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40 CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Patent Application

61/639,21 1 , entitled improved Fractionation Process, filed April 27, 2012, and to U.S. Provisional Patent Application 61/653,030, entitled Improved Fractionation Process, fiied May 30, 2012. The patent applications identified above are incorporated herein by reference in their entirety to provide continuity of disclosure.

FiELD

[0002] The present approach relates to methods for producing fats and oils. Specifically, the present approach pertains to methods for producing fractions of palm oil having low levels of monochSoropropanediol contaminants and glycido! ester contaminants and methods for making the fractions.

BACKGROUND ART

[0003] Contaminants causing potential health hazards have recently been found in vegetable oils, especially palm oil, Monochloropropanediols (MCPD), MCPD esters and g!ycidoj esters (GE) are among the contaminants. When palm oil is processed, color and meta! impurities are removed by bleaching, !n addition, free fatty acids and other impurities are removed by physical refining (steam deodorization) at high temperatures and/or long retention times in a deodorizer to obtain refined palm oil. Valuable fat fractions are obtained from refined palm oil by the process of fractionation, which produces fractions enriched in harder, more solid fat and fractions enriched in softer, more liquid oil. Fractionation has been described in, for example, Deffense, E. "Fractionation of Palm Oil," Journal of the American Oil Chemists' Society 62(2), 376-385 (1985).

SUMMARY OF INVENTION TECHNICAL PROBLEM

{00013 The content of GE and MCPD in crude palm oil before physical refining is typically low, and may be below defection limits. The exposure of oil to the elevated temperatures and/or long treatment times used in the physical refining process used to remove free fatty acids from palm oil problematically results in the formation of MCPD, The level of MCPD in palm oil after physical refining is typically 1-5 ppm. but may be much higher.

[00023 Fractionation of physically refined palm oil problematically

concentrates MCPD in the more liquid fraction, called an "olein" fraction. Subsequent additional fractionation steps, such as second stage, third stage, and fourth stage fractionations can concentrate the MCPD in further olein fractions, such as second oiein and third oiein fractions. Palm oil fractions frequently require bleaching and deodorization. The deodorization process is similar to the physical refining process, and in deodorization the palm fractions are subjected to further temperature stress. Thus, the content of GE and MCPD and i paim fractions frequently increases further during bleaching and deodorization. Palm oil fractions, such as palm olein, have been categorize as food oils having high levels (greater than 4 mg/kg) of MCPD (Larsen, J. C, "3-MCPD Esters in Food Products/' Summary Report of a Workshop held in February 2009 in Brussels, Belgium, International Life Sciences Institute).

[0003] Conventional paim oil refining is accompanied by the generation of GE and MCPD in the bleaching and physical refining steps, respectively, which take place prior to fractionation. Thus, the problem encountered in fractionation is the concentration of the contaminants in certain fractions. There is a need in the food industry fo vegetable oil fractions, especially paim oil fractions, especially palm oieins, which are low in GE and MCPD contaminants.

SOLUTION TO THE PROBLEM

[00043 We have created a solution by combining chemical refining (alkali refining) with palm oil fractionation, thereby suppressing the formation of GE and MCPD. After reducing the free fatty acid content of palm oil by alkaii refining, a reduced temperature and shorter retention time can be applied to the oil in the deodorization process yielding oil with low levels of GE and MCPD. The fractions we obtain, including olein fractions, are very Sow in GE and MCPD, even after

deodorization.

ADVANTAGEOUS EFFECTS OF INVENTION

[0005] Fractions of palm oil can be produced with much lower levels GE and

MCPD than are available by conventional physical refining of paim oil.

BRIEF DESCRIPTION OF DRAWINGS

[0006] Figure 1 shows a scheme for selected methods of palm oil

fractionation. Fraction names and Iodine values (IV) are not limiting but are typical of some grades of fractions.

[0007] Figure 2 shows a scheme for a method of palm oil fractionation described in Example 5. Fraction names and Iodine values (IV) are not limiting but are typical of some grades of fractions.

DESCRIPTION OF EMBODIMENTS [0008] The present approach relates to producing compositions of palm oil fractions having low levels of GE and CPD contaminants.

[0009] As used herein, "crude oi!" means unprocessed oil after it has been extracted from vegetable or animal raw materia!. Crude oils normally need refining to render them fit for human consumption.

