value beyond the orifice, the flow of steam will
be proportional to the absolute pressure on the upstream side of the orifice and the
orifice surface (Table 16).
Orifice plates are usually on each steam sparge coil to allow an independent
adjustment and control of the steam flow rates. Steam from the main low-pressure
TABLE 16. Steam Flow Rates for Orifices of Different Size at Different Steam Pressure.
Pressure (bar) 0.5 0.7 0.9 1.1 1.3 1.5 1.7 1.9
Orifice Size (mm) Steam Flow Rate (kg/hr)
1 0.15 0.21 0.27 0.33 0.39 0.45 0.51 0.67

1.5 0.34 0.48 0.61 0.75 0.88 1.02 1.16 1.29
2 0.61 0.86 1.09 1.33 1.37 1.82 2.06 2.30
2.5 0.95 1.32 1.70 2.08 2.46 2.84 3.21 3.59
3 1.36 1.90 2.45 2.99 3.54 4.08 4.62 5.17
4 2.42 3.38 4.35 5.31 6.28 7.25 8.21 9.18
5 2.78 5.29 6.80 8.31 9.82 11.5 12.8 14.3
370 DEODORIZATION
sparge steam line (3–5 bar) is distributed to different deodorizer compartments.

Before entering into the sparge steam coils, the steam pressure is reduced to the
required pressure by means of a pressure reducing valve. Usually, there is one pres-
sure reducer per compartment to allow different steam injection rates over different
deodorizer trays.
Aside from a higher stripping efficiency, a packed column is also characterized
by a very short holdup time. This may be sufficient for the stripping of certain
volatile components (e.g., FFA, tocopherols, etc.) but not enough for a complete
deodorization. Therefore, a holding vessel is usually placed after a packed column
to properly deodorize the oil. The steam introduced in the retention vessel can be
reused as stripping vapor for the packed column, which reduces overall steam con-
sumption. The reuse of this ‘‘dirty’’ steam, however, may have a negative effect on
the final oil quality.
4.4. Vapor-Scrubbing Systems

The volatile components, stripped during deodorization, are condensed and usually
recovered in a direct condenser or vapor scrubber (Figure 15).
The vapor from the deodorizer consists mainly of steam, volatile fatty
substances, and some noncondensables (e.g., air). The volatile substances are
condensed by creating an intimate contact between the vapor and the fatty acid
distillate circulating in the scrubber. This is done either by a series of sprayers
Deaerator Deodorizer Vapor scrubber Vacuum unit
802
s 822 MS
1 841
D
Heating 2
D
3
W
Deodorizing
D 823 881AG
4 814
D W
5
M FATTY ACIDS
Cooling D
6
7 D 881 P808AG
816
DEODORIZED
FEEDSTOCK OIL
M
P801 P822
DE SMET "MULTISTOCK" DEODORIZING
Figure 15. Flowsheet of a stock change deodorizer (De Smet).

TABLE 17. Composition of Deodorizer Distillates from Single- and Dual-Temperature

Condensation.
Dual-Temperature Condensation Single Temperature

———————————————————————
Distillate 1 Distillate 2 Condensation
——————————————————————————————————-
Vegetable Oil1 FFA (%) Tocos (%) FFA (%) Tocos (%) FFA (%) Tocos (%)
Soybean oil 84.0 1.10 62.0 7.4 76.0 3.5

Sunflower oil 86.0 0.65 61.0 5.3 77.0 2.4
Palm oil 93.0 0.25 40.0 1.7 84.5 0.8
1
Initial FFA: 1%.
mounted in the ducts or through a packed bed (random or structured packing) in the
scrubber vessel. The distillate is usually circulated at the lowest possible tempera-
ture (just above the melting point) to obtain the best possible condensation of the
fatty matter present in the vapor phase that leaves the deodorizer.
A demister is sometimes installed at the top of the scrubber ahead of the vacuum
unit, to reduce liquid carryover of small oil droplets, which would otherwise end up
in the water from the barometric condenser or in the condensate from the cold (or
dry) condensers.
Apart from efficient cooling of the vapor and condensing of the fatty matters, the
pressure drop in the scrubber should be kept as low as possible because it directly
affects the operating pressure of the main deodorizer. The pressure drop should be
below 1 mbar, and preferably below 0.5 mbar.
The conventional vapor-scrubber design results in one single deodorizer distil-
late. The main factors determining the overall composition of the distillate have
been discussed earlier in this chapter. Recently, improved scrubbers operating at
two different temperatures (so-called dual condensation principle) have been intro-
duced. Especially in case of physical refining, this design can result in higher value-
added distillates because it allows the collection of a first distillate enriched in FFA
and a second distillate with a higher concentration of unsaponifiable components
(sterols, tocopherols, etc.) (Table 17).
4.5. Vacuum Systems

