DE2063128A1 - Hydrolysis of plant phosphatides to phospha - tide emulsifiers - Google Patents

Abstract

Phosphatide emulsifiers for oil/water or water/oil emulsions in foodstuffs, cosmetics and pharmaceutical prepns. are prepared by partial hydrolysis of natural or modified plant phosphatides or plant oils containing these at a pH of 3-5 and a temp. of 50-100 degrees C with SO2 gas or aqueous solution, or (NH4)2SO3, to give a lyso phosphatide yield of 30-40%. pH is maintained by (NH4)2SO3 or formic acid. The product is purified by vaccum evaporation.

Description

Process for the production of phosphatide emulsifiers for oil-in-water and water-in-oil emulsions by partial hydrolysis of natural and modified Plant Phosphatides The invention relates to a process for partial hydrolysis plant-based phosphatide kit the Zic @ suitable emulsifiers for sch @@ oil-in-water as aunn water-in-oil emulsions to sch @ sn, @ich @eben g @ ton S @@ properties and unsophiness to the hardness builders of the water moreover through a Excellent color and good taste and therefore insbessonde @@ for Tem @ smi @ telemulsions are signed.

It is well known that the emulsifying effect is more vegetable Phosphatides, especially those used in the extraction of vegetable oils as by-products accruing so-called

Plant lecithins can be improved by having them in the presence partially hydrolyzed by substances containing enzymes or in the presence of: acids or alkalis with elimination of free fatty acids Iiysolecithin and Lysokephalin form, which have a good emulsifiability. However, the known processes have certain disadvantages.

So is the process in which heat is inactivated for hydrolysis it used pancreatin is quite costly.

On the other hand, the acid or alkali catalyzed hydrolysis has the disadvantage that when temperatures above 5 C and longer residence times are used Obtained products of quite dark color and a caramel-like aftertaste that are not universally usable. Furthermore, one already has pure lecithin in peroxide-free ether solution with snake venom enzymes at room temperature treated for a period of 24 hours. Besides that snake venom is great is expensive and its toxic properties are enhanced by additional treatment, e.g. One such procedure is to be rendered ineffective with acids.

when carried out on a large scale, because of its use ether as a solvent is not only dangerous but also uneconomical.

It has now been found that a partial Hydrolysis of vegetable phosphatides is achieved when this is done in the presence of sulfur dioxide and hydrolyzed water.

The invention is as a method of manufacture of phosphatide emulsifiers for O / W and W / O emulsions through partial hydrolysis of natural or modified plant phosphatides, and the process is thereby characterized in that water-containing phosphatide emulsions in the presence of sulfur dioxide or sulfur dioxide-containing compounds at pH values of about 2 to 10 and Temperatures of 20 to 100 ° C hydrolyzed until the lysophosphatide yield has a numerical value between 20 and about 65 Io, preferably between 30 and 50%, whereupon the hydrolyzate, possibly after further purification, by evaporation in vacuo is freed of water and sulphurous acid when evaporating the water-containing Hydrolyzate gives products. which is much brighter than the starting material are and due to their content of lyso compounds an excellent emulsifying effect for both O / W and W / O systems.

The starting material for the present process is primarily the so-called by-products from the solvent extraction of seeds, Raw vegetable lecithins such as soy, rapeseed, peanut and cottonseed oil lecithin into consideration.

Furthermore, those from fractionation are suitable as starting materials obtained the said raw vegetable phosphatides phosphatide-containing Components such as those according to the method of the French patent specification t 1 488 086 desugarized phosphatides or those obtained by the process of DBP 1 154 706 obtained oil-free phosphatides.

Choline-lecithin-rich or cephalin-rich phosphatide fractions can also be used can be used, for example by treating phosphatide mixtures with alcohols according to French patent 1,403,578 were prepared. as well are partially acetylated phosphatides, which by the method of the French U.S. Patent 1,507,922 can be produced.

In the method according to the application, for example, one of the above-mentioned Starting materials emulsified with 1 to 5 times Henge water and the emulsion one aqueous solution of sulfur dioxide added instead of adding an aqueous one Sulfur dioxide solution can also introduce sulfur dioxide gas into the water-containing emulsion will.

But you can also directly from the with the hydration of the raw oils Go out of the lecithin slimes obtained in the water and add sulfur dioxide to them. which has the advantage that an evaporation operation and bacterial decomposition are saved be avoided.