[0010] As used herein, "deodorization" means steam distillation of refined oil to remove impurities. Exemplary oils include but are not limited to soybean oil, canoSa oil, corn oil, sunflower oil, palm oil, palm kernel oil, and saffiower oil, and fractions of any thereof.

[0011] As used herein, "alkali refining," "neutralizing," or "chemical refining" means removing free fatty acids from oil by contacting with a solutio of alkali and removal of resulting fatty acid soaps that form from the bulk of triaeySglyceroSs. Alkali refined oil may be, but not always, subsequently bleached and deodorized before being considered to be edible grade.

[0012] As used herein, "physical refining" means high temperature steam distillation of oil under conditions which remove most free fatty acids while keeping the bulk of triacylgl cerols intact. Physical refining is similar to deodorization, except physical refining is often carried out to remove free fatty acids in addition to the impurities removed by deodorization. Physical refining is typically carried out at temperatures of 240- 270 °C.

[0013J As used herein, "palm fraction" means a component of palm oil obtained from fractionation of palm oil.

[0014] As used herein, "fractionation" means a physical separation process applied to fats or oils resulting in fractions of the fat or oil having different

compositions. One type of fractionation includes by cooling under defined conditions until a solid forms. Further filtration or decanting of the cooled fat results in fat being split into at least a low melting liquid fraction {olein) and a higher-melting solid fraction (stearin). Fractionation can take place in the absence (dry fractionation) or presence (wet fractionation) of an additional solvent, such as acetone, liquid vegetable oil, or hexane. Fractionation is carried out by cooling oil until crystals form (stearin), then filtering the cooled oil to separate the liquid olein from the stearin crystals. The stearin crystals ma retain liquid olein in the interstitial space in and among crystals, and stearin ma be subjected to pressing to remove the retained olein. Fractionation parameters include the rate of cooling, the final cooling temperature, the duration of holding at a given temperature, the diameters and distribution of perforations in filter screens, and the amount and duration of pressure that is optionally applied to stearin. The temperatures and pressures needed for fractionation are varied according to the properties of the starting materials and desired products according to procedures widely known to those of the art.

[0015] As used herein, "olein" and "stearin" refer to the two fractions obtained in a fractionation step. "Olein" refers to the fraction having a higher iodine value and "stearin" refers to the fraction having a lower iodine value. Olein fractions are enriched in oil components having a lower melting point than either the unfractionated oil or the stearin fraction and are thus softer that the corresponding stearin fraction. Olein is predominantly liquid oil at a fractionation temperature, and stearin is predominantly solid oil at fractionaiton temperatures. Generaily the iodine value of an olein fraciion is higher than the iodine value of the. oil or fraction from which it was derived. As used herein, "palm stearin" means a palm fraction enriched in palm oil components having a higher melting point than the unfractionated palm oil from which it was obtained, or ^¬ is predominantly solid oii at the filtration temperature. The iodine value of a stearin fraction is lower than the iodine value of the oil or fraction from which it was derived. The yields of olein and stearin from a given filtration step can be varied within relatively broad ranges. For example, in a fractionation the yield of stearin can comprise 10- 90 weight percent of the starting material; the corresponding yield of olein will comprise 90- 10 weight percent of the starting material, so that the weights of the stearin and olein will sum to approximately the weight of the starting material. Each olein or stearin fraction can be designated with a number indicating the iodine value of the fraction. Palm fractionators often develop their own unique terminology for each fraction. However, regardless of any other names ascribed to a fraction, the question of which fraction from a fractionation step is the stearin or the olein can be answered by comparing their iodine values.

[00 6] As used herein, "first stage fractionation" or "primary fractionation" means fractionation of an oil that has not been previously subjected to a fractionation step. A stearin fraction and an olein fraction are obtained. Palm fractionators often refer to the first olein as "palm olein" and the first stearin as "hard stearin." As used herein, "palm olein" or "first olein" refer to the olein fraction obtained in a first fractionation. As used herein, "hard stearin" or "first stearin" refer to the stearin obtained in a first stage fractionation of palm oil. A first olein obtained in first stage fractionation first oiein may have an IV of 56 and can thus be denoted "oiein 56." The corresponding stearin may have an IV of 33 and can thus be denoted "stearin 33."

