WO2006079362A1

WO2006079362A1 - Solubilizate of a water-soluble organic acid and method for producing the same

Info

Publication number: WO2006079362A1
Application number: PCT/EP2005/004802
Authority: WO
Inventors: Dariush Behnam
Original assignee: Aquanova German Solubilisate
Priority date: 2005-01-28
Filing date: 2005-05-03
Publication date: 2006-08-03
Also published as: EP1843748A1; DE102005004228A1

Abstract

The invention relates to a solubilizate that is constituted of an aqueous solution of citric acid and/or a citric acid hydrate and/or a citric acid anhydrate and an emulsifier having an HLB value of 9 to 18, for example a polysorbate.

Description

EPO - Dn - / DESCRIPTION ^u 'A 594-1

Solubilizate of a water-soluble organis ~ ch ⁷ e n 0 S7ä. u 2reQ0 s <o [as a method to his

Production (55)

The invention relates to a solubilizate of a water-soluble organic acid and to a process for its preparation.

The document EP 1 338 271 A1 describes an aqueous solution of ascorbic acid which is micellated with an excess of an emulsifier having an HLB value of about 9 to about 18, for example a polysorbate. This ascorbic acid solubilizate has the advantage that it can be easily incorporated into fatty end products from the cosmetics or food sector without further processing steps, so that the antioxidant effect of ascorbic acid in fats substantially increased and the durability of fats in relation to other antioxidants such Ascorbyl palmitate or BHT is significantly extended. This beneficial effect is further improved by a mixed solubilizate, which in addition to the ascorbic acid still has an addition of a tocopherol. Incidentally, the document DE 101 04 847 A1 describes a tocopherol concentrate which can be micellized by polysorbate 20 or polysorbate 80.

In the preparation of foods and the formulation of ointments and the like cosmetic products, citric acid has found wide use, for example, as a flavor improver for mineral waters or as a decolorization agent for oils. The invention is therefore based on the object to improve the effectiveness of citric acid, especially in oily or greasy media.

For this purpose, according to the invention, a solubilizate is used, which consists of an aqueous solution of citric acid and / or a citric acid hydrate or anhydrate and an emulsifier having an HLB value of 9 to 18, for example a polysorbate. The invention is an optically clear solubilizate which readily mixes with compositions to be protected or purified. The effectiveness of citric acid, which inhibit especially in vegetable oils and fats occurring auto-oxidation, thereby significantly improved. Further, the solubilizate of the present invention is more effective in decolorizing oils of dark color, such as, for example, feed oil oils (palm oil). At a lower salary of citric acid in the solubilisate, at about 10% by weight, an addition of a medium-chain triglyceride containing, for example, caprylic acid and / or capric acid is particularly favorable for solubilization. The invention can be used as a food additive, auxiliaries or even in the removal of heavy metals from correspondingly contaminated soils.

On the one hand, citric acid is a synergist for antioxidants and, on the other hand, it is able to neutralize heavy metals, such as lead, by complex formation. Especially mixed tocopherols often contain traces in the range of 1-10 ppm of heavy metal compounds, so that it is recommended to form a solubilizate of citric acid, a tocopherol and / or a tocopherol acetate and a polysorbate in a further development of the invention. The tocopherol contained in the micelles is freed by the citric acid also present from active heavy metal traces and supported in its antioxidant effect. As tocopherols α-tocopherol are preferred, although good results with mixed tocopherol can be achieved.

Nonionic emulsifiers having an HLB value of 12 to 18 are preferred, with a polysorbate, in particular polysorbate 80 or polysorbate 20, being particularly advantageous.

Suitably, the content of polysorbate in the solubilizate according to the invention is between about 50% by weight and about 75% by weight. The citric acid can be used, for example, in the form of its monohydrate or its anhydrate. Their content is preferably between about 10% by weight and about 25% by weight. About 10% by weight of triglycerides can be added to the solubilizate according to the invention. The tocopherol content is suitably between about 5 wt.% And about 10 wt.%.

A process for the preparation of the solubilizate according to the invention provides that citric acid and / or its hydrate is stirred into water heated to about 85 ° C. and dissolved until the solution is clear, then the emulsifier, preferably polysorbate 80 or polysorbate 20, is added slowly and well mixed and well homogenized at about 85 ° C. At lower citric acid content of about 10% by weight, it is advisable to add the clear citric acid solution at about 85 ° C Add medium chain triglyceride, such as Miglyol 812, with stirring and then incorporate the polysorbate.

