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Separating Tocotrienols from Palm Oil by Molecular Distillation

Donghong Liu a; John Shi b; Luidy Rodrguez Posada c; Yukio Kakuda c; Sophia Jun Xue b
a
Department of Food Science and Nutrition, Zhejiang University, Hangzhou, Zhejiang, China b Guelph Food
Research Center, Agriculture and Agri-Food Canada, Guelph Ontario, Canada c Department of Food
Science, University of Guelph, Guelph Ontario, Canada
Online Publication Date: 01 October 2008

To cite this Article Liu, Donghong, Shi, John, Posada, Luidy Rodrguez, Kakuda, Yukio and Xue, Sophia Jun(2008)'Separating

Tocotrienols from Palm Oil by Molecular Distillation',Food Reviews International,24:4,376 391

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Food Reviews International, 24:376391, 2008

Copyright Taylor & Francis Group, LLC
ISSN: 8755-9129 print / 1525-6103 online
DOI: 10.1080/87559120802303840

1525-6103
8755-9129
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Food
Reviews International
International, Vol. 24, No. 4, July 2008: pp. 132

Separating Tocotrienols from Palm

Oil by Molecular Distillation

DONGHONG LIU1, JOHN SHI2,

LUIDY RODRGUEZ POSADA3,
YUKIO KAKUDA3, AND SOPHIA JUN XUE2

Separating
Liu
et al. Tocotrienols from Palm Oil by Molecular Distillation

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Department of Food Science and Nutrition, Zhejiang University, Hangzhou,

Zhejiang, China
2
Guelph Food Research Center, Agriculture and Agri-Food Canada, Guelph
Ontario, Canada
3
Department of Food Science, University of Guelph, Guelph Ontario, Canada
Crude palm oil contains approximately 1% minor components, including carotenoids
and vitamin E (tocopherols and tocotrienols), which contribute to the stability and
nutritional properties of palm oil. Palm oil is considered one of the best sources of
vitamin E. The vitamin E content in palm oil is unique because it is composed of tocotrienols rather than tocopherols. Palm fatty acid distillate (PFAD) is the volatile
organic material recovered as a valuable by-product in the deodorization of palm oil.
Several processes have been proposed for recovering tocopherols and tocotrienols
from PFAD. For this separation process, it is necessary to develop a processing procedure to extract the valuable tocotrienols and other minor components from PFAD
using molecular distillation. Molecular distillation occurs at low temperatures and
reduces the problem of thermal decomposition. High vacuum also eliminates oxidation
that might occur in the presence of air. The rate of evaporation is controlled by the
rate at which the molecules escape from the free surface of the liquid and condense on
the condenser. The effects of feed-flow rate and temperature of distillation on extraction of minor components from PFAD are based on concentrations, distribution coefficients, and relative volatilities. The separation of tocotrienols from PFAD approached
maximum values at low temperatures and fell drastically as temperature increased.
For the optimum conditions for the extraction of tocotrienols with high yield and
purity, it is necessary to determine the effect of processing variables on the extraction
of minor components (i.e., tocotrienols, a-tocopherol) from the PFAD in terms of concentrations in the liquid and vapor phases, to reveal the behavior of target components
in the evaporation process, and to determine the evaporation and volatility properties
of tocotrienols and other minor components from PFAD.
Keywords evaporation, free fatty acids, molecular distillation, palm oil, separation,
tocotrienols, volatility

Introduction
Palm oil is extracted from the fleshy orange-red mesocarp of the fruit of the oil palm
(Elaeis guineensis). This plant, indigenous to West Africa, has spread to the tropical and
subtropical zones of the world, particularly Malaysia and Indonesia.(1) Crude palm oil
Address correspondence to Dr. John Shi, Guelph Food Research Center, Agriculture and
Agri-Food Canada, Guelph, Ontario N1G 5C9, Canada. E-mail: shij@agr.gc.ca

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Separating Tocotrienols from Palm Oil by Molecular Distillation

