Emulsifier Composition Obtainable from Free Fatty Acids

Abstract

A method for preparing a non-hydrogenated, non-palm emulsifier composition, comprises the steps of:providing a fatty acid composition comprising at least 80% by weight free fatty acids, andreacting the fatty acid composition with glycerol, wherein the emulsifier composition comprises: at least 20% by weight monoglycerides; less than 60% by weight of diglycerides; and and from 0-80% by weight triglycerides, wherein the weight % is with respect to the total of monoglycerides, diglycerides and triglycerides, and wherein the fatty acid residues bound to the monoglycerides, diglycerides and triglycerides in the emulsifier composition comprise: from 5% to 80% by weight stearic acid (C18:0); from 10% to 80% by weight oleic acid (C18:1); and from 1% to 10% by weight palmitic acid (C16:0), based on the total weight of C8 to C24 fatty acids.

Claims

1. A method for preparing a non-hydrogenated, non-palm emulsifier composition, comprising the steps of: providing a fatty acid composition comprising at least 80% by weight free fatty acids, and reacting the fatty acid composition with glycerol, wherein the emulsifier composition comprises: at least 20% by weight monoglycerides; less than 60% by weight of diglycerides; and and from 0-80% by weight triglycerides, wherein the weight % is with respect to the total of the monoglycerides, diglycerides and triglycerides, and wherein fatty acid residues bound to the monoglycerides, diglycerides and triglycerides in the emulsifier composition comprise: from 5% to 80% by weight stearic acid (C18:0); from 10% to 80% by weight oleic acid (C18:1); and from 1% to 10% by weight palmitic acid (C16:0), based on the total weight of C8 to C24 fatty acids.

2. The method according to claim 1, wherein the fatty acid composition is obtained from shea butter, shea olein, shea stearin, sal butter, sal stearin, sal olein, or mixtures thereof.

3. The method according to claim 1, wherein the reaction of the fatty acid composition with glycerol is carried out in the presence of an enzymatic catalyst.

4. The method according to claim 1, wherein the reaction of the fatty acid composition with glycerol is carried out in the presence of an inorganic salt.

5. A non-hydrogenated, non-palm emulsifier composition comprising: at least 20% by weight monoglycerides; less than 60% by weight of diglycerides; and from 0-80% by weight triglycerides, wherein the weight % is with respect to the total of the monoglycerides, diglycerides and triglycerides, and wherein fatty acid residues bound to the monoglycerides, diglycerides and triglycerides in the emulsifier composition comprise: from 5% to 40% by weight stearic acid (C18:0); from 45% to 80% by weight oleic acid (C18:1); and from 1% to 10% by weight palmitic acid (C16:0), based on the total weight of C8 to C24 fatty acids.

6. The composition according to claim 5, wherein the weight ratio of stearic acid to oleic acid is from 1:8 to 9:10.

7. The composition according to claim 5, comprising from 20% to 50% by weight monoglycerides.

8. The composition according to claim 5, comprising from 30% to 60% by weight diglycerides.

9. The composition according to claim 5 comprising: at least 85% by weight monoglycerides; less than 10% by weight of diglycerides; and less than 5% by weight triglycerides.

10. The composition according to claim 5, comprising from 1% to 12% by weight linoleic acid (C18:2).

11. The composition according to claim 5, comprising from 10% to 35% by weight stearic acid.

12. The composition according to claim 5, comprising from 50% to 70% by weight oleic acid.

13. The composition according to claim 5, comprising from 4.5% to 8% by weight palmitic acid.

14. A non-hydrogenated, non-palm emulsifier composition comprising: at least 20% by weight monoglycerides; less than 60% by weight of diglycerides; and and from 0-80% by weight triglycerides, wherein the weight % is with respect to the total of the monoglycerides, diglycerides and triglycerides, and wherein fatty acid residues bound to the monoglycerides, diglycerides and triglycerides in the emulsifier composition comprise: from 50% to 90% by weight stearic acid (C18:0); from 10% to 30% by weight oleic acid (C18:1); and from 1% to 10% by weight palmitic acid (C16:0), based on the total weight of C8 to C24 fatty acids.