According to a further embodiment of the invention, the treatment with sulfur dioxide can also be carried out in such a way that the after extraction crude vegetable oils obtained by pressing or extraction, which are usually 0.2 to 2% phosphatides with 1 to 5% water, based on the amount of oil one for partial hydrolysis sufficient amount of sulfur dioxide contains, hydrated and the accumulated mucus, which by centrifugation is separated1 left to stand for some time at temperatures of 50 to 1000 C.

The phosphatides separated with aqueous solutions of sulfur dioxide, which are preserved in their original composition; can be essentially easier to separate by centrifugation than those obtained with water alone This Arbeitsrjieise results in the further advantages that on the one hand practical completely phosphatide-free oils with a phosphatide content of less than 0.05% and On the other hand, phosphatides are obtained which may contain 5% more acetone-insolubles than the phosphatides obtained in the usual way. Usually you get this by hydrating the crude oils with 1 to 5% water and then centrifuging them off of the swollen phosphatides Both this process is not complete so that - depending on the quality of the oils - 0.3 to 0.8, phosphatides remain in the oil which can only be removed by subsequent refining The addition of the sulfur dioxide required for the partial hydrolysis for the aqueous phosphatide emulsion can either by introducing gaseous sulfur dioxide or by adding a Solution of sulfur dioxide in water, alcohol, acetone or the like, or by adding it an aqueous solution of its alkali, ammonium or alkaline earth salts such as, for example Na2SO3, K2SO3. (NH4) 2SO3, (NH4) HSO3, Ca (HSO3) 2, Mg (HSO3) 2, Na2S2O5 and K2S2O5.

The hydrolysis is carried out at a pH in the range of about 2 to 10 preferably performed at about 3 to 5.

The adjustment of the desired pH value can be done with one of the above sulfur dioxide compounds mentioned, e.g.

by introducing gaseous sulfur dioxide into the aqueous phosphatide emulsion or by adding a solution of these substances in one of the aforementioned Solvent under electrometric control. 1 To achieve a pH value of 4, for example, the addition of about 1% by weight of sulfur dioxide is necessary.

Light-colored lysophosphatide preparations can also be obtained by that the phosphatide emulsion is first mixed with inorganic or organic food acids, such as, for example, dilute hydrochloric acid, phosphoric acid, lactic acid, formic acid or the like acidified to pH 4, 0.1-0.5% of a sulfite, e.g., Kalimetabisulfite or other compounds from which SO2 is formed, added and then hydrolyzed. The acid can also be added after the sulfite has been added.

To set a pH value in the alkaline range you can Using an alkali sulfite is preferred, however, in the presence of sulfur dioxide or sulphurous acid worked, since you then enter after the evaporation of the water completely acid-free end product is obtained, which of course does not apply if in the presence is hydrolyzed by non-volatile acids.

To carry out the hydrolysis process according to the invention is one Concentration of at least 0.05% S029 which can also be bound, based on the anhydrous raw lecithin required, The upper limit is given by the solubility of SO2 in water. Ilydrolysis can take place at temperatures between 20 and 1000 C, preferably between 50 and 1000 Cs, The duration of the hydrolysis depends on the pH and the temperature of the phosphatide emulsion addicted. The time required for hydrolysis is shorter, the higher the temperature and the lower the pH.

At a certain pH and temperature, the Lysophosphatide yield, the quotient of the amount of lysophosphatide formed and the amount of phosphatides that have disappeared (difference between that in the starting material amount of phosphatide contained and the amount of phosphatide contained in the hydrolyzed product) proportional to the time spent on hydrolysis, and after a certain Time span reached a maximum. This increases the acid number and can cause a Achieve value. which is 2 to 3 times the original value.

The lysophosphatide yield is defined as f: (% LL +% LK) .100 % Lysophosphatide yield = #% L + #% K products with an optimal emulsifying effect are obtained if the hydrolysis is carried out for a long time, until the lysophosphatide yield a numerical value between 20 and about 65 5 "c, preferably between 30 and 50% having.

after the hydrolysis has been stopped, the hydrous Hydrolysis by evaporation in vacuo, if necessary after Addition of ammonia or other mildly alkaline agents, freed from water and sulphurous.

If the hydrolysis was not carried out at a pH value in the acidic range, $ Water $ can, $ water $ can. $ Sulfur dioxide vapor an inorganic or organic Acid such as phosphoric acid, citric acid or lactic acid in one 1 to 2 t can be added. Werner can add the Ilydrolyzate before evaporation diluted with water at 700 ° C. and the aqueous phase centrifuged off, with another wash can be carried out in the centrifuge by adding fresh water can.