377

consists mainly of glycerides and small quantities of non-glyceride components. The nonglyceride components include free fatty acids (FFA), trace metals, moisture, impurities,
and minor components.(2) Crude palm oil contains approximately 1% minor components,
which include carotenoids, vitamin E (tocopherols and tocotrienols), sterols, phospholipids, glycolipids, terpenic, and aliphatic hydrocarbons.(3) The carotenoids, tocopherols and
tocotrienols are the most important of these minor components. They contribute to the
stability and nutritional properties of palm oil.(4)
Carotenoids impart the characteristic orange-red color to palm oil. Oil from the tenera variety, which is widely planted in Malaysia, has a carotenoid content of about 500700 mg/L.(3)
Alpha and -carotenes are the major components present (ca. 36 and 54%, respectively),
and the rest are -carotene, lycopene, and xanthophylls. Carotenes, particularly -carotene,
are converted into vitamin A in vivo. Unfortunately, most of the carotenoids are degraded
during the refining, bleaching and deodorization processes, which traditionally produce
the light colored oils preferred by most consumers.(1,5)
Palm oil is potentially one of the best sources of vitamin E. The vitamin E content in
palm oil is unique in that it is composed of tocotrienols rather than tocopherols.(6) Palm oil
normally contains 6001,000 mg/L, of which 43% is -tocotrienol, 24% is -tocotrienol,
11% is -tocotrienol, and 21% is -tocopherol.(7) Tocopherols and tocotrienols are potent
natural antioxidants that play an important role in the stabilization of oils and fats.(6,8)
They extend the induction period and delay the time when oxidation produces off-flavors
and/or odors.(1)
Palm tocotrienols may also have beneficial health impacts as they have been reported
to lower plasma cholesterol by inhibiting the activity of HMG-CoA reductase, which
regulates cholesterol synthesis in the liver.(9) Tocotrienols may also play an important role
in suppressing the progression of certain types of cancer particularly breast cancer.(7)
The molecular distillation process for recovering tocopherols using soya oil deodorizer distillate is in commercial production.(8) During steam deodorization and distillation
of FFA approximately 1557% of the tocotrienols and tocopherols are removed from the
palm oil. Most of the tocopherols and tocotrienols are not lost but accumulate in the palm
fatty acid distillates (PFAD). The levels of tocopherols and tocotrienols in the distillates
may be as high as 0.71.0%, and therefore, this by-product represents a potential source
for the recovery of these valuable compounds.(5) In addition to tocopherols and
tocotrienols, other valuable minor components are concentrated in the PFAD such as sterols and terpenic hydrocarbons (e.g., squalene). Their value lies in their health promoting
functionality in the food and pharmaceutical industries.

Tocotrienols and Tocopherols in Palm Oil

Fat soluble 6-hydroxychroman compounds exhibit biological activity,(8,10) and can be
divided into two subgroups, tocopherols and tocotrienols (Fig. 1). Figure 2(ab) shows a typical GC chromatogram of simultaneous analysis of FFA, tocopherols, tocotrienols, sterols
and squalene in a residue fraction. Figure 3 shows a HPLC chromatogram of analysis of
tocopherols and tocotrienols in palm oil. The analysis of tocotrienols in palm oil by HPLC
(Fig. 3) allowed the assignment of tocotrienol peaks in the GC chromatogram (Fig. 2ab).
Tocopherols are found in high concentrations in a variety of foods, while tocotrienols
are relatively rare and found in appreciable levels only in a few specific vegetables oils,
such as palm oil (Table 1).(11) Structurally, as seen in Fig. 1, the tocopherols and
tocotrienols can be viewed as consisting of a chromanol head, formed by phenolic and heterocyclic rings, and a phytyl tail (10). The tocopherols and tocotrienols are designated as

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Liu et al.

OH

R1
CH3 H
2

R2
R3

OH

4
R4

Tocopherol structure

CH3

CH3

2
R3

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R1

R2

Tocopherol/tocotrienol

CH3 H

R4

3
Tocotrienol structure

R1

R2

R3

R4

CH3
CH3
H
H

CH3
H
CH3
H

CH3
CH3
CH3
CH3

CH3
CH3
CH3
CH3

Figure 1. Structures of tocopherols and tocotrienols.

