METHOD FOR DEGUMMING COMPOSITIONS CONTAINING TRIGLYCERIDE

Abstract

The present invention relates to a method for degumming compositions containing triglyceride with addition of a solubilizer, and to a composition containing triglyceride which has been degummed by the method according to the invention.

Claims

1. A method of degumming triglyceride-containing compositions, comprising the steps of (a) contacting a triglyceride-containing composition with at least one solubilizer; (b) removing the gum phase from the triglyceride-containing composition.

2. The method as claimed in claim 1, wherein the at least one solubilizer has an HLB value of 5.5 to 13.5.

3. The method as claimed in claim 1, wherein the at least one solubilizer is selected from the group consisting of polyhydroxyl compounds, polyglycols, alcohols and mixtures thereof.

4. The method as claimed in claim 3, wherein the polyhydroxyl compounds have an asymmetric molecular structure.

5. The method as claimed in claim 1, wherein the at least one solubilizer is selected from the group consisting of propane-1,2-diol, propane-1,3-diol, butane-1,2-diol, methyl-glycol, methylpropane-1,3-diol, 1-octanol, 2,2-dimethylpropane-1,3-diol, butane-2,3-diol, butanol, ethanol, isopropanol, ethylene oxide-propylene oxide monobutyl ether, 1-pentanol, 3-pentanol, 2-methylpentane-2,4-diol, 1-hexanol, 3-hexanol, hexane-1,6-diol, hexane-2,5-diol, 1-heptanol, 3-heptanol, heptane-1,7-diol, sucrose esters, mono- and diacetyltartrates of monoglycerides, polyglycerol esters, sorbitan esters, polyoxyethylene sorbitan esters, polyethylene glycols, copolymers of ethylene oxide and propylene oxide units and mixtures thereof.

6. The method as claimed in claim 1, wherein separation of the gum phase from the triglyceride-containing composition in step (b) is preceded by addition of at least one enzyme to the triglyceride-containing composition.

7. The method as claimed in claim 6, wherein the at least one solubilizer is added before the at least one enzyme.

8. The method as claimed in claim 6, wherein the at least one enzyme is selected from the group consisting of phospholipid-cleaving enzymes, glycoside-cleaving enzymes and mixtures thereof.

9. The method as claimed claim 6, wherein the at least one enzyme has alpha- or beta-glucosidase activity.

10. The method as claimed in claim 6, wherein the at least one enzyme is selected from the group consisting of phospholipase A1, phospholipase A2, phospholipase C, acyltransferase, alpha-glucosidase, beta-glucosidase and mixtures thereof.

11. The method as claimed in claim 6, wherein the at least one enzyme comprises an amylase.

12. The method as claimed in claim 1, wherein the triglyceride-containing composition used is crude vegetable oil or pre-degummed vegetable oil.

13. The method as claimed in claim 1, wherein the triglyceride-containing composition is crude vegetable oil and, prior to the contacting in step (a), water and/or acid and/or alkali is added to the crude vegetable oil without conducting any removal step prior to the separation of the gum phase in step (b).

14-15. (canceled)

Description

EXAMPLES AND FIGURES

[0087] The invention is elucidated in detail below by means of examples and figures. It is here emphasized that the examples and figures are merely illustrative in nature and illustrate particularly preferred embodiments of the present invention and do not limit the scope of the present invention in any way.

[0088] The figures show:

[0089] FIG. 1 the oil yield after the degumming of crude soybean oil with different concentrations of propane-1,2-diol in comparison with standard degumming without propane-1,2-diol;

[0090] FIG. 2 the oil yield after the degumming of crude soybean oil with different concentrations of propane-1,2-diol and 0.5 U/g oil of PLA1 in comparison with PLA1 standard degumming (0.5 U/g oil) without propane-1,2-diol

[0091] FIG. 3 separation of the soybean oil on the pilot plant scale after the aqueous degumming

[0092] FIG. 4 separation of the soybean oil on the pilot plant scale after the aqueous degumming with addition of 2.2% by weight of propane-1,2-diol

[0093] The examples were carried out on the basis of the following reaction variants, to which they relate:

TABLE-US-00001 TABLE 1 Solubilizers used HLB Additive Formula value Propane-1,2-diol [00001] 8.70 1-Octanol [00002] 2.65 2,2-Dimethyl- propane-1,3-diol [00003] 6.56 Butane-2,3-diol [00004] 7.57 Butanol [00005] 4.62 Ethanol [00006] 7.42 Isopropanol [00007] 5.69 Polyglycol Ethylene oxide-polypropylene oxide 9.58 B11/50 monobutyl ether, mean molecular weight: 1300 g/mol 1-Pentanol [00008] 3.89 3-Pentanol [00009] 3.89 2-Methylpentane- 2,4-diol [00010] 5.78 1-Hexanol [00011] 3.36 3-Hexanol [00012] 3.36 Hexane-1,6-diol [00013] 5.78 Hexane-1,2-diol [00014] 5.78 Hexane-2,5-diol [00015] 5.78 1-Heptanol [00016] 2.96 3-Heptanol [00017] 2.96 Heptane-1,7-diol [00018] 5.17
Reaction Variant 1: Degumming of Crude Oil with Citric Acid, Complete Neutralization

[0094] The amount of crude oil to be treated, from 400 to 600 g, is introduced into a 1000 mL DN120 Duran reactor, and samples are taken for analysis. The oil in the Duran reactor is heated by means of a hotplate to a temperature of from 40 to 85 C., preferably from 45 to 80 C. As soon as the desired temperature is reached, the pre-conditioning is begun. To that end, a defined amount, dependent on the amount of oil, of citric acid (e.g. 1000 ppm) is metered into the oil. The mixture is then dispersed with an Ultraturrax for 5 seconds to 1 minute and the reaction mixture is mixed thoroughly at 150 rpm for a further 15 minutes until the reaction of the acid has taken place. Alternatively, the reaction mixture can be incubated at approximately 600 rpm with vigorous stirring. A defined amount of sodium hydroxide solution (1 mol/L, residual amount to 1.5 to 2.5% by volume minus water from acid addition and enzyme addition) is then added. The aim of adding the sodium hydroxide solution is complete neutralization of the acid including the free fatty acids in the oil. This requires an alkali excess of 10-30%, preferably 20%. The amount of sodium hydroxide solution required is calculated by the amounts of the acids and the molar mass thereof. Alternatively, a pH of from 7 to 8 can be established with an excess of sodium hydroxide solution. After cooling to 48 C. or after the temperature has been maintained at 45 C. or 80 C., the sodium hydroxide solution can be dispersed with an Ultraturrax for 5 seconds. The reaction mixture is mixed thoroughly for a further 10 minutes. Subsequently, the residual amount of water (0.5 to 5%) minus the amount of water already added through addition of acid and alkali is fed in. The temperature over the entire reaction remains at 45 to 48 C. or at 80 C.