[0017] As used herein, "second stage fractionation" or "secondary

fractionation" means fractionation of a first oiein fraction or a first stearin fraction that has been obtained in a first fractionation step. For example, first oiein (palm o!ein) from first stage fractionation can be fractionated in a second stage fractionation to form a second oiein fraction and a second stearin fraction. As used herein, "double fractionated oiein" means a second oiein resulting from the second stage fractionation of a first oiein. Second oiein is enriched in unsaturated oils relative to first oiein, and the iodine value of doub!e fractionated oiein (second oiein) is higher than the iodine va!ue of the palm oiein {first oiein) from which it was derived. Second oiein may also be called "super oiein," or "double oiein," and may have an iodine value of 64, in which case it may be called "oiein 64" or "olein(64)".

[0018] Turning now to the other fraction obtained in second stage

fractionation, second stearin is enriched in saturated oils relative to first oiein, and the iodine value of second stearin is lower than the iodine value of both the first oiein from which it was derived and the second oiein. Second stearin may also be cailed "soft PMF," "soft palm mid fraction" or "sPMF" and may have an !V of 45, in which case it may be called "sP F(45)".

[0019] As used herein, "third stage fractionation" means fractionation of a fraction that has bee obtained in a second fractionation step, such as a second stearin or a second oiein. When a second stearin resulting from second stage fractionation is subjected to third stage fractionation, the resulting oiein is called "third oiein." For example, a third oiein having an iodine value of 49 may be called

"P F(49)." A third stearin is also formed in third stage fractionation; for example, a third stearin having an iodine value of 30 may be called "hard palm mid fraction (30)."

[0020] As used herein, "fourth stage fractionation" means fractionation of a third oiein or third stearin that has been obtained in a third fractionation step. When a third oiein, such as PMF(49), obtained from third stage fractionation is subjected to fourth stage fractionation, the resulting fourth oiein fraction having an iodine value of 54 is called "oiein fiussig(54)" and the resulting fourth stearin fraction having an iodine value of 39 is called "palm mid fraction{39)" or ^H P F{39)".

[0021] As used herein, "monochioropropanedioi" means a mono- chloropropane- 1 ,2-diol and includes 3- mono-chioropropane-1 ,2-diol (3- CPD) and 2- mono-chioropropane-1 ,2-diol (2-MCPD). MCPD is a contaminant that occurs in food in its non-esterified (diol) form,

[0022] As used herein, "MCPD esters" means a monoester or diester (with fatty acids) of MCPD, MCPD esters are contaminants that occur in food in an esterified (with fatty acids) form.

[0023] As used herein, "glycidol ester" refers to a fatty acid ester of giycidol. Giycidol esters are contaminants that occur in food in an esterified (with fatty acids) form.

[0024] As used herein, "iodine value" refers to a measure of the unsaturation of fats and oils and is expressed in terms of the number of centigrams of iodine absorbed per gram of sample (% iodine absorbed). Higher iodine values indicate a more liquid fraction having a greater degree of unsaturation (greater number of double bonds).

[0025] One non-limiting aspect of the present disclosure is directed to a composition comprising a palm oi! fraction, wherein the palm oil fraction contains less than two parts per million of at least one of a MCPD or a GE, less than 1.5 parts per million of at least one of a MCPD or a GE, less than one part per million of at least one of a MCPD or a GE, less than 0.5 parts per million of at least one of a MCPD or a GE, less than 0.1 parts per million of at least one of a MCPD or a GE, or is below the limit of detection of a detection method. In one non-limiting aspect of the present disclosure the detection is carried out according to a method selected from the group consisting of the 3~in~1 method of SGS Hamburg and the DGF Standard Method C-fV 18 (10). In one non-limiting aspect of the present disclosure the palm oil fractions are produced from a starting palm oil containing greater than 1.5% free fatty acids.

[0026] One non-limiting aspect of the present disclosure is directed to the palm oil fractions produced by alkali refining palm oil to obtain refined palm oil, and fractionating the refined palm oil in one or more fractionation steps to obtain two or more palm fractions. In a non-limiting aspect of the present disclosure the refined oil is produced by subjecting the oil to acid treatment before alkali refining.

[0027] In a further non-limiting aspect of the present disclosure the fractions may be bleached.