Those freed from water and sulfur dioxide, partially hydrolyzed Phosphatides are excellent emulsifiers for both oil-in-water and for Water-in-oil emulsions. They can be used in food, cosmetic and pharmaceutical Preparations as well as in feed are used, likewise they are for stabilization of W / O emulsions, e.g. suitable as an anti-splash agent in margarine.

Because of the presence of sulfur dioxide the formation of brown dyes largely prevented during hydrolysis, are obtained by the new process Phosphatides of a much lighter color than the previously known, partially hydrolyzed Phosphatide. On the other hand, they are useful after the water has evaporated Free of sulfur dioxide, which makes them particularly suitable for food emulsions sindo products with an increased emulsifying effect are obtained from the raw hydrolyzate through cleaning operations known per se, e.g. by distance water-soluble accompanying substances with dilute edible acidsq 50% aqueous acetone respectively.

50% aqueous alcohols, by removing fatty acids and Neutral oil by treatment with acetone, methyl acetate, hexane-acetone, etc. and finally by fractionation with 90 to 100% strength low molecular weight alcohols. It can several of these operations can also be coupled together in most cases cleaning is also associated with a further improvement in taste and smell.

Example 1 200 g of soybean charcoal cithin containing 67.5% of acetone-insolubles became with 200 ml of water in which 0.2 g of sodium metabisulphite (Na2S2O5) were dissolved, to one Stirred emulsion. This was increased by adding 1.65 ml of 98% formic acid adjusted to pH 4 and then heated to 95 ° C. with continued stirring.

From time to time samples were taken and evaporated in vacuo freed at 65 ° C from the water and the added acids.

The lecithin preparations obtained were analyzed and checked for their emulsifiability checked in O / W systems.

To test the emulsifiability, one egg cylinder was placed in from 100 ml content 50 ml water at 500 C and a solution of 1 g of the to be examined Lecithin preparation in 9 g soft peanut fat with a melting point of 32 ° C and cooked through Swiveling the cylinder 20 times around 1800 produced a coarse emulsion. The cylinder was then heated to 500 C in a Given water bath and the time in hours (half-life) is noted that elapsed before 25 ml of water was found had deposited.

The test results are shown in the table below: Results: Duration of hydrolysis, hours: 0 3.2 7.6 12.6 Analysis data iodine color 1: 10 26 28 30 60 acid number 26 33 41 49% choline lecithin 16.6 13.0 10.0 7.7% kephalin 12.2 8.5 6.6 4.0% Lysolecithin 0 2.6 3.8 6.2% Lysokephalin 0 0 1.5 2.0 Emulsification test, 50 ° C half-life (hours) in dist. Water 0.03 6 2.8 0.7 in water at 13 ° dH 0.006 0.7 2.4 0.5 Example 2 200 g of the soy lecithin used in Example 1 were used stirred with 200 ml of water to form an emulsion. Now it was at the same temperature so much sulfur dioxide introduced that the pH-7ert of the mixture was 4, after 7 hours The emulsion was heated to 950 ° C. in vacuo at 60 to 700 ° C. until it was water-free ei, ndamped. 200 g of one resulted partially hydrolyzed Lecithins with the analysis data: iodine color 1:10 25 acid number 44% choline lecithin 8.5% Kephalin 5.4% Lysolecithin 4.0% Lysokephalin 1.8 To demonstrate the emulsifying effect This preparation in the W / O system became the anti-splash effect in 80% milk margarine according to the UNILEVER method described in "Fette-Seifen-Anstrichmittel" 65 29 (1963) certainly. The following results were obtained: Addition (g / kg fat): 0 0.25 0.5 1 2 4 Spray pattern 1 4 4 6 7 8 One obtained under analogous conditions with citric acid The iodine color of the hydrolysis product had the same acid number as 50.

contained only 4% lysophosphatides and unfolded in margarine in one Addition of 8 g / kg fat only has a moderate anti-spray effect according to the spray pattern 3.

The spray pattern numbers mean: 9 = too soon 4 = unsatisfactory 8 = very good 3 = bad 7 = good 2 = very bad 6 = sufficient 1 = unusable 5 sufficient example 3 100 g rapeseed lecithin (iodine color 1: 10 = 85, SZ = 30, 70% acetone-insoluble, 13.8% Lecithin, 7.2% cephalin) were emulsified with 200 ml of water. The emulsion was acidified with gaseous sulfur dioxide to pH 3.0 and 4.5 hours at 95 ° C hydrolyzed. The product obtained after evaporation was in taste and Color improved significantly and had the following analytical data: Iodine color 1:10 43 Acid number 51% choline lecithin 7.8% cephalin 3.9% lysolecithin 3.9 of an 80% When added to milk margarine, the preparation had the same anti-splash effect as the hydrolyzed one Soy lecithin.

according to example 2.

