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Palm oil fractionation

Article April 2007 with 5,542 Reads
DOI: 10.1002/ejlt.200600309

1st Marc Kellens

2nd Vronique Gibon

23.64 Desmet Ballestra Group

3rd Marc Hendrix

4th Wim De Greyt

30.94 Desmet Ballestra

Abstract
Modification techniques like fractionation, interesterification (chemical or enzymatic) and
hydrogenation allow proposing a large range of new fatty products. At a time when trans fatty
acids are questioned, fractionation of fats and oils catches more and more interest; in this
context, dry fractionation is by far the simplest and cheapest fractional crystallization technique
(no chemicals, no effluent and no losses). The oil processing industry uses dry fractionation to
extend the application of a whole variety of fatty matters as well as to replace, fully or partially,
the chemical modifications. Due to the continuous developments of the dry fractionation process,
a whole variety of products normally produced by solvent fractionation can now be obtained
with a high degree of selectivity with dry fractionation. As the crystallization operates in the
bulk, viscosity problems limit the degree of crystallization in one single step, and multi-step
operations are currently used, giving rise to a wide range of fractions suitable for different
applications. The secret is to combine proper crystal development with highly efficient
separation by using membrane press filters allowing squeezing out the stearin cake for as much
liquid occlusion (olein) as possible. The original booming of the dry fractionation process has
helped mostly palm oil to conquer a strong position on the commodity market in one single
stage; today, palm oil is without doubt the most widely fractionated oil. New demands for special
cuts drifted the industry towards a more sophisticated approach: high-iodine value super and top
oleins, palm red fractions (high carotene and tocopherol/tocotrienol contents) or solvent-free
cocoa butter equivalents (palm mid fractions) are certainly what the future has in store.