For the recovery of a citric acid tocopherol solubilisate, the addition of a medium chain triglyceride is replaced by the addition of tocopherol to the clear citric acid solution and then the polysorbate is incorporated.

Suitable emulsifiers are all food-approved emulsifiers. Since the authorizations vary from state to state, the invention is not limited to the use of polysorbates.

Incidentally, preferred embodiments of the invention are specified in the subclaims. Hereinafter, some recipes are given as embodiments of the invention.

example 1

Cϊtronenoic acid / D-α-tocopherol solubilisate with Polsorbat 80

Ingredients:

100 g of citric acid; e.g. Citric Acid Monohydrate OR Citric Acid Anhydrate from Brenπtag (BBCA-Ware) (AGT Material No: 10745/037 or 10743/037)

100 g of distilled water. (AGT No .: 10180)

50 g of D-α-tocopherol

750 g of pofysorbate 80; Lamesorb SMO 20; Cogpiis (Article No .: 65274) (AGT No .: 10530/016)

Execution:

• Mix citric acid with water and heat until the citric acid has completely dissolved to clarity. Then stir in polysorbate.

• Add D-α-tocopherol and stir well.

• Then add polysorbate 80 with stirring (this can be slightly heated beforehand - makes the process easier).

• Heat everything again to approx. 85 ^° C and stir well.

Appearance:

Storage: dark, at room temperature (<25 ^a C)

Processing information:

Remarks: Example 2

Citric acid / DL-cc-tocopherol solubilisate with polysorbate 80

Ingredients:

100 g of citric acid; For example citric acid monohydrate OR citric acid anhydrate from Brenntag (BBCA product) (AGT Material No: 10745 / G37 or 10743/037)

100 g of distilled water. (AGT No .: 10180) 50 g DL-σ-tocopherol, BASF (AGT-Materia [-No .: 10711/005] 750 g polysorbate 80; Lamesorb SMO 20; Cogpiis (Article No .: 65274) (AGT Material No .: 10530/016)

Execution:

Mix citric acid with water and heat until the citric acid has completely dissolved until it is clear. Then stir in polysorbate.

Add DL-α-tocopherol and stir well.

Then add polysorbate 80 with stirring (this can be slightly heated beforehand - facilitates the process).

Heat everything again to about 85 ^D C and stir well.

Appearance:

Storage: dark, at room temperature (<25 ° C)

Verarbejtunqshiπweis:

Remarks: Example 3

Citric acid / D-α-tocopherol acetate solubilisate with polysorbate 80

Ingredients;

100 g of citric acid; 2, B. Ceftrotic acid monohydrate OR citric acid anhydrate from Brenntag (BBCA product) (AGT Maierial No: 10745/037 or 10743/037)

100 g of distilled water. (AGT No .: 10180)

50 g of D-α-tocopherol acetate, z. From ADM (Vitamin E 6-92) or Cognis (Copherol 1250) (AGT-Materia! No .: 10722/001 or 10722/016)

750 g polysorbate 80; Lamesorb SMO 20; Cognis (Article No .: 65274) (AGT Material No .: 10530/016)

Execution:

Mix citric acid with water and heat until the citric acid has completely dissolved to clarity. Then stir in polysorbate.

Add D-α-tocopherol acetate and stir well.

Heat everything again to about 85 ^D C and stir well.

Appearance:

Storage: dark, at room temperature (<25 ^° C)

Processing instructions:

B_emerkunαeπ: Beisc

Citric acid / DL-α-tocopherol-acetate solubu sulfate with polysorbate 80

Ingredients:

100 g of citric acid; e.g. Citric Acid Monohydrate OR Citric Acid Anhydrate from Breππtag (BBCA-Ware) (AGT-Matβrial-Nπ: 10745/037 or 10743/037)

100 g of distilled water. (AGT No.: 10180) 50 g of DL-α-tocopherol acetate (Vitamin E acetate), BASF (AGT Material No .: 10721/005)

750 g polysorbate SO; Lamesorb SMO 20; Fa. Cognis (Item No .: 65274) (AGT-Material-Nr .: 10530/016)

Execution:

• Add DL-α-tocopherol acetate and stir well.

• Heat everything again to approx. 85 ^° C and stir well.