, , , or depending on the methyl substitutions on the phenolic ring.(12) The only difference in the structure of tocotrienols and tocopherols is in the phytyl tail; tocotrienols contain
three isolated double bonds in their phytyl tail, while tocopherols have a saturated tail.(10)
The tocopherols possess three chiral centers at position 2 of the chromanol head and
at positions 4 and 8 of the phytyl tail, making a total of eight stereoisomeric forms possible.
All naturally occurring tocopherols have the RRR configuration (2D, 4D, 8D, d-tocopherols,
or (+)-tocopherols). Synthetic -tocopherol (all-rac--tocopherol) is a racemic mixture of
equal parts of each stereoisomer. On the other hand, the tocotrienols only have one chiral
center at position 2; therefore, they only have two stereoisomers. However, since there are
two double bonds at positions 3 and 7, four cis / trans geometrical isomers are possible.
Therefore, a total of 8 isomers could be present for each tocotrienol. Only the 2R, 3-trans,
and 7-trans isomers exist in nature.(13)
Two new tocotrienols have been identified from rice bran by HPLC using a normal
phase silica column.(14) These new tocotrienols have been designated desmethyl tocotrienol
(d-P21-T3) and didesmethyl tocotrienol (d-P25-T3). Using the same scheme as in Fig. 1, R1,
R2, R3, and R4 must be substituted by H, H, H, and CH3, respectively, to get the molecular
structure of d-P21-T3, and by H, H, H, and H to get the molecular structure of d-P25-T3. Evidence suggests that these tocotrienols, along with the other tocotrienols, might have therapeutic value in the prevention and treatment of cardiovascular disease and breast cancer.(14)
Antioxidant Activity of Tocotrienols and Tocopherols
The biological activity of tocopherols is generally believed to be due to their antioxidant
activity against lipid peroxidation in biological membranes. These compounds are able to
scavenge the chain-propagating peroxyl radicals. The antioxidant function per se is

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(a)

(b)

Figure 2. GC chromatogram of simultaneous analysis of FFA, tocopherols, tocotrienols, sterols and

squalene; (a) represents time from 0 to 12 minutes, (b) represents time from 14 to 30 minutes. Peak d-T3,
-tocotrienol; g-T3, -tocotrienol; a-T, -tocopherol; a-T3, -tocotrienol; HDS, heptadecanyl stearate.

located in the chromanol head, where the phenolic hydroxy group donates an H-atom to
quench lipid radicals. The phytyl tail has no effect on the chemical reactivity of tocopherols but is responsible for the very strong lipophilic properties of these compounds,
which determines their proper positioning in the biomembranes.(15) For tocotrienols, their
antioxidant reaction mechanisms are expected to be similar to those of tocopherols. It is
not known, either, if the unsaturation of the phytyl tail makes any difference on the activity of the tocotrienols relative to the corresponding tocopherols.(10)
The antioxidant activity of 1 mg of all-rac--tocopheryl acetate equals the activity
of 0.67 mg of d--tocopherol.(8,16) Table 2 shows the biological activities of some
tocopherols and tocotrienols relative to natural d--tocopherol as assayed by the rat
resorption-gestation test.(10) d--tocopherol has the highest antioxidant activity, while
d--tocotrienol manifest only about 30% of this activity. However, there is evidence
that suggests that d--tocotrienol has higher antioxidant activity than d--tocopherol.
For example, d--tocotrienol possesses 4060 times greater antioxidant activity against
(Fe2+ + ascorbate)- and (Fe2+ + NADPH)-induced lipid peroxidation in rat liver
microsomal membranes and 6.5 times better protection of chytochrome P-450 than d-tocopherol.(15) Another study showed that the tocotrienol rich-fraction from palm oil
(TRF) has the ability to inhibit oxidative damage induced by ascorbate-Fe2+ and light

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Liu et al.

Figure 3. HPLC chromatogram of analysis of tocopherols and tocotrienols in palm oil. Peak a-T,
-tocopherol; a-T3, -tocotrienol; g-T3, -tocotrienol; d-T3, -tocotrienol.

Table 1
Tocotrienols and tocopherols levels (mg/L) in common dietary oils(11)
Dietary oil
Palm
Rice bran
Wheat germ
Coconut
Palm-kernel
Cocoa butter
Corn
Cottonseed
Peanut
Olive
Safflower
Soybean
Sunflower

Total
-Tocopherol -Tocotrienol -Tocotrienol -Tocotrienol tocotrienols
152
324
133
5
12
11
112
389
130
51
387
101
487

205
236
26
5
21
2

439
349

94

19

738
586
26
25
21
2
0
0
0
0
0
0
0

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381

Table 2
Biological activity of some tocopherols and tocotrienols(10)