4.5.1. Conventional Vacuum Systems The low absolute pressure required in a
deodorizer, usually between 2 and 4 mbar, is commonly generated by vacuum sys-
tems consisting of a combination of steam ejectors (boosters), vapor condensers,
and mechanical (liquid ring) vacuum pumps (Figure 16). Liquid ring pumps are
used in the final stage of the vacuum system to remove the noncondensable gases.
As a result of the large volume of vapor to be removed, motive steam consumption
in such steam ejectors is quite high and may account for up to 85% of the steam
consumed in a deodorizer.
A way to reduce motive steam consumption in a steam-ejector system with baro-
metric condensers is to lower the temperature of the water recirculating in the
372 DEODORIZATION
motive steam
A C A process vapour from column

B B scrubber
C to ejector vacuum system
3 4 D hotwell
1 6 E plate heat exchanger
5 F cooling tower
2
1-3 boosters/ejector
4 stand by ejector
7 5-6 direct contact condensers
8 7 liquid ring vacuum pump
8 separator
D
F
E
COMBINED STEAM CHEST

AND NOZZLE
PRESSURE DIFFUSER
TAP
STEAM INLET
DISCHARGE
SUCTION
Figure 16. Vacuum steam ejector system with barometric condensers used in edible oil
deodorization (Körting).
barometric condensers (Table 18). The benefit of the lower motive steam consump-
tion, however, must be weighed against the extra chilling capacity required and,
thus, the electrical energy needed to cool the barometric condenser water. Another
benefit from using a lower barometric condenser water temperature is a better con-
densation of volatile odoriferous material, which, in turn, reduces the odor emission
problem. Together with the condensed steam and highly volatile material, a small
TABLE 18. Effect of Barometric Condenser Water Temperature on Motive Steam

Consumption in Steam Ejector System.
Pressure kg Motive Steam per kg Strippng Steam

Booster Deodorizer 30 C (1) 10 C (2)
2.5 3 mbar 4.5 1.6

1.5 2 mbar 6.2 2.5
Note: (1) Barometric condenser water inlet temperature: 24 C; outlet temperature: 30 C.
(2) Barometric condenser water inlet temperature: 5 C; outlet temperature: 10 C.
amount of fatty matter is usually found in the condenser water, 1% of the strip-
ping steam. This fatty matter may decant partially and separate from the water. The
waste water is usually sent to a water effluent treatment plant where it is mixed with
other effluent streams from the refinery.
4.5.2. Dry Condensing Systems Special vacuum production units have been
developed to obtain lower pressures and operating costs and, at the same time, to
reduce emissions by more efficient condensation of the volatiles. The dry conden-
sing system is becoming more and more standard in new refining plants. With this
system, the sparge steam is condensed on surface condensers working alternately at
a very low temperature (around 30 C). The remaining noncondensables are
removed either by mechanical pumps or roots blowers in series with a liquid
ring pump or by a vacuum steam-ejector system (booster). The dry condensing sys-
tem reduces the motive steam consumption but requires extra electrical energy.
As a result of the relatively high capital cost, the return on investment (ROI) for
a dry condensing system may take several years and depends largely on the ratio
between the cost of steam and electricity. In Europe, with higher fuel costs, the pro-
duction cost of steam is higher, which improves the ROI of a dry condensing system
compared with a classic vacuum system. As an additional benefit, much lower
waste water quantities are produced by dry condensing, which significantly reduces
the cost of effluent treatment, thereby also improving ROI.
The pressure in the deodorizer is always slighlty higher (0.5–1.5 mbar) than on
the suction side of the vacuum unit, because of pressure losses caused by the oil
demisters, the fatty matter scrubbers, and other equipment. Consequently, to reach
an effective deodorization pressure of 2 mbar, a pressure of not more than 1.5 mbar
at the suction side is required. To obtain an efficient steam sublimation at this low
pressure, special stripping steam condensers operating at extremely low tempera-
tures (30 C) are required. (Table 19).
The commercially available dry condensing systems consist of two or more
freeze condensers with horizontally or vertically orientated straight tubes, a refrige-
ration plant for the generation of cold refrigerant, which is evaporated in the tubes,
and a vessel with relatively warm water for defrosting and cleaning of the tubes
after a certain period of freezing.
TABLE 19. Effect of Suction Pressure on Sublimation Point

of Stripping Steam.
Pressure at Condenser Side (mbar) Sublimation Point of Water ( C)
0.5 27.3
1 20.3
2 12.9
3 8.4
5 2.4
10 7.0
20 17.5
30 24.1
374 DEODORIZATION
Condenser Cooling water