Example 4 466 g of a water-retaining hydrolyzate obtained according to Example 1 Soy lecithin with 275 g of dry matter was mixed with 354 ml of water and 547 ml Acetone intimately mixed for 1/2 hour. The suspension was settled and Centrifugation in three layers (oil phase, sugar and bitter-containing acetone-water phase and phosphatide-lysophosphatide phase) separate which, each for itself, were evaporated, 244 g of a purified hydrolyzate were obtained which contained 12.5% choline lecithin, 9.5% cephalin and 6.0% lysolecithin contained. The taste threshold was increased from 0.5 to 1.0% compared to the non-purified hydrolyzate.

Example 5 1,000 g of raw extracted soybean oil containing 0.0923% phosphorus and an acid number of 1.27 were heated to 70 ° C and degumming within a few seconds with vigorous stirring with genat dosed amounts of water offset. After the water had been introduced, stirring was continued for 2 minutes and then centrifuged. From the separated clear oil the color became the acid number and the phosphorus content is determined.

A series of experiments with sulfur dioxide-containing Running water. The results of both experiments are shown in the table below listed.

Slimming agent Properties of the extracted oil Jodfarbo SZ % P 1% H20 21 0.42 0.0102 2% H20 21 0.44 0.0105 3% H20 21 0.45 0.0109 4% H20 21 0.45 0.0105 5% H20 21 0.45 0.0103 1% H20 with 5% SO2 21 0.45 0.0051 2% "19 0.42 0.0017 3% "19 0.43 0.0012 4%" 19 0.41 0.0006 5% "19 0.44 0.0004 TJie Slime substances obtained after both experiments were at 900 ° C. for 8 hours left to stand and then evaporated in vacuo at 650 e. That in the present Product hydrolyzed by SO2 had an iodine color (1:10) 15 and an acid number 40 and 6% lysophosphatide (lysokephalin + lysolecithin), whereas that in the absence Product treated in the same way by SO2 has an iodine color (1:10) 30, an acid number 25 and had no appreciable amount of lyophosphatides.

Example 6 200 g of soy lecithin (AN = 21,% acetone-insolubles = 68.5, % Lecithin = 16.7,% cephalin = 11.6) were combined with 350 g of water at 500 ° C. to form one Stirred emulsion. So many milliliters of a saturated emulsion were added to this emulsion A solution of SO2 in water was added so that a pH of 3.5 resulted.

The mixture was then heated to 650 ° C. while stirring slowly, Maintained at this temperature for 5 hours and then in vacuo at a maximum 70 ° C evaporated 200 g of a light-colored hydrolyzate resulted with the following Properties: SZ = 93.3,% lecithin = 10.7,% cephalin = 7m3,% lysolecithin = 3.7, lysophosphatide yield = 36%.

The emulsification test (see example 1) had the following values at 50 ° C: in distilled water: 1.25 hours

in water of 13 ° dH: @, 5 "The anti-splash effect (see example 2) was significantly improved over the starting lecithin.

Additive (g / kg fat) spray pattern 0 0.25 0.5 1 2 4 hydrolyzate 1 4 3 4 6 7 Starting lecithin 1 1 1 2 4 5 Example 7 500 g of an alcohol-insoluble fraction from soy lecithin (SZ = 22,% acetone-insolubles = 65.7,% lecithin = 12.3,% cephalin = 11.5) were melted at 30 ° C with 900 g of distilled water to form an emulsion stirred and by adding 100 ml of a 5% SO2 solution to pH 6 set. The batch was heated to 95 ° C. and stirred gently for 8 hours kept at this temperature.

The mixture was then evaporated at 70 ° C. in vacuo.

This resulted in 495 g of an anhydrous hydrolyzate having the following Properties: SZ = 51% cephalin = 5.0% lecithin = 5.2% lysophosphatide yield = 48% Lysophosphatide = 6.5 The emulsification test (see Example 1) had the following at 50 ° C Results: in distilled water: 5.6 hours

in water of 13 ° dH: 8.3 "Example 8 1.065 g of soy lecithin flakes (70% dry matter and 72% acetone-insoluble in the dry matter) were with 1.950 ml of water were stirred into an emulsion. The mixture was acidified with a aqueous SO2 solution acidified to pH 3.6 and then by adding adjusted to pH 10 with 25% ammonia mass. With stirring and exclusion of air the mixture was then heated to 95 ° C. for 10 hours and then in a rotary evaporator evaporated under vacuum.