15. A bakery or confectionery product comprising the composition according to claim 5.

16. The product according to claim 15, wherein the product is selected from the group consisting of puff pastry, cake, Danish rolls or water-based fillings.

17. The method according to claim 2, wherein the fatty acid composition is obtained from shea olein.

18. The method according to claim 3, wherein the enzymatic catalyst is a lipase.

19. The method according to claim 4, wherein the inorganic salt is zinc chloride.

20. The composition according to claim 5, comprising from 22% to 40% by weight monoglycerides.

Description

EXAMPLES

Example 1

[0129] Crude shea olein is obtained after solvent fractionation of crude shea butter. Crude shea olein naturally contains approximatively 10-15% free fatty acids. The free fatty acids were distilled by means of short path distillation at a temperature of about 190 C. to 205 C. and a pressure of about 110.sup.3 to 810.sup.3mbar. The free fatty acids were collected as distillate. The fatty acid composition of the products is given in the following Table 1.

TABLE-US-00001 C8:0 0 C10:0 0 C12:0 0.2 C15:0 0 C14:0 0.1 C16:0 6 C16:1C 0.1 C16:1T 0 C17:0 0.1 C18:0 32.1 C18:1 51.9 C18:1T 0.1 C18:1C 51.9 C18:2 8 C18:2T 0 C18:2C 8 C18:3 0.3 C18:3T 0.1 C18:3C 0.2 Total Trans 0.2 C20:0 0.7 C20:1C 0.3 C20:20 0 C22:0 0.1 C22:1 0 C22:1T 0 C22:1C 0 C24:0 0 C24:1C 0

[0130] In the above table: [0131] Cx:y refers to a fatty acid having x carbon atoms and y double bonds; and [0132] C refers to cis fatty acids and T to trans fatty acids; levels determined by GC-FAME (ISO 12966-2 and ISO 12966-4).

[0133] 358.5 g free fatty acids after distillation was esterified with 89.6 g glycerol in the presence of immobilized lipase originating from Candida antarctica B (Novozym 435). When the reaction was completed, after approximatively 24 hours, the product was filtered. Then this product was bleached and deodorised at low temperature (mild refining) to obtain the emulsifier composition, which has the following composition, w/w (Table 2):

TABLE-US-00002 C8:0 0 C10:0 0 C12:0 0.2 C15:0 0 C14:0 0.1 C16:0 6.1 C16:1C 0.1 C16:1T 0 C17:0 0.1 C18:0 32.7 C18:1 52 C18:1T 0.1 C18:1C 51.9 C18:2 7.1 C18:2T 0 C18:2C 7.1 C18:3 0.2 C18:3T 0.1 C18:3C 0.2 Total Trans 0.1 C20:0 0.8 C20:1C 0.3 C20:2C 0 C22:0 0 C22:1 0 C22:1T 0 C22:1C 0 C24:0 0.1 C24:1C 0 Triglyceride 22.6 Diglyceride 47.7 Monoglyceride 26.5

[0134] In the above table: [0135] Cx:y refers to a fatty acid having x carbon atoms and y double bonds; [0136] C refers to cis fatty acids and T to trans fatty acids; levels determined by GC-FAME (ISO 12966-2 and ISO 12966-4); and [0137] Triglyceride/Diglyceride/Monoglyceride were determined by HPLC (ISO 18395: 2005(E)).