Appearance:

Storage: dark, at room temperature (<25 ° C)

Processing information:

Remarks: Example 5

Cϊtronensäure / Mϊsch-Tocopherol Solubilisat with Polssorbat 80

Ingredients:

100 g of citric acid; e.g. Citric Acid Monohydrate OR Citric Acid Anhydrate from Brenπtag (BBCA-Ware) (AGT Material No: 10745/037 bΣw. 10743/037)

100 g of distilled water. (AGT-Nn: 10180) 50 g of Mϊsch-tocopherol, e.g. Coviox T-70 (proportion mixed tocopherols = 70%) from Cognis (AGT Material No .: 10727/016)

Execution:

Add mixed tocopherol and stir well.

Heat everything again to about 85 ° C and stir well.

Appearance:

Storage: dark, at room temperature (<25 ^° C)

Processing information;

Remarks: Example 6

Citric acid / D-α-tocopherol solubilate with polysorbate 20

Ingredients:

100 9 citric acid; e.g. Cystrophic Acid Monohydrate OR Lemonic Acid Anhydrate from Brenntag (BBCA-Ware) (AGT Material Nos.: 10745/037 and 10743/037)

100 g of aqua dest (AGT No .: 10180)

100 g of D-α-tocopherol

700 g polysorbate 20; Lamesorb SML 20; Fa. Cognis (Article No .: 638252} (AGT No .: 10520/016)

Execution:

• Add D-α-tocopherol and stir well.

• Then add polysorbate 20 with stirring (this can be slightly heated beforehand - facilitates the process).

• Heat everything again to approx. 85 ° C and stir well.

Appearance:

Storage: dark, at room temperature (<25 ° C)

Verarbeitungshmweis:

Remarks : Example 7

Cϊtronensäure / DJL-σ-tocopherol SolubiUsat with polysorbate 20

Ingredients:

100 g of citric acid; e.g. Citric Acid Monohydrate OR Citric Acid Anhydrate from Brenntag (BBCA-Ware) (AGT Material No: 10745/037 or 10743/037)

100 g of distilled water. (AGT No .: 10180)

100 g DL-α-tocopherol, BASF (AGT Materiai No .: 10711/005) 700 g polysorbate 20; Lamesorb SML 20; Fa. Cognis (Article No .: 638252) (AGT-Materia! ~ No .: 10520/016)

Execution:

• Add DL-α-tocopherol and stir well.

• Heat everything again to approx. 85 ° C and stir well.

Appearance;

Storage: dark, at room temperature (<25 ° C)

Processing information:

Remarks: Example 8

Citric Acid / P-α-Tocopherol Acetate SolubiHsate with Polysorbate 20

Ingredients:

100 g of citric acid; e.g. Citric acid monohydrate OR citric acid anhydrate from Brenntag (BBCA product) (AGT material no .: 10745/037 or 10743/037)

100 g of distilled water (AGT No .: 10180) 100 g of D-α-tocopherol acetate, eg. From ADM (Vitamin E 6-92) or Cognis (Copherol 1250) (AGT Material No .: 10722/001 or 10722/016)

700 g polysorbate 20; Lamesorb SML 20; Cognis (Article No .: 638252) (AGT Material No .: 10520/016)

Execution:

• Add D-α-tocopherol acetate and stir well.

• Heat everything again to approx. 85 ^° C and stir well.

Appearance:

Storage: dark, at room temperature (<25 "C)

Verarfaeitunqshinweis:

Remarks: Example 9

Cϊtronenoic acid / DL-α-tocopherol acetate solubiHsate with polysorbate 20

Ingredients:

100 g of Cϊtroπensäure; 2 B. Citric acid monohydrate OR citric acid anhydrate from ßreππtag (BBCA product) (AGT Material Nπ: 10745/037 or 10743/037)

100 g of distilled water (AGT No .: 10180) 100 g of DL-σ-tocopherol acetate (vitamin E acetate), BASF (AGT material no .: 10721/005)

700 g polysorbai 20; Lamesorb SML 20; Cognis (Article No .: 638252) (AGT Material No .: 10520/016)

Execution:

Citroπeπsäure mix with water and heat until the Cttroπensäure has completely resolved to clarity. Then stir in polysorbate.

Add DL-α-tocopherol acetate and stir well.

Then add polysorbate 20 with stirring (this can be slightly heated beforehand - facilitates the process).