Separator
Compressor
From distillate scrubber
Freeze condenser Valve, open

Valve, closed
To de-aeration
Vapor (vacuum)
Refrigerant (ammonia)
Non-condensable gases
Melt vessel Condensate

LP steam
Figure 17. Schematic diagram of a dry condensing system with horizontal freeze condensers
(e.g., Niro-Gea, Körting).
Dry condensing equipment can be equipped with either with horizontal or

vertical freeze condensers (Figures 17 and 18). Advantages of ‘‘horizontal’’ dry
condensing systems are the relatively simple and compact construction of the freeze
condensers. On the other hand, the mass of the refrigerant in the gravity system is
typically high.
Condenser Cooling water

Separator
Compressor
From distillate scrubber
Freeze condenser
Valve, open
Valve, closed
To de-aeration Vapor (vacuum)
Refrigerant (ammonia)
Non-condensable gases
Melt vessel Condensate

LP steam
Figure 18. Schematic diagram of a dry condensing system with vertical freeze condensers
(e.g., Graham Corporation).
Compared with horizontal systems, ‘‘vertical’’ freeze condensers have a more

efficient removal of ice and fatty matter from the tubes, which can drain freely
by gravity. A disadvantage of the vertical orientation is the static pressure of the
refrigerant column in the vertical tubes, which causes higher evaporating tempera-
tures at the bottom. In order to guarantee sufficient sublimation of sparge steam
over the entire height of the tubes, this evaporating temperature increase should
be compensated by a similar reduction of the refrigerant temperature in the separa-
tor, reducing the energy efficiency of the refrigeration plant.
The most essential feature of the recently developed SUBLIMAX system is the
vertical orientation of the freeze condensers, combined with individual refrigerant
injection at the top of the tubes to produce a falling film (Figure 19). This design
results in high-heat-transfer coefficients and constant evaporating temperatures
along the entire tube length.
Figure 19. Schematic diagram of the SUBLIMAX Dry Condensing system (De Smet-
Solutherm).
376 DEODORIZATION
5. COMMERCIAL DEODORIZER SYSTEMS
Deodorization can be performed in different ways (continuous, semicontinuous, or

batch). The selection of most appropriate deodorizer technology depends on many
factors, such as the number of feedstock changes, heat recovery, investment, and
operating costs.
5.1. Batch Deodorization

Batch deodorization is especially suitable for small capacities (<50 ton/day), irre-
gular production, or in processing small batches of different oils that demand mini-
mum cross-contamination. Batch deodorizers mainly consist of a single-shell
welded vertical cylindrical vessel (Figure 20). Their major advantages are very sim-
ple construction and low capital cost. Low capacities, high operating costs (high
steam consumption, very low heat recovery), and relatively long processing times
(sometimes up to 8 h) have made batch deodorization less attractive in today’s oil-
refining industry.
5.2. Semicontinuous Deodorization

Semicontinuous deodorizers are basically batch systems designed for larger capa-
cities. Their main application is in plants with frequent feedstock changes of oils
sensitive to cross contamination. In most designs, a batch of oil is transferred into
W S W S
Batch deodorization process
VACUUM UNIT
DEODORIZER FATTY
ACIDS
SCRUBBER
W
TC
HEATING
steam LC
COOLING
Cooling Sparge FATTY
water Steam ACIDS To clean
water
W
OIL to
DEODORIZE
COOLING
DEODORIZED
OIL
POLISHING
FILTER
Figure 20. Flowsheet of a batch deodorization process (De Smet).

