The Possible Mitigation

Procedures for the Reduction of

the Formation of Chloropropanol
Esters and Related Compounds
Siew Wai Lin*; Ainie Kuntom*; Nuzul Amri Ibrahim*; Muhamad Roddy Ramli*
and Raznim Arni Abd Razak*

INTRODUCTION organochloro- compounds in crude

palm oil. In the work by Destaillats
Fatty acids esters of chloropropanols are food-processed contaminants et al. (2012), it was shown that the
formed as a result of high temperature reactions. They have been found triacylglycerol (TAG) species are
in a wide variety of food products (Weißhaar, 2011). In many of these the more reactive species involved
foods, the free form of the ester is present as well. While the free form is in the formation of 3-MCPD esters
a known carcinogen, the toxicological significance of the esters is still be- with the organo-chlorines. On the
ing evaluated. In 2006, Zelinkova et al. (2006) first reported high levels other hand, diacylglycerol (DAG)
of 3-Monochloropropane-1,2-diol esters (3-MCPD esters) in some edible has a more prominent role in the
oils. Since then, many research publications and presentations in confer- formation of glycidyl esters. As
ences have referred to the higher levels noted in refined oils, particularly palm oil is known to have a higher
palm oil (Weißhaar and Perz, 2010; Kuhlmann, 2011). concentration of DAG, it would
therefore appear that the pieces of
So, what is possibly in palm refining of crude palm oil involves puzzle are now in place to form a
oil which, under high temperature a physical process, where the crude clearer picture. However, there are
processing results in the formation oil is first degummed, bleached and still pieces that do not seem to fit;
of 3-MCPD esters and glycidyl es- deodorised at a high temperature as were found samples that had
ters? The picture is increasingly be- of 260°C. The less common alkali reasonably high DAG levels, and
coming clearer as many research- refining process uses a lower de- yet had low and even undetectable
ers have worked on this topic. The odorisation temperature of 240°C. glycidyl esters, when subjected to
formation of 3-MCPD esters occurs We now know that even at 220°C, high temperature.
between lipids (triacylglycerols, some formation of 3-MCPD esters
diacylglycerols, monoacyglycerols) and glycidyl esters already occurs. Many possible options have
and chlorides at high processing been put forth for the reduction of
temperature of 200°C and above. The formation of 3-MCPD es- these contaminants. These range
As crude palm oil is extracted at ters requires the presence of chlo- from upstream approach (dealing
low temperatures (<100°C), these rides. Hrncirik and Duijn (2011) with the crude oil), modification of
compounds are not detected. The showed that the chloride content refining and downstream approach
in palm oil varies from 3-10 mg (cleaning up the refined oil). This
* Malaysian Palm Oil Board,
P.O. Box 10620, 50720 Kuala Lumpur, kg-1, while studies by Nagy et al. paper reviews the practical aspects
Malaysia. (2011) have shown the presence of of some of these mitigation ap-
E-mail: siew@mpob.gov.my