[0028] One non-limiting aspect of the present disclosure is directed to a deodorized palm oil fraction, wherein the deodorized palm oil fraction contains less than two parts per million of at least one of a MCPD or a GE, less than 1.5 parts per million of at least one of a MCPD or a GE, less than one part per million of at least one of a MCPD or a GE, less than 0,5 parts per million of at least one of a MCPD or a GE, less than 0.1 parts per million of at least one of a MCPD or a GE, One non- limiting aspect of the present disclosure is directed to deodorized palm oil fraction wherein at least one of a MCPD or a GE of the deodorized palm oil fraction is below detection limits of a detection method. In one non-limiting aspect of the present disclosure the detection is carried out according to a method selected from the group consisting of the 3~in~1 method of SGS Hamburg and the DGF Standard Method C-iV 18 (10).

[0029] In non-limiting aspects of the present disclosure the deodorized palm fraction comprises a fraction resulting from at least one of a first stage fractionation, a second stage fractionation, a third stage fractionation, and a fourth stage

fractionation. One non-limiting aspect of the present disclosure is directed to deodorized palm oil fraction wherein the deodorized paim fraction comprises a palm mid fraction resulting from fourth stage fractionation of palm oil.

[0030] One non-limiting aspect of the present disclosure is directed to a method of producing palm oil fractions wherein a starting palm oil is alkali refined (chemically refined) to obtain refined palm oil, and fractionated in one or more fractionation steps to obtain two or more palm fractions, such as palm olein and palm stearin, wherein the level of MCPD in the palm fractions is less than one part per million or the level of GE in the palm fractions is less than one part per million. In certain non-limiting aspects, the starting palm oil may contain greater than 1.5% free fatty acids before alkali refining. In other non-limiting aspects, the refined oil is produced by subjecting the oil to acid treatment before alkali refining, in non-limiting aspects, paim fractions, may be subjected to further fractionation, forming further fractions reduced in a MCPD, such as hard stearin, super stearin, soft stearin, soft palm mid fraction, super olein, hard palm mid fraction, oieins, top o!ein, stearin(33), hard stearin(35), olein(56), palm olein(56), olein(64), super olein(64), sPMF(45), soft PMF(45), super stearin (40), PMF(49), hard palm mid fraction(30), PMF{30), olein flussig(54) _! and PMF(39), first stearin, second stearin, third stearin, fourth stearin, first olein, second olein, third olein, fourth olein, and combinations of any thereof. In certain non-limiting aspects, the level of a MCPD in these further palm fractions is less than two parts per million of at least one of a MCPD or a GE, less than ,5 parts per million of at least one of a MCPD or a GE, less than one part per million of at least one of a MCPD or a GE, less than 0.5 parts per million of at least one of a MCPD, and iess than 0.1 parts per million of at least one of a MCPD. One non-iimiting aspect of the present disclosure is directed to deodorized paim oil fraction wherein at least one of a MCPD or a GE of the deodorized paim oil fraction is below detection limits of a detection method. In certain non-limiting aspects, any of these fractions may be further subjected to bleaching, deodorizing, or bleaching and deodorizing to obtain bleached, deodorized, or bleached and deodorized paim fractions. In certain non- iimiting aspects, the MCPD levels of the bleached, deodorized, or bleached and deodorized palm fractions may be iess than two parts per million of at least one of a MCPD or a GE, less than 1.5 parts per million of at ieast one of a MCPD or a GE, less than one part per million of at least one of a MCPD or a GE, less than 0.5 parts per million of at ieast one of a MCPD, and iess than 0,1 parts per million of at Ieast one of a MCPD. One non-limiting aspect of the present disciosure is directed to deodorized palm oil fraction wherein at least one of a MCPD or a GE of the

deodorized palm oil fraction is below detection limits of a detection method, including the 3-in-1 method of SGS Hamburg, Germany and the DGF Standard Method C-iV 18 (10).

[0031] in certain non-limiting aspects, products may be obtained by the methods outlined herein, and products obtained by the methods outlined herein may be used, for example in food fat, food ingredients, frying oil, blending oil, biscuits, bakery, cookies, margarine, fried foods, shortenings, infant formulas, chocolate spreads, confectioneries, coffee whitener, filled miik, biscuit cream, cookie cream, and coating fats.

EXAMPLES

[0032] The following examples illustrate methods for removing MCPDs and

GE from oil, and compositions of oils containing low levels of MCPDs and GEs, according to the present invention. The following examples are illustrative only and are not intended to limit the scope of the invention as defined by the appended claims.