[0095] The addition of one or more solubilizers (0.05 to 0.3% by weight of solubilizer/oil) can be effected at different times during the overall reaction; see table 2 below. For this purpose, the stirrer speed can be increased for a short time (1 minute at 900 rpm), and then stirring is continued at a lower speed (150 rpm).

[0096] Samples are taken at defined time intervals. The sample is taken by means of a pipette, introduced into a temperature-controlled glass centrifuge tube (temperature of the reaction mixture), the temperature is adjusted, and it is centrifuged at 3000 rpm for at least 4 minutes in order to separate the gum phase from the oil. For documentation purposes, the result of the phase formation is photographed; samples of the supernatant are taken for determination of the phosphorus, calcium and magnesium content.

[0097] The separation of the gum phase from the oil is effected by the following steps:

1. Switching off the stirrer
2. Transferring the oil to a centrifuge cup
3. Heating the filled centrifuge cup in a drying cabinet at 80 C. for 15 minutes
4. Separating oil and heavy phase in the Eppendorf 5810 R laboratory centrifuge at 4000 rpm for 10 minutes.

Dosage Variants for the Solubilizers:

[0098] The solubilizers listed above can be added to reaction variant 1 at various times. The dosage times are examples and can be effected at any time during the reaction.

TABLE-US-00002 TABLE 2 Varying dosage times for the solubilizers in the course of acid degumming with full neutralization: A Prior to addition of acid B Simultaneously with addition of acid C After the addition of acid, prior to the addition of alkali D Simultaneously with addition of alkali E After the addition of alkali, prior to the addition of water F After addition of water G Before the end of the reaction

Reaction Variant 2: Crude Oil, Aqueous Pre-Degumming (Lecithin Production)

[0099] In a further reaction variant, 0.05 to 5% by volume of water is added to the crude oil. The emulsion is mixed thoroughly. Ideally, the reaction is conducted at 30 to 80 C., preferably at 40 to 78 C. Subsequently, the phase separation is awaited and the solids settle out or can be removed by a standard method known to the person skilled in the art, for example via centrifugation or filtration.

[0100] The separation of the gum phase from the oil is effected by the following steps:

1. Switching off the stirrer
2. Transferring the oil to a centrifuge cup
3. Heating the filled centrifuge cup in a drying cabinet at 80 C. for 15 minutes
4. Separating oil and heavy phase in the Eppendorf 5810 R laboratory centrifuge at 4000 rpm for 10 minutes.

[0101] The addition of one or more solubilizers (0.05 to 0.3% by weight of solubilizer/oil) can be effected at different times, for example prior to the addition of water or after the addition of water, over the entire reaction; see table 3 below. For this purpose, the stirrer speed can be increased for a short time (1 minute at 900 rpm), and then stirring is continued at a lower speed (150 rpm).

Dosage Variants for the Solubilizers:

[0102] The solubilizers listed above can be added to reaction variant 2 at various times. The dosage times are examples and can be effected at any time during the reaction.

TABLE-US-00003 TABLE 3 Varied dosage times for the solubilizers in the course of water degumming: A Prior to addition of water B After the addition of water C At the end of the reaction

Reaction Variant 3: Crude Oil, Partial Neutralization

[0103] The amount of crude oil to be treated, from 400 to 600 g, is introduced into a 1000 mL DN120 Duran reactor, and samples are taken for analysis. The oil in the Duran reactor is heated by means of a hotplate to a temperature of from 40 to 85 C., preferably from 48 to 80 C. As soon as the temperature is reached, the pre-conditioning is begun. To that end, a defined amount, dependent on the amount of oil, of citric acid (e.g. 1000 ppm) is metered into the oil. The mixture is then mixed thoroughly with an Ultraturrax for 1 minute. Alternatively, the mixture is incubated at approximately 600 rpm for 15 minutes with stirring, in order to await the reaction of the acid. A defined amount of sodium hydroxide solution (4 mol/L, residual amount to 1.5 to 2.5% by volume minus water from acid addition) is then added until a pH of about 4 to 5 has been attained, and the mixture is incubated while stirring for further a 10 minutes. Subsequently, the residual amount of water (0.5 to 5% by volume) minus the amount of water already added through addition of acid and alkali is fed in. The temperature over the entire reaction remains at 45 to 80 C.

[0104] The addition of one or more solubilizers (0.05 to 0.3% by weight of solubilizer/oil) can be effected at different times during the overall reaction; see table 4. For this purpose, the stirrer speed can be increased for a short time (1 minute at 900 rpm), and then stirring is continued at a lower speed (150 rpm).

[0105] Samples are taken at defined time intervals. The sample is taken by means of a pipette, introduced into a temperature-controlled glass centrifuge tube (temperature of the reaction mixture), the temperature is adjusted, and it is centrifuged at 3000 rpm for at least 4 minutes in order to separate the gum phase from the oil. For documentation purposes, the result of the phase formation is photographed; samples of the supernatant are taken for determination of the phosphorus, calcium and magnesium content.

[0106] The separation of the gum phase from the oil is effected by the following steps:

1. Switching off the stirrer
2. Transferring the oil to a centrifuge cup
3. Heating the filled centrifuge cup in a drying cabinet at 80 C. for 15 minutes
4. Separating oil and heavy phase in the Eppendorf 5810 R laboratory centrifuge at 4000 rpm for 10 minutes.

Dosage Variants for the Solubilizers:

[0107] The solubilizers listed above can be added to reaction variant 3 at various times. The dosage times are examples and can be effected at any time during the reaction.

TABLE-US-00004 TABLE 4 Varied dosage times for the solubilizers in the course of acid degumming with partial neutralization: A Prior to addition of acid B Simultaneously with addition of acid C After the addition of acid, prior to the addition of alkali D Simultaneously with addition of alkali E After the addition of alkali, prior to the addition of water F After addition of water G Before the end of the reaction
Reaction Variant 4: Crude Oil, Partial Neutralization with Enzyme

[0108] The amount of crude oil to be treated, from 400 to 600 g, is introduced into a 1000 mL DN120 Duran reactor, and samples are taken for analysis. The oil in the Duran reactor is heated by means of a hotplate to a temperature of from 40 to 85 C., preferably from 48 to 80 C. As soon as the temperature is reached, the pre-conditioning is begun. To that end, a defined amount, dependent on the amount of oil, of citric acid (e.g. 1000 ppm) is metered into the oil. The mixture is then mixed thoroughly with an Ultraturrax for 1 minute. Alternatively, the mixture is incubated at approximately 600 rpm for 15 minutes with stirring, in order to await the reaction of the acid. A defined amount of sodium hydroxide solution (4 mol/L, residual amount to 1.5 to 2.5% by volume minus water from acid addition and enzyme addition) is then added until a pH of about 4 to 5 has been attained, and the mixture is incubated while stirring for a further 10 minutes. After cooling to 48 C., an enzyme, an enzyme mixture or an immobilizate is added, for which the stirrer speed can be increased briefly (to 900 rpm for 1 minute), then stirring is continued at a lower speed. Subsequently, the residual amount of water (0.5 to 5% by volume) minus the amount of water already added through addition of acid and alkali is fed in. The temperature over the entire reaction remains at 45 to 80 C. The choice of temperature depends here on the thermal stability of the enzyme or enzyme mixture used in each case.