COMMERCIAL DEODORIZER SYSTEMS 377
Figure 21. Semicontinuous deodorizer for frequent stock changes (Multistock-De Smet).
the system and then flows by gravity in a time sequence through a number of ver-
tically stacked compartments or trays (Figures 15 and 21).
The semicontinuous design allows a more efficient heat recovery than a
batch system. Heat recovery is perfomed by means of indirect economizers
(Figure 12). Steam produced in the bottom deodorized oil-cooling section is sent
in a closed thermosiphon loop to the top bleached oil-heating section to heat the
incoming oil. A single thermosiphon system has a recovery efficiency of 50%.
With a double system, coupled with a low-pressure steam-production device, up
to 75% of heat can be recovered.
Today, even for small capacity plants (10–50 TPD), semicontinuous deodorizers
are clearly more suitable than conventional batch deodorizers. The shorter hold-up
time in a semicontinuous deodorizer is a good argument in its favor, even in cases
when small capacities with very frequent feedstock changes are required. Com-
pared with continuous systems, the main advantages of semicontinuous deodoriza-
tion are its shorter time for feedstock change as well as its much lower cross
contamination. Heat recovery is, however, less efficient than in continuous
operation.
5.3. Continuous Deodorization

Continuous deodorizers are generally preferred for high-capacity plants with few
stock changes. The main advantages are the moderate investment costs, the possi-
bility of high heat recovery and the easy maintenance.
378 DEODORIZATION
Figure 22. Continuous multivessel horizontal deodorizer (Tirtiaux).
There are several configurations of continuous deodorizers: horizontal vessels,

vertical tray-type deodorizers, and packed columns.
Horizontal deodorizers consist of a series of horizontal single-shell cylindrical
vessels, with agitation steam injected by multiple pipe distributors running the
length of the vessel (e.g., Tirtiaux—Figure 22). Heating, deodorization, and heat
recovery are performed in separate horizontal vessels. The deodorization vessels
have an upper and lower deck with oil flowing from one side to the other in a shal-
low bed. Collection of the vapors from the different vessels is done in a separate
vertical manifold. Scrubbing is performed in a combined spray and packed-
tower-type fatty acid condenser.
Vertical tray-type deodorizers are probably the most commonly used type of
continuous deodorizers. Their design is based on a series of trays or compartments
stacked vertically in a cylindrical shell, with each tray designed for a specific task
(e.g., De Smet—Figure 23). All operations, heating, deodorization, and heat
Figure 23. Continuous vertical deodorizer (Unistock-De Smet).

COMMERCIAL DEODORIZER SYSTEMS 379
recovery are combined in a single vessel. Steam is injected through multiple coils,
sometimes in combination with gas lift pumps to ensure perfect agitation. The oil
flows in a concentric path from the inner to the outer ring, ensuring a nearly perfect
plug flow. The vapors from the different compartments are collected in a central
chimney and sent to a separate vapor scrubber with sprayer system. In some cases,
an extra structured packing is installed in the scrubber to improve condensation and
to reduce fatty matter carryover to the barometric water-condenser system.
The single vessel concept allows easy installation and maintenance as well as
reducing the risk of air leakages.
Although not a real deodorizer, packed columns are also used in edible oil deo-
dorization. A packed column is basically a single-shell vertical vessel in which a
structured packing has been installed. Deaerated and fully heated oil flows over
the packing from the top to the bottom while stripping steam is injected counter-
currently (e.g., Alfa Laval—Figure 24). A structured-type packing with a surface of
250 m2/m3 is most commonly used. Packed columns typically have a packing
height of 2– 4 m and a capacity of 10 ton/h
m2 cross section at a pressure
drop of 0.2–0.5 mbar per meter packing.
Packed columns are often installed to increase the capacity of existing deodo-
rizers. Their main function is to reduce the vapor load of the deodorizer vessel
Figure 24. Packed column stripper (Soft Column–Alfa-Laval).