EXAMPLE 1

[0033] Fractionation of physicaily-refined palm oil in a comparative example, physical refining of crude palm oil containing 5.4 % free fatty acid (ADM, Hamburg, Germany, 20 tons) was carried out. Crude paim oil was first acid treated (oil was heated to 90 *C, 0.1 wt% of a 75% solution of phosphoric acid was added and the oil was agitated at 90 °C for 20 minutes). After acid treatment, the acid-treated oi! was subjected to conventional bleaching at 100 X under 0.9 bar vacuum for 6.0-90 minutes in a continuous bleacher using clay {Sudchemie 212 or 1 12 or Taiko Classic 2H), plus 0.3% activated carbon and 0.4% citric acid. The oil was filtered, producing bleached oil. The bleached oil was physically refined in a semi-continuous deodorizer by heating to 270 °C under vacuum (< 3 m ar absolute) with sparge steam.

Residence time in the deodorizer was 60 minutes. After cooling, physically refined palm oil was obtained.

[00343 The physically refined palm oil was fractionated. First stage

fractionation of physically-refined palm oil was carried out in a one-iiter jacketed vessel equipped with an overhead double-paddie scraped-surface stirrer operated at 3 RPM. The temperature of the palm oil was controlled using a circulating cooling bath to circulate cold water through the jacket of the vessel. The temperature of the fat in the vessel was monitored with a calibrated temperature probe. Physicaliy- refined palm oil was heated to 62X and homogenized, and 800 grams of the palm oil was added to the fractionating batch vessel. The vessel temperature was set to 55 ^C C. For first stage fractionation, the physicaf!y-refined palm oil was subjected to the procedure outlined in Table 1. Table 1. First stage fractionation procedure, _

On ^' cooied fro 55 ^' to ^' 28 "C ^' in ^" 3 hours I _. JZI ^' |

Stirred at 3 RPM for 15 hours (temperature rose to 35 X) j

" Cool dlrom 35 X to 28 Xln 5 minutes ΓΠ J

St e¥at 28 for 3.5 hours ^{" ' "} [

[0035] The cooled physically refined palm oil was vacuum filtered through black ribbon filter paper (12 - 25 microns) at room temperature to obtain 23.1 % palm stearin and 76.9% palm olein. The stearin and olein fractions were separately subjected to bleaching with 1 % clay at 70 X and deodorized for 3 hours at 230 X. The palm stearin and palm olein were tested for GEs, 3-!VICPD and 2-MCPD during the process by the "3~in~1 method," SGS Germany GmbH, Hamburg, Germany (Table 2). Table 2. Levels of 3- CPD, 2-MCPD, GE and free fatty acids in physically refined palm oil and palm fractions obtained by first stage fractionation. Values for glycidol ester, 2-MCPD and 3-MCPD are in ppm. 3-MCPD 2-MCPD Glycidol Free fatty ester acid (%)

Crude palm oil ' δ.ϊο <0.10 «0.10 5,40

Physicaiiy refined paim oil 4,12 2.01 9.53 0.04

Stearin before bleaching 3.1 1.61 7.59 0.03

Stearin after bleaching 3.05 1.54 0.ΪΪ 0

Stearin after bleaching and 2.75 1.52 <0.10 0.02 deodorizing

Olein before bleaching 4.48 2,32 0.03

Olein after bleaching 4,48 2.35 0.14 0

Olein after bleaching and 3.62 2.15 <0.10 0.02 deodorizing

[0036] Physical refining crude palm oil caused undesirable increases in the levels of 3-MCPD, 2-GE and MCPDs from less than 0.1 ppm to relatively high levels. The high levels of contaminants passed into the subsequently fractionated oils. The levels of 3-MCPD and 2-MCPD in both stearin from physically refined oil and olein from physically refined oil were greater than 1 ppm even after bleaching and deodorizing. The levels of GE in both stearin from physically refined oil and olein from physically refined oil were ver high (greater than 7 ppm) but were reduced by bleaching and deodorizing. Palm fractions containing less than one part per million of MCPD were not obtained before bleaching, after bleaching, or after bleaching and deodorizing, illustrating the problem with physical refining.