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Palm Oil Developments 57

proaches, with a view to offering increasing formation of 3-MCPD in the oils. Chlorides are ubiquitous
possible solutions to the issue. esters. in nature, and are found in water,
acids, bleaching clays, etc. and in
EXAMINING CRUDE PALM OIL Although these extracts con- the oil as well. Nagy et al. 2011 and
(CPO) QUALITY tain high amounts of DAG, it can- Craft et al. (2012a) described the
not be concluded that DAG is the type of chlorides present in palm
Several researchers (Matthäus et component affecting the 3-MCPD oil. According to them, inorganic
al., 2011; Rahn and Yaylayan, esters formation, as there may be compounds of ferric and ferrous
2011) have suggested that DAG other polar components in the ex- chlorides, magnesium and calcium
is one of the possible components tracts as well, such as chlorides. In chlorides exist in the oil. Not
reactive enough to form MCPD addition, a purified oil from the col- surprisingly, iron compounds have
and glycidyl esters. In spite of good umn (TAG) when added with a 2% long been known to be present in
correlation figures shown of the polar extract which was removed crude oils. Another source of the
relationship when DAG was added from column chromatography of chlorides apparently comes from
to oils (Matthäus et al., 2011), in palm oil using only methanol, also organic forms. Their presence is not
practice the trend for the correla- showed higher 3-MCPD esters surprising, given that plants need
tion between the DAG content of when heated. As the pure TAG and chlorides for their growth, and
CPO and its tendency to form these the methanol eluted polar extracts chlorides are present in soil, water
esters is not so clear cut. Hrncirik contain no DAG, it can be con- and fertilisers. The total chlorides
and Ermacora (2010) discussed the cluded that DAG is not necessar- in CPO averaged at about 16.5
possibility of other factors being ily the lipid component involved in ppm, with a range of 8-29 ppm
involved, and that the DAG con- the formation. It confirms Hrncirik’s for 11 samples. Table 1 shows
tent was not the limiting factor; an work, who concludes that DAG is the disappearance of chlorides
extraction of polar compounds in not the limiting factor impacting from the oil in the mill extraction
CPO by column chromatography the formation, as many other polar process. It is perhaps possible that
followed by an addition of these compounds are present in the ex- efficient removal of chlorides from
compounds to another clean CPO tracts as well. Furthermore, some the oil can be further fine-tuned
sample revealed results shown in oils with high DAG contents have in the mills. Further centrifugation
Figure 1. The addition of polar ex- not shown very high MCPD esters. in the laboratory could actually
tracts of crude palm oil obtained by reduce chloride content from 6.5
eluting a column of oil with 15% Another factor in the equation to 1 ppm. Among chemicals used
diethyl ether in hexane, showed is obviously the chloride contents in processing, bleaching earths
3-MCPD esters (ppm)

DAG content in oil (%)

Note: Purified oil obtained by column chromatography; 1st extract – TAG oil, 2nd extract – polar extract containing DAG, 3rd
extract – polar extracts obtained with methanol.

Figure 1. 3-MCPD esters formation in purified palm oil with addition of its polar components obtained
via column chromatography.