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Vronique Gibon
Wim De Greyt
Marc Kellens
De Smet Technologies
and Services,
Zaventem, Belgium
Palm oil refining
Crude palm oil is rich in minor components that impart unique nutritional properties.
The most relevant are tocopherols and tocotrienols (vitamin E) and carotenoids (a- and
b-carotene). Palm oil is generally refined by the physical process, which is preferred
over the chemical process since high acidity (up to 5%) can lead to excessive loss of
neutral oil in the soapstock after alkali neutralization. The quality of the crude oil is to be
considered as it can greatly affect the efficiency of the refining process and the quality
of the end-products. The deterioration of bleachability index (DOBI) is a good indicator
of the capability of palm oil to be successfully refined. Beside commodities, especially
refined oils open a market for new high-quality products like golden palm oil, red palm
oil, white soaps, fractionated products (CBE), etc. Optimization of the deodorization
technology and of the process conditions for a maximal retention of natural char-
acteristics without affecting the quality of the palm oil is an important challenge.
Keywords: Chemical refining, physical refining, crude palm oil quality, DOBI, nutri-
tional quality, carotenoids, tocopherols, tocotrienols.
Eur. J. Lipid Sci. Technol. 109 (2007) 315335 DOI 10.1002/ejlt.200600307 315
1 Introduction
The production of crude oils and fats, by normal opera-
tions of rendering, crushing or solvent extraction, results
in the incorporation of variable amounts of minor com-
ponents like free fatty acids (FFA), partial acylglycerols,
phosphatides, sterols, tocopherols, tocotrienols, hydro-
carbons, pigments, vitamins, sterol glycosides, protein
fragments, traces of pesticides, dioxins, heavy metals,
etc. Not all constituents are undesirable: tocopherols and
tocotrienols, for example, perform the important function
of protecting oil against oxidation and possess vitamin E
activity. The sterols, on the other hand, are colorless, heat
stable and, for all practical purposes, inert; hence, they
pass unnoticed unless present in unusually large
amounts. Unsaturated fatty acids (mainly the poly-
unsaturated ones) are particularly sensitive to oxidation;
this sensitivity is amplified by the presence of metal tra-
ces like iron or copper which should be removed. Phos-
phatides in the crude oil need to be removed because
they will interfere within further processing.
To become acceptable for human consumption, most
oils must be purified. Mainly, a light color, a bland taste
and a good and oxidative stability are required. To
achieve this, the oils are submitted to several treatments.
The objective of the refining is to remove the objection-
able minor constituents in the oil with the least possible
damage to the acylglycerols and minimal loss of the
desirable constituents.
2 Minor components of crude palm oil
As a fruit flesh oil, palm oil is produced at the oil mill by
cooking, pressing and clarification. The quality of the
crude oil will affect the efficiency and yield of refining and
the quality of the fully processed product.
The minor components of palm oil have been reviewed by
Berger [1]; beside triacylglycerols, the remaining compo-
nents consist in a multitude of chemical entities, some of
them having actual or potential commercial value.
2.1 FFA and partial acylglycerols
In over-ripe fruits or during harvesting, a very active
lipase, most probably originating from yeast cells, will be
responsible for increased production of FFA and partial
acylglycerols. While it is possible to obtain a crude palm
oil with only 0.02% FFA from fresh ripe fruit, the acidity of
commercial crude palm oils is on average about 3.5%.
The monoacylglycerol (MAG) content in crude palm oil is
very low (below 0.5%). Jacobsberg and Oh [2] reported a
total diacyglycerol (DAG) concentration in crude palm oils
ranging from 5.3 to 7.7%. They also noticed no correlation
between FFA, MAG and DAG contents: DAG found in
crude palm oil is probably a residual by-product of the
Correspondence: Vronique Gibon, De Smet Technologies and
Services, Da Vincilaan, 2 Bus G1, 1935 Zaventem, Belgium.
Phone: 132 2 716 1111, Fax: 132 2 716 1109, e-mail: giv@
desmetgroup.com
2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.ejlst.com
Review Article
316 V. Gibon et al. Eur. J. Lipid Sci. Technol. 109 (2007) 315335
biosynthesis of the TAG. These observations have been
confirmed by Goh and Timms [3] who also reported a
significant correlation (based on a statistical study) be-
tween MAG and DAG. More 1,3-DAG than 1,2-DAG iso-
mers (in a proportion of about 2 : 1) are observed in all
crude oils.
2.2 Phosphatides and glycolipids
According to Goh et al. [4], the main phosphatide com-
ponent in palm oil is phosphatidylcholine and the major
glycolipid is galactosyldiacylglycerol. On the other hand,
Kulkarni et al. [5] have shown that Indian crude palm oil
contains (beside phosphatidycholine) phosphatidyletha-
nolamine, phosphatidylinositol (more than 20% each)
and, in lower quantities, phosphatidylglycerol. A detailed
study of phosphatides in crude palm oil showed that most
of the phosphorus determined in the oil is in fact inorganic
phosphate rather than from phospholipids. Typically, the
inorganic phosphorus content is eight times that of the
phospholipid phosphorus. Detailed studies of these two
forms of phosphorus compounds in crude palm oil indi-
cate that they are unlikely to be the direct cause of some
oil quality problems such as poor bleachability or
increased susceptibility to oxidation. The inorganic phos-
phate presumably arises from the degradation of phos-
phatides by phospholipases and further chemical trans-
formation [6].
2.3 Tocopherols and tocotrienols
Characteristic of crude palm oil is its high content in
tocotrienols (mainly g-, a- and d-tocotrienols). g-Toco-
pherol and a-tocopherol are the main tocopherols[1], with
the total content (tocopherols and tocotrienols) ranging
from 600 to 1000 ppm [4]; the tocopherol/tocotrienol ratio
is usually around 20%. Compared to other oils, palm oil
has a high proportion of tocopherols and tocotrienols in
relation to its unsaturation; the ratio tocopherols 1toco-
trienols (ppm) to polyunsaturated fatty acids (PUFA)
(expressed in %) is about 50 (while it is only 19 for soy-
bean and 12 for sunflower oils). Conjugated effects of
high tocopherols and tocotrienols and low PUFA could
explain why palm oil would present a greater oxidative
stability, for instance, in frying [1].
2.4 Carotenoids
As its deep red color testifies, crude palm oil is a rich
source of carotenoid components (5002000 ppm). a-
Carotene and mainly b-carotene are the main constitu-
ents (about 90% of the total) [7]. Light-colored crude palm
oil demonstrates a low carotene content and suggests
high oxidation of the crude oil. A spectrophotometric
method is available to determine the carotene content of
palm oil using n-hexane as solvent; the absorbance close
to 450 nm multiplied by an empirical factor 427 is fre-
quently used to express carotene in ppm.
Carotenoids (and in particular b-carotene) are known for
their pro-vitamin A activity and are strongly associated
with the prevention of certain types of cancer [4]. Most of
the carotenoids in palm oil are destroyed during the
refining process, giving rise to light-colored products.
Various methods of extraction and recovery of car-
otenoids from crude palm oil are described, including
saponification, adsorption, precipitation, solvent extrac-
tion, molecular distillation and transesterification.
2.5 Sterols, methylsterols, triterpene and
isoprenoid alcohols and hydrocarbons
The total sterol content in crude palm oil is around 500 ppm
[7]. b-Sitosterol is the most abundant sterol (up to 60%).
Campesterol, stigmasterol and cholesterol are observed in
lower quantities. Sterols are observed as free or esterified
(50 : 50) [1]; free and mainly acylated sterol glucosides are
also detected (up to 300 ppm). Methylsterols and tri-
terpene alcohols are present at a concentration of
800 ppm. Isoprenoid alcohol in crude palm oil is about
80 ppm. Squalene, which is the major hydrocarbon in
crude palm oil, ranges between 200 and 500 ppm; the
content in non-terpene hydrocarbon is about 3050 ppm.
Crude palm oil contains also 1080 ppm of ubiquinone-10
and 5 ppm of ubiquinone-5, which are related to vitamin K
and have antioxidant properties [1].
3 Crude palm oil quality
Important aspects of the quality of the crude feedstock
have to be considered in that they affect the refining pro-
cess (effect of ripeness, storage, transportation, etc.).The
chemical and physical properties of Malaysian crude
palm oil have been thoroughly determined from several
surveys and the data have been incorporated in stand-
ards (Tabs. 1 and 2) [8, 9].
3.1 FFA content
A powerful hydrolytic enzyme is present on the exterior of
the palm fruits, and if it is not deactivated promptly after
harvesting, any oil escaping from damaged fruits or dur-
ing processing splits rapidly into FFA and partial
acylglycerols.
2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.ejlst.com
Eur. J. Lipid Sci. Technol. 109 (2007) 315335 Palm oil refining 317
Tab. 1. Quality requirements for crude palm oil (source:
MS 814/1994) [8].
Characteristics Special
quality
(SQ) grade
Standard
quality
I
Standard
quality
II
FFA (as palmitic) [% max] 2.5 3.5 5.0
Moisture and impurities
[% max]
0.25 0.25 0.25
Peroxide value [meq O2/kg max] 2.0
Anisidine value (max) 4.0
DOBI [min] 2.8 2.5 2.2
Tab. 2. Specifications for crude palm oil [9].
Special
grade
Lotox Standard Contractual
FFA (as palmitic) [% max] 2.5 2.5 3.5 5.0
Moisture [% max] 0.2 0.2 0.2 Basis pure
Impurities [% max] 0.02 0.02 0.02 Basis pure
Peroxide value
[meq O2/kg max]
33 5
Anisidine value (max) 4 3.5
Carotene [ppm max] 600700
Fe [ppm max] 4 4 5
Cu [ppm max] 0.02 0.2 0.2
Freshly expelled crude palm oil, promptly dried and
cooled, will show low hydrolysis and oxidation. Crude
palm oil can be produced at less than 2.5% FFA and
0.15% H20; at this moisture level, both hydrolysis and
oxidation are slowed [10, 11]. An FFA content below
3% gives some guarantee that fresh and unbruised
fruits were used and that the crude oil was stored and
transported under good conditions. Too high levels
(together with high iron and copper picked up during
storage and transportation) will lead to too high oxida-
tion [12].
3.2 Phosphatide content
The phosphorus content of crude palm oil is quite vari-
able, both in amount and in quality. Normally in the range
of 1020 ppm, values less than 5 ppm have been reported
as well as values exceeding 30 ppm. As already men-
tioned, only 1030% of this phosphorus occurs as phos-
phatides; the major content being described as inorganic.
The exact nature of this phosphorus component is still
unknown [4, 6].
3.3 Oxidation products and metal traces
Values as low as a peroxide value (PV) of 4 meq O2/kg, an
anisidine value (AnV) of 4, iron of 3 ppm and copper of
0.1 ppm are desirable in the crude oil. Whereas in 1970
crude palm oil at a maximum content of 10 ppm iron and
0.2 ppm copper was commonly offered, good crude palm
oil at a maximum of 3 ppm iron and 0.02 ppm copper is
available today. Copper is particularly unwanted as
quantities below 0.02 ppm are capable of encouraging
oxidative attack [13]: copper is considered as ten times
more active as pro-oxidant than is iron. Contamination
with trace metals mainly arises because of mechanical
wear and corrosion at the oil mill or during storage and
transportation; use of stainless steel can greatly reduce
this level. Also, oil recovered from effluent treatment is
particularly rich in iron [9].
As specified before, crude palm oils of several grades are
commercially available, with the FFA content varying be-
tween 2.8 and 5%. High FFA levels generally result in high
iron and copper levels, picked up during transportation
and storage, resulting in an acceleration of oxidation and
an increase in Totox (two times PV 1AnV) which cannot
be sufficiently reduced during refining.
Refiners using good-quality palm oil can easily fulfill the
requirements of a good-quality refined oil based on FFA,
iron, copper and color. But the Totox value seems to be
critical: because transport conditions are governed more
by commercial requirements than by quality require-
ments, this value can increase greatly during transporta-
tion, obliging the European refiners to re-treat the already
processed oil.
3.4 Oxidized carotenoids
Good-quality crude palm oils of different origins show
absorption peaks in the region of 458 nm (UV spectros-
copy) due to carotenoids. Modest deviations from a pre-
cise absorption pattern are explicable by some variation
in the carotenoids present in different species. If the crude
oil has suffered from damage, the height of the absorption
peak is diminished and a displacement towards 450 nm is
observed [13]. Low-grade crude palm oils may suffer
autoxidation of the carotenoids, giving rise to off-flavors.
It is also shown that carotene has a pro-oxidant behavior
that can overcome the positive effect of up to 0.1% of
tocopherols and tocotrienols as scavengers of oxygen-
free radicals [14].
Nitrogen blanketing of storage tanks during transporta-
tion retards oxidation. Antioxidants can be added to the
crude oil (combination of TBHQ and citric acid), assuring
2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.ejlst.com
318 V. Gibon et al. Eur. J. Lipid Sci. Technol. 109 (2007) 315335
a better color of the oil after refining and allowing the
reduction of bleaching earth consumption because the
amount of oxidized crude oil has been substantially
reduced [11].
3.5 Deterioration of bleachability index
The deterioration of bleachability index (DOBI) is a good
test to assess the quality of a crude palm oil [15]. The
DOBI is basically the ratio between the content of car-
otenes (measured at 446 nm) and secondary oxidation
products (measured at 269 nm). Practically, the crude oil
is dissolved in iso-octane or n-hexane and the absorb-
ance at 269 nm and 446 nm is measured. It must be said
that the DOBI is now recognized as an ISO method [ISO
7932:2005].
DOBI Absorbance at 446 nm
Absorbance at 269 nm
An arbitrary scale has been suggested [13]:
DOBI 3.25 (very satisfactory quality); DOBI =62.75
(average quality); DOBI ,2.0 (very poor oil).
However, other sources [16] propose less severe classifi-
cations:
DOBI .2.3 (more easily refined); DOBI = 2.02.3 (unpre-
dictable); DOBI ,2.0 (difficult to refine).
4 Refining practices for crude palm oil
Crude oils are refined to remove all impurities such as
undesirable odor, flavor and color, but at the same time
retaining the beneficial components such as vitamins,
pro-vitamins and antioxidants. Refining can be operated
