Process for producing a glyceride composition

Abstract

A process for the production of a composition comprising 1,3-dioleoyl-2-palmitoyl glyceride (OPO) comprises: providing one or more palm oil stearin fractions comprising tripalmitoyl glyceride and having an iodine value between about 18 and about 40; interesterifying the one or more palm oil stearin fractions to form a randomly interesterified palm oil stearin; subjecting the randomly interesterified palm oil stearin to enzymic transesterification with oleic acid or a non-glyceride ester thereof using an enzyme having selectivity for the 1- and 3-positions of a glyceride; and separating palmitic acid or palmitic non-glyceride esters from the product obtained in (iii) to form a composition comprising OPO glyceride.

Claims

1. A process for the production of a composition comprising 1,3-dioleoyl-2-palmitoyl glyceride (OPO), wherein the process comprises: providing one or more palm oil stearin fractions comprising tripalmitoyl glyceride and having an iodine value between about 18 and about 40; (ii) interesterifying the one or more palm oil stearin fractions to form a randomly interesterified palm oil stearin having a SN-2 value for C16:0 of from 0.300 to 0.333; (iii) subjecting the randomly interesterified palm oil stearin to enzymic transesterification with oleic acid or a non-glyceride ester thereof using an enzyme having selectivity for the 1- and 3-positions of a glyceride; and (iv) separating palmitic acid or palmitic non-glyceride esters from the product obtained in (iii) to form a composition comprising OPO glyceride, wherein the composition comprises not more than 45 wt % of palmitic acid, based on total fatty acid content, and wherein at least 53 wt % of the palmitic acid residues are present in the 2-position of the glyceride.

2. A process according to claim 1, wherein the one or more palm oil stearin fractions is or are bleached and deodorised before step (ii).

3. A process according to claim 1 or claim 2, further comprising the step (v) of dry fractionating the product obtained in (iv) to form a fraction comprising an increased amount of OPO.

4. A process according to claim 1, wherein step (ii) is carried out enzymatically.

5. A process according to claim 1, wherein the one or more palm oil stearins is or are provided by fractionating palm oil or a derivative thereof.

6. A process according to claim 5, wherein fractionating palm oil comprises dry fractionation.

7. A process according to claim 1, wherein the palm oil stearin has an iodine value between about 18 and about 35.

8. A process according to claim 1, wherein the palm oil stearin comprises a mixture of at least two palm oil stearins having different iodine values.

9. A process according to claim 1, wherein the palm oil stearin comprises a mixture of a first palm oil stearin having an iodine value of from about 10 to about 20 and a second palm oil stearin having an iodine value of from about 25 to 50.

10. A process according to claim 1, further comprising the step of blending the composition of (iv) or the fraction of (v) with at least one vegetable oil.

11. A process according to claim 10, wherein the vegetable oil is selected from sunflower oil, high oleic sunflower oil, palm kernel oil, rapeseed oil and soybean oil, and mixtures thereof.

12. A process according to claim 1, further comprising the step of blending the composition of (iv) or the fraction of (v) with a source of docosahexaenoic acid (DHA) or eicosapentaenoic acid (EPA).

13. A process according to claim 1, wherein at least 55 wt % of the palmitic acid residues are present in the 2-position of the glyceride.

14. A process according to claim 1, wherein the composition or fraction comprises not more than 42 wt % of palmitic acid, based on total fatty acid content, and wherein at least 56 wt % of the palmitic acid residues are present in the 2-position of the glyceride.

15. A process according to claim 14, wherein at least 58 wt % of the palmitic acid residues are present in the 2-position of the glyceride.

16. A process according to claim 1, wherein the tripalmitoylglyceride (PPP) content of the composition or fraction is less than 9% by weight of the composition.

Description

EXAMPLES

Example 1

(1) Randomisation of Palm Oil Stearin Fraction by Chemical Means

(2) Chemical randomisation was carried out to have a reference for the enzyme-catalysed randomisation. 1 kg of palm oil stearin fraction with iodine value of 14 (POs14) was heated under vacuum to 110 C. for 15 minutes to remove all water. The vacuum was interrupted to add 0.15% sodium-ethanolate and the reaction was continued under vacuum during 30 minutes at 110 C. The reaction was stopped by washing the oil several times with demineralised water at 95 C.

(3) Finally the fat was dried by vacuum. The analysis results are given below in Example 2.

Example 2

(4) Randomisation of Palm Oil Stearin Fraction Enzymatically in Batch Reaction

(5) The following three parameters apply to the randomisation of palm oil stearin fraction and to the manufacturing of a structured lipid comprising OPO (1,3-dioleyl-2-palmitoyl glyceride) in general. Overall fatty acid composition: FAME triglyceride carbon number: C48 tripalmitoyl glyceride, C50 mono-oleyl-dipalmitoyl glyceride, C52 dioleyl-monopalmitoyl glyceride, C54 trioleyl glyceride relative position of palmitic acid: Sn-2 C16:0.