[0109] The addition of one or more solubilizers (0.05 to 0.3% by weight of solubilizer/oil) can be effected at different times during the overall reaction; see table 5. For this purpose, the stirrer speed can be increased for a short time (1 minute at 900 rpm), and then stirring is continued at a lower speed (150 rpm).

[0110] Samples are taken at defined time intervals. The sample is taken by means of a pipette, introduced into a temperature-controlled glass centrifuge tube (temperature of the reaction mixture), the temperature is adjusted, and it is centrifuged at 3000 rpm for at least 4 minutes in order to separate the gum phase from the oil. For documentation purposes, the result of the phase formation is photographed; samples of the supernatant are taken for determination of the phosphorus, calcium and magnesium content.

[0111] The separation of the gum phase from the oil is effected by the following steps:

1. Switching off the stirrer
2. Transferring the oil to a centrifuge cup
3. Heating the filled centrifuge cup in a drying cabinet at 80 C. for 15 minutes
4. Separating oil and heavy phase in the Eppendorf 5810 R laboratory centrifuge at 4000 rpm for 10 minutes.

Dosage Variants for the Solubilizers:

[0112] The solubilizers listed above can be added to reaction variant 4 at various times. The dosage times are examples and can be effected at any time during the reaction.

TABLE-US-00005 TABLE 5 Varied dosage times for the solubilizers in the course of acid degumming with partial neutralization and addition of enzyme: A Prior to addition of acid B Simultaneously with addition of acid C After the addition of acid, prior to the addition of alkali D Simultaneously with addition of alkali E After the addition of alkali, prior to the addition of water F After addition of water G Before the end of the reaction

Reaction Variant 5: Crude Oil

[0113] The amount of crude oil to be treated, from 400 to 600 g, is introduced into a 1000 mL DN120 Duran reactor, and samples are taken for analysis. The oil in the Duran reactor is heated by means of a hotplate to a temperature of from 40 to 85 C., preferably from 48 to 80 C. As soon as the desired temperature is reached, the pre-conditioning is begun. To that end, a defined amount, dependent on the amount of oil, of citric acid (e.g. 1000 ppm) is metered into the oil. The mixture is then mixed thoroughly with an Ultraturrax for 1 minute. Alternatively, the mixture is incubated at approximately 600 rpm for 15 minutes with stirring, in order to await the reaction of the acid. A defined amount of sodium hydroxide solution (1 mol/L, residual amount to 1.5 to 2.5% by volume minus water from acid addition and enzyme addition) is then added until a pH of about 4 to 5 has been attained, and the mixture is incubated while stirring for a further 10 minutes. Alternatively, it is possible to use an excess of sodium hydroxide solution to set a pH of 7 to 8 and incubate while stirring for a further 10 minutes. After cooling to 48 C. or after keeping the temperature at 80 C., propane-1,2-diol is added as solubilizer (0.05 to 0.3% by weight of propane-1,2-diol oil), for which the stirrer speed can be increased briefly (to 900 rpm for 1 minute), then stirring is continued at lower speed.

[0114] Samples are taken at defined time intervals. The sample is taken by means of a pipette, introduced into a temperature-controlled glass centrifuge tube (temperature of the reaction mixture), the temperature is adjusted, and it is centrifuged at 3000 rpm for at least 4 minutes in order to separate the gum phase from the oil. For documentation purposes, the result of the phase formation is photographed; samples of the supernatant are taken for determination of the phosphorus, calcium and magnesium content.

Reaction Variant 6: Crude Oil

[0115] The amount of crude oil to be treated, from 400 to 600 g, is introduced into a 1000 mL DN120 Duran reactor, and samples are taken for analysis. The oil in the Duran reactor is heated by means of a hotplate to a temperature of from 40 to 85 C., preferably from 48 to 80 C. As soon as the temperature is reached, the pre-conditioning is begun. To that end, a defined amount, dependent on the amount of oil, of citric acid (e.g. 1000 ppm) is metered into the oil. The mixture is then mixed thoroughly with an Ultraturrax for 1 minute. Alternatively, the mixture is incubated at approximately 600 rpm for 15 minutes with stirring, in order to await the reaction of the acid. A defined amount of sodium hydroxide solution (1 mol/L, residual amount to 1.5 to 2.5% by volume minus water from acid addition and enzyme addition) is then added until a pH of about 4 to 5 has been attained, and the mixture is incubated while stirring for a further 10 minutes. After cooling to 48 C., propane-1,2-diol as solubilizer and an enzyme, an enzyme mixture or an immobilizate are added, for which the stirrer speed can be increased briefly (to 900 rpm for 1 minute), then stirring is continued at lower speed.

[0116] Samples are taken at defined time intervals. The sample is taken by means of a pipette, introduced into a temperature-controlled glass centrifuge tube (temperature of the reaction mixture), the temperature is adjusted, and it is centrifuged at 3000 rpm for at least 4 minutes in order to separate the gum phase from the oil. For documentation purposes, the result of the phase formation is photographed; samples of the supernatant are taken for determination of the phosphorus, calcium and magnesium content.

EXAMPLES

Example 1

[0117] According to reaction variant 5, a crude soybean oil with the following starting contents was used: phosphorus 860 ppm, calcium 63 ppm, magnesium 60 ppm and a content of free fatty acids of 0.45%. The crude oil was heated to 80 C. and subjected at this temperature to pre-conditioning by means of aqueous citric acid (1000 ppm) and was then neutralized to pH 7 to 8 with aqueous sodium hydroxide solution (1 mol/L). Different concentrations of propane-1,2-diol (0.05 to 0.2% by weight propanediol) were then added and stirring was continued. As comparison, a sample was stirred without propane-1,2-diol (standard degumming). The oil/water ratio (weight) was 98.5:1.5. Samples were taken at regular intervals (see table 6). At the end of the reaction, the gum phase was removed by centrifugation and the oil yield was determined via mass weighing.