according to two main routes: chemical refining or physi-
cal refining. The principal difference between the two
routes is how the FFA are removed. In a physical opera-
tion, most FFA are removed in the deodorizing unit; oper-
ating conditions (temperature, vacuum and steam) are
carefully selected in order to allow removal of the acids; a
well-designed deodorizer operating at an acceptable
efficiency will reduce the costs of the process. As distilla-
tion requires a high-temperature treatment, the oil must
be carefully degummed and bleached before entering the
deodorizing unit. At the opposite, if the chemical refining
option is chosen, the oil is cleared from gums and FFA
during the alkali neutralization step and soapstocks are
produced. More than 95% of crude palm oil in Malaysia is
refined through the physical route [refined, bleached and
deodorized (RBD) palm oil].
The physical refining process can offer important advan-
tages to the refiner, such as higher oil yield, reduction of
the use of chemicals (like phosphoric acid, sulfuric acid
and caustic soda), reduction of water and effluent, and
hence considerable reduction of the environmental
impact [17, 18]. Unfortunately, bleaching earth consump-
tion will be higher.
The final choice between chemical and physical refining
will depend on a number of factors: the quality and the
acidity of the crude oil, the ability to get rid of the soap-
stock, and local environment legislation. Although physi-
cal refining can be applied to almost any quality of crude
oil, the process more depends on the crude oil quality
than chemical refining. This can be explained by the fact
that a wide range of undesirable products is much more
easily removed by alkali neutralization than by degum-
ming.
For crude palm oil with low phosphatides, high initial FFA
(up to 5%) and high carotene content, physical refining is
preferred in terms of operating costs and refining losses;
deodorization at reduced temperature and improved
vacuum are an alternative when retention of minor com-
ponents like tocopherols and tocotrienols is important.
Chemical refining is still used at a limited capacity [neu-
tralized, bleached and deodorized (NBD) palm oil]. Crude
palm oil is mixed with citric or phosphoric acid for easy
removal of gums prior to neutralization of the FFA. Neu-
tralized oil is separated from the soapstock by cen-
trifugation; the neutralized oil is then washed with warm
water to reduce the residual soaps and dried under
vacuum, before proceeding to bleaching and deodoriza-
tion.
5 Physical refining practices
5.1 Degumming
Water degumming is the simplest method for phospha-
tide reduction. However, mainly the hydratable phospha-
tides [phosphatidyl choline (PC) and phosphatidyl inositol
(PI)] can be removed by mixing the oil just with water.
Oils with a low content in phosphatides can be degum-
med straight according to a wet acid degumming tech-
nique. The hot crude oil (8090 7C) is thoroughly mixed
with phosphoric or citric acid, followed by a retention time
of approximately 520 min; then 25% water is mixed
with the oil before going to a centrifugal separation. In
fact, one common property of phospholipids is that they
form hydrates in contact with water, and these hydrates
are insoluble in oil. The rate of hydration of phospholipids
varies substantially at 80 7C. PC and PI hydrate very fast
while phosphatidic acid (PA) and phosphatidyl ethanola-
mine (PE) (mainly present as calcium and/or magnesium
2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.ejlst.com
Eur. J. Lipid Sci. Technol. 109 (2007) 315335 Palm oil refining 319
salts) react considerably more slowly with water. The PC
hydrate is not only rapidly formed but it can also encap-
sulate PA 1PE 1PI at about 80% of its own weight [19].
This means that when the phospholipids in the crude oil
contain about 55% PC, they all can be removed by fast
hydration at elevated temperature. If the phospholipids
contain only about 3035% PC, fast hydration will give
only partial removal of the slowly hydrating phospholip-
ids. An acceleration of the rates of hydration of the cal-
cium and magnesium salts of PA and PE can be obtained
by addition of a strong acid prior to hydration. This
explains the varied performance of wet acid degumming
according to the composition of the gums. Wet acid
degumming is mainly used for crude palm oils with high
phosphatide and iron contents.
Soft degumming [20] is another option to remove phos-
phatides from crude palm oil with high phosphatide and
iron contents. In this case, the oil is heated (7585 7C) and
mixed with a water solution (2%) containinga complexing
molecule [ethylene diamine tetracetic acid (EDTA)] and,
eventually, a wetting compound [sodium dodecyl sulfate
(SDS)]. EDTA is able to form strong chelates with magne-
sium, calcium and iron. As a consequence, non hydrat-
able phospholipids will be more easily removed. After
20 min of retention time followed by centrifugation, less
than 1 ppm of phosphorus can be achieved. Iron is
reduced to below 0.1 ppm as it forms an oil-insoluble
complex with EDTA.
For palm oil, dry degumming is the most common way.
Classically, crude palm oil is first mixed with about 0.05
0.1% concentrated phosphoric acid; after a short reten-
tion time, about 1 or 2% acid-activated bleaching earth is
added under vacuum at a temperature of 80120 7C. After
a suitable contact time, the spent earth is removed by fil-
tration. The phosphoric acid disrupts non-hydratable
phosphatides by decomposing magnesium and calcium
complexes; it coagulates the phosphatides, sequestrates
iron and copper, before being removed by adsorption on
bleaching earth. Sometimes citric acid is also used, but
due to economical reasons, phosphoric acid is mainly
used by Malaysian refiners. The amount of acid intro-
duced into the oil is quite critical: under- or over-dosage
may lead to darkening of the oil during deodorization.
Phosphatides (due to low acid dosage) break down at the
deodorization temperature, leading to darkening and off-
flavor problems [13]. An excess of phosphoric acid (over-
dosage) also promotes darkening of the RBD palm oil
[21].
When using concentrated phosphoric acid with 85%
strength (commonly 0.050.1%), there is a danger to
promote phosphorylation of some triacylglycerols (lipo-
philic phosphorus) [13, 16]. Sometimes, calcium carbon-
ate is added to neutralize any remaining phosphoric acid
before filtering, but this is not good since non-hydratable
calcium phosphatides are formed, leading to less satis-
factory phosphorus removal [22]; when strong phosphor-
ic acid is used (85%), iron removal seems to be more dif-
ficult [23]. These problems can be avoided by using citric
acid (0.05 wt-% dose of citric acid as a 30 or 50% solu-
tion in water), a mixture of phosphoric and citric acids
(2 : 1), or a diluted phosphoric acid solution (.50%).
Adsorptive cleansing should reduce the phosphorus level
to an acceptable limit (below 2 ppm), lower the trace
metal content (Fe ,0.1 ppm) and minimize oxidation
products. The color of palm oil after earth bleaching alone
seems to be not important as carotenoids are known to
be efficiently thermally bleached under the conditions of
deodorization. After 20 min at 180 7C, half the carotene
has disappeared, at 200 7C about 70%, and at 240 7C
more than 98% [24, 25].
At a certain moment, the question was raised as to
whether the thermal bleaching and deodorization of palm
oil at temperatures around 270 7C for a few minutes or at
220240 7C for longer times give rise to polycyclic aro-
matic hydrocarbons from the carotenoid pigments; it is
now clear that this effect should be negligible [4, 26].
5.2 Bleaching
Adsorptive bleaching is an integral part of the process of
refining edible oils and can only exceptionally be omitted
if the oil to be refined is very low in components requiring
removal.
5.2.1 Principle
The removal of minor components through adsorptive
bleaching is based on several adsorption mechanisms.
Part of the coloring pigments (carotenoids in the case of
palm oil) are physically adsorbed on the bleaching clays,
involving Van der Waals surface attraction forces. Other
components are chemically bound to the bleaching clay
surface via covalent or ionic bonds. Part of the impurities
is removed through molecular entrapment in the porous
structure of the clays. During bleaching, some minor
components are chemically altered due to the catalytic
activity of the clays: a typical example is the decomposi-
tion of the hydroperoxides into unsaturated conjugated
products.
The most important factors affecting absorptive bleach-
ing are temperature and humidity, but the structure (par-
ticle size distribution) and the type of bleaching earth
[heat- (neutral) or acid-activated] also play a crucial role.
2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim www.ejlst.com
320 V. Gibon et al. Eur. J. Lipid Sci. Technol. 109 (2007) 315335
Neutral bleaching clays are aluminum silicates which
contain relatively high amounts of calcium, magnesium or
iron. These clays are normally activated through heat
treatment; the high metal content limits the adsorptive
activity of these clays. The metals can be removed from
the reactive spots by means of an acid treatment, result-
ing in acid-activated clays with a much higher adsorptive
capacity. It is generally assumed that the spent filter cake
contains about 2030 wt-% oil, but is has been proved
[27] that the amount of neutral oil losses when disposing
of the cakes is considerably higher than generally recog-
nized (above 45%).
5.2.2 Bleaching process
The bleaching process is by far the most expensive pro-
cess in refining when considering the utility costs. The
relatively high cost of the bleaching clays as well as the
oil-in-earth losses and bleaching adsorbent disposal
costs largely affect the operating cost of a bleaching
plant.
The strong environmental regulations are also forcing all
refiners to reduce as much as possible the solid waste
streams as they are difficult to treat. Several bleaching
processes have been developed over the years to reduce
the bleaching earth consumption.
Bleaching is performed in several stages:
Prior to bleaching, the oil is properly deaerated and dried
under reduced pressure (,100 mbar) to a moisture con-
tent of 0.1%. Deaerated bleaching earth is added to the
oil under controlled conditions of temperature, acidity and
humidity for a specific residence time (2030 min). The
bleaching clay is dosed directly to the oil or in a slurry
form (pre-mix of oil with bleaching earth). It is of great
importance that both oil and bleaching earth are free from
oxygen before mixing, to avoid oxidation and hence
deterioration of the oil. The oil is further heated under
reduced pressure and intensively mixed, sometimes by
injection of steam to ensure intimate contact between the
bleaching earth and the oil. Finally, the mixture is trans-
ferred to a filter, usually a hermetic leaf filter (horizontal or
vertical) with stainless-steel mesh elements, followed by
polishing filtration. The first oil that passes through the
leaf filter is normally recycled back to the bleacher vessel
as it may still contain too much bleaching earth. The
bleached oil is afterwards diverted to the bleached oil
storage tanks and kept under nitrogen. Bleaching filtra-
tion is sometimes improved with a pre-coat of diatomac-
eous earth. The spent bleaching earth cake is blown by
steam or nitrogen to recover as much as possible the
entrained oil from the cake.
5.2.3 Single-step bleaching
The oldest method of bleaching, which is still followed in
various bleaching plants, is the batch bleaching where all
operations are executed in the same vessel (except for
the filtration).
Continuous vacuum bleaching protects the oil from oxi-
dation since deaeration is more efficient. The total holding
time of the oil is much shorter, which minimizes the risk of
unwanted side reactions such as conversion of soaps into
FFA in the case of acid bleaching earth. Another benefit of
continuous bleaching is the energy savings that can be
obtained by heat recovery. In the case of dry degumming
of crude palm oil, there is no separate degumming step;
the acid-activated phosphatides are adsorbed on the
bleaching clay and as such removed from the oil (Fig. 1).
5.2.4 Multi-step bleaching
In order to reduce bleaching earth consumption, alter-
native multi-step bleaching processes have been devel-
oped.
The most known are the two-stage co-current and coun-
ter-current bleaching processes.
The co-current process is the least complicated and less
performing two-stage process: bleaching earth is added
in two consecutive stages to the oil, with a filtration after
every stage. The counter-current bleaching process is the
most efficient (Fig. 2). In this process, the spent bleached
earth from the second bleaching stage is re-used in the
first stage. The efficiency of the counter-current process
is largely affected by the way the filtration with spent
bleaching clay is performed. The easiest way is to use a
third filter operating in counter-current at the inlet of the
bleacher. The pre-filtration of the oil through the spent
bleaching clay cakes in the filter, built up during the sec-
ond bleaching stage, already results in a saving of 10
15% bleaching earth as compared to conventional single-
stage bleaching. The main function of pre-filtration is to
remove all solid impurities as well as to absorb most of
the phosphatides and soaps. This allows a more efficient
bleaching in the second stage. Even more efficient than
the counter-current pre-filtration process is the Oehmi
process [28] which guarantees savings up to 40%. This
process features two bleachers and two sets of filters
(Fig. 3). The spent bleaching clay of the second filtration is
mixed back into the degummed oil in a specific manner
and subsequently filtered. It is interesting to note that over
60% of the undesirable substances are removed in the
first process stage.
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Eur. J. Lipid Sci. Technol. 109 (2007) 315335 Palm oil refining 321
Fig. 1. Classical single-stage bleaching (continuous vacuum bleaching with acid pre-treatment)
[17].
Fig. 2. Two-stage counter-current bleaching with pre-filtration.
For palm oil, bleaching earth consumption has been
quantified with conventional single-stage and counter-
current processes [17]. A bleaching earth consumption of
1% can be reduced to 0.8% with a conventional pre-fil-
tration, and up to 0.6% with the full counter-current sys-
tem.
Recently, a multi-stage modular bleaching system
(Combiclean) has been developed [29]. Basically, it
combines silica pre-treatment, pre-filtration with spent
bleaching clays, bleaching, and eventually activated-car-
bon post-treatment (Fig. 4). Savings of up to 30% are