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Name / configuration
d--Tocopheryl acetate (2R,4R,8R)
2R,4R,8S-d--tocopheryl acetate
2R,4S,8S-d--tocopheryl acetate
2R,4S,8R-d--tocopheryl acetate
1--Tocopheryl acetate (2S,4R,8R)
2S,4R,8S-d--tocopheryl acetate
2S,4S,8R-d--tocopheryl acetate
2S,4S,8S-d--tocopheryl acetate
d--Tocopherol
d--Tocopherol
d--Tocopherol
d--Tocopherol
d--Tocotrienol
d--Tocotrienol
d--Tocotrienol
d--Tocotrienol

Relative biological activity (%)

100
90
73
57
31
37
21
60
100
50
10
3
30
5
Not known
Not known

photosensitization in rat liver microsomes. Among the constituents of TRF, d-tocotrienol was the most effective followed by its - and -isomers. The protective ability of TRF, against both protein oxidation and lipid peroxidation, was significantly
higher than that of d--tocopherol.(17)
Role of Tocotrienols in the Prevention of Cardiovascular Heart Disease
Cell culture and animal studies have shown that tocotrienols, in contrast to tocopherols, possess hypercholesterolemic activity.(11) Studies indicate that tocotrienols inhibit the activity of
3-hydroxy-3-methylglutaryl-coenzyme A (HMG-CoA) reductase, the rate- limiting enzyme
in cholesterol synthesis.(9) d-P25-T3 was found to be the most potent in inhibiting HMG-CoA
reductase activity in chickens.(14) Tocopherols, on the other hand, have no effect on plasma
concentrations of total cholesterol, low-density lipoproteins (LDL), high density lipoproteins
(HDL) and very-low density lipoproteins (VLDL), and triacylglycerols.(18)
A tocotrienol rich fraction from palm oil containing d-P21-T3 and d-P25-T3 (TRF25)
reduced total serum cholesterol, LDL, apolipoprotein B, platelet factor 4, thromboxane B2,
glucose, and triglycerides in swine expressing hereditary hypercholesterolemia.(19) The
effect of tocotrienols on cholesterol-lowering might be related to HMG-CoA activity.(20)
Human studies used a TRF or TRF25 oil capsule that was administered to hypercholesterolemic individuals. The TRF mixture contained d--tocopherol and d--, d--, and
d--tocotrienol; the TRF25 contained the TRF mixture plus d-P21-T3 and d-P25-T3. Participants received 100200 mg per day for 410 weeks. Results showed a significant
decrease in total plasma cholesterol, LDL cholesterol, and apolipoprotein B levels.(21,22) In
addition, a synergistic effect between TRF25 and lovastina HMG-CoA reductase
inhibitorwas found on the reduction of cholesterol.(23)
The most effective supplements provided 1520% d--tocopherol and 60% d-- and tocotrienol, while the least effective supplements consisted of < 30% d--tocopherol and 45%

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d-- and -tocotrienol. It was postulated that the d--tocopherol attenuated the action of tocotrienols on HMG-CoA reductase activity. It was also suggested that high doses of tocotrienols
were not beneficial since a conversion of tocotrienols to tocopherols was likely to occur.(22)
Studies have shown that dietary supplementation with tocotrienols result in carotid
atherosclerosis regression. One study found a significant reduction in the atherosclerotic
lesion size of apoE mice fed d-P25-T3 or rice bran.(23) In another study, a positive effect of
TRF on the inhibition of LDL oxidation and endothelial cell lipid peroxidation in human
umbilical vein endothelial cells was found.(24) Enhanced endothelial cell activation and/or
dysfunction are associated with accelerated development of atherosclerosis.(11)
Tocotrienols have been shown to improve endothelial function by at least four mechanisms: a) decreased susceptibility of LDL oxidation; b) decreased monocyte-endothelial
cell adhesion; c) suppression of vascular smooth muscle cell proliferation; and d) suppression of platelet activation and aggregation.
Role of Tocotrienols in the Prevention of Breast Cancer
Tocotrienols from TRF have been shown to inhibit the proliferation of human breast cancer cell lines. The inhibition was found to be independent of the estrogen receptor status of
the cell lines.(7) Similarly various tocotrienols have shown concentration-dependent suppression of B16 melanoma cells proliferation.(14) In general, tocotrienols display potent
antiproliferative and apoptotic activity against breast cancer cells at doses that have no
adverse effects on cell growth or viability in vitro. Tocotrienols have also shown greater
anticancer activity than tocopherols in a variety of in vitro experimental models.(11) These
results suggest that dietary supplementation of tocotrienols might lower the risk of breast
cancer in women.