380 DEODORIZATION
by prestripping most of the volatile material. The deacidified oil is then sent to the
deodorizer for the final deodorization. In palm oil deodorization, for example, the
FFA level is first reduced from 3–5% to < 0.5 % in a packed column before the oil
enters the deodorizer vessel. In this way, the capacity of a deodorization plant can
be increased significantly.
The main advantages of the packed column are the higher stripping efficiency
and the short residence time (only a few minutes).
The higher stripping efficiency is important because it will result in a lower over-
all steam consumption to achieve a given final FFA content. However, part of this
advantage is lost because of the pressure drop over the structured packing.
The combination of high stripping efficiency and short residence time make
packed columns a suitable solution for the stripping of valuable minor components
(tocopherols, sterols, etc.) or contaminants (pesticides, light PAH, PCB, etc.) from
heat-sensitive oils. Stripping of these minor components in a classical tray-type
deodorizer usually requires a higher stripping-steam consumption and longer
residence time. The latter, in particular, is not desirable because it may
induce unwanted side reactions such as the formation of trans-fatty acids, degrada-
tion of polyunsaturated fatty acids (e.g., in fish oil) or a less favorable crystalliza-
tion (e.g., cocoa butter).
At the same time, however, the short residence time does not provide a great deal
of heat bleaching or effective deodorization. To overcome this, a holding vessel is
provided as part of the system, before or after the packed column.
Packed columns entail a higher risk of fouling due to the large oil-metal contact
surface. Consequently, more frequent cleaning is required to secure consistent oil
quality and, at the same time, prolong the lifetime of the structured packing. The
frequency of cleaning depends largely on the type of oil processed, the frequency of
plant shutdowns and feedstock changes, the purity of the feedstock, and the air
tightness of the deodorizer equipment.
Risk of fouling is highest during the start-up and shut-down of the plant. Packed
columns are therefore usually not recommended for semicontinuous plants.
Furthermore, packed columns running on physically refined oils require more fre-
quent cleaning (once every 6–10 months), and the structured packing needs to be
replaced more often (every 2–3 years) than when processing chemically refined oils
(cleaning once every year and a lifetime of 3– 4 years).
In recent years, new developments in deodorization technology were mainly
determined by the strong demand from edible oil refiners to reduce the capital
and operating cost of deodorizers and the increased importance of the nutritional
aspects of food oils and fats.
A fully modular single vessel (continuous) stand-alone deodorizer has been
designed that requires no building and miminum piping. In this way, the erection
costs can be significantly reduced. (Figure 25—Qualistock, De Smet). This concept
allows the integration of different processing options with specific functions to
improve the overall quality of the deodorized oil (deodorization at two different
temperatures: so-called dual-temperature concept, deep-or shallow-bed deodoriza-
tion, inclusion of a packed column section, etc.).
FUTURE CHALLENGES 381
Figure 25. Modular single-vessel stand-alone deodorizer (Qualistock-De Smet).
5.4. Suppliers for Oil Deodorization Processes

In addition to equipment suppliers already mentioned in this chapter (Alfa-Laval,
De Smet, Tirtiaux), there are a number of other suppliers of commercial-deodorizer
systems for oils and fats (e.g., Andreotti, CMB, Crown, Kirchfeld, Krupp, Lipico,
Oiltek, etc.).
A detailed description of the features of every commercial deodorizer design
available today is beyond the scope of this chapter.
In addition to the deodorizer types described here, there are also other designs
including deodorizers custom designed for a specific company. Deodorizers are
usuallly purchased as a unit based on performance guarantees, utility requirements,
and quality of finished oil. Furthermore, the engineering competence and technical
support of the supplier, as well as the after-sales service and financial credibility, are
becoming more and more important factors in the final decision
6. FUTURE CHALLENGES
New developments in deodorization technology are driven mainly by the continu-

ous need for more efficient processes and increased attention to the nutritional qual-
ity of food oils and fats.
Profit margins in edible oil deodorization are low. In that respect, further reduc-
tion of the operating cost is a critical factor. New heat exchangers are being devel-
oped to improve heat recovery. More efficient sparge-steam-distributor systems
have been designed and, for some specific applications, packed columns have
been integrated to improve stripping efficiency and, hence, reduce sparging steam
consumption. Maximum valorization of the side streams (e.g., deodorizer distillate)
becomes more important, to improve the overall profitability of the refining process.
382 DEODORIZATION
For this purpose, new types of scrubbers operating at two different temperatures
(‘‘dual condensation’’ concept) have been developed.
Optimizing deodorization technology and process conditions for the removal of
specific contaminants (pesticides, PAH, dioxins, PCB, mycotoxins,. . . .) and maxi-
mum retention of the natural characteristics will be an important challenge for the
future as well. In that respect, the development of new (dry condensing) vacuum
systems capable of reaching a very low operating pressure in the deodorizer
(1 mbar) is very important because it allows a reduction of the deodorization tempe-
rature without affecting the stripping efficiency in a negative way. Negative tem-
perature effects (geometrical cis-trans isomerization, positional isomerization,
and polymerization, etc.) can be minimized further by use of dual-temperature deo-
dorizers. These deodorizers operate at different temperatures to reach the best com-
promise between required residence time for deodorization (at a low temperature)
and heat bleaching and final stripping at a high temperature (for a short period).
Furthermore, the increasing pressure to limit environmental pollution from refi-
neries and crushing plants as much as possible makes further improvement of the
air-cleaning systems and effluent treatment plants necessary.
There remain some exciting challenges in the oil-refining industry for the future.
The introduction of new technologies (e.g., use of enzymes, ultrafiltration, etc.)
may require the development of specific refining and deodorization methods.
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Deodorization - W. de Greyt and M. Kellens