reported. Pre-treatment with silica is particularly interest-
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322 V. Gibon et al. Eur. J. Lipid Sci. Technol. 109 (2007) 315335
Fig. 3. Two-stage counter-current bleaching according to
the Oehmi principle. (1) Bleacher 1 (pre-bleaching),
(2) pump, (3) pump, (4) bleacher 2 (final bleaching),
(5) mixer, (6) bleaching earth doser, and (7) filter [32].
ing to selectively remove phosphatides and soaps if cer-
tain unwanted minor components have to be considered.
In some cases, active carbon is applied to take out non-
volatile contaminants such as high-molecular-weight
polycyclic aromatic hydrocarbons or dioxins. Active car-
bon is added together with bleaching earths or mixed with
the bleached oil after bleaching. Full separation of
bleaching clays and active carbon is preferred as it results
in two separated waste streams: non-toxic spent bleach-
ing earth and potentially toxic spent activated carbon.
Such separation may be important for further utilization or
disposal. On top of that, active-carbon consumption is
reduced by 50%.
5.2.5 Packed (fixed)-bed bleaching
Packed- (or fixed-) bed bleaching is used in some re-
fineries; it refers to pre-loading all or some of the bleach-
ing earth on a filter and pressing the oil through the
packed-bed instead of continuously mixing all the earth
with oil [13]. This ensures the optimum use of the bleach-
ing earth by pre-coating it onto a filter in the form of a
short, wide chromatography column [27]. Silica adsor-
bents are mainly used in combination with bleaching
earth to prevent blocking of the oil flow due to soaps and
phosphatides; in this case, the filter cake consists of two
layers: a first layer with silica and a second layer with
bleaching earths. Residual bleaching capacity is con-
tinuously monitored by on-line measurement of a specific
component; when this capacity has been reached, the
filter is cleaned in the normal way and re-coated.
5.2.6 Wet and dry bleaching
Continuous bleaching units are often operating by means
of the wet bleaching concept. With wet bleaching, the
removal is more effective and the consumption of
bleaching earths can be reduced. It is known that during
bleaching, soaps are converted into FFA due to the acidic
Fig. 4. Multi-stage modular bleaching (Combiclean) [29].
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Eur. J. Lipid Sci. Technol. 109 (2007) 315335 Palm oil refining 323
properties of the bleaching earth. Another side reaction
that can occur during bleaching, in case the oils are not
sufficiently dried or the earths are still too wet, is the
hydrolysis of TAG that will increase the DAG and FFA
contents [30]. The second side reaction can be avoided
by simply drying the oil before bleaching and assuring
that the bleaching earths are not too wet. Nevertheless, it
can be desirable that the oil contains sufficient amount of
water when bleaching earth is added. During the so-
called wet bleaching [31], non-hydratable phosphatides
are hydrated in the presence of chelating acids and water;
the presence of water will increase the cation exchange
capacity of the bleaching earth. The best performance is
observed for an amount of water of about 50100% of the
amount of bleaching earth, which is not always econom-
ically acceptable. In wet bleaching, the materials are
allowed to come into contact with each other under at-
mospheric pressure for 20 min at about 7090 7C. This is
followed by the usual bleaching process under vacuum
for 1530 min. During this step, the excess water evapo-
rates so that the bleaching earth can be filtered without
problems.
Certain silica gels with a water content of 6070% can
also be used instead of wet bleaching to remove phos-
phatides. Compared to the normal bleaching earths,
these materials have a much higher adsorption capacity
for phosphatides, soaps and metal traces and can par-
tially replace the bleaching earths. However, pigments
(chlorophyll, carotenoids) are weakly adsorbed by these
silical gels [32].
5.2.7 Residual phosphorus content after
bleaching
After bleaching, the oil should be almost free from phos-
phorus, iron and copper.
According to Zschau [32], the efficiency of phosphorus
removal in dry degumming of palm oil depends on the
conditions chosen; temperatures below 120 7C and acti-
vation of phosphatides with diluted phosphoric acid or
with citric acid are preferred (Tab. 3). If instead of phos-
phoric or citric acid, pure water (up to 1.5%) is added at
the same time as the clays at atmospheric pressure (wet
bleaching), phosphorus removal is very efficient; the data
correlate with the quantity of water (Tab. 4) [32]. Indeed,
the clays have also acidic properties and ion exchange
capacity and could take the role of phosphoric and citric
acids. When quite concentrated phosphoric acid is used
(.75%), there is a critical relationship between the acid
and bleaching earth dosages and the residual phos-
phorus content (Tab. 5) [33].
Tab. 3. Influence of temperature and acid (concentration
and type) on residual phosphorus content (ppm) of
bleached palm oil$[32].
Temperature
[7C]
0.15% Phosphoric
acid (85%
solution)
0.15% Phosphoric
acid (10%
solution)
1.5% Citric
acid (10%
solution)
90 9.8 3.3 1.7
120 21.1 3.6 1.3
150 38.8 3.7 3.4
$Crude palm oil: P: 9.9 ppm; FFA: 5.6% (as palmitic).
Bleaching earth: 1.5% Tonsil Supreme FF.
Calcium carbonate used after phosphoric acid treatment.
Tab. 4. Influence of added water and temperature on
residual phosphorus content (ppm) of bleached palm oil$
[32].
Temperature
[7C]
0%
Water
0.5%
Water
1.0%
Water
1.5%
Water
120 8.5 5.3 3.2 2.7
135 6.8 4.5 3.0 2.9
150 6.6 4.0 2.5 3.2
$Crude palm oil: P: 17.1 ppm.
Bleaching earth: Tonsil Supreme FF.
5.2.8 Adsorption of pigments
In the physical refining of crude palm oil, full reduction of
carotene by bleaching is not necessary as carotenoids
are mainly decomposed by heat during deacidification
(heat bleaching; see Section 5.1).
When palm oil is to be used for biodiesel production, the
color is of minor importance; removal of phosphatides is
then the most critical aspect of the pre-treatment; in this
case, the addition of bleaching earth might not be neces-
sary and simple acid washing or soft degumming is a
suitable alternative option (Tab. 6) [33].
Rossi et al. [34] have studied the effect of bleaching on the
color of degummed palm oil. Five concentrations of one
neutral and two acid-activated bleaching clays mixed
with a fixed amount of synthetic silica were used for
bleaching (110 7C, 20 min under vacuum) after acid
degumming. Neutral bleaching clays seem to be less
efficient than acid-activated clays to remove carotenoids
(Tab. 7). For the activated clays, pigment removal clearly
increases with the amount.
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324 V. Gibon et al. Eur. J. Lipid Sci. Technol. 109 (2007) 315335
Tab. 5. Influence of acid dosage on dry degumming effi-
ciency of crude palm oil [33].
0.07% Phosphoric acid (75%); 1% Tyco Classic bleaching earth
Crude palm oil Degummed palm oil
FFA (as palmitic) [%] 5.68
P [ppm] 17.5 4.6
Fe [ppm] 7.5 0.1
Ca [ppm] 18.2 0.2
Mg [ppm] 4.9 0.1
0.055% Phosphoric acid (75%); 1% Tyco Classic bleaching earth
Crude palm oil Degummed palm oil
FFA (as palmitic) [%] 3.94
P [ppm] 13.6 1.7
Fe [ppm] 3.2 0.04
Ca [ppm] 12.7 0.2
Mg [ppm] 3.7 0.02
0.045% Phosphoric acid (75%); 1% Tyco Classic bleaching earth
Crude palm oil Degummed palm oil
FFA (as palmitic) [%] 5.04
P [ppm] 16.0 1.4
Fe [ppm] 5.3 0.2
Ca [ppm] 19.2 0.3
Mg [ppm] 3.6 0.05
0.03% Phosphoric acid (75%); 1% Tyco Classic bleaching earth
Crude palm oil Degummed palm oil
FFA (as palmitic) [%] 4.38
P [ppm] 17.1 not detected
Fe [ppm] 6.2 0.1
Ca [ppm] 14.0 0.2
Mg [ppm] 4.5 0.1
Tab. 6. Influence of several pre-treatments on residual
phosphorus content of crude palm oil [33].
Pre-treatment Residual P Residual Fe
Water washing$13 10
Acid water washing$64
Soft degumming2.5 0.5
Acid conditioning followed by
partial caustic treatment and
water washing$
7.5 1
$Crude palm oil: FFA: 4.8%; P: 16.0 ppm; Fe: 13.0 ppm.
Crude palm oil: FFA: 4.8%; P: 13.7 ppm; Fe: 3.8 ppm.
5.2.9 Catalytic properties of bleaching earths
Some reactions observed during bleaching can be clearly
attributed to the catalytic properties of the clays. The
most important one is the decomposition of hydroper
Tab. 7. Influence of degumming and bleaching earth
quality and quantity on carotenoid retention (ppm) in palm
oil (bleaching conditions: 110 7C, 50 mbar, 20 min;
0.125% synthetic silica added to the bleaching clays)
[34].
Treatment Carotenoids
[ppm]
Crude palm oil 455.8
Acid-degummed palm oil 415.0
Bleached with acid-activated clay 1:
0.5% bleaching clay 1 297.0
0.75% bleaching clay 1 245.8
1.0% bleaching clay 1 223.4
Bleached with acid-activated clay 2:
0.5% bleaching clay 2 327.9
0.75% bleaching clay 2 313.9
1.0% bleaching clay 2 258.6
Bleached with neutral clay:
0.5% neutral clay 324.4
0.75% neutral clay 329.9
1.0% neutral clay 304.0
oxides; while PV decrease rapidly during bleaching, AnV
only decline. This leads to the reasonable deduction that
the catalytic decomposition of peroxides is preferred over
the adsorption of aldehydes and ketones on the active
site of the clays [13]. It is described that oils refined using
acid-activated earth during bleaching have a better final
acidity and oxidative stability than oils refined using non-
acid-activated earth [35]. It has also been reported that
refined oil bleached with low-quality clay exhibits less
stability in color, FFA and peroxides [30].
Conjugated dienes and trienes are formed during bleach-
ing of palm oil as a result of the decomposition of hydro-
peroxides [36]. For a given oil, the amount of conjugated
dienes, measurable at 233 nm, is related to the bleaching
earth dosage; bleaching earth below 1% seems to allow
less formation of conjugated dienes. An increase of con-
jugated trienes during bleaching depends on the crude
palm oil quality, independently of the bleaching earth
used. Some of these conjugated trienes can be removed
later during deodorization. Low conjugated dienes and
trienes in the refined oil are an indicator of mild refining
conditions and good-quality crude oil.
5.2.10 Irradiation bleaching
Recently, irradiation bleaching has been described [37]
on red palm oil, palm olein and palm stearin. The bleach-
ing level achieved by irradiation is comparable to the
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Eur. J. Lipid Sci. Technol. 109 (2007) 315335 Palm oil refining 325
bleaching achieved by heating. The general quality of the
resulting oils is better if they are bleached with irradiation,
as the amount of the polar fraction resulting from irradia-
tion is minimal relative to that found in heat-treated oil.
The conclusion is that infrared bleaching is economically
more viable than solar irradiation techniques and heat
bleaching, as it can be performed easily with no oil losses
and less energy consumption.
5.3 Deodorization
5.3.1 Process parameters and conditions
Deodorization is basically a vacuum steam stripping at
elevated temperature, during which FFA and volatile odi-
ferous components are removed to obtain a bland and
odorless oil. Although the process is commonly named
deodorization, it is actually a combination of three dif-
ferent operations: (a) distillation, i.e. stripping of volatile
components (FFA, tocopherols, tocotrienols, sterols and
contaminants like pesticides or light polycyclic aromatic
hydrocarbons, etc.); (b) actual deodorization, i.e. removal
of odoriferous components; and (c) heating effect, i.e.
thermal destruction of pigments (carotenoids) while
maintaining low side reactions such as cis-trans iso-
merization, polymerization, etc.
Optimal deodorizing parameters (temperature, operating
pressure and amount of stripping gas) are determined by
the type of oil and the selected refining process (chemical
or physical refining), but also by the deodorizer design.
Physical refining requires more severe conditions than
chemical refining. This is mainly because of the distillative
removal of the FFA, which is more critical in physical
refining as the initial FFA levels are considerably higher.
5.3.2 Theory
The stripping medium requirements are described by the
following mathematical equation derived from Daltons
and Raoults laws.
S
OPt
E:P0
i
:ln Va
V0Pt
E:P0
i 1
!
:Va Vo(1)
whereby S= total moles of steam; O= total moles of oil; Pt
= total pressure; Pio= vapor pressure of a given fatty
acid i; E= vaporization efficiency; Va= initial molar con-
centration of the volatile component in the oil; and V0=
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, (VaV0) becomes so small that
Eq. (1) can be simplified to:
S
OPt
E:P0
i
:ln Va
V0(2)
In the case of physical refining, the partial pressure of the
fatty acids cannot be neglected, and omitting the term
(VaV0) would lead to a considerable underestimation of
the stripping medium requirements.
This simplified Eq. (2) is also known as the Bailey Equa-
tion. It states that the amount of steam required for deo-
dorization or physical deacidification is directly propor-
tional to the amount of oil and the absolute pressure in the
deodorizer and inversely proportional to the vapor pres-
sure of the pure volatile component at the process tem-
perature and the overall vaporization efficiency E.
The last factor in Eq. (2) (ln Va/V0) indicates that it is
impossible to eliminate all volatile components from the
oil, since this would require an infinite amount of stripping
medium.
5.3.3 Deodorizer systems
Deodorization can be conducted in different ways (batch,
semi-continuous and continuous) [38]. The selection of
the most appropriate deodorizer technology depends on
many factors, such as the oil quality requirements, the
number of feedstock changes, heat recovery, investment
and operating costs.
Batch deodorization is especially suitable for small ca-
pacities, irregular production, or in processing small
batches of different oils. Semi-continuous deodorizers
are basically batch operating systems designed for larger
capacities. In most designs, a batch of oil is transferred
into the system and then sent by gravity in a time
sequence through a number of vertically stacked com-
partments or trays.
Continuous deodorizers are most preferred by high-ca-
pacity plants with few stock changes. The main advan-
tages are the moderate investment costs, the possible
high heat recovery and the easy maintenance. Vertical
tray-type deodorizers are probably the most used type of
continuous deodorizers (Fig. 5). 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.
All operations, heating, deodorization and heat recovery,
are combined in a single vessel. All different deodorizer
designs attempt to provide the best contact between the
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326 V. Gibon et al. Eur. J. Lipid Sci. Technol. 109 (2007) 315335