(6) Sn-2 is as defined above and refers to the number of moles (or weight) of palmitoyl residues present at the 2-position of the glyceride divided by the total number of moles (or weight) of palmitoyl residues present in the glyceride.

(7) POs14 (palm oil stearin fraction with iodine value of 14) was randomised in batch reaction using immobilised lipase TL-IM (Thermomyces lanuginosus, Novozymes) as catalyst.

(8) 170 g POs14 was melted in a 250 ml roundbottom flask at 70 C. under nitrogen. 0.5% g/g or 0.85 g enzyme was added and the flask was closed. The reaction time was six days, while stirring with a magnetic stirrer. At intervals samples were taken for analysis.

(9) There is a prominent decrease in the tripalmitin concentration (C48) and increase in the mono-olein-dipalmitin concentration (C50).

(10) The results of the analyses are listed in Table 1. It appears that enzymatic randomisation indeed increases the Sn-2 C16:0 value to about the maximal random value of 0.33.

(11) The tripalmitoyl glyceride content (C48) decreases from 62% to 56% and the dioleyl-monopalmitoyl glyceride content (C50) increases from 24.5% to 33-34%.

(12) Comparison with the analyses obtained from the chemical randomisation shows that the enzymatic reaction was almost complete.

(13) TABLE-US-00001 TABLE 1 Randomisation of POs14 with lipase TL-IM, analysis data randomised Pos14 regular POs14 chemical enzymatic C14:0 1.2 1.2 C16:0 80.3 79.8 C18:0 5.2 5.4 C18:1 10.4 10.6 C18:2 2.1 2.3 C46 (PPM) 3 2.8 3.2 C48 (PPP) 62.3 55.8 55.8 C50 (PPO&POP) 24.5 33.4 33.6 C52 (OPO&OOP) 8.5 6.7 6.8 C54 (OOO) 1.7 0.6 0.8

Example 3

(14) Manufacture of Structural Lipid Containing 1,3-Dioleyl-2-Palmitoyl Glyceride (OPO) with Regular and with Randomised Palm Oil Stearin Fraction (POs14)

(15) The structural lipid comprising OPO was manufactured by enzymatic 1,3-specific acidolysis between oleic fatty acid and POs14. A continuous packed bed reactor containing enzyme was used. This enzyme was lipase D (Rhizopus delemar, Amano) immobilised on microporous polypropylene beads (Accurel).

(16) The source oil consisted of a mixture of POs14 and oleic fatty acid with ratio 1:1.4 g/g. The mixture was pumped slowly through a column containing the immobilised enzyme. During the passage of the oil/fatty acid mixture, the acidolysis reaction takes place, whereby the conversion level is proportional to the residence time in the column. The residence time is the void volume in the enzyme bed divided by the flow rate. The residence time used in this example was 53 minutes.

(17) Water was added in order to keep the enzyme active. The water content in the POs14/oleic acid mixture was maintained at 0.15% g/g. The reaction temperature was 60 C. The duration of each experiment was three days.

(18) The product emerging from the column was at intervals analysed for its Sn-2 value and glyceride content by carbon number.

(19) In Table 2, the average results of four experiments, two with regular and two with randomised POs14, are listed. The composition of each POs14 source is included in columns 2 and 4.

(20) From these data the following can be deduced. 1. The difference between the regular and randomized POs14, which were from another randomisation reaction is essentially the same as shown in Example 2. 2. The large difference in C-number composition between both POs14 sources does not have much effect on the corresponding C-number composition of the resulting fats, which are surprisingly alike. 3. There is a significant increase of the Sn-2 value in the fat originating from the randomised POs14.

(21) TABLE-US-00002 TABLE 2 Average analysis of fat product from regular POs14 and from random POs14 (2 2 experiments) regular structured fat structured fat POs14 product randomized POs14 product C48 60.5 8.8 53.7 8.6 C50 24.3 34.3 32.5 34.7 C52 8.8 43.5 7.2 44.6 C54 2.4 11.6 3.0 10.4 Sn-2 0.297 0.555 0.005 0.319 0.584 0.002

Example 4

(22) Enzymatically Randomized POsIV35 (ER(POsIV35)) as Feedstock

(23) About 9.0 kg of POsIV35 was enzymatically randomized by stirring the oil at 70 C. for 48 hours in the presence of 3% (wt) lipase Lipozyme TL IM (Thermomyces lanuginosa, Novozymes). After this, the enzyme was filtered off and the oil was physically refined. Physically refining includes bleaching the randomized oil with 0.5% (wt) bleaching earth at 90 C. and deodorizing after filtration at 215 C. for 3 hours. A sample of the refined oil was submitted for analysis. The results are shown in Table 3.