Example 2

[0138] The distilled fatty acid product obtained in Example 1 was dry-fractionated using a lab-scale crystallizer. The fractionation was performed at 30 C. to 45 C. The free fatty acids were first heated to 70 C. and then cooled down to 30 C. to 45 C. in 5 to 10 hours and held at this temperature for 5 to 10 hours. The crystals formed were separated by means of filter pressing. The slurry was pressed using the following program: increase pressure from 0 to 24 bar in 60 minutes and squeeze at 24 bar for 30 minutes. A high oleic acid olein fraction was obtained. The analytical results are shown in Table 3.

TABLE-US-00003 C8:0 0 C10:0 0 C12:0 0.2 C15:0 0 C14:0 0.1 C16:0 6.2 C16:1C 0.1 C16:1T 0 C17:0 0.1 C18:0 13.2 C18:1 68.7 C18:1T 0.1 C18:1C 68.6 C18:2 9.7 C18:2T 0 C18:2C 9.6 C18:3 0.3 C18:3T 0.1 C18:3C 0.2 Total Trans 0.2 C20:0 0.8 C20:1C 0.4 C20:2C 0 C22:0 0.1 C22:1 0 C22:1T 0 C22:1C 0 C24:0 0 C24:1C 0

[0139] In the above table: [0140] Cx:y refers to a fatty acid having x carbon atoms and y double bonds; and [0141] C refers to cis fatty acids and T to trans fatty acids; levels determined by GC-FAME (ISO 12966-2 and ISO 12966-4).

[0142] 205.5 g of the high oleic acid olein fraction was esterified with 94.5 g glycerol in the presence of zinc chloride at 190 C. to 200 C. and 50 to 150 mbar. When the reaction was completed, after approximatively 1 hour, the product was filtered and then mildly refined. After mild refining, an emulsifier composition was obtained, which had the following composition, w/w (Table 4):

TABLE-US-00004 C8:0 0 C10:0 0 C12:0 0.1 C15:0 0 C14:0 0.1 C16:0 6.1 C16:1C 0.1 C16:1T 0 C17:0 0.1 C18:0 13.2 C18:1 68.9 C18:1T 0.1 C18:1C 68.8 C18:2 9.5 C18:2T 0 C18:2C 9.4 C18:3 0.3 C18:3T 0.1 C18:3C 0.2 Total Trans 0.2 C20:0 0.8 C20:1C 0.4 C20:2C 0.1 C22:0 0.1 C22:1 0 C22:1T 0 C22:1C 0 C24:0 0.1 C24:1C 0 Triglyceride 11.1 Diglyceride 46.5 Monoglyceride 38.1

[0143] In the above table: [0144] Cx:y refers to a fatty acid having x carbon atoms and y double bonds; [0145] C refers to cis fatty acids and T to trans fatty acids; levels determined by GC-FAME (ISO 12966-2 and ISO 12966-4); and [0146] Triglyceride/Diglyceride/Monoglyceride were determined by HPLC (ISO 18395: 2005(E)).

Example 3

[0147] 600 g of the high oleic acid olein fraction obtained such as in Example 2 was esterified with 150 g glycerol in the presence of immobilized lipase originating from Candida antarctica B (Novozym 435). When the reaction was completed, after approximatively 24 hours, the product was filtered. Then this product was bleached and deodorised at low temperature (mild refining) to obtain the emulsifier composition, which has the following composition, w/w (Table 5):

TABLE-US-00005 C8:0 0 C10:0 0 C12:0 0.2 C15:0 0 C14:0 0.1 C16:0 6.4 C16:1C 0.1 C16:1T 0 C17:0 0.1 C18:0 13.1 C18:1 68.7 C18:1T 0.1 C18:1C 68.6 C18:2 9.6 C18:2T 0 C18:2C 9.6 C18:3 0.3 C18:3T 0.1 C18:3C 0.2 Total Trans 0.2 C20:0 0.7 C20:1C 0.4 C20:2C 0 C22:0 0.1 C22:1 0 C22:1T 0 C22:1C 0 C24:0 0.1 C24:1C 0 Triglyceride 22.6 Diglyceride 48.4 Monoglyceride 25.2

[0148] In the above table: [0149] Cx:y refers to a fatty acid having x carbon atoms and y double bonds; [0150] C refers to cis fatty acids and T to trans fatty acids; levels determined by GC-FAME (ISO 12966-2 and ISO 12966-4); and [0151] Triglyceride/Diglyceride/Monoglyceride determined by HPLC (ISO 18395: 2005(E)).