Fig. 5. Continuous vertical deodorizer (De Smet) [38].
gas phase and the oil phase by creating large contact
surfaces and/or thin oil films together with an optimal
sparge steam distribution (for an optimum level of vapor-
ization efficiency). The sparge steam is introduced into
the oil through special distributors, which can be sparge
coils with very fine holes (between 0.5 and 2.5 mm) (shal-
low-bed deodorizer) or even sintered metal pipes (deep-
bed deodorizers). Steam lift pumps have been introduced
in order to improve agitation and overall deodorization
efficiency by continuously refreshing the oil in the top
layer [38]. The vapors from the different compartments
are collected in a central chimney and sent to a separate
vapor scrubber with a sprayer system. In some cases, an
extra structured packing is installed in the scrubber to
improve condensation and to reduce fatty matter carry-
over to the barometric water condenser system.
Due to the new market demands for minimizing trans
fatty acid and tocopherol and tocotrienol retention, a
dual-temperature concept has been recently developed.
In the first tray, the incoming oil is heated to moderate
temperature, after which it passes through the first deo-
dorization trays. In these trays, deacidification and deo-
dorization take place under mild conditions (moderate
temperature/moderate stripping). After the first trays, the
oil passes a second heating tray in which the oil is heated
to a final and higher temperature. In the last tray, final
stripping and heat bleaching occur. The process param-
eters can be adjusted to arrive at the desired tocopherol
and tocotrienol level in the refined oil. In general, the dual-
temperature deodorizer shows a number of benefits that
are important for oil refiners. The benefits include low
trans fatty acid formation because the time at high
temperature is restricted, maximum heat bleaching
effect, and adjustable tocopherol and tocotrienol
removal, mainly by steam injection at high temperature.
Packed columns (Fig. 6) are more and more used in edible
oil deodorization. A packed column is basically a single-
shell vertical vessel in which a structured packing is
installed. In fact, in the past, a structured packing was
often installed to increase the capacity of existing deo-
dorizers. Its main function was to reduce the sparge
steam consumption of the deodorizing unit by pre-strip-
ping the main part of the volatile material. The deacidified
oil is then sent to the deodorizer for the final deodoriza-
tion. In palm oil deodorization, for example, the FFA level
is first reduced from 35% to below 0.5% in a structured
packing before the oil enters the deodorizer. In this way,
the capacity of a deodorizing plant can be significantly
increased. The main advantages of the structured packed
column are the higher efficiency to remove FFA and the
short residence time (only a few minutes).
Recently, a fully modular single-vessel (continuous)
stand-alone deodorizer was designed (Qualistock) (Fig. 7)
which requires no building and minimal piping. In this way,
the erection costs can be significantly reduced. This con-
cept allows the integration of different processing options
with specific functions to improve the overall quality of the
deodorized oil: dual-temperature treatment, deep- or
shallow-bed deodorization, packed column pre-strip-
ping, dual condensation, etc.
5.3.4 Dry (or ice) condensing systems
Normal deodorizers operate at 34 mbar. Today, special
vacuum production units have been developed to reach
lower pressures (,2 mbar) and better operating costs
and, at the same time, to reduce emissions and effluents
by a more efficient condensation of the volatiles. The dry
condensing system [38] is becoming more and more the
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Eur. J. Lipid Sci. Technol. 109 (2007) 315335 Palm oil refining 327
Fig. 6. Packed column stripper (Alfa-
Laval) [38].
Fig. 7. Modular single-vessel stand-alone deodorizer (Qualistock-De Smet) [38].
standard in new refining plants. In this system, the vapor
is condensed on surface condensers working alternately
at very low temperature (around 30 7C). The remaining
non-condensables 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 system significantly reduces the motive
steam consumption, but requires extra electrical energy.
The commercially available dry condensing systems
consist of two or more condensers, with either horizon-
tally or vertically orientated straight tubes, a refrigeration
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328 V. Gibon et al. Eur. J. Lipid Sci. Technol. 109 (2007) 315335
plant for the generation of cold refrigerant (usually NH3)
which is evaporated in the tubes, and a vessel with rela-
tively warm water for defrosting and cleaning of the tubes
after a certain period of freezing. A new dry condensing
system has recently been developed [38]; the most
essential feature of this system (Sublimax) (Fig. 8) is the
vertical orientation of the freeze condensers, combined
with individual refrigerant injection in the tubes and
sparge steam inlet at the top.
5.3.5 Side effects of deodorization
Possible changes that may occur on the chemical and
physical properties of palm oil and palm fractions under
different refining conditions have been described. In the
case of palm olein and palm mid fraction, trans fatty
acids are mainly formed at 280 7C after a residence time
of 4 h (2.1 and 1.5%, respectively) [36]. In commercial
refined palm oil products, not more than 0.6% of total
trans fatty acids are reported for processing conditions
of 260275 7C and a residence time of 4590 min.
Intra-molecular rearrangements of fatty acids can be
observed in oils subjected to drastic refining conditions
(above 270 7C for long residence times); intra-esterifica-
tion may occur during deodorization of palm oil, resulting
in an increase in saturated fatty acids at the 2-position of
the TAG. This intra-esterification has a detrimental effect
on the efficiency of dry fractionation of palm oil and on the
quality of the final fractions.
Removing FFA and partial acylglycerols (mainly MAG) will
also change the physical properties of palm oil; mainly the
solid fat content at low temperature will be affected
(increased in the refined palm oil).
6 Chemical refining practices
In the case of chemical refining, the non-hydratable
phosphatides which remain in the oil after acid treatment
are further removed during the neutralization stage. It is
assumed that caustic soda converts the non-hydratable
phosphatides into sodium salts, which are more easily
removed as they are less oil soluble. On the other side,
both calcium hydroxide and magnesium hydroxide are
strong bases and therefore do not replace easily the
equally strong base sodium hydroxide. In this context, it is
known [39] that the pH must be very high for the residual
phosphorus to be ,5 ppm.
The high soap content in combination with intense water
washing improves the removal of the phosphatides. The
only drawback is the soapstock which needs to be treat-
ed accordingly.
The long mix technique (American route) was developed
based on a long time/low temperature sequence. Histori-
cally, it has been especially designed to treat fresh North
American soybean oil. On the other hand, the short mix
technique (European route) consists in a short contact
time at higher temperature.
Fig. 8. Schematic diagram of the improved Sublimax Dry Condensing system [38].
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Eur. J. Lipid Sci. Technol. 109 (2007) 315335 Palm oil refining 329
6.1 Typical process conditions
The non-hydratable phosphatides are removed by add-
ing 0.030.1 wt-% of concentrated phosphoric acid to
the crude palm oil. The quantity of caustic solution is
calculated based on the FFA content of the oil; in a
short mix process, 20227B caustic soda (1030%
excess) is generally used and mixed to the oil at 90
95 7C in order to avoid emulsion formation. The contact
time is generally 30 s to prevent high saponification
losses. The soapstock/oil mixture is delivered to
separators. The outgoing light phase is the neutralized
oil containing traces of soaps, free caustic, phospha-
tides and other soluble impurities. The neutral oil losses
should be usually between 20 and 30%. Soft water at
about 90 7C is added to the oil for washing and sepa-
rated in a second centrifuge into water-washed oil as
light phase and soapy water as heavy phase. The range
of the FFA content in neutralized oil is usually between
0.08 and 0.25%, and the soap content is below
50 ppm. After drying, the neutralized oil is sent for
bleaching and deodorization (220240 7C) to remove
mainly odoriferous components and to bring the final
acidity into the range of 0.020.08%.
6.2 Soapstock splitting
Soapstock splitting is closely connected with caustic
refining and is completely omitted in physical refining
plant facilities. Soapstock from alkali refining is pumped
to the splitting plant for acid oil production. The total
fatty matter of diluted soapstock is usually around 10
15%. Sulfuric acid is mixed and the reaction takes place
in a decantation tank, to break down the emulsion
formed due to the presence of phosphatides, proteins
and other mucilaginous substances. Acid water is
removed, leaving acid oil to pass through a separator,
allowing the removal of last traces of water and mucila-
ginous material. Extra washing is performed to assure
that no sulfuric acid is left in the acid oil. Soap splitting is
generally done at pH ,3. The FFA content of the acid oil
produced is usually between 40 and 70%, depending on
the quality of the soapstock used and more especially
the amount of neutral oil in the soapstock. The main
components of palm acid oil are FFA, neutral oil and
moisture. It is mainly used for making laundry soaps and
for producing calcium soaps for animal feed formula-
tions.
Properties (quality and oxidative parameters) of palm
oil acid oil have been carefully analyzed in order to
build up specifications and a clear definition of palm
fatty acids (Tab. 8) [40]; moisture, FFA, PV, iodine
Tab. 8. Quality and oxidative parameters of palm acid oil
(mean of 27 samples) [40].
Parameter Mean
value
Standard
deviation
Moisture content [%] 0.98 0.53
Free fatty acids [%] 62.6 11.5
Peroxide value [meq O2/kg] 4.1 3.8
Iodine value 50.2 5.3
Saponification value 186 5.6
Unsaponifiable matter [%] 0.53 0.42
value, saponification value and unsaponifiable matter
have been quantified. A few samples showed the pres-
ence of aldehydes, ketones, furans and volatile acids.
7 Deodorizer distillate
7.1 Composition of deodorizer distillate
The composition of the deodorizer distillate is not only oil
dependent, but it is also determined by the refining tech-
nique applied (physical or chemical) and the operating
conditions during deodorization [17, 18] (Tab. 9). In the
case of physical refining of palm oil, the distillate mainly
consist of FFA (8388%) with only small amounts of unsa-
ponifiable components (24%) and neutral oil (813%).
Deodorizer distillate is generally sold as a source of indus-
trial fatty acids or eventually for soap production in some
cases after deodorizing to reduce the color. It can also be
considered as a feedstock for biodiesel production.
Tab. 9. Typical composition (%) of a deodorizer distillate
from a chemical and a physical refining plant [18].
Composition Chemical
refining
Physical
refining
Neutral oil 2533 510
Fatty acids 3350 8085
Unsaponifiable matter (including
tocopherols and sterols)
2533 510
7.2 Neutral oil losses during deodorization
Neutral oil losses during deodorization generally depend
on the oil composition and deodorizing conditions [38]. In
the case of chemical refining, improvement of the deo-
dorizer design has significantly reduced entrainment los-
ses to 0.10.2%. For physical refining of palm oil, addi-
tional loss directly proportional to the FFA content and
mainly due to mechanical carryover has to be taken into
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330 V. Gibon et al. Eur. J. Lipid Sci. Technol. 109 (2007) 315335
account. Higher MAG contents of high acidity oils also
contribute to losses. In practice, there is also limited
hydrolysis during deodorization; under normally applied
deodorizing conditions, hydrolysis results in the produc-
tion of 0.0150.020% additional FFA [41].
7.3 Dual condensing system or washing section
The FFA content of palm deodorizer distillate is usually
around 8590%. With the introduction of a dual
condensing system [33], in some designs also called
washing section [42], the content of acylglycerols (MAG,
DAG and TAG), tocopherols, sterols, squalene, etc., in the
condensed fatty acids can be reduced. The composition
of palm oil distillate without and with this system is pre-
sented in Tab. 10; the total amount of FFA is increased to
98% min.
Tab. 10. Composition (%) of palm fatty acid distillate
including or not a washing section [42].
Components Without washing
section
With washing
section
FFA 87.4 98.1
MAG 2.0 0.7
DAG 0.7 0.05
TAG 8.0 0.1
Tocopherols, sterols,
squalene
1.9 1.0
8 Special products
8.1 Golden palm oil
A golden palm oil rich in carotene, tocopherols and toco-
trienols can be obtained by physical refining.
The characteristics of a high-vitaminic physically refined
palm oil (produced under pilot conditions) have been
described [43]. It has been claimed that this golden oil
should retain 20% of the initial carotene and 89% of the
tocopherol and tocotrienol content (Tab. 11), which looks
to be very high compared to physically refined palm oil
produced in Malaysia. Long retention time at relatively
low temperature combined with high steam consumption
are the necessary conditions to decrease the acidity to
sufficiently low levels while preserving carotenoids, toco-
pherols and tocotrienols.
More recently, it has been proved [33] that dual tempera-
ture and low pressure (using an ice condensing vacuum
system) can be used to produce an industrially physically
Tab. 11. Characteristics of golden palm oil produced by
physical refining at pilot scale [43].
Crude
palm
oil
Degummed
bleached
palm oil
RBD
golden
palm oil
FFA (as palmitic) [%] 3.8 0.08
Phosphorus [ppm] 19 ,2
Iron [ppm] 2.1 0.1
Lovibond 51/4 (R/Y) 50/20 18/20
Carotenes [ppm] 520 380 105
Tocopherols/
tocotrienols [ppm]
856 790 760
0.5 mbar, 180 7C, 3% steam, 180 min.
refined palm oil with improved quality parameters: more
natural color and higher tocopherol tocotrienol contents:
dual temperature at 200220 7C combined with low pres-
sure, 1 mbar (Tab. 12), seems to be the best option for a
maximal retention of carotenoids, tocopherols and toco-
trienols, for a good oxidative stability and efficient
removal of the FFA.
8.2 Red palm oil with high vitamin content
With the removal of FFA also comes in a considerable