EXAMPLE 2

[G0373 Alkali refining of palm oil and fractionation of alkali refined palm oil Starting (crude) palm oil (about 5 kg, ADM, Hamburg, Germany) containing 5.4 % free fatty acid was acid treated (oil was heated to 90 °C, 0.1 wt% of a 75% solution of phosphoric was added and the oil was agitated at 90 "C for 20 minutes. The oil was allowed to cool to SO °C and the acidity of the resulting oil was measured in-line). Alkali refining was then carried out by adding an amount of sodium hydroxide corresponding to 125% of the stoichiometric equivalent of acidity in the oil at 80 °C and incubating with the oil for 10 minutes. About 1 volume % water was added and the mixture was centrifuged and dried at 70 °C under vacuum (100 mbar) for 5 minutes to produce alkali-refined oil. A sample of the neutralized oil was washed with nine sequential aliquots (500 ml) of 60 water until the soap content was below 20 ppm. The oil was then dried by heating to 70 °C under vacuum for 30 minutes. After testing for 3-MCPD, 2-MCPD, GE and free fatty acids, first stage fractionation of alkali-refined palm oil was carried out substantially as outlined in Example 1. After being subjected to fractionation cooling, the cooled alkali-refined palm oil was vacuum-filtered through black ribbon fitter paper (12 - 25 microns) at room

temperature to obtain palm fractions (28.5 weight percent palm stearin and 71.5 weight percent palm olein). The palm stearin and palm olein were separately bleached with 1 % clay at 70 °C and deodorized. The levels of 3-MCPD, 2-MCPD, and GE were determined by during the process using the DGF Standard Method "3~in-1 method," SGS Germany GmbH, Hamburg, Germany (Table 3).

[00383 The starting palm oil contained 5.4% free fatty acids, and the free fatty acid level after alkali refining was substantially reduced. To demonstrate the solution for obtaining Sow MCPD palm fractions, starting palm oil was alkali refined to obtain palm stearin and palm olein having MCPD levels of less than one part per million of 3- MCPD and 2-MCPD and GE before bleaching, after bieaching. in fact, the levels of 2- MCPD, 3-MCPD and GE were below the detection limits of the detection method. After bleaching and deodorizing, bleached and deodorized palm oil fractions containing less than one part per million of MCPD and less than one part per million GE were obtained. In addition, the bleached and deodorized first olein contained less than one part per million of MCPD and the level of GE of the first olein was below the detection limit of the 3-in-1 method of SGS Hamburg, Germany.

EXAMPLE 3 [0039] Crude palm oil (ADM, Hamburg, Germany) was subjected to alkali refining substantially as outlined in Example 2 and dried by heating to 70 under vacuum for 30 minutes. First stage fractionation of alkali-refined palm oil was carried out substantially as outlined in Example 1 to obtain palm fractions. For first stage fractionation, the alkaii-refined palm oil was subjected to the procedure outlined in Tab!e 4.

Table 4. Fjrst stage fractionation procedure.

[0040] The cooled aikaSi-refined pa!m oil was vacuum-filtered through black ribbon filter paper (12 - 25 microns) at room temperature to obtain palm fractions (30 weight percent first stearin and 70 weight percent first olein). The first stearin (palm stearin, stearin(42)) and first olein (pa!m olein, olesn(56)) were tested for Iodine Value, 3-MCPD, 2-GE and MCPDs (Table 5). The levels of 3-MCPD and GE were

determined by the 3-in-1 method of SGS Hamburg, Germany at. SGS Germany GmbH, Hamburg, Germany.

Table 5. Levels of 3-MCPD, 2-MCPD, GE and iodine values in alkali refined paim oil and fractions obtained by first st age fractionation.

£0041] Palm fractions containing less than one part per million of MCPD and less than one part per million GE were obtained. The levels of 3-MCPD, 2-GE and MCPDs in palm stearin and palm olein obtained by first stage fractionation of alkali- refined palm oil were at or below the detection limits of the DGF Standard Method "3- in-1 method." The levels of GE and MCPD after subsequent deodorizaiion of the palm stearin and palm olein are expected to be less than one part per million of MCPD as demonstrated in Example 2 (Table 3).

[0042] The first oiein obtained by first stage fractionation of alkali-refined palm oil was subjected to second stage fractionation in the same equipment used for first stage fractionation (Table 6). Table 6. Second stage fractionation procedure for fractionation of oiein(56),

[ The olein(56) was heated to 70 °C in t e fractionation batch vessel ]

Cooled with constant stirring from 70 ° to 28 °C in 65 minutes j

! Stirred for 85 minutes, while allowing the temperature to increase to 29.3 j

I °C ________ ί

I Cooled for 5 n¾tes ^' to 20 ^"