(24) The randomized POsIV35 was interesterified with oleic acid in a continuous process. This reaction was performed at 60 C. and catalyzed by Lipase D (from Rhizopus delemar). After the acidolysis reaction, the excess of fatty acids was removed by mean of short path distillation. A sample was submitted for analysis. The results are shown in Table 3.

Example 5

(25) POsIV35 as Feedstock

(26) POsIV35 was directly interesterified with oleic acid in a continuous process. This reaction was performed at 60 C. and catalyzed by Lipase D (from Rhizopus delemar). After the acidolysis reaction, the excess of fatty acids was removed by mean of short path distillation. A sample was submitted for analysis. The results are shown in Table 3.

(27) TABLE-US-00003 TABLE 3 Analysis of samples removed during the production of Fat base from ER(POsIV35) and POsIV35 Refined Fat base Fat base POsIV35 ER(POsIV35) ER(POsIV35) POsIV35 sn-2 C16 19.3 34 56.5 37.2 Carbon numbers C46 2 1.9 0.7 0.1 C48 24.7 24.1 4.8 4.9 C50 41.9 41.8 24.4 21.3 C52 25.2 25.8 46.4 42.2 C54 5.9 6.2 22.9 30.6 C56 0.3 0.3 0.8 0.9 Fatty acid composition C12:0 0.14 0.19 0.21 0.17 C15:0 0.1 0.1 0 0 C14:0 1.2 1.3 0.7 0.6 C16:0 58.3 57.2 31.6 29.4 C18:0 4.7 4.9 3.8 3.1 C18:1T 0.1 0 0.1 0.2 C18:1C 28.1 28.8 56.6 58.5 C18:2T 0.2 0.2 0.2 0.2 C18:2C 6.2 6.4 5.5 6.6 Total 0.3 0.2 0.4 0.4 Trans C20:0 0.4 0.4 0.3 0.3 C20:1C 0.1 0.1 0.2 0.2 C22:0 0.1 0.1 0.3 0.3 C24:0 0.1 0 0.1 0.1 SAFA 65.1 64.2 37.1 34 MUFA 28.4 29.1 57 59 PUFA 6.5 6.7 5.9 7

Example 6

(28) Randomisation of Palm Oil Stearine Fraction POs20 in an Enzyme Packed Bed Reactor

(29) Palm oil stearine fraction POs20having an iodine value IV of 20was made by mixing POs14 and POs35 in a 2:1 ratio. This mixture was pumped in plug-flow mode through a packed bed reactor containing immobilized lipase TL-IM (Thermomyces lanuginosus, Novozymes). The pump rate was about 2 bedmasses of oil per hour, at a temperature of 70 C. At various intervals samples were collected to determine the glyceride composition with carbon number analysis and the relative amount of palmitic acid on the 2-position of the glycerol, Sn-2 C16:0.

(30) The analyses of regular and randomized POs20 are shown in Table 4, columns 2 and 4. The Sn-2 C16:0 increases from 0.267 to 0.316.

Example 7

(31) Manufacture of Structural Lipid Containing 1,3-Dioleyl-2-Palmitoyl Glyceride (OPO) with Regular and with Randomised Palm Oil Stearine Fraction POsIV20

(32) The structural lipid comprising OPO was manufactured by enzymatic 1,3-specific acidolysis between oleic fatty acid and regular or randomized POs20. As in Example 4, a continuous packed bed reactor containing immobilized lipase D (Rhizopus delemar, Amano) was used, and the ratio of POs20 and oleic acid was 1:1.4 g/g, alike with regular or randomized POs20

(33) At various intervals samples were collected to determine the glyceride composition with carbon number analysis and the relative amount of palmitic acid on the 2-position of the glycerol, Sn-2 C16:0.

(34) In Table 4, the average results of two experiments, one with regular and one with randomised POs20, are listed. The composition of each POs20 source and the resulting structured fat product are given.

(35) TABLE-US-00004 TABLE 4 Analysis of non-randomized POs20 and of randomized POs20, and of the structured fat products thereof POs20 non- structured fat POs20 structured fat randomized product randomized product C48 50.0 7.7 43.6 7.1 C50 29.2 31.4 39.0 32.2 C52 14.0 43.1 12.4 45.9 C54 3.4 16.5 1.6 13.5 Sn-2 C16:0 0.267 0.489 0.316 0.551