extent of removal of impurities. It has been shown that an
efficient alkali refining plant is able to purify crude palm oil
so effectively that it can be deodorized directly (without
bleaching) or in the worst case with very small amounts of
non-activated bleaching earths or silica [13]. Such a pro-
cess will require very-good-quality crude palm oil (low
FFA and high DOBI), with the cleansing action of neu-
tralization being mainly limited to phosphorus removal
while keeping the carotenoids unaffected.
In some applications, the thermal bleaching would only
operate during deodorization conducted around 240 7C
and with a very short residence time, resulting in reduced
losses in tocopherols and tocotrienols and very good
oxidative stability for the final product (Tab. 13).
Thermal bleaching conducted at lower temperature
would result in limited destruction of carotenoids, to-
gether with keeping high amounts of tocopherols and
tocotrienols in the oil.
Dedicated products issued from special refining proce-
dures and labeled as Red Cooking Oils are available on
the Asian market: Carotino Cooking Oil and Nutrolein
Golden Palm Oil are the main representative products.
Nutrolein for example (which is produced by Unitata Ber-
had in Malaysia) is a superolein issued from dry-fractio-
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Eur. J. Lipid Sci. Technol. 109 (2007) 315335 Palm oil refining 331
Tab. 12. Relationship between process conditions (physical refining) and oil characteristics for
golden palm oil production [33].
ReferenceABCDE
FFA (as palmitic) [%] 0.07 0.20 0.08 0.04 0.07 0.07
Lovibond 51/4 (R/Y) 2.5/25 11.6/70 4.8/50 2.9/29 6.2/50 4.1/42
Tocopherols/tocotrienols [ppm] 544 709 629 431 671 699
OSI at 97.8 7C [h] 70.5 61.5 50.6 36.7 63.0 53.4
RBD palm oil refined under classical conditions.
A: 200 7C, 1 mbar, 1.5% steam, 60 min.
B: 220 7C, 1 mbar, 1.5% steam, 60 min.
C: 260 7C, 3 mbar, 1.5% steam, 60 min.
D: Dual temperature: 200220 7C, 1 mbar, 1.5% steam, 60 min.
E: Dual temperature: 220240 7C, 3 mbar, 1.5% steam, 60 min.
Tab. 13. Characteristics of palm oil chemically refined
without bleaching earth [9].
Crude
palm
oil
Degummed
and
neutralized
palm oil
Degummed,
neutralized and
deodorized
palm oil
FFA (as palmitic) [%] 2.56 0.06 0.03
M [%] 0.08 0.01 0.01
I [%] 0.03 0.02 0.003
Carotene [ppm] 580 579 1.0
DOBI 3.1
Phosphorus [ppm] 16 3 0
Tocopherols [ppm] 733 679 566
Induction period at 100 7C [h] 49 34 44
nated, chemically refined high-quality crude palm oil. Its
carotenoid content is announced to be above 800 ppm,
with a vitamin E concentration superior to 900 ppm.
Same quality oils are available in the Latin American mar-
ket, like Sioma Oil (produced by Danec S.A. in Ecuador),
which is a more unsaturated variety of palm oil, obtained
from the hybrid palm.
8.3 Production of white soaps from palm
Production of white soaps from palm oil is not evident:
the main problem is the too dark color (.5R 51/4) which
is usually achieved during the saponification step [44].
Good results (saponification color of 3R 51/4 or lighter)
can only be expected when a crude palm oil of high
quality is used for refining and if the refining procedure is
performed under optimized conditions. Recent research
has shown [33] that very good saponification colors
(around 2.5R 51/4) can only been obtained from a very
light RBD palm oil (0.6R 51/4) that can only be produced
from crude palm oil having a DOBI above 3 (Tab. 14).
8.4 Feedstock for fractionated products
For usage of palm oil in dry fractionation, it is clear that its
properties (mainly related to its TAG composition) should
not be modified during refining. Crude palm oil has nor-
mally a PPO content below 5% which should stay at that
level before fractionation. Production of palm mid frac-
tions (CBE) mainly consists in a maximum increase of
symmetrical oleo-dipalmitin: POP; enrichment in asym-
metrical PPO due to intra-esterification during the deo-
dorization is of detrimental effect for the palm mid fraction
quality [36]. The effect of deodorization time and temper-
ature has been extensively studied by Willems and Padley
[12]. The change of the ratio is significant if the oil is sub-
jected to temperatures around 270 7C for long residence
times. To avoid these intra-esterification problems, deo-
dorization temperatures and residence times need to be
limited; for this reason, chemical refining or physical
refining at low pressure and shorter residence times are
preferred.
Also, a tailing effect which depends on the deodorization
conditions can be observed in the solid fat content profile
of oleins [36]. This tailing effect observed in palm olein
subjected to 280 7C for 4 h is significant compared to
refining at 250 7C for 2 h; it is once again produced by
intra-esterification of the fatty acids promoted at high
temperatures and resulting in early crystallization of palm
olein during storage.
9 Refined palm oil quality
9.1 Effect of crude oil quality on color reversion
It is clear that good-quality refined palm oil cannot be
produced from low-quality oils. Crude palm oil with a very
low DOBI can be processed using a higher bleach-
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332 V. Gibon et al. Eur. J. Lipid Sci. Technol. 109 (2007) 315335
Tab. 14. Production of white soaps with low saponification color through physical refining of
palm oil
[33].
Crude palm oil (DOBI: 3.3)
Refining conditions RBD oil color Saponification color
(R 51/4 Lovibond) (R 51/4 Lovibond)
Bleaching with 1.5% BE and refining at 280 7C 0.9 3.6
Bleaching with 1.5% BE 10.4% AC and refining at 280 7C 0.7 2.8
Bleaching with 2.5% BE 10.5% AC and refining at 280 7C 0.6 2.5
BE: Tonsil Optimum 210 FF.
AC: activated carbon.
ing earth dosage (up to 56%) to produce acceptable FFA
and color in refined products, but such a product has very
poor quality. As such, it cannot be called a refined product
that could meet the requirements of the customers. As
seen above, carotenoids in crude palm oil are easily
removed during adsorptive bleaching and/or deodoriza-
tion. The amount of carotenoids in the crude oil does not
determine the residual color of the refined oil, which is
probably due to unknown high-molecular-weight com-
pounds [45]. Every step in palm oil refining is important,
and great care is taken in order to produce a stable
refined palm oil with minimal chances of color reversion.
Although in most cases the color reversion is rectifiable, it
means extra costs. Color reversion during processing is
normally associated with poor quality of the crude oil or
with improper degumming and bleaching processes. The
reversion could be due to colored pigmentspresent in the
crude oil or as a result of the oxidation of carotenoids
during deodorization; oils derived from badly damaged
palm fruits contain brown pigments from decomposed
protein and carbohydrates that are resistant to bleaching.
Moreover, oxidized crude oils may contain colored com-
pounds of quinoid nature developed from oxidation of
colored materials. It seems that oxidation not only devel-
ops new pigments but also stabilizes the pigments
against their removal by adsorption [16].
It has been shown that bleached oil color cannot be used
to predict the final deodorized oil color and quality; in
order to determine the effect of the bleaching temperature
on the final oil quality, a simple test has been developed
[46]. Palm oil was bleached at 95, 105, 120 and 135 7C
with 2.5% bleaching earth. Bleached oil colors decreased
as the temperature increased, while the heat-bleached
(refined) oil colors did the opposite. It was assumed that
the rise in refined oil red color could be due to color for-
mation caused by both oxidized fatty acids and oxidized
carotenoids: elevated temperatures would increase the
formation of the color bodies. Although the refined oil
color rose with increasing bleach temperature, the oxida-
tive stability index (OSI) values indicated an optimum
around 120 7C, in agreement with other work [13, 32]. It
may be argued that by increasing the bleaching earth
dosage or by altering other refining parameters, oil of any
DOBI value could be adequately refined. However,
another study showed [47] that the oxidative stability of
low DOBI refined palm oil is always lower, as compared to
refined palm oils with DOBI above 2.3.
A bleachability test has been developed [33] at laboratory
scale by which the final color of palm oil could be pre-
dicted. Six crude palm oils from different origins with an
initial FFA content between 1.9 and 7.2% were prepared.
Afterwards, the samples were bleached at 260 7C for
50 min at a pressure of 3 mbar, with the addition of only
small amounts of steam (to ensure good mixing and heat
transfer). The low DOBI values combined with elevated
levels of fatty acids and peroxides in some samples gave
an indication that these oils were difficult to bleach (final
color 51/4 above 3) (Tab. 15). Moreover, a direct rela-
tionship between the DOBI and the final color of the heat-
bleached palm oil was observed [33]. A heat-bleached
palm oil with color below 2R can be produced when crude
palm oil had a DOBI above 2.5. These observations con-
firmed earlier findings [47] that DOBI values are a good
indicator for palm oil refinability. It was also shown [33]
that the bleaching temperature did not affect the final
color after heat-bleaching. These observations confirm
that the bleached oil color cannot be used to predict the
refined oil color.
9.2 Maximum retention of tocopherols and
tocotrienols
The influence of the bleaching conditions on the toco-
pherol and tocotrienol retention of physically refined palm
oil has been reported (Tab. 16) [34]. The total quantity of
identified tocopherols/tocotrienols increased during
bleaching in correlation with the bleaching earth quantity,
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Eur. J. Lipid Sci. Technol. 109 (2007) 315335 Palm oil refining 333
Tab. 15. Relationship between initial FFA content and DOBI of crude oils of different qualities
(16)
and final color of refined oils after a bleachability test at laboratory scale (260 7C, 3 mbar, 50
min) [33].
123456
FFA (as palmitic) [%] 7.21 4.32 3.54 4.91 2.79 1.90
DOBI 1.34 1.76 2.02 2.23 2.67 3.13
Peroxide value [meq O2/kg] 2.33 3.79 3.15 3.54 0.36 1.03
Oil grade bad poor poor poor fair good
Lovibond (51/4) 3.1R/33Y 3R/35Y 2.2R/20Y 2R/20Y 1.3R/15Y 1.4R/15Y
Tab. 16. Effect of bleaching and deodorization conditions on residual tocopherol and tocotrienol
contents (ppm) of palm oil
(bleaching conditions: 110 7C, 50 mbar, 20 min; deodorization conditions: 250 7C, 3 mbar, 2.5
h) [34].
Crude
Bleached RBD
0.5%
acid-activated
clay
0.75%
acid-activated
clay
1.00%
acid-activated
clay
from 0.5%
acid-activated
clay
from 0.75%
acid-activated
clay
from 1.00%
acid-activated
clay
a-tocopherol 190 220 233 223 147 125 150
a-tocotrienol 131 155 162 156 140 112 147
g-tocotrienol 339 291 286 250 213 201 251
d-tocotrienol 113 127 135 206 51 69 62
Total 773 794 815 834 551 506 610
which is in accordance with earlier observations [48]
where regeneration of the free form from dimeric or
esterified compounds was assumed. This release does
not seem to be indiscriminate, as the g-tocotrienol con-
tent decreases with increasing bleaching earth quantities.
An average tocopherol and tocopherol retention of 80%
was obtained after steam refining, which is quite high. The
relative concentration of single tocopherols/tocotrienols
was modified by steam refining, probably due to differ-
ences in volatility among various forms and to different
stabilities under the refining conditions [47].
More recently, the influence of bleaching and deodoriza-
tion conditions on total tocopherol and tocotrienol reten-
tion has been studied [33] (Tab. 17). In this case, an
increase of tocopherol and tocotrienol contents was not
observed during bleaching. Pre-treatment with active
carbon decreased the b-carotene contents of the
bleached and of the refined oil. Low quantities of steam
did not modify the b-carotene content of the refined oil,
while affecting the final acidity and improving tocopherol
and tocotrienol retention.
10 Future developments in palm oil refining
It becomes clear that good-quality palm oils are made in
the plantation and not in the factory. Indeed the quality of
a fully refined palm oil is highly dependent on and com-
pletely inseparable from the quality of the crude oil. The
high acidity of crude palm oil places physical refining as
the first option, mainly for economical reasons but also for
environmental issues. The latest developments in the
refining technology have been driven by the increased
attention to the nutritional quality. Optimizing the deodor-
ization technology and the process conditions for max-
imum retention of the natural characteristics will be an
important challenge for the future.
The development of vacuum systems (ice condensing)
capable to reach low operating pressure (around 1 mbar)
is very important [49] because it allows a reduction of the
deodorization temperature without affecting the vapor-
ization efficiency.
Even if single-temperature deodorizers are still the most
economical for palm oil, working at different tempera-
tures (dual temperature) is an asset to reach the best
compromise between the required residence time for
deodorization (performed at low temperature) and heat
bleaching and final stripping at higher temperature for a
brief period.
Furthermore, a design including a structured packing for
oil stripping, able to reduce steam consumption and
operating costs, perfectly fits with the requirements of a
high-acidity oil like palm oil.
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334 V. Gibon et al. Eur. J. Lipid Sci. Technol. 109 (2007) 315335
Tab. 17. Effect of pre-treatment and deodorization conditions on tocopherol and tocotrienol
contents of palm oil [33].
Pre-treatment conditions$Deodorization conditions FFA (as
palmitic)
[%]
b-Carotene [ppm]
before and after
deodorization
Tocopherols and
tocotrienols [ppm] before
and after deodorization
Acid pre-treatment and bleaching with
1.5% BE (95 7C, 30 min)
260 7C, 3 mbar, 0.2% steam, 50 min 0.09 107/2.0 808/684
260 7C, 3 mbar, 1% steam, 50 min 0.03 107/1.5 808/496
Acid pre-treatment, bleaching with
1.5% BE (95 7C, 30 min) and treatment
with 0.4% AC (80 7C, 30 min)
260 7C, 3 mbar, 0.2% steam, 50 min 0.08 87/1.0 797/659
260 7C, 3 mbar, 1% steam, 50 min 0.03 87/1.0 797/487
$Crude palm oil: FFA, 5.3% (as palmitic); DOBI, 2.5; b-carotene, 459 ppm; tocopherol and
tocotrienol content, 972 ppm.
BE: Tonsil Optimum 210 FF; AC: activated carbon.
State-of-the-art is the introduction of a double scrubber
unit (double condensing unit) for the improvement of the
fatty acid purity in the distillate.
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Citations68
References64