Methods for Extraction and Concentration of Tocotrienols

from Palm Oil and PFAD
Many attempts have been made to recover minor components from crude palm oil. Most
methods of recovery depend either on chemically transforming the triglycerides (e.g.,
saponification or transesterification) so that they can be removed, or by using adsorbent
materials to selectively adsorb them.(5) The transesterification reaction converts palm oil
triglycerides into fatty acid esters, leaving the minor components intact. Carotenoids have
been partially purified from these esters by various methods such as adsorption, solventsolvent extraction and distillation.(3)
Tenera oil palm species has been transesterified with methanol/ethanol using sodium
hydroxide as a catalyst.(3,25) The fatty acid esters were separated from the glycerol fraction
by water washings. The carotenes were recovered by distilling the esters under high
vacuum in a falling-film distillation apparatus. Concentrations of carotenoids of more than
80g/L were obtained along with vitamin E and sterols.(25) Chemical transformation is,
however, undesirable because the glyceride structure of the oil changes, limiting its use as
a foodstuff. Therefore, palm oil is not the best source of minor components unless a
greater market for the methyl esters is created (e.g., oleo chemical industry or diesel
substitution). Palm fatty acid distillate (PFAD) seems to be a better choice.
PFAD is the volatile organic material recovered as a valuable by-product in the deodorization of palm oil. Deodorization, a high temperature, high vacuum steam distillation is the
last step in edible oil processing, which improves the taste, odor, color, and stability of oils
by removing undesirable volatiles (e.g., free fatty acids, aldehydes, and ketones) and

Separating Tocotrienols from Palm Oil by Molecular Distillation

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pigments.(26) In addition to the undesirable components, valuable minor components are

concentrated in the PFAD such as tocopherols, tocotrienols, sterols, and squalene.
Several processes have been proposed for recovering tocopherols and tocotrienols
from PFAD. There is, however, just one product available commercially, which was
developed by The Malaysian Palm Oil Board (MPOB) and is called Palm Vitee.(27) The
process has the following steps.
1. Treating the PFAD with an alkyl alcohol and appropriate catalysts to convert free fatty
acids (by esterification) and glycerides (by transesterification) into alkyl esters.
2. Distilling the product under reduced pressure to remove a major part of the alkyl esters and
leave the tocopherols, tocotrienols, and other higher boiling point substances in the residue.
3. Cooling the residue to bring about crystallization of higher melting point substances
and other impurities and filtering off the crystalline material to leave the tocopherols
and tocotrienols in the filtrate.
4. Treating the filtrate from step 3 using an ion-exchange procedure with a high selectivity
anionic resin to produce a concentrated tocopherol and tocotrienol fraction (an acidic
solution is used for desorbing the tocopherols and tocotrienols from the resin).
5. Removing the solvent from the tocopherol and tocotrienol fraction by evaporation.
6. Washing and drying the product.
7. Subjecting the dried product to molecular distillation to produce a further concentrated
tocopherol and tocotrienol product.
8. Deodorizing the tocopherol and tocotrienol product.
In a modified process, free fatty acid and acylglycerols are converted into methyl
esters by an esterification process, and then these esters are removed by distillation. The
PFAD could be distilled to remove a major part of the free fatty acids.(28) The overall yield
is about 65% and the purity of the vitamin E is increased to 8095%.(27,28) However, this
modified process is extremely complex, and requires additional steps such as solvent
extraction and solvent purification.
Another process for the preparation of tocopherol and tocotrienol concentrates from
vegetable oil distillates produces a product containing 2080% of tocopherols and tocotrienols by weight, with an overall recovery of 7297%.(29) In this process, the vegetable oil
distillates are subjected to esterification, in which the sterols react with the free fatty acids
already present in the mixture to form high-boiling sterol esters. Any other alcoholic matter,
triterpenoid alcohols, methyl-sterols, and the like, are converted to high-boiling fatty acid
esters and waxes. The esterified mixture is then subjected to a series of distillation steps in
which components boiling higher and lower than the tocopherols and the tocotrienols are
separated. The resulting product is a tocopherol and tocotrienol concentrate comprised
primarily of tocopherols, tocotrienols and hydrocarbons with similar boiling points.(29)
In a third process using Candida Antarctica lipase to enzymatically hydrolyze the
PFAD, the liberated FFA is neutralized using alkali and the salt formed is then washed off.
To maximize vitamin E levels, the hydrolysis should be carried out with 2.5% of lipase
and 45.247.3% (v/w) of water for 5.55.7 hours.(30)
Other processes include the formation of complexes with the fatty acids present in the
PFAD. It was discovered that urea forms an inclusion complex with C6 to C22 fatty acids
and glycerides, in which hydrogen-bonded urea molecules are oriented in a helical lattice
into which the fatty acid or the glyceride molecule fits.(31) This complex does not entrap
the sterols, tocotrienols, tocopherols, and other bulky molecules present in the deodorizer
sludge or distillate. Using this fact, a process for recovering tocopherols from deodorizer
sludge was developed.(31) It has the following steps:

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1. forming a mixture with the deodorizer sludge and a solution of urea dissolved in methanol;
2. heating the mixture to form a urea complex of the fatty acids and glycerides. The reaction is controlled so as not to go above 64C;
3. cooling the mixture to precipitate the urea complex from the mother liquor containing
the tocopherols and tocotrienols; and
4. separating the mother liquor from the precipitate.
A process similar to urea complexation was developed that treated the PFAD with
calcium hydroxide in the presence of a solvent medium containing water and an inert
water miscible organic solvent to form calcium salts of the naturally occurring free fatty
acids.(32) These salts were precipitated and removed. After removal of the calcium salts,
the material in the liquid phase contained the natural tocopherols and tocotrienols in a far
more concentrated form than that present in the starting material.(32)
When PFAD is used directly in the molecular distillation process, it would not be
efficient to obtain a product with high tocotrienol and tocopherol concentration, as was the
result from the process using deodorizer distillate of soya oil.(8) Conventionally preparing
high-purity concentrate of tocotrienols and tocopherols normally involves a series of physical and chemical treatment steps. The process requires a pretreatment to transform heavier
components into components of small molecular weights. Because deodorized distillate is a
complex mixture and the properties of its components are very similar, it is difficult to
recover high-quality concentrates of tocotrienols and tocopherols with good yield. As seen
in the above examples, most of the processes developed for recovering tocopherols and
tocotrienols from PFAD are difficult to perform due to their complexity, inefficiency or cost.

Molecular Distillation Process

Molecular distillation is a type of evaporation that happens in extremely low pressures and
in low temperatures, and it is used for the separation of constituents from mixtures by
partial evaporation. It is based on the fact that the vapor is relatively richer in the component with the highest vapor pressure, i.e., the more volatile component. It can be carried
out either as simple distillation or fractional distillation (rectification). In simple distillation, the vapors are recovered by condensation. In rectification, successive vaporization
and condensation are carried out simultaneously, and a part of the condensed liquid
called the refluxflows down the column countercurrent to the flow of vapors. Several
new methods have been developed for the separation and recovery of minor components
from vegetable oil such as palm oil.(33,34,35) Esterified palm oil is subjected to molecular
distillation giving a concentrate rich in minor components. The concentrate is then
adsorbed by adsorbents such as normal phase silica gel, reversed phase silica gel, or neutral alumina, as well as polymer absorbents, such as polyethylene glycol and polyacrylate
polyalcohol. With the same method, tocopherols and tocotrienols from palm oil can be
separated and recovered.
Distillation at Reduced Pressure
When vacuum is applied, there are three major reduced pressure ranges that can be utilized for distillation(36):
1. distillation at moderate vacuum or equilibrium distillation;
2. unobstructed path distillation; and
3. molecular distillation.