[0118] The results are summarized in table 6. It can clearly be seen that an increasing concentration of propane-1,2-diol leads to a decrease in the calcium (Ca), magnesium (Mg) and phosphorus (P) ions. In the standard degumming of the soybean oil, the following ion values were achieved after a reaction time of one hour: Ca: 4.7 ppm; Mg: 3.7 ppm and P: 42 ppm. After a reaction time of one hour, the following ion values were achieved with 0.2% by weight propane-1,2-diol: Ca: 1.1 ppm; Mg: 0.69 ppm and P: 10 ppm. In addition, the oil yield increases with propane-1,2-diol from 95.5 to 95.8% by weight. The values were confirmed in repeat determinations. It was thus shown that the oil degumming is more effective and a higher oil yield is achieved as a result of the addition of propane-1,2-diol.

TABLE-US-00006 TABLE 6 Degumming with different concentrations of propane-1,2-diol in comparison with standard degumming Test 10 min. 60 min. Oil yield [%] Standard Ca [ppm] 7.6 4.7 95.5 degumming Mg [ppm] 6.5 3.7 P [ppm] 77 42 FFA [%] 0.11 0.16 0.05% Ca [ppm] 1.5 2.2 95.5 propane-1,2- Mg [ppm] 1.2 1.8 diol P [ppm] 12 20 FFA [%] 0.07 0.15 0.1% Ca [ppm] 1.6 2.2 95.6 propane-1,2- Mg [ppm] 1.2 1.7 diol P [ppm] 12 18 FFA [%] 0.08 0.12 0.2% Ca [ppm] 1.6 1.1 95.8 propane-1,2- Mg [ppm] 1.2 0.9 diol P [ppm] 13 10 FFA [%] 0.11 0.15

Example 2

[0119] According to reaction variant 6, a crude soybean oil with the following starting contents was used: phosphorus 860 ppm, calcium 63 ppm, magnesium 60 ppm and a content of free fatty acids of 0.45%. The crude oil was subjected to pre-conditioning by means of aqueous citric acid (1000 ppm) and was then neutralized to pH 4-5 with aqueous sodium hydroxide solution (1 mol/L). A phospholipase A1 (PLA1) from Thermomyces lanuginosus and various concentrations of propane-1,2-diol (0.05 to 0.2% by weight) were then added according to reaction variant 6 and stirring was continued. As comparison, a sample without propane-1,2-diol (PLA1 standard degumming) was stirred. The oil/water ratio (weight) was 98.5:1.5. Samples were taken at regular intervals. At the end of the reaction, the gum phase was removed by centrifugation and the oil yield was determined via mass weighing. The reaction temperature was kept at 48 C. over the entire reaction time. With regard to the separation, the procedure was as described in reaction variant 6. Prior to the separation, the samples were each preheated to 80 C.

[0120] The results are summarized in table 7. It can clearly be seen that an increasing concentration of propane-1,2-diol leads to an increased oil yield and that the use, for example, of 0.2% by weight propane-1,2-diol+PLA1 permits a further increase by approximately 1% degummed soybean oil. The values were confirmed in repeat determinations. It was thus shown that the oil degumming is more effective and a higher oil yield is achieved as a result of the addition of propane-1,2-diol.

TABLE-US-00007 TABLE 7 Degumming with different concentrations of propane-1,2-diol and PLA1 in comparison with PLA1 standard degumming Oil yield Test 10 min. 60 min. [%] 0.5 U/g PLA1 Ca [ppm] 0.5 0.5 95.8 standard Mg [ppm] 0.5 0.5 degumming P [ppm] 4.7 4.8 FFA [%] 0.15 0.31 Gum [%] 6.6 4.9 0.025% Ca [ppm] 1 0.3 96.2 propanediol + Mg [ppm] 0.9 0.3 0.5 U/g P [ppm] 10 3.6 PLA1 FFA [%] 0.26 0.45 Gum [%] 3.9 2.8 0.1% Ca [ppm] 0.9 1 96.6 propanediol + Mg [ppm] 0.9 1 0.5 U/g P [ppm] 7.5 9.6 PLA1 FFA [%] 0.20 0.32 Gum [%] 5.5 3.1 0.2% Ca [ppm] 1 0.3 96.8 propanediol + Mg [ppm] 0.9 0.3 0.5 U/g P [ppm] 10 3.6 PLA1 FFA [%] 0.26 0.45 Gum [%] 3.9 2.8

Example 3: Water Degumming/Lecithin Production in the Case of Crude Soybean Oil and Crude Rapeseed Oil (Reaction Variant 2)

[0121] Within the scope of this example, the effect of the additives of the invention on the aqueous degumming of crude soybean oil and crude rapeseed oil was examined. For this purpose, the solubilizers were used in a concentration of 0.2% by weight based on the amount of oil. The crude vegetable oils used for this purpose are characterized by the following analytical data:

TABLE-US-00008 TABLE 8 Characterization data of the oils used in example 3 Crude soybean oil Crude rapeseed oil Ca content [ppm] 195 230 Mg content [ppm] 150 74 P content [ppm] 1100 1150 FFA content [%] 0.42 1.2

[0122] 530 g of crude vegetable oil (crude soybean and rapeseed oil), after weighing the reactor pot, were introduced into a Duran reactor, heated to 60 C. and stirred at a stirrer speed of 150 rpm.

[0123] This was followed by the addition of water and any solubilizer: 2.5% total water was used in the case of soybean oil and 3% total water in the case of rapeseed oil.

[0124] In the inventive batches, the additive was first mixed with the water in a beaker and then introduced into the Duran reactor via a funnel. The mixture was stirred at 60 C. for 60 minutes. Thereafter, samples for the analyses of the content of P, Ca, Mg and the free fatty acids were taken from the reaction mixture.

[0125] Finally, the reaction mixture was heated up to 80 C. to prepare for the separation, the stirrer was switched off and the reaction mixture was left to stand for 5 minutes. Thereafter, the oil (reaction mixture) was transferred into a centrifuge cup and heated at 80 C. in a drying cabinet for another 15 minutes, then centrifuged at 4000 rpm in a laboratory centrifuge for 10 minutes. Finally, the oil phase was emptied and the mass of heavy phase was determined via the weighing of the centrifuge cup. Finally, the oil yield was determined by weighing the oil remaining after the degumming using the mass of the oil used.