o allization. In the solvent-assisted process the melted native fat was used to mix
with a solvent medium and was left to crystallize at a lower temperature. The
precipitated fat was filtered off in order to give a high-melting fraction (HMF)
while the mother-liquor was evaporated to produce a liquid called low-melting
fraction (LMF) (DEFFENSE, 1993;KELLENS et. al, 2007;O'BRIEN,
2004;TAYLOR, 1976;TIMMS, 2005). In recent times, solvent-assisted
fractionation has been investigated for a series of tropical fats that include palm
oil (MARIKKAR andGHAZALI, 2011), coconut oil (MARIKKAR et al., 2013),
cocoa butter (YANTY et al., 2013), engkabang fat (YANTY et al., 2013a),
avocado butter (YANTY et al., 2013b),

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 o On their part, commercial oil palm producers should implement good agricultural
practices as stated out in the RSPO principles and criteria or guidelines so as to
enhance sustainable development of the sector. Despite the controversies
surrounding the oil palm industry, and with reference to the bulk of scientific
knowledge developed so far from diverse studies on the oil palm and other plants
(Van Der Vossen, 1974; Noiret & Wuidart, 1976; Corley & Tinker, 2003; Singh
et al., 2007; Kellens et al., 2007; Billotte et al., 2010; Singh et al., 2013; Montoya
et al., 2014), it could be interesting if this crop is considered beyond just serving
economic interests. The oil palm (Elaeis guineensis Jacq.) could constitute a
pertinent biological or murine model for scientific development.