22
 The Possible Mitigation Procedures for the Reduction of the Formation of Chloropropanol Esters and Related Compounds

TABLE 1. REMOVAL OF CHLORIDES (PPM) IN CRUDE PALM OIL PRODUCTION

Sample Mill 1 Mill 2

CPO before dilution 588 1088

CPO after dilution 677 16

CPO after purifier 17 6.5

contain the most chlorides (51- in partitioning the precursors into separator and before drier. This
152 ppm), while citric acid and liquid and solid fractions, and allows the water to remove chloride
phosphoric acids contain much therefore being less available in precursors as well as separate easily
lower contents (1-2 ppm). So far, each fraction for the formation of with centrifuges and then dried. In
no correlation has been observed 3-MCPD esters during refining. this way, there is minimal additional
between chlorides in bleaching cost. Data on water washing of
earths and formation of 3-MCPD In the paper by Craft et al. CPO carried out in this research is
esters, and it is assumed that the (2012b), they described several tabulated in Table 2.
chloride present in the oil is the strategies for mitigation of MCPD
more critical chloride to watch out diesters, such as by application MODIFICATION IN THE REFINING
for. of glycerol and ethanol to oil PROCESS
during deodorisation, ethanol-
UPSTREAM APPROACHES water (1:1) washing of CPO An obvious consideration is
prior to deodorisation, and also the lowering of deodorisation
Sime Darby Malaysia Berhad filed water washing of palm fruit pulp temperature. What is the present
a patent WO 2011/002275 A1, (mesocarp). Both glycerol and state of technology for a lower
whereby fresh fruit bunches (FFB) ethanol together with ethanol: deodorisation temperature process
are harvested to produce an oil of water washing method resulted which would yet be able to produce
free fatty acids (FFA) less than 1.5 in a lowering of about 25%-35% low colours, FFA and odourless
wt.% and DAG less than 5.5 wt.%, in the MCPD formation, while the oil? Some options are available
and the crude oil is fractionated water washing of fruit pulp was for dual temperature operations,
prior to refining. The main claims found to be the most effective, (low-high, high-low) which may
are in the harvesting and collection with 95% reduction. The high cost help to reduce deodorisation time
of fruits for immediate extraction of both ethanol and water wash, at the higher temperature range. In
such that oil quality is excellent, and glycerol and ethanol would addition, stronger vacuum systems
as defined by FFA and other deter refiners from trying these may be useful if a high temperature
parameters. Fruit processing, two procedures. Water washing of is used for the operation. Lower
otherwise follows the norm for palm the pulp appears to be the better deodorisation temperature will
oil extraction. In this process, loose option as seen from the significant therefore prevent the formation
fruits are not acceptable as they reduction. of 3-MCPD esters, particularly if
contribute to higher FFA and DAG other precautions are also taken
levels. The process would incur However, considering the in degumming and bleaching
high cost due to the harvesting of voluminous amount of oil palm processes.
slightly under-ripe fruits and the pulp in any mill, water washing of
rejection of loose fruits, resulting the pulp does not appear practical. WO/2010/063450 provides
in high oil losses. For large Besides, the emulsification a method for reducing the
corporations, these loose fruits can properties of phospholipids, and 3-MCPD content in refined oils by
be channeled to other mills for the other components present would degumming with either water or
production of CPO to be utilised for cause difficulties in separation of acid and bleaching earth added.
biodiesel production, etc. It is not water from oil. The better option In addition, water can be added
clear how fractionation can assist in here is to utilise water washing at to the acid at the degumming
reducing chloropropanols, except the stage in palm oil mill, before stage, followed by bleaching with

23
Palm Oil Developments 57

TABLE 2. WATER WASHING EFFECT ON CRUDE PALM OIL

Type of sample 3-MCPD esters level (ppm) 3-MCPD esters level after heat test (ppm)

CPO 1 0.263 (± 0.177) 5.061 (± 0.475)

After washing 1 < LOD 0.6915 (± 0.026)

After washing 2 < LOD 0.646 (± 0.028)

CPO 2 < LOD 3.007 (± 0.035)

After washing 1 < LOD 0.6065 (± 0.067)

After washing 2 < LOD 0.537 (± 0.027)

Note: LOD= 0.25 ppm.

suitable earths. The inventors generally required. This might work Another two patents filed
showed that without adding in the against producing oils with low in 2011, were by Nestec S.A.
degumming agent and bleaching 3-MCPD esters as acidic conditions described processes of modifying
earth, 3-MCPD formation is high tend to enhance formation. Thus, current refining practices. In the
(5.50 µg kg-1), and that phosphoric the recommendations are best WO/2011/009841 application,
acid degumming without bleaching applied to generally better quality an ion exchange resin or a
earths, in contrast to water oils. If acidity is retained in the oil carboxymethyl cellulose is
degumming resulted in even after bleaching, higher 3-MCPD contacted with the oil. In the
higher formation (11.80 µg kg-1 esters will be formed during description, at least three
vs. 6.15 µg kg-1). These findings deodorization. It may be helpful adsorbents are required, viz a viz
have been corroborated by Ramli to neutralise the acidity by adding 0.5% Trisyl silica, 2% bleaching
et al’s (2011) study. The difference calcium carbonate to the bleaching earth, and varying amounts of ion
lies in the type of bleaching clays, process or to the degummed oil. exchange resin or carboxymethyl
whereby WO/2010/063450 Another aspect of the study uses cellulose. In pack bed form,
recommends a certain brand of water as the degumming agent contacting time of 1-5 hr had
earth. in place of acid. This reduces been given as an example, while in
the formation by about 60% batch process, dosage of between
Work by Ramli et al. (2011) especially when combined with 1%-20% has been recommended.
examines other aspects of refining low pH earths. However, it is Another embodiment of the
which contribute to increasing noted that only with excellent process also involves the use of
levels of 3-MCPD esters and crude oil quality is this process an inert gas such as nitrogen in
have found that high acidity feasible, as the water degumming the stripping step before or during
from degumming acids and acid procedure is not sufficient for oils deodorisation. Similarly, a co-patent
activated clays enhances the having high iron and phosphorus application WO/2011/009843
formation of 3-MCPD esters during contents. Thus, refined, bleached described the use of inert gas as
deodorisation. From this study, it is and deodorised palm oil (RBDPO) a stripping agent either before or
recommended that for good quality may not be able to achieve the during the deodorisation step. How
crude palm oils, a lower dose of required specifications under and why this works is not very
degumming agent and natural such circumstances. On the other clear, presumably, the inert gas
bleaching earths could help provide hand, if water degumming is prevents the direct contact of the
a refined oil with lower 3-MCPD combined with some Trisyl silica, chloro-compound with the oil. The
esters. However, with poorer oil improvements in removal of use of three types of adsorbents
quality, more degumming agent metallic impurities such as copper would be costly and deter refiners
and highly acid activated earths are and iron are better. from adopting the process. In