TABLE-US-00009 TABLE 9 Results of the aqueous degumming of crude soybean oil with and without additives of the invention Soybean oil Oil yield Experiment 60 min. [%] Water degumming Ca [ppm] 147 94.7 (standard degumming) Mg [ppm] 67 P [ppm] 275 FFA [%] 0.32 Gum [%] 5.8 0.20% Ca [ppm] 135 94.8 1-octanol Mg [ppm] 61 P [ppm] 245 FFA [%] 0.29 Gum [%] 5.3 0.20% Ca [ppm] 152 95.0 1-heptanol Mg [ppm] 69 P [ppm] 290 FFA [%] 0.31 Gum [%] 5.7 0.20% Ca [ppm] 145 95.0 3-heptanol Mg [ppm] 66 P [ppm] 275 FFA [%] 0.29 Gum [%] 5.7 0.20% Ca [ppm] 145 94.9 1-hexanol Mg [ppm] 62 P [ppm] 310 FFA [%] Gum [%] 5.1 0.20% Ca [ppm] 136 94.9 3-hexanol Mg [ppm] 63 P [ppm] 250 FFA [%] 0.3 Gum [%] 5.5 0.20% Ca [ppm] 145 95.0 1-pentanol Mg [ppm] 66 P [ppm] 275 FFA [%] 0.29 Gum [%] 5.5 0.20% Ca [ppm] 150 95.0 3-pentanol Mg [ppm] 68 P [ppm] 295 FFA [%] Gum [%] 5.5 0.20% Ca [ppm] 116 95.7 heptane-1,7-diol Mg [ppm] 57 P [ppm] 210 FFA [%] Gum [%] 3.8 0.20% Ca [ppm] 128 95.2 2-methylpentane-2,4-diol Mg [ppm] 61 P [ppm] 235 FFA [%] 0.31 Gum [%] 4.5 0.20% Ca [ppm] 155 95.6 hexane-1,6-diol Mg [ppm] 76 P [ppm] 260 FFA [%] Gum [%] 3.2 0.20% Ca [ppm] 145 95.2 hexane-1,2-diol Mg [ppm] 62 P [ppm] 300 FFA [%] Gum [%] 4.6 0.20% Ca [ppm] 153 95.6 hexane-2,5-diol Mg [ppm] 75 P [ppm] 250 FFA [%] Gum [%] 3.7 0.20% Ca [ppm] 142 95.5 2,2-dimethylpropane-1,3-diol Mg [ppm] 62.3 P [ppm] 250 FFA [%] 0.30 Gum [%] 4.0 0.20% Ca [ppm] 140 95.1 butane-2,3-diol Mg [ppm] 65 P [ppm] 260 FFA [%] 0.29 Gum [%] 4.4 0.20% Ca [ppm] 140 95.1 propane-1,2-diol Mg [ppm] 70 P [ppm] 255 FFA [%] Gum [%] 4.6

[0126] The studies with different solubilizers at a dosage of 0.2% by weight in each case show a significant increase in the oil yield for some of the solubilizers. The best results are shown by heptane-1,7-diol, hexane-2,6-diol, hexane-2,5-diol and 2,2-dimethylpropane-1,3-diol. With these additives, under the conditions specified, an increase in the oil yield by 1% or more is achieved.

[0127] Table 10 relating to example 3: Results of the aqueous degumming of crude rapeseed oil with and without additives of the invention

TABLE-US-00010 Rapeseed oil Oil yield Experiment 60 min. [%] Water degumming Ca [ppm] 43 93.8 (standard degumming) Mg [ppm] 6.3 P [ppm] 50 FFA [%] 0.91 Gum [%] 5.7 0.20% Ca [ppm] 50 93.6 1-octanol Mg [ppm] 7.1 P [ppm] 56 FFA [%] 0.94 Gum [%] 5.8 0.20% Ca [ppm] 46 93.6 3-heptanol Mg [ppm] 6.4 P [ppm] 52 FFA [%] 1.02 Gum [%] 4.6 0.20% Ca [ppm] 59 94.4 heptane-1,7-diol Mg [ppm] 8.4 P [ppm] 70 FFA [%] 0.92 Gum [%] 4.4 0.20% Ca [ppm] 61 93.8 2-methylpentane-2,4-diol Mg [ppm] 8.9 P [ppm] 80 FFA [%] 0.95 Gum [%] 5 0.20% Ca [ppm] 48 93.8 propane-1,2-diol Mg [ppm] 7.4 P [ppm] 63 FFA [%] 0.92 Gum [%] 5.5

[0128] The results in the above table show that it is also possible with individual additives of the invention to increase the oil yield in the aqueous degumming of rapeseed oils.

[0129] Both in the aqueous degumming of soybean oil and in the aqueous degumming of rapeseed oil, the additives of the invention do not reduce the P values to a significant degree. This effect is desired because, in lecithin production from the aqueous gum, the non-hydratable phospholipids which remain in oil in this case should not be transferred to the aqueous gum. In the processing of the lecithin, these would merely dilute the hydratable phospholipids and especially the phosphatidylcholine and would have to be removed in a complex manner.

Example 4: Water Degumming/Lecithin Production with Varied Times for Solubilizer Dosage for Soybean Oil (Reaction Variant 2)

[0130] In order to examine the influence of the time of dosage of the solubilizers on the oil yield, the solubilizer heptane-1,7-diol and propane-1,2-diol was selected. The studies were conducted with soybean oil according to example 3. The procedure followed was generally analogous to example 3, except that the time of dosage for the two solubilizers used was varied:

TABLE-US-00011 TABLE 11 relating to example 4: Water degumming/lecithin production with varied times of solubilizer dosage for soybean oil (using heptane-1,7-diol and propane-1,2-diol as solubilizer) Soybean oil - heptane-1,7-diol solubilizer oil yield Experiment 60 min. [%] Water degumming Ca [ppm] 147 94.7 No solubilizer Mg [ppm] 67 P [ppm] 275 FFA [%] 0.32 Gum [%] 5.8 0.20% Ca [ppm] 116 95.7 heptane-1,7-diol Mg [ppm] 57 as standard P [ppm] 210 with addition of water FFA [%] Gum [%] 3.8 0.20% Ca [ppm] 150 95.5 heptane-1,7-diol Mg [ppm] 70 5 minutes before addition of P [ppm] 280 water FFA [%] 0.31 Gum [%] 4 0.20% Ca [ppm] 156 95.3 heptane-1,7-diol Mg [ppm] 72 30 minutes after addition of P [ppm] 295 water FFA [%] 0.31 Gum [%] 4 0.20% Ca [ppm] 157 95.0 heptane-1,7-diol Mg [ppm] 73 5 minutes before the end of P [ppm] 300 reaction FFA [%] 0.32 Gum [%] 4 Soybean oil - propane-1,2- Ca [ppm] 140 95.1 diol solubilizer Mg [ppm] 70 0.20% propane-1,2-diol P [ppm] 255 as standard FFA [%] with addition of water Gum [%] 4.6 0.20% Ca [ppm] 140 95.2 propane-1,2-diol Mg [ppm] 68 5 minutes before addition of P [ppm] 270 water FFA [%] 0.3 Gum [%] 4 0.20% Ca [ppm] 108 95.2 propane-1,2-diol Mg [ppm] 53 30 minutes after addition of P [ppm] 210 water FFA [%] 0.3 Gum [%] 4.5 0.20% Ca [ppm] 145 95.4 propane-1,2-diol Mg [ppm] 69 5 minutes before end of P [ppm] 290 reaction FFA [%] 0.35 Gum [%] 4.5

[0131] For the heptane-1,7-diol solubilizer, it is found that it is best used together with the water directly at the start of the lecithin production for the achievement of a maximum oil yield. For propane-1,2-diol, the dosage of the additive shortly before the end of the reaction is the most favorable. The results suggest that the most favorable time of dosage is dependent on the chemical structure of the solubilizer.