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Separating Tocotrienols from Palm Oil by Molecular Distillation

385

Distillation at moderate vacuum is characterized by the use of conventional distillation equipment. Its lowest pressure limit is of the order of 1 torr, i.e., one mm-Hg.
Unobstructed-path distillation is defined as distillation in which the path between the
evaporator and the condenser is not blocked, in other words when there is a free transfer of
molecules.(37) When the distance of transfer is comparable with the mean free path of the
vapor molecules, the distillation is known as molecular distillation.
Mean free path is defined as the average distance a molecule will travel in the vapor
phase without colliding with another vapor molecule.(37) This implies that, in molecular
distillation, the vapor molecules can reach the condenser without intermolecular collisions. A dynamic equilibrium can not, therefore, be established between the vapor and the
liquid. As well, concepts like theoretical plates, stages, and other common distillation terminology do not apply. There is, however, no certainty that an individual molecule that
has evaporated will be able to travel any distance without a collision.
Molecular distillation occurs at low temperatures and, therefore, reduces the problem
of thermal decomposition. High vacuum also eliminates oxidation that might otherwise
occur in the presence of air. Unobstructed path and molecular distillation are often classified together as short-path or high vacuum distillation. They employ the same kind of
equipment; the difference is in the dimensions and operating conditions. Unobstructed
path distillation is carried out at pressures as low as 102 torr, while in molecular distillation pressures of 103 torr, i.e., a mtorr, are used. Another useful distinction between the
methods of vacuum distillation can be made with reference to the way in which the vapor
phase is formed: a) ebullition, b) evaporative distillation, or c) molecular distillation.
Ebullition is accompanied by the formation of bubbles when the saturated vapor pressure exceeds the pressure of the surrounding gas. The only limit to the rate of evaporation
in this case is the rate at which heat can be transferred to the liquid. Evaporative distillation, on the other hand, occurs when the pressure of the surrounding gas is higher than the
vapor pressure of the liquid at a given temperature, so that bubbles are not formed. The
rate of evaporation is controlled by the temperature of the liquid and the conditions above
the liquid surface.
In molecular distillation, which can also be called molecular evaporative distillation,
the rate of evaporation is controlled by the rate at which the molecules escape from the
free surface of the liquid and condense on the condenser. Theoretically, as mentioned
before, the condenser should be in the immediate vicinity of the evaporating surface. In
practice, however, distances of 510 cm are not uncommon, despite the fact that more
intermolecular collisions are likely to occur.
Rate of Evaporation Under Molecular Distillation
The theoretical evaporation rate in molecular distillation is defined by the LangmuirKnudsen Equation, which is derived from kinetic theory considerations(38):
.

GT = PO

M
,
2RT

(1)

where GT is the theoretical rate of evaporation in kg/m2 s, PO is the equilibrium vapor

pressure in Pa at absolute temperature T in Kelvin (K), M is the molecular weight of the
substance, and R is the universal gas constant in J/kmol K. It is interesting to note that
Eq. (1) indicates that molecular distillation is a function of the molecular species and the
surface temperature. It is, therefore, a surface phenomenon.(39)

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Liu et al.

When an appreciable number of collisions can occur in the vapor space, some of the
molecules will return to the liquid. This leads to a decrease in the number of molecules
that reach the condensation surface. This quantity divided by the time and area of evaporation gives the actual rate of evaporation G. The Langmuir-Knudsen Equation, therefore,
provides a limiting value for the rate of molecular distillation.(39,40) The ratio of the actual
to the theoretical rate of evaporation is defined as the evaporation coefficient f:
.

f =

G
.

(2)

GT

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The coefficient f, which represents the fraction of vaporized molecules that reach the
condenser, can be calculated as follows(41):

f = F + (1 F ) (2e N e 2 N ),

(3)

where

F=

AC
h
and N =
,
AC + AE
kb

where, AC is the condensation surface area in m2; AE is the evaporation surface area in m2;
h is the distance between the evaporator and condenser in m; k is a factor that has to be
determined experimentally; and is the mean free path at equilibrium conditions in m.(41)
The following empirical equation is used to calculate k for a short-path, falling-film
evaporator(42):

log k = 0.2 F + 1.38 ( F + 0.1).

(4)

Relative Volatility
In a mixture of two components, the relative volatility , which is also called the separation factor, represents the ratio of the observed volatility of component 1, i.e., the more
volatile, to that of component 2. It can be expressed as Eq. (5)(41):

a=

y1 x2
,
x1 y2

(5)

where x and y are the mol fractions in the liquid and vapor phases, respectively. Further
consideration shows that, if a mixture of two components obeys Raoults law, their relative volatility is equal to P1/P2, i.e., the ratio of their equilibrium vapor pressures in the
pure state at the prevailing temperature. The ratio y/x is the distribution coefficient (when
equilibrium conditions are present it is the equilibrium distribution constant). At high rates
of evaporation under high vacuum, i.e., molecular distillation, the relative volatility
becomes(43):

Separating Tocotrienols from Palm Oil by Molecular Distillation

a=

P1O

M2
,
M1

P2O

387

(6)

where M1 and M2 are the molecular weights of component 1 and 2, respectively.