24
 The Possible Mitigation Procedures for the Reduction of the Formation of Chloropropanol Esters and Related Compounds

addition, ion exchange resins adsorbent. The silicate is preferably not be very feasible, without re-
have strong amine odour, which of neutral to basic type, of which deodorisation. The other steps such
may be imparted to the oil, and magnesium silicate is highlighted as chemical interesterification and
would need further deodorisation. as one of the preferred silicate. The enzyme treatment will change oil
Furthermore, high oil loss would be dosage of the silicate is described composition and properties and
incurred, depending on amount of to be between 0.3%-10%, and can only be used if such results
adsorbents used. preferably at less than 5% of the are desired. Contact with an acid
oil. Examples given use about 2% needs the removal of traces of
DOWNSTREAM APPROACHES silica. Contact time range between acid. Ethanol, carbon dioxide or
5 and 200 min, preferably within nitrogen sparging are expensive
Downstream approaches take the 60 min. According to the inventors, steps to consider, as is the use of
form of either adsorbents or possibly at least 50% reduction of 3-MCPD adsorbents.
enzymes. The use of adsorbents esters can be achieved, leaving the
was described by Strijowski et al. oil with less than 50 µg kg-1. CONCLUSION
(2011) and other several patent
applications, while the use of Another example of the use Mitigation steps for the reduction
enzymes were described by Kasai of silica is also given by Archer of 3-MCPD esters and glycidyl
et al. (2006) and Bornscheuer Daniels Midland Company esters can involve costly
and Hesseler (2010). Enzymatic (WO 2011/069028 A1). In procedures, which, oil refiners or
approaches require several different this application, gylcidyl esters food product manufacturers can
enzymes for final conversion of the reduction is the main focus of the ill adopt. Approaches that are
monochloropropanol fatty acid inventors. A wide range of possible more practical are necessary in
ester to glycerol. While effective procedures were described, the search for ways to prevent or
in the laboratory, the high cost ranging from using silica, enzyme, reduce the formation of 3-MCPD
of enzymes, and the possible low temperature deodorisation, esters. Past research has shown
modification in composition of the deodorisation with either ethanol, that most processes used thus far,
oil substrates, as well as high oil carbon dioxide or nitrogen sparge, involve costly procedures requiring
losses, make such approaches non- contacting the refined oil with an high doses of adsorbents and
viable on an industrial scale. acid, and re-bleaching. Generally, longer reaction time consequently
some or all of the steps are similar resulting in lower throughputs, and
Patent Application WO201104 to the ones reported above. Among oil losses. The more practical steps
0539 on the method for reducing the methods given, contacting with appear to be upstream approaches,
chloropropanols and formative Magnesol R60TM and re-bleaching removing precursors in the oil
substances thereof, glycidol fatty are the most effective ways of during the extraction process. A
acid esters, in glyceride oils, uses removing or reducing glycidol simple solution is discussed in the
silica gel and/or a basic activated esters from refined oils. However, light of various options available.
carbon with the decolorised and interestingly enough, the inventors The best option currently appears
deodorised oil in a solvent medium. gave two contrasting examples to be the removal of precursors
The solvent would have to be of the effect of using Magnesol through a thorough water wash at
removed, in a solvent distillation R60TM. In one case, treating refined the mill, or/and with modifications
process. The reduction of glycidol soyabean oil spiked with glycidol of degumming combined with
esters occurs through the contact esters of 13.6 ppm with Magnesol the use of non-acidic type earths.
of the deodorised oil with an acid. R60TM was able to reduce the Removal of precursors such as
levels down to less than 0.1 ppm. chlorides can be improved at the
WO2011/005081A1 also However, if refined and deodorised mills. Acidic earths may be used,
describes a similar type of process palm oil is treated with the provided the residue acids in the
for removing unwanted propanol adsorbents and then re-deodorised, earths have been well removed.
components from unused there is increase in glycidyl esters Lowering the temperature during
triglyceride oil, by contacting instead. If adsorbents impart an deodorisation may be considered,
refined oils with a silicate odour to the oil, this process may if other quality specifications are