Example 5

[0132] Partial Neutralization in the Crude Oil at 48 C. without Enzyme, Separation at 80 C.Experiments with Soybean Oil and Rapeseed Oil (Reaction Variant 3)

[0133] In this reaction variant, conditions as typically established in enzymatic oil degumming were established, but no enzyme was metered in. These measurements serve as reference for the reaction mixtures examined in later examples for the enzymatic oil degumming. The influence of the additives on the starting situation for the enzymatic oil degumming can be examined here. In addition, the results document the positive influence of the additives of the invention in the case of partial neutralization of the citric acid.

[0134] The following table shows the characterization data of the oils used:

TABLE-US-00012 TABLE 12 Characterization data of the oils used in example 5 Crude soybean oil Crude rapeseed oil Ca content [ppm] 172 230 Mg content [ppm] 129 74 P content [ppm] 800 1150 FFA content [%] 0.99 1.2

[0135] 530 g of crude vegetable oil (crude soybean oil and rapeseed oil), after the reactor pot had been weighed, were introduced into a Duran reactor, heated to 48 C. and stirred at a stirrer speed of 150 rpm. Thereafter, 1000 ppm of 50% citric acid (depending on the calcium and magnesium values and on the phosphorus value) were metered in and the mixture was stirred for a further 15 minutes. This was followed by partial neutralization with 4 molar (16%) sodium hydroxide solution to pH 4. The amount of alkali required for the purpose had been determined beforehand in a titration curve with citric acid. After an additional reaction time of 10 minutes, the water (comparative experiments) or the water with the added solubilizer (inventive procedure) was metered. In the case of the degumming of soybean oil, 2.5% total water were employed here, and in the case of rapeseed oil 3% total water. The amount of water added at this stage corresponded to the total water minus the amount of water added with acid and alkali, and 0.2% solubilizer.

[0136] If the additives of the invention were used, these (0.2% by weight of additive in each case, based on the total amount of oil) were mixed with the water in a beaker and subsequently added to the reaction mixture via a funnel. The reaction time was 60 minutes. For analyses, samples were taken from the reaction mixture after 10, 30 and 60 minutes.

[0137] Finally, the reaction mixture, for preparation for the separation, was heated up to 80 C., the stirrer was switched off and the reaction mixture was left to stand for 5 minutes. Thereafter, the oil (reaction mixture) was transferred into a centrifuge cup and heated in a drying cabinet at 80 C. for another 15 minutes, then centrifuged in a laboratory centrifuge at 4000 rpm for 10 minutes. Finally, the oil phase was emptied and, via the weighing of the centrifuge cup, the mass of heavy phase was determined.

TABLE-US-00013 TABLE 13 relating to example 5: Partial neutralization of soybean oil after citric acid treatment: Soybean oil Oil 10 30 60 yield Experiment min. min. min. [%] Partial neutralization Ca [ppm] 41 31 34 95.3 without enzyme Mg [ppm] 24 16 15 (standard degumming) P [ppm] 160 95 90 FFA [%] 0.9 0.87 Gum [%] 3.5 4 4 0.20% Ca [ppm] 43 24 25 95.6 1-octanol Mg [ppm] 30 14 14 P [ppm] 195 96 90 FFA [%] 0.87 0.9 Gum [%] 3.3 4.2 4 0.20% Ca [ppm] 37 30 33 95.7 1-heptanol Mg [ppm] 21 12 13 P [ppm] 140 73 72 FFA [%] Gum [%] 4.2 4.7 4.1 0.20% Ca [ppm] 44 44 28 95.4 3-heptanol Mg [ppm] 29 29 11 P [ppm] 190 190 62 FFA [%] Gum [%] 3.3 4.7 4.9 0.20% Ca [ppm] 46 34 34 95.5 1-hexanol Mg [ppm] 26 14 14 P [ppm] 180 87 87 FFA [%] Gum [%] 3.5 4.5 4.3 0.20% Ca [ppm] 34 32 33 95.3 3-hexanol Mg [ppm] 9.5 6.8 6.5 P [ppm] 56 40 37 FFA [%] Gum [%] 4.5 4 4 0.20% Ca [ppm] 32 22 24 95.6 1-pentanol Mg [ppm] 22 12 13 P [ppm] 152 83 83 FFA [%] 0.86 0.92 Gum [%] 3.9 4.5 3.7 0.20% Ca [ppm] 33 27 30 95.7 3-pentanol Mg [ppm] 21 13 14 P [ppm] 148 83 83 FFA [%] 0.84 0.9 Gum [%] 4 4.5 4 0.20% Ca [ppm] 20 18 18 96.4 heptane-1,7-diol Mg [ppm] 8.2 6.5 6.2 P [ppm] 53 44 40 FFA [%] Gum [%] 4 4 4.3 0.20% Ca [ppm] 24 23 23 96.0 2-methylpentane-2,4- Mg [ppm] 12 9.8 8.4 diol P [ppm] 82 65 51 FFA [%] Gum [%] 4.7 4.2 4.3 0.20% Ca [ppm] 68 40 51 95.6 hexane-1,6-diol Mg [ppm] 29 9.8 14 P [ppm] 190 45 74 FFA [%] Gum [%] 4.5 4.5 4.2 0.20% Ca [ppm] 29 21 21 96.4 hexane-1,2-diol Mg [ppm] 11 6.4 6.3 P [ppm] 64 42 41 FFA [%] Gum [%] 4.5 4.5 4.5 0.20% Ca [ppm] 40 30 30 96.8 hexane-2,5-diol Mg [ppm] 18 11 9.8 P [ppm] 110 59 56 FFA [%] Gum [%] 4 4 4 0.20% Ca [ppm] 18 16 16 96.1 2,2-dimethylpropane- Mg [ppm] 9.3 7.3 6.3 1,3-diol P [ppm] 63 46 39 FFA [%] 0.94 0.92 Gum [%] 4 4 4 0.20% Ca [ppm] 37 28 29 96.1 butane-2,3-diol Mg [ppm] 19 13 12 P [ppm] 125 78 69 FFA [%] Gum [%] 4.5 4.4 4.3 0.20% Ca [ppm] 38 33 36 95.8 propane-1,2-diol Mg [ppm] 21 14 14 P [ppm] 135 79 75 FFA [%] 0.88 0.91 Gum [%] 4 4.3 4.3

[0138] The measurement results for soybean oil in the above table show that the solubilizers of the invention lead to an increase in the oil yield under these reaction conditions. At the concentration of 0.2% by weight used, it is possible to achieve increases in oil yield of up to 1.5%. The additives also contribute to a reduction in the P content in the oil and to a reduction in the divalent Mg.sup.2+ and Ca.sup.2+ ions in the oil.