Vapor pressure data for -tocopherol, tripalmitin, tristearin, palmitic acid, stearic acid
and monopalmitin are shown in Table 3. These data were fitted to the following model
using the generalized least squares method(46):

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LnP O =

A
+ B,
T

(7)

where PO is the equilibrium vapor pressure in Pa at absolute temperature T in K, and A

and B refer to regressed parameters. The model was used to estimate the equilibrium
vapor pressures of the components at the temperatures of distillation.
Short-Path Evaporators
There are several basic design variations with short-path evaporators. These are the shortpath falling film evaporator, the centrifugal molecular still, and the short-path, wiped-film
evaporator. They operate at the lowest pressure of any system and are capable of high
throughput per unit size, due to their continuous nature. They also offer the shortest
thermal exposure of any process.(37)
Short-path, falling film evaporators can handle materials with viscosities up to 5000 cP,
and the residence time, temperature, and pressure can be controlled. This is the simplest of
the short-path stills, but more current designs use either centrifugal force or roller-wipers
to spread the feed material on the evaporator surface. In the centrifugal molecular still,
feed material is fed into the center of a heated, spinning rotor. The material is evenly
spread towards the edge and condensed in front of the rotor. The short-path, wiped-film
still uses mechanically agitated, wiped films combined with an internal condenser.(37)
Molecular Distillation Applications
Molecular distillation, with its important characteristics of low pressure and low temperature, has great potential for separation, purification, and concentration of natural products
that usually consist of complex and thermally sensitive molecules. Recovery of special
components used in the nutrition, pharmaceutical, and cosmetic areas from natural
Table 3
Component parameters for the vapor pressure model(44,45)
Component
-tocopherol
Palmitic acid
Stearic acid
Tripalmitin
Tristearin
Monopalmitin

14886
11365
11841
19131
19710
11365

34.230
30.663
30.819
35.450
35.646
28.393

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Liu et al.

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products by molecular distillation has gained wide application, including products derived
from refined vegetable oils. For example, deodorizer distillate of vegetable oils; palm oil
for obtaining tocotrienols and tocopherols; oil of rice for the oryzanol recovery;
monoglycerides concentration; carotenoids recovery from palm oil; heavy petroleum
characterization, and herbicides.(8,29,47,48,49,50) Molecular distillation is often used to separate or purify high-boiling materials that decompose, oxidize, or polymerize at elevated
temperatures.(51) This process can be considered for industrial uses if both distillate and
residue are high value-added products.(52) Some specific uses of molecular distillation are
listed below.
1. Production of biologically active substances such as vitamins, sterols and antioxidants
from natural oils and fats. Examples include extraction of vitamin A from fish liver and
whale oil and carotenoid recovery from esterified palm oil.(24)
2. Separation of mono and diglycerides in partially saponified fats.(52)
3. The refining of crude animal and vegetable oils. For instance, a Malaysian company
produces Carotino, an edible red palm oil, using a process that involves a pretreatment
of crude palm oil (i.e., degumming with phosphoric acid and treatment with bleaching
earth) followed by deacidification and deodorization using molecular distillation.(4)
Recently a new process of molecular distillation was developed for recovery of tocotrienols and tocopherols from rapeseed by combination of acid-catalysed methyl esterification and crystallization followed by fractional distillation of derived products.(53,54)

Conclusions
Molecular distillation has shown great potential in the separation, purification and concentration of natural products such as tocotrienols and tocopherols as well as other minor
health-promoting components from palm fatty acid distillates (PFAD). Because it uses
very low levels of temperatureunder high vacuum and short operating time for separation, while using no solventsit avoids problems of toxicity. The effects of feed-flow rate
and temperature of distillation on extraction of minor components from PFAD are related
to the yield, purity, and rate of evaporation in terms of concentrations, distribution coefficients, and relative volatilities. The molecular distillation process can remove maximum
amount of free fatty acids to increase the concentration of tocotrienols and tocopherols
without adding extra components to the system. The percentage of free fatty acids in the
distillation steam of the molecular still is larger at low feed-flow rates and low evaporator
temperatures, thus avoiding thermal decomposition.

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