25
Palm Oil Developments 57

maintained. Finally, for premium Removal of chlorinated glycerides K (2011). Effects of degumming
oils and sensitive products for from processed foods. LWT- Food and bleaching on 3-MCPD esters
infants, adsorbents may provide Science and Technology, 39: 86- formation during physical refining.
the answer. 90. J. Am. Oil Chem. Soc., 88: 1839-
1844.
Acknowledgement Hrncirik, K and Ermacora, A
(2010). Formation of 3-MCPD es- Strijowski, U; Heinz, V and
The authors thanked the Director- ters in vegetable oils: Effect of par- Franke, K (2011). Removal of
General for permission to publish tial acylglycerols. 8th Euro Fed Lipid 3-MCPD esters and related sub-
this paper. Congress. 21-24 November 2010. stances after refining by adsorbent
Munich, Germany. material. Eur. J. Lipid Sci. Technol.,
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ing palm (Elaeis guineensis) oil Matthäus, B; Pudel, F; ester reduction in oil. Applicant:
production. Food Additives and Fehling, P; Vosmann, K Archer Daniels Midland Company.
Contaminants: Part A: Chemistry, and Freudenstein, A (2011).
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Risk Assessment, 29: 354-361. 3-MCPD esters and related com- ducing chloropropanols and for-
pounds in vegetable oils. Eur. J. mative substances thereof, glycidol
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W; Dubois, M and Destaillats, Applicants: Fuji Oil Co. Ltd.
F (2012b). Glycidyl esters in refined Nagy, K; Sandoz, L; Craft, B D
palm (Elaeis guineensis) oil and re- and Destaillats, F (2011). Mass- WO/2011/009843: A deodorised
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ommendations for effective mitiga- tures to reveal the source of chlori- bound MCPD and process of mak-
tion. Food Chemistry, 132: 73-79. nated palm oil contaminants. Food ing using an inert gas. Applicants:
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Sandoz, L and Nagy, K (2012). 618467. WO/2011/009841: Deodorised
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Kasai, N; Suzuki, T and Idogaki, Ramli, M R; Siew, W L; Nuzul, WO/2010/063450: Method for
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of esters of dichloropropanols: Razak, R A A and Nesaretnam,

26
 The Possible Mitigation Procedures for the Reduction of the Formation of Chloropropanol Esters and Related Compounds

refined vegetable oils. Applicant: acid esters. Applicant: Sime Darby Zelinkova, Z; Svejkova, B;
Sϋd-Chemie AG, Schurz, K. Malaysia Berhad. Velisek, J and Dolezal, M
(2006). Fatty acid esters of 3-chlo-
WO/2011/002275 A1: Process WO/2011/005081 A1: Process ropropane-1,2-diol in edible oils.
for manufacturing palm oil frac- for removing unwanted propanol Food Additives and Contaminants,
tions containing virtually no components from unused triglyc- 23: 1290-1298.
3-Monochloropropanediol fatty eride oil. Applicant: Sime Darby
Berhad.

27