[0152] The product containing monoglycerides was distilled in order to separate monoglyceride from triglycerides and diglycerides by means of short path distillation at a temperature of about 180 C. and a pressure of about 110.sup.2 mbar. The concentrated monoglyceride fraction was collected as distillate. The concentrated monoglyceride emulsifier has the following composition, w/w (Table 6):

TABLE-US-00006 C8:0 0 C10:0 0 C12:0 0.2 C15:0 0 C14:0 0.2 C16:0 6.9 C16:1C 0.1 C16:1T 0 C17:0 0.1 C18:0 13.8 C18:1 67.7 C18:1T 0.1 C18:1C 67.7 C18:2 9.4 C18:2T 0 C18:2C 9.4 C18:3 0.3 C18:3T 0.1 C18:3C 0.2 Total Trans 0.2 C20:0 0.6 C20:1C 0.3 C20:2C 0 C22:0 0 C22:1 0 C22:1T 0 C22:1C 0 C24:0 0 C24:1C 0 Triglyceride 0.6 Diglyceride 2.6 Monoglyceride 92.1

[0153] In the above table: [0154] Cx:y refers to a fatty acid having x carbon atoms and y double bonds; [0155] C refers to cis fatty acids and T to trans fatty acids; levels determined by GC-FAME (ISO 12966-2 and ISO 12966-4); and [0156] Triglyceride/Diglyceride/Monoglyceride were determined by HPLC (ISO 18395: 2005(E)).

Example 4

[0157] The distilled fatty acid product obtained such as in Example 1 was dry-fractionated using a lab-scale crystallizer. The fractionation was performed at 30 C. to 45 C. The free fatty acids were first heated to 70 C. and then cooled down to 30 C. to 45 C. in 5 to 10 hours and held at this temperature for 5 to 10 hours. The crystals formed were separated by means of filter pressing. The slurry was pressed using the following program: increase pressure from 0 to 24 bar in 60 minutes and squeeze at 24 bar for 30 minutes. A high stearic acid stearin fraction was obtained. The analytical results are shown in Table 7.

TABLE-US-00007 C8:0 0 C10:0 0 C12:0 0.2 C15:0 0 C14:0 0.1 C16:0 4.8 C16:1C 0 C16:1T 0 C17:0 0.1 C18:0 70.8 C18:1 18.9 C18:1T 0 C18:1C 18.9 C18:2 3.2 C18:2T 0 C18:2C 3.2 C18:3 0.1 C18:3T 0 C18:3C 0.1 Total Trans 0 C20:0 1.5 C20:1C 0.1 C20:2C 0 C22:0 0.1 C22:1 0 C22:1T 0 C22:1C 0 C24:0 0 C24:1C 0

[0158] In the above table: [0159] Cx:y refers to a fatty acid having x carbon atoms and y double bonds; and [0160] C refers to cis fatty acids and T to trans fatty acids; levels determined by GC-FAME (ISO 12966-2 and ISO 12966-4).