TABLE-US-00014 TABLE 14 example 5: Partial neutralization of rapeseed oil after citric acid treatment Rapeseed oil Oil 10 30 60 yield Experiment min. min. min. [%] Partial neutralization Ca [ppm] 9.4 6.6 4.2 93.8 (standard degumming Mg [ppm] 1.9 1.4 1 without additive) P [ppm] 18 14 13 FFA [%] 0.93 0.97 Gum [%] 6 6 5.7 0.20% Ca [ppm] 10 6.8 4 94.0 1-octanol Mg [ppm] 1.7 1.2 0.7 P [ppm] 16 14 12 FFA [%] 0.97 0.96 Gum [%] 6.5 6 6.0 0.20% Ca [ppm] 7.1 5 2.7 93.9 3-heptanol Mg [ppm] 1.3 1.1 0.9 P [ppm] 14 11 12 FFA [%] Gum [%] 6 6 5.5 0.20% Ca [ppm] 14 9.3 6.8 95.1 heptane-1,7-diol Mg [ppm] 2.4 1.9 1.4 P [ppm] 25 21 17 FFA [%] 0.98 1.01 Gum [%] 5.5 5 5.2 0.20% Ca [ppm] 13 8.8 5.2 93.9 2-methylpentane-2,4- Mg [ppm] 2.2 1.5 1.1 diol P [ppm] 23 19 15 FFA [%] 0.97 1.00 Gum [%] 6 5.7 5.2 0.20% Ca [ppm] 12 7.9 4.4 93.8 propane-1,2-diol Mg [ppm] 2.2 1.7 1.3 P [ppm] 20 17 16 FFA [%] 0.94 0.96 Gum [%] 6 5.5 5.5

[0139] The table shows that it is possible with individual additives of the invention to increase the oil yield of the invention in the degumming of rapeseed oil under these conditions as well. Heptane-1,7-diol is especially suitable for this purpose.

Example 6: Partial Neutralization in Crude Oil at 48 C. without Enzyme, Separation at 80 C. with Varied Times of Addition for Solubilizer Addition (Reaction Variant 3)

[0140] Within the scope of this example, the influence of the time of dosage on the oil degumming in partial neutralization in crude oil is examined, as shown in example 5. In order to assure the comparability of results, the same soybean oil was used as for example 5:

TABLE-US-00015 TABLE 15 Characterization data of the soybean oil used in example 6 Measurement Ca content [ppm] 172 Mg content [ppm] 129 P content [ppm] 800 FFA content [%] 0.99

[0141] For the performance of the degumming of the soybean oil, the procedure was exactly as described in example 5. Merely different times of dosage were chosen for the additives of the invention:

Variant 4a: 0.2% solubilizer addition 5 minutes prior to the addition of acid
Variant 4b: 0.2% solubilizer addition together with the addition of acid
Variant 4c: 0.2% solubilizer addition 7 minutes after the addition of acid
Variant 4d: 0.2% solubilizer addition together with the addition of alkali
Variant 4e: 0.2% solubilizer addition 5 minutes after the addition of alkali
Variant 4f: 0.2% solubilizer addition 30 minutes after the addition of water
Variant 4g: 0.2% solubilizer addition 5 minutes before the end of the reaction

TABLE-US-00016 TABLE 16 relating to example 6 partial neutralization of soybean oil and heptane-1,7-diol and propane-1,2-diol as additive Soybean oil Oil 10 30 60 yield Experiment min. min. min. [%] Partial neutralization Ca [ppm] 41 31 34 95.3 without enzyme Mg [ppm] 24 16 15 (standard degumming) P [ppm] 160 95 90 FFA [%] 0.9 0.87 Gum [%] 3.5 4 4 0.20% Ca [ppm] 20 18 18 96.4 heptane-1,7-diol Mg [ppm] 8.2 6.5 6.2 as standard P [ppm] 53 44 40 with addition of water FFA [%] Gum [%] 4 4 4.3 0.20% Ca [ppm] 20 15 15 96.2 heptane-1,7-diol Mg [ppm] 13 7.8 6.7 5 minutes before P [ppm] 93 52 45 addition of acid FFA [%] 1.04 1.01 (variant a) Gum [%] 3.5 4 4.1 0.20% Ca [ppm] 44 44 42 96 heptane-1,7-diol Mg [ppm] 17 15 14 with addition of acid P [ppm] 92 80 74 (variant b) FFA [%] 0.99 1.02 Gum [%] 4.1 4.4 4.8 0.20% Ca [ppm] 46 46 43 96.4 heptane-1,7-diol Mg [ppm] 18 17 14 7 minutes after P [ppm] 92 83 75 addition of acid FFA [%] 0.96 1.05 (variant c) Gum [%] 4.2 4.6 4.4 0.20% Ca [ppm] 30 25 25 95.9 heptane-1,7-diol Mg [ppm] 15 10 9.3 with addition of P [ppm] 98 60 52 alkali (variant d) FFA [%] 1.01 1.01 Gum [%] 3.9 4 4 0.20% Ca [ppm] 42 31 30 96.0 heptane-1,7-diol Mg [ppm] 26 14 11 5 minutes after P [ppm] 165 80 60 addition of alkali FFA [%] 1.01 0.95 (variant e) Gum [%] 3 4 4 0.20% Ca [ppm] 57 28 33 96.1 heptane-1,7-diol Mg [ppm] 41 16 17 30 minutes after P [ppm] 280 103 105 addition of water FFA [%] 1.01 0.97 (variant f) Gum [%] 3.5 4 4 0.20% Ca [ppm] 46 23 19 96.0 heptane-1,7-diol Mg [ppm] 33 14 13 5 minutes before end P [ppm] 230 95 89 of reaction (variant FFA [%] 0.94 1 g) Gum [%] 3.5 4 4 0.20% Ca [ppm] 38 33 36 95.8 propane-1,2-diol Mg [ppm] 21 14 14 as standard P [ppm] 135 79 75 with addition of water FFA [%] 0.88 0.91 Gum [%] 4 4.3 4.3 0.20% Ca [ppm] 36 21 19 96.0 propane-1,2-diol Mg [ppm] 27 14 8.9 5 minutes before P [ppm] 200 100 56 addition of acid FFA [%] 0.92 0.89 (variant a) Gum [%] 3.5 4.4 4.4 0.20% Ca [ppm] 35 24 23 95.7 propane-1,2-diol Mg [ppm] 26 16 11 with addition of acid P [ppm] 185 110 60 (variant b) FFA [%] 0.99 0.91 Gum [%] 3.5 4.5 4.5 0.20% Ca [ppm] 34 36 26 95.9 propane-1,2-diol Mg [ppm] 24 18 11 7 minutes after P [ppm] 165 110 65 addition of acid FFA [%] 0.93 0.89 (variant c) Gum [%] 3 4.5 4.5 0.20% Ca [ppm] 47 25 35 95.9 propane-1,2-diol Mg [ppm] 29 15 14 with addition of P [ppm] 200 103 78 alkali (variant d) FFA [%] 0.96 0.88 Gum [%] 3.5 4.3 4.2 0.20% Ca [ppm] 26 25 27 95.9 propane-1,2-diol Mg [ppm] 18 12 12 5 minutes after P [ppm] 130 78 70 addition of alkali FFA [%] 0.97 0.96 0.95 (variant e) Gum [%] 4 4.5 4 0.20% Ca [ppm] 33 23 28 96.2 propane-1,2-diol Mg [ppm] 24 13 13 30 minutes after P [ppm] 168 83 82 addition of water FFA [%] 0.9 0.93 0.95 (variant f) Gum [%] 4 4.8 4 0.20% Ca [ppm] 36 25 28 96.1 propane-1,2-diol Mg [ppm] 26 14 13 5 minutes before end P [ppm] 200 88 77 of reaction (variant FFA [%] 1 0.94 1.02 g) Gum [%] 3.5 4 4.3