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8

Degumming GUMS Degumming

Neutralisation SOAPS Bleaching

Bleaching Steam Refining-

Chemical refining: Sequence of process stages, which definitively includes alkali

Although the process is commonly named deodorization, it is actually a combina-

TABLE 1. Typical Operating Conditions for Deodorization of Vegetable Oils.

Temperature ( C) 250–260 220–240 230–250

TABLE 2. Effect of Pressure and Temperature on Sparge

Pressure Volume in m3/kg Steam

4 581 592 604

steam refining temperature. A high temperature is beneficial for a good stripping of

TABLE 3. Effect of Deodorizer Pressure on Steam and Fuel Consumption.a

Pressure Stripping Steam Booster Steam Fuel

2.1. Theoretical Considerations of Stripping

Component Mol. Weight Relat. volatility

Figure 2. Vapor pressure-temperature relationship for different components in edible oils.

Caprylic acid 96240 0.1398 26.33

2.1.2. Activity Coefficient a The efficient removal of volatile substances during

2.1.3. Vaporization Efficiency E According to Dalton’s law,

with E ¼ vaporization efficiency.

2.1.4. Principles of Deodorization/Steam Refining The stripping medium

2.2. Actual Deodorization

2.3. Temperature Effect

3. REFINED OIL QUALITY

The quality of a refined oil is usually evaluated by traditional quality parameters

3.1. Free Fatty Acids

Group Minor Components

Valuable minor components Tocopherols, sterols, squalene, oryzanol

Vegetable Oils Rape/Soybean Corn/Sun Palm Lauric Oils

Effect of temperature on fatty acid Effect of pressure on fatty acid

250°C 1.5 mbar

3.2. Fat Isomerization and Degradation Products

50 260 °C 4.5 260 °C

TABLE 7. Trans-Fatty Acid and Dimeric Triacylglycerols in Commer-

Oil Type Trans-Fatty Acids (%) Dimeric Triacylglycerols (%)

Soybean oil 0.9–3.5 0.6–1.3

3.2.2. Polymeric and Oxidized Triacylglycerols Other substances, such as

3.3. Tocopherols and Sterols

Trivial name Chemical name R1 R2 R3

Figure 5. Structure formula and nomenclature for the different tocopherols.

TABLE 8. Tocopherol Content and Composition of Some Oils and Fats.

Cocoa butter 275–290 6 — 91 3

Vitamin E ¼ a-toco þ 0:25 b=g-toco þ 0:01 d-toco: ð11Þ

Consequently, oils rich in a-tocopherol (sunflower seed, cottonseed oil) in particu-

Figure 7. Overview of the most common phytosterols.

4a, 5-epoxy-a-tocopherolquinone, 7,8-epoxy-a-tocopherolquinone, and a-tocopherol

TABLE 9. Sterol Content and Composition of Some Oils and Fats.

Sterol Composition (%)

Soybean 2000–4000 15–21 10–24 57–72 —

3-hydroxyl group of the phytosterol part is esterified to a fatty acid or a phenolic

3.4.2. Polycyclic Aromatic Hydrocarbons Only the light polycyclic aromatic

3.4.3. Polychlorinated Biphenyls and Dioxins ‘‘Dioxin’’ is the systematic

Polychlorinated biphenyls (PCBs) are a group of 209 discrete synthetic chemical

3.5. Deodorizer Distillate

TABLE 10. PCB and Dioxin Stripping from Fish Oil.

Dioxins (pptb) 5.3 1.8

Soybean Corn Sunflower Seed Rapeseed

Squalene 1.3–2.1 0.6 0.2–1.0 0.7 1.0 0.1–0.4

processed oil characteristics, the applied refining mode (chemical or physical

TABLE 12. Polycyclic Aromatic Hydrocarbon Content (PAH) of Refined

Naphtalene 3.3 1670

Own research data; coconut oil from Southeast Asian origin.

For Nitrogen SðN2 Þ ¼ ½0:0590 þ 0:000400 t 100; ð14Þ