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o Moreover, this oil has a low level of linoleic acid (18:2), making it less prone to
oxida- tion [13]. RBDPS has been well reviewed and reported to be a suitable
CBA [14, 17]. Binary systems of fats/oils have been recently gaining interest for
producing CBAs for compound chocolates and other confectionery applications
because fats/oils such as PMF, RBDPKO and RBDPS are comparatively cheap
and are readily available in the market.

Blending of Palm Mid-Fraction, Refined Bleached Deodorized Palm Kernel Oil or Palm Stearin for
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o Effect of polyglycerol esters (PGE) additive on nucleation and early
crystallization Crystallization of oils and fats consists of a few stages;
supercooling of the melt, nucleation, and crystal growth (Kellens, Gibon,
Hendrix, & Greyt, 2007). Nucleation occurs when the melt becomes supercooled,
whereby the temperature of the melt is much lower than the thermodynamic
equilibrium temperature (Kellens et al., 2007; Lawler & Dimick, 2002 ). The
effects of additives with respect to nucleation are alterations of nucleation time,
shift in nucleation temperature, and changes in the number and nature of the
nuclei formed (Smith et al., 2011).

Effect of polyglycerol esters additive on palm oil crystallization using focused beam reflectance
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o For this reason both solvent and dry crystallization methods were used to
fractionate PMTAG in an attempt to optimize yield and composition of the
fractions, particularly with respect to the synthesis of polyols and rigid
polyurethane foams. Several studies regarding the fractionation of palm oil by dry
as well as solvent aided crystallization have been published (Hasmadi et al., 2002;
Kellens et al., 2007; Ramli et al., 2008). The present work reports on the
fractionation of PMTAG and the synthesis of polyols from the fractions.

Metathesized palm oil: Fractionation strategies for improving functional properties of lipid-based
polyols and derived polyurethane foams

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Suresh S. Narine Suresh S. Narine

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o For this reason both solvent and dry crystallization methods were used to
fractionate PMTAG in an attempt to optimize yield and composition of the
fractions, particularly with respect to the synthesis of polyols and rigid
polyurethane foams. Several studies regarding the fractionation of palm oil by dry
as well as solvent aided crystallization have been published (Hasmadi et al., 2002;
Kellens et al., 2007; Ramli et al., 2008). The present work reports on the
fractionation of PMTAG and the synthesis of polyols from the fractions.

Metathesized palm oil polyol for the preparation of improved bio-based rigid and flexible
polyurethane foams

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Article Jan 2016

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