Heat everything again to approx. S5 ^β C and stir well.

Appearance:

Storage: dark, at room temperature (<25 ° C)

Processing information:

Remarks: Example 10

Citric acid / mixed tocopherol solubilisate with polysorbate 20

Ingredients:

100 g of citric acid; e.g. Citric Acid Monohydrate OR Citric Acid Anhydrate from Breππtag (BBCA-Ware) (AGT Material No: 10745/037 or 10743/037)

100 g of distilled water. (AGT No: 10180) 100 g mixed tocopherol, e.g. Coviox T-70 (proportion mixed tocopherols = 70%) from Cognis (AGT Material No .: 10727/016)

700 g polysorbate 20; Lamesorb SML 20; Fa. Cognis (Item-No .: 638252) (AGT-Material-Nr .: 10520/016)

Execution:

• Add mixed tocopherol and stir well.

• Heat everything again to approx. 85 ° C and stir well.

Appearance:

Storage: dark, at room temperature (<25 ° C)

Verarbeitungshinwefs:

Remarks: Example 11

10% citric acid solubilisate (Poly 80)

Ingredients:

100 g of distilled water (AGT No .: 10180)

100 g of citric acid, anhydrous; Synopharm (Article No .: 700309) (AGT

No .: 10743/036)

100 g Miglyol 812 (MCT oil); Fa. Sasol (AGT No .: 10460/069)

700 g Polysorbate 80 (AGT No .: 10530) (for example from Cognis, Lamesorb SMO20;

Article No .: 65274) (AGT No .: 10530/016)

Execution:

- Heat the water to approx. 85 ° C.

- Stir in citric acid and dissolve in water until clear. Temperature about 85 ° C.

- Add MCT oil with stirring. (Temp. 85 ° C)

- Slowly add polysorbate 80 and mix well.

- Homogenise well for several minutes at approx. 85 ° C.

- Allow to cool slowly; fill at approx. 6O ⁰ C

Appearance: transparent, viscous, dark yellow (brownish yellow) Storage: cool and dark Processing instructions: Remarks: Example 12

10% citric acid solubilate (poly 20)

Ingredients:

100 g of distilled water. (AGT No .: 10180)

100 g of citric acid, anhydrous; Synopharm (Article No .: 700309) (AGT

No .: 10743/036)

100 g Mϊgiyol 812 (MCT oil); Fa. Sasol (AGT No .: 10460/069)

700 g Polysorbate 20 (AGT No .: 10520) (for example from Cognis, Lamesorb SML 20;

Product No .: 638252) (AGT No .: 10520/016)

Execution:

- Heat the water to approx. 85 ^° C.

- Add MCT oil with stirring. (Temp. 85 ⁰ C)

- Slowly add polysorbate 20 and mix well.

- Homogenise well for a few minutes at approx. 85 ° C.

- Allow to cool slowly; at about 60 ⁰ C fill.

Appearance: turbid !!, viscous, pale yellow Storage: cool and dark Processing: Remarks: Example 13

20% citric acid solubilisate (poly80)

Ingredients:

200 g of aqua dest (AGT No .: 10180)

200 g of citric acid, anhydrous; Synopharm (Article No .: 700309) (AGT

No, 10743/036)

Article No .: 65274) (AGT No .: 10530/016)

Execution:

- Heat the water to approx. 85 ° C.

- Stir in citric acid and dissolve in water until clear. Temperature about 85 ⁰ C.

- Slowly add polysorbate 80 and mix well.

- Homogenise well for a few minutes at approx. 85 ^° C.

- Allow to cool slowly; fill at about 60 ° C.

Appearance: transparent, very viscous (gluey), dark yellow (brownish yellow)

Storage: cool and dark

Verarbeituπgshanwβis:

Remarks:

Example 14

20% pure citric acid solubilisate (poly 20)

Ingredients:

200 g Aqua des! (AGT No .: 10180)

200 g of citric acid, anhydrous; Synopharm (Article No .: 700309) (AGT

No .: 10743/036)

Article No .: 65274) (AGT No .: 10520/016)

Execution:

- Heat water to approx. 85 ^β C.

- Slowly add Poiysorbate 20 and mix well.

- Homogenise well for a few minutes at approx. 85 ^° C.