740 g of a light, very light-colored lecithin preparation were obtained obtained the following properties: iodine color 1:10 15 acid number 43% acetone-insoluble 60.5% choline lecithin 10.3% kephalin 6.3% lysolecithin 3.5% lysokephalin 2.1 % Lysophosphatide yield 67.5 Emulsification test at 50 ° C: in dist. Water, hrs. 13.2 in water of 130 n, h 7.1 Example 9 297 g of soy lecithin gruel with 200 g of lecithin and 67.9% acetone insolubles became one with 900 ml of water Stirred emulsion and then by adding 34 ml of a 5.5% aqueous SO2 solution adjusted to a pH of 3.45. The emulsion was heated to 70 ° C and chilled at this temperature for 30 minutes in a gentle mist. The separated one The sugar-containing aqueous phase was siphoned off and the resulting desugarized lecithin slime further concentrated by centrifugation. The combined aqueous phases were evaporated.

The lecithin flake was now turned by adding 5 ml of SO2 solution adjusted to pH 3.5, heated to 95 ° C. for 3 1/4 hours for partial hydrolysis and then evaporated in the Rotavapor.

Yields of sugar-containing extract: 17.89 g = 8.95% lecithin hydrolyzate: 182 g = 91% analysis of the lecithin hydrolyzate iodine color 1: 10 35 acid 43.7% acetone-insoluble 53.8% P 2.15% choline lecithin 10.0% kephalin 6.4% lysolecithin 4.4% lysophosphatide yield 49.5 Emulsification test, 50 ° C, hrs.

distilled water 20 water of 13 ° dH 1.87 anti-splash effect in Margarine additive (g / kg fat) 0 0.25 0.5 1 2 4 Spray pattern 1 3 4 6 8 9 for comparison: untreated lecithin 1 1 1 2 3 4

Claims (11)

Claims 1. Process for the production of phosphatide emulsifiers for O / W and W / O emulsions by partial hydrolysis of natural or modified ones Plant phosphatides, characterized in that water-containing phosphatide emulsions in the presence of sulfur dioxide or compounds containing sulfur dioxide hydrolyzed pH values of around 2 to 10 and temperatures of 20 to 100 ° C for as long as until the lysophosphatide yield is a numerical value between 20 and about 65%, preferably between 30 and 50%, whereupon the hydrolyzate, possibly after further purification, is freed from water and sulphurous acid by evaporation in vacuo. 2. The method according to claim 1, characterized in that the partial Hydrolysis is carried out at pH values of 3 to 5. 3. The method according to claims 1 and 2, characterized in that the partial hydrolysis is carried out at temperatures from 50 to 100 ° C. 4. The method according to claims 1 to 3, characterized in that the a solution of sulfur dioxide is added to the aqueous phosphatide emulsion. 5. The method according to claims 1 to 3, characterized in that in the water-containing phosphatide emulsion sulfur dioxide gas is introduced 6th Method according to claims 1 to 3, characterized in that the setting the pH value of the water-containing phosphatide emulsion with an inorganic and / or organic food acid and a sulfite is made. 7. Process according to claims 1 to 3, characterized in that adjusting the pH of the water-containing phosphatide emulsion by adding an aqueous solution of ammonium sulfite takes place., 8. The method according to the claims 1 to 7, characterized in that commercially available raw vegetable lecithins are used as the starting material be used. 9, method according to claims 1 to 7 7, characterized in that that as a starting material in the technical hydration of crude vegetable oils accumulating phosphatide mucilage is used. 10. The method according to claims 1 to 3 and 9, characterized in that that one in the hydration of crude vegetable oils with sulfur dioxide-containing water accumulating phosphatide slime is used ' 11. The method according to the claims 1 to 7 characterized in that desugarized phosphate tides as the starting material be used. 12. The method according to claims 1 to 7, characterized in that that oil-free phosphatides are used as the starting material. 13a method according to claims 1 to 7, characterized in that that phosphatide fractions are used as starting material. 14. The method according to claims 1 to 7, characterized in that that partially acetylated phosphatides are used as starting material. 150 Process according to Claims 1 to 14, characterized in that that soy phosphatides are used as the starting material.