Γ Stinred at 20 ^' forls hours ^{"" ~~} _

l ^" CooTed from 2Q ^{" "} to ^" T§ ^"" 1 10 minutes ^'

rCooled ^' from 18 °C to 16 ln 30 minutes ^{' '}

\ Cooled from 16 ^C C to 14 °C in 50 minutes (crystal formation observed)

I ^'' Cooied from 14 lo ^' l2 °C in 110 ^~ mlnutis

I Stirred at 1 °C for 155 minutes (many big crystals observed) j

[0043] The cooled first olein was vacuum filtered through black ribbon filter paper (12 - 25 microns) at room temperature to obtain palm fractions. A second stearin fraction (soft PMF(55), 69 weight percent) and a second olein fraction (double fractionated olein(59), 31 weight percent were obtained. The iodine value and levels of MCPD and GE were determined (Table 7).

Table 7. Levels of 3-MCPD, 2-JvlCPD, GE and iodine values in first oiein, second stearin, and second olein, resulting from second stage fractionation of first olein olein 56)).

[0044] Palm fractions containing less than one part per million of MCPD and less than one part per million GE were obtained. The second stearin fraction (soft PMF{55)) obtained by second stage fractionation of first olein (oIein(56)) from alkali- refined palm oil did not contain any detectable amounts of 3-MCPD, 2-MCPD or GE when tested by the DGF Standard Method "3-in-1 method," The second oiein fraction (double fractionated ofein(59)) obtained by second stage fractionation of first olein (olein(56)) from alkali-refined palm oil contained only 0.12 ppm 3-MCPD and did not contain any detectable amounts of 2-MCPD o GE when tested by the DGF Standard Method "3-ii>1 method." The levels of GE and MCPD after subsequent deodorization of the soft PMF(55) and doubie fractionated oiein(59) are expected each to be less than one part per miilion of MCPD as demonstrated in Example 2 (Table 3).

EXAMPLE 4

[00453 Palm oil containing 5.5 % free fatty acid was alkaii refined

substantially as outlined in Example 2 except that the crude palm oil was not subjected to an acid treatment step before the alkali refining step. Alkali-refining of crude palm oil (about 5 kg, ADM, Hamburg, Germany) was carried out after

measuring the acidity of the oil by adding an amount of sodium hydroxide

corresponding to 125% of the stoichiometric equivalent of acidity at 80°C and incubating with the oil for 10 minutes. About 1 volume % water was added and the mixture was centrifuged and dried at 70 °C under vacuum (100 mbar) for 5 minutes to produce neutralized oil. A sampie of the neutralized oil was washed with sequential aliquots (500) of 60 °C water until the soap content was below 20 ppm. The oil was then dried by heating to 70 °C under vacuum for 30 minutes. The oil was bleached with 1% clay at 70 °C, An aliquot of oil was deodorized and tested.

[0046] First stage fractionation of alkali-refined, bleached palm oil was carried out substantially as outlined in Example 1. The cooled alkali-refined, bleached palm oil was vacuum-filtered through black ribbon filter paper (12 - 25 microns) at room temperature to obtain palm fractions (207 weight percent palm stearin and 79.3 weight percent palm oiein). The palm fractions were deodorized for 3 hours at 220 °C. The firstm stearin and first olein were tested for 3-MCPD, 2-MCPD, GEs, and free fatty acids (Table 8). The levels of 3-MCPD and GE were determined by the 3-irv1 method of SGS Hamburg, Germany at SGS Germany GmbH, Hamburg, Germany,

Table 8. Levels of 3-MCPD, 2-MCPD, GE and iodine values in palm oil not subjected to acid pretreatment before alkaii refining, and palm fractions obtained by first stage fractionation of alkali refined, bleached palm oil. _____

first stearin containing less than one part per million of MCPD and less than one part per million GE was obtained after deodorizing the palm stearin. The corresponding first olein contained slightly more than one part per million of MCPD and less than one part per million GE.

EXAMPLE 5

[0048] Crude palm oil (ADM, Hamburg, Germany) was alkali refined substantially as in Example 2 then bleached substantially as in Example 1 , The caustic refined, bleached oii was deodorized substantially as in Example 1 , to obtain 100 metric tons of oil containing 1 ppm 3-MCPD, then fractionated. Four stages of fractionation were carried out, with each stage being carried out with variable temperatures and pressures as required to obtain the desired fractions according to procedures widely known in the art of fractionation, The fractions that were obtained are described in Table 9 and in Figure 2.