[0161] 301.6 g high stearic acid stearin fraction was esterified with 75.4 g glycerol in the presence of immobilized lipase originating from Candida antarctica B (Novozym 435). When the reaction was completed, after approximatively 24 hours, the product was filtered. Then this product was bleached and deodorised at low temperature (mild refining) to obtain the emulsifier composition, which has the following composition, w/w (Table 8):

TABLE-US-00008 C8:0 0 C10:0 0 C12:0 0.2 C15:0 0 C14:0 0.1 C16:0 4.6 C16:1C 0 C16:1T 0 C17:0 0.1 C18:0 71.1 C18:1 18.9 C18:1T 0 C18:10 18.8 C18:2 3.1 C18:2T 0 C18:2C 3.1 C18:3 0.1 C18:3T 0 C18:3C 0.1 Total Trans 0.1 C20:0 1.5 C20:1C 0.1 C20:2C 0 C22:0 0.1 C22:1 0 C22:1T 0 C22:1C 0 C24:0 0 C24:1C 0 Triglyceride 21 Diglyceride 51.6 Monoglyceride 26.1

[0162] In the above table: [0163] Cx:y refers to a fatty acid having x carbon atoms and y double bonds; [0164] C refers to cis fatty acids and T to trans fatty acids; levels determined by GC-FAME (ISO 12966-2 and ISO 12966-4); and [0165] Triglyceride/Diglyceride/Monoglyceride determined by HPLC (ISO 18395: 2005(E)).

Comparative Example

[0166] 271.7 g refined shea butter was reacted with 26.9 g glycerol in the presence of 1.5 g potassium hydroxide flakes at 200 C. and under vacuum lower than 100mbar. When the reaction was completed, after approximatively 30 minutes, the product was bleached and deodorized in order to obtain a comparative example, which has the following composition

[0167] (Table 9):

TABLE-US-00009 C8:0 0 C10:0 0 C12:0 0.4 C15:0 0 C14:0 0.2 C16:0 4 C16:1C 0.1 C16:1T 0 C17:0 0.1 C18:0 43.9 C18:1 43.3 C18:1T 0.1 C18:1C 43.2 C18:2 5.8 C18:2T 0.1 C18:2C 5.8 C18:3 0.2 C18:3T 0.1 C18:3C 0.1 Total Trans 0.2 C20:0 1.4 C20:1C 0.2 C20:2C 0 C22:0 0.1 C22:1 0 C22:1T 0 C22:1C 0 C24:0 0.1 C24:1C 0 Triglyceride 18.3 Diglyceride 42.6 Monoglyceride 25.7

[0168] In the above table: [0169] Cx:y refers to a fatty acid having x carbon atoms and y double bonds; [0170] C refers to cis fatty acids and T to trans fatty acids; levels determined by GC-FAME (ISO 12966-2 and ISO 12966-4); and [0171] Triglyceride/Diglyceride/Monoglyceride determined by HPLC (ISO 18395: 2005(E)).

Example 5

[0172] An emulsion stability test was performed in order to evaluate the functionality of the emulsifiers. Besides the Comparative ExaMple, a commercial emulsifier product Durem 35NG from 101 Loders Croklaan US was also included, which has the following composition (Table 10):

TABLE-US-00010 C8:0 0 C10:0 0 C12:0 0.3 C15:0 0.1 C14:0 1.1 C16:0 42.3 C16:1C 0.2 C16:1T 0 C17:0 0.1 C18:0 4.6 C18:1 41.1 C18:1T 0.1 C18:1C 41 C18:2 9.2 C18:2T 0.6 C18:2C 8.6 C18:3 0.2 C18:3T 0.1 C18:3C 0.1 Total Trans 0.8 C20:0 0.4 C20:1C 0.2 C20:2C 0 C22:0 0.1 C22:1 0 C22:1T 0 C22:1C 0 C24:0 0.1 C24:1C 0 Triglyceride 10.7 Diglyceride 48.3 Monoglyceride 40.2

[0173] In the above table: [0174] Cx:y refers to a fatty acid having x carbon atoms and y double bonds; [0175] C refers to cis fatty acids and T to trans fatty acids; levels determined by GC-FAME (ISO 12966-2 and ISO 12966-4); and [0176] Triglyceride/Diglyceride/Monoglyceride determined by HPLC (ISO 18395: 2005(E)).