- Allow to cool slowly; fill at approx. 6O ⁰ C

Appearance: transparent, viscous, pale yellow Storage: cool and dark Processing instructions: Remarks:

Be i spi el 15

25% citric acid solubilisate (Poly 80)

Ingredients:

250 g distilled water. (AGT No .: 10180)

250 g of citric acid; e.g. Citric acid monohydrate OR citric acid

Anhydrate from Brenntag (BBCA-Ware) (AGT-Material-Nr :: 10745/037 or 10743/037)

500 g polysorbate 80 (for example from Cognis, Lamesorb SMO 20, article no .: 65274)

(AGT Material No: 10530/016)

Execution:

- Mix water and citric acid and dissolve by heating (60-70 ° C) until clear.

- Slowly add polysorbate 80 and mix well.

- Homogenise well for several minutes at approx. 85 ° C.

- Allow to cool slowly; at about 60 ⁰ C fill.

Appearance: dark yellow, transparent, very viscous Storage: cool and dark Processing instructions: Remarks:

When manufacturing on the production line, it must be ensured that the control of the clarity (= complete micelle formation) is carried out by means of a laser beam. At the age of 16

25% citric acid solubilisate (poly 20)

Ingredients:

250 g distilled water. (AGT No .: 10180)

250 g of citric acid; e.g. Citric acid monohydrate OR citric acid

Anhydrate from Brenntag (BBCA-Ware) (AGT-Material-Nπ: 10745/037 or 10743/037)

500 g Polysorbate 20 (for example from Cognis, Lamesorb SML20, Article No .: 49032)

(AGT Material No .: 10520/016)

Execution:

- water and citric acid mix and dissolve with heating (60-70 ⁰ C), until clear.

- Slowly add polysorbate 20 and mix well.

- Homogenise well for several minutes at approx. 85 ° C.

- Allow to cool slowly; fill at about 60 ° C.

Appearance: pale yellow, transparent, viscous Storage: cool and dark Processing instructions: Remarks:

When manufacturing on the production line, it must be ensured that the control of the clarity (= complete micelle formation) is carried out by means of a laser beam.

Claims

CLAIMS A 594-1

1. Solubilisate consisting of an aqueous solution of citric acid and / or a citric acid hydrate and / or an anhydrate and an emulsifier having an HLB value of 9 to 18, for example a polysorbate.

2. Solubilisat according to claim 1 additionally consisting of a medium-chain triglyceride.

3. Solubilisat according to claim 2, wherein the triglyceride substantially caprylic acid and / or capric acid.

4. Solubilisat according to any one of claims 1-3, additionally consisting of a tocopherol and / or a tocopherol acetate.

The solubilisate of claim 4, wherein the tocopherol is substantially α-tocopherol.

A solubilisate according to claim 4 wherein the tocopherol is a mixed tocopherol.

7. Solubilisat according to any one of the preceding claims, with polysorbate 20 or polysorbate 80th

8. Solubilisat according to any one of the preceding claims having a content of citric acid and / or citric acid hydrate between about 10% by weight and about 25% by weight.

9. Solubilisat according to any one of the preceding claims having a water content of about 10% to about 25% by weight.

10. Solubilisat according to any one of claims 2 to 9 with a content of about 10% by weight of triglycerides.

11. Solubilisat according to any one of claims 4 to 10 having a tocopherol content of between about 5% by weight and about 10% by weight.

12. Solubiiisat according to any one of the preceding claims, containing 5 polysorbate between about 50% by weight and about 75% by weight

13. A process for the preparation of a solubilizate according to any one of the preceding claims, wherein the citric acid and / or citric acid hydrate and / or anhydrate dissolved in water to the clear solution and slowly into the solution

I ₀ an emulsifier with an HLB value of 9 to 18 incorporated, well stirred and homogenized.

14. The method of claim 13, wherein the citric acid and / or citric acid hydrate dissolved in about 85 ° C heated water and the i ₅ emulsifier is incorporated into the warm solution.

15. The method of claim 13 or 14, wherein in the warm solution, a medium-chain triglyceride stirred and then the emulsifier is incorporated. 0

16. The method of claim 13 or 14, wherein in the warm solution, a tocopherol stirred and then the emulsifier is incorporated.

17. The method according to any one of claims 13 to 16, wherein as an emulsifier s polysorbate, suitably polysorbate 20 and / or polysorbate 80, is used.

18. Use of the solubilizate according to any one of claims 1 to 12 as a food additive, a technical excipient or in the purification of 0 contaminated soils.