Table 9. Fractionation of palm oil that has been alkali refined, bleached, and deodorized. In any given fractionation, the harder fractions are shown to the left of the softer fractions. Each ro represents the next stage of fractionation of one fraction from the row above. In each row, the stearin fraction (Sower IV fraction) is to the left of the corresponding olein fraction (higher IV fraction), IV= Iodine value. 3-MCPD values are given in parts per million.

[0049] In a first fractionation stage, palm oil was fractionated info a first stearin fraction designated "hard stearin" or ^f, stearin(35)" (IV- 35) and a first oiein fraction, designated "palm oiein" or "olein(56") 0V= 56). Exemplary yields of stearin{35) ranged from 10-30 weight percent of the starting paim oil, with

Gorresponding exemplary yields of olesn(56) ranging from 90-70 weight percent of the starting paim oil The 3- CPD content of the starting palm oil was 1.0 ppm, and fractionation resulted in a first stearin (stearin(35)) fraction containing 0.3 ppm 3- CPD and a first olein (oSein(56)) fraction containing 1.2 ppm 3-MCPD.

[0050] In a second fractionation stage, Olein(56) from the first fractionation stage was fractionated into a second stearin fraction (Soft PMF(45), iV~ 45), and a second olein fraction designated Oiein(64)" (IV= 64). Exemplary yields of Soft

PMF(45) ranged from 30-60 weight percent of the starting Olein(56), with

corresponding exemplary yields of Olein(64) ranging from 70-40 weight percent of the starting Olein(56). The 3-MCPD content of the starting Olein(56) was .2 ppm, and second stage fractionation resulted in Soft PMF(45) containing 10 ppm 3-MCPD and Super oiein(64) containing 1.4 ppm 3-MCPD.

[0051] In a third fractionation stage, second stearin (Soft PMF(45)) was further fractionated into a third stearin fraction designated "PMF(30)" (!V= 30) and a third olein fraction designated MF(49)" (IV ^™ 49). Exemplary yields of PMF(30) ranged from 15-35 weight percent of the starting sPMF{45), with corresponding exemplary yields of PMF(49) ranging from 85-65 weight percent of the starting Soft FMF(45). The 3-MCPD content of the starting Soft PMF(45) was 1.0 ppm, and fractionation resulted in PMF(30) containing 0.8 ppm 3-MCPD and PMF(49) containing 1.1 ppm 3-MCPD. [0052] In a fourth fractionation stage, the third olein (P F(49)) from the third fractionation stage was further fractionated into a fourth stearin fraction designated "PMF{39)" (IV=39) and a fourth oiein fraction designated "Olein fiussig(54)" (IV=54). Exemplary yields of P F(39) ranged from 20-50 weight percent of the starting P F(49) _; with corresponding exemplary yields of Olein flussig(54) ranging from 80-50 weight percent of the starting PMF(49). The 3-MCPD content of the starting P F(49) was 1.1 ppm, and fractionation resulted in PMF{39) containing 0.6 ppm 3-MCPD and Olein flussig(54) containing 1.3 ppm 3-MCPD. Thus, when starting with 100 tons of palm oil, a yield of 9.45 tons of PMF(39) containing only 0,6 ppm 3-MCPD was obtained.

INDUSTRIAL APPLICABILITY

[0053] Due to improvements in analytical methodology and increases in understanding of toxicology, government regulation and intervention are expected to limit the levels of GE and MCPD in food ingredients and foodstuffs. There is a significant commercial demand for palm oil fractions that are low in MCPD and/or GE and palm oil in all areas of food manufacturing, e.g. food fat, food ingredients, frying oil, blending oil, biscuits, bakery, cookies, margarine, fried foods, shortenings, infant formulas, chocolate spreads, confectioneries, coffee white ner, filled milk, biscuit or cookie cream, coating fats, etc.

CITATION LIST

NON-PATENT LITERATURE

[0054] Larsen, J. C„ "3-MCPD Esters in Food Products," Summary Report of a Workshop held in February 2009 in Brussels, Belgium, International Life Sciences Institute.

[0055] Deffense, E. _t "Fractionation of Palm Oil," Journal of the American Oil

Chemists' Society 62(2), 376-385 (1985).

[0056] While the foregoing invention has been described in some detail for purposes of clarity and understanding, it will be appreciated by one skilled in the art from a reading of this discfosure that various changes in form and detail can be made without departing from the true scope of the invention and appended claims.