[0177] 0.8 g of the emulsifier of each of Example 1, Example 2, Example 4, the Comparative Example and Durem 35NG respectively were totally dissolved in 80 g rapeseed oil. Each mixture was put into a 120 ml glass bottle and mixed with a propeller with four symmetrical square blades of 0.8 cm each at a speed of 750 rpm. When the temperature of each mixture is at approximatively 30 C., 20ml demineralized water was gently added into each mixture within 15 seconds. Each emulsion was further mixed at room temperature under the same mixing conditions for 1 minute. Then, each emulsion was poured into a 100 ml glass graduated cylinder at room temperature. After 30 minutes, the volume of water layer was read respectively in order to evaluate the emulsion stability. One control test was done without any emulsifier. The stability was calculated with the following formula:

[00001]$\mathrm{Emulsion}.Math..Math.\mathrm{stability}.Math..Math.\%=\frac{20-\mathrm{Volume}.Math..Math.\mathrm{of}.Math..Math.\mathrm{water}.Math..Math.\mathrm{layer}.Math..Math.\mathrm{after}.Math..Math.\mathrm{separation}.Math.}{20}.Math.\%$

[0178] The results are shown in the following table (Table 11):

TABLE-US-00011 Compar- Con- Exam- Exam- Exam- ative Durem trol ple 1 ple 2 ple 4 Example 35NG Volume of 17 9 6 10 15 13 water layer after sepa- ration (ml) Emulsion 15% 55% 70% 50% 25% 35% stability %

[0179] Example 1, Example 2 and Example 4 show better emulsion stability than the Comparative Example and Durem 35 NG.

Example 6

[0180] An emulsion stability test was performed in order to evaluate the functionality of the emulsifiers. A commercial emulsifier product Dimodan HP MB from Danisco, DuPont Group was included, which has the following composition (Table 12):

TABLE-US-00012 C8:0 0 C10:0 0 C12:0 0.3 C15:0 0.1 C14:0 1.2 C16:0 55.2 C16:1C 0 C16:1T 0 C17:0 0.1 C18:0 42.4 C18:1 0.1 C18:1T 0 C18:1C 0 C18:2 0 C18:2T 0 C18:2C 0 C18:3 0 C18:3T 0 C18:3C 0 Total Trans 0 C20:0 0.5 C20:1C 0 C20:2C 0 C22:0 0.1 C22:1 0 C22:1T 0 C22:1C 0 C24:0 0.1 C24:1C 0 Triglyceride 0.1 Diglyceride 2.5 Monoglyceride 97.1

[0181] 0.4 g emulsifier of each of Example 3 and Dimodan HP MB respectively was totally dissolved in 80 g rapeseed oil. Each mixture was put into a 120 ml glass bottle and mixed with a propeller with four symmetrical square blades of 0.8 cm each at a speed of 750 rpm. When the temperature of each mixture is at approximatively 30 C., 20ml demineralized water was gently added into each mixture within 15 seconds. Each emulsion was further mixed at room temperature under the same mixing conditions for 1 minute. Then, each emulsion was poured into a 100 ml glass graduated cylinder at room temperature. After 30 minutes, the volume of water layer was read respectively in order to evaluate the emulsion stability. One control test was done without any emulsifier. The stability was calculated with the following formula:

[00002]$\mathrm{Emulsion}.Math..Math.\mathrm{stability}.Math..Math.\%=\frac{20-\mathrm{Volume}.Math..Math.\mathrm{of}.Math..Math.\mathrm{water}.Math..Math.\mathrm{layer}.Math..Math.\mathrm{after}.Math..Math.\mathrm{separation}.Math.}{20}.Math.\%$

[0182] The results are shown in the following table (Table 13):

TABLE-US-00013 Control Example 3 Dimodan HP MB Volume of water layer 17 13 15 after separation (ml) Emulsion stability % 15% 35% 25%

[0183] Example 3 shows better emulsion stability than Dimodan HP MB.