[0142] In the case of heptane-1,7-diol as additive, both with regard to the oil yield and with regard to the lowering of the P and ion values, it is found that dosage with the water or the acid is the most favorable.

Example 7: Enzymatic Degumming with Phospholipase A1 Partial Neutralization in Crude Oil at 48 C. with Enzyme, Separation at 80 C. (Reaction Variant 6)

[0143] Within the scope of this example, the influence of the solubilizers of the invention on the enzymatic oil degumming with phospholipase A1 is examined. In order to be able to separate the effects of enzyme and additives, the measurement data should be compared with the results in example 5 (identical experimental conditions, but working without addition of enzyme).

[0144] The following table shows the characterization data of oils used:

TABLE-US-00017 TABLE 17 Characterization data of the oils used in example 7 (identical oil to examples 5 and 6) Crude soybean oil Crude rapeseed oil Ca content [ppm] 172 230 Mg content [ppm] 129 74 P content [ppm] 800 1150 FFA content [%] 0.99 1.2

[0145] For these studies, the procedure was analogous to the partial neutralization described for example 5 (without enzyme); in other words, the same conditions as in example 5 were chosen, but only one enzyme was added. The enzyme used was PLAT in an amount of 0.5 U/g of oil.

[0146] The solubilizers were used in a concentration of 0.2% by weight based on the oil. The enzyme dosage followed the partial neutralization with the addition of water (and solubilizer in the inventive batches). As in example 5, 2.5% total water was used in the case of soybean oil and 3% total water in the case of rapeseed oil, minus the amount of water added with acid and alkali, and 0.2% solubilizer based on the amount of oil used.

[0147] The solubilizer and enzyme are first mixed with the water in a beaker and then added to the reaction mixture through a funnel. The further procedure thereafter was as described in example 5.

TABLE-US-00018 TABLE 18 for example 7: Enzymatic degumming of soybean oil Soybean oil Oil 10 30 60 yield Experiment min. min. min. [%] Partial neutralization Ca [ppm] 16 15 9 96.0 with 0.5 U/g PLA1 Mg [ppm] 8.7 7.2 4.3 (standard degumming) P [ppm] 57 44 24 FFA [%] 0.95 Gum [%] 5.1 4.5 4 0.20% Ca [ppm] 10 10 7 95.9 1-octanol + Mg [ppm] 6.3 5.5 3.4 0.5 U/g PLA1 P [ppm] 37 30 16 FFA [%] 0.82 0.96 Gum [%] 5.8 4.5 4.5 0.20% Ca [ppm] 18 18 8.2 96.2 1-heptanol + Mg [ppm] 9.2 7.4 3.7 0.5 U/g PLA1 P [ppm] 54 38 18 FFA [%] 0.91 1.08 Gum [%] 5.4 4.5 4 0.20% Ca [ppm] 27 22 22 96.3 3-heptanol + Mg [ppm] 12 8.6 8.1 0.5 U/g PLA1 P [ppm] 58 39 37 FFA [%] 0.92 1.09 Gum [%] 5.6 4.5 3.5 0.20% Ca [ppm] 20 20 16 96.3 1-hexanol + Mg [ppm] 7.9 7.5 5.7 0.5 U/g PLA1 P [ppm] 48 42 28 FFA [%] 0.8 1.03 Gum [%] 4.2 4.5 4 0.20% Ca [ppm] 28 48 34 96.1 3-hexanol + Mg [ppm] 7.9 14 6.3 0.5 U/g PLA1 P [ppm] 41 85 29 FFA [%] 0.95 0.9 Gum [%] 4 4.5 3.5 0.20% Ca [ppm] 20 16 12 96.2 1-pentanol + Mg [ppm] 9.4 8.3 5.4 0.5 U/g PLA1 P [ppm] 56 42 25 FFA [%] 0.87 1.01 Gum [%] 5.3 4.5 3.8 0.20% Ca [ppm] 21 18 15 96.2 3-pentanol + Mg [ppm] 11 8.8 6.6 0.5 U/g PLA1 P [ppm] 61 46 33 FFA [%] 0.85 1.06 Gum [%] 5 4 3.7 0.20% Ca [ppm] 12 15 14 96.4 heptane-1,7-diol + Mg [ppm] 5.7 5.9 5.8 0.5 U/g PLA1 P [ppm] 36 39 36 FFA [%] 0.97 1.09 Gum [%] 4 3.7 3.5 0.20% Ca [ppm] 21 11 17 96.5 2-methylpentane-2,4- Mg [ppm] 7.9 4 5.4 diol + 0.5 U/g PLA1 P [ppm] 45 21 27 FFA [%] 0.9 1.1 Gum [%] 4.7 4 3.5 0.20% Ca [ppm] 44 43 33 96.2 hexane-1,6-diol + Mg [ppm] 11 9.4 7.3 0.5 U/g PLA1 P [ppm] 52 43 28 FFA [%] 0.85 1.01 Gum [%] 5.7 3.7 3.7 0.20% Ca [ppm] 16 14 11 96.5 hexane-1,2-diol + Mg [ppm] 6.3 5.5 3.9 0.5 U/g PLA1 P [ppm] 38 34 24 FFA [%] 0.97 1.15 Gum [%] 4 3.9 3 0.20% Ca [ppm] 12 24 22 96.2 hexane-2,5-diol + Mg [ppm] 6.8 8.2 7.5 0.5 U/g PLA1 P [ppm] 33 43 40 FFA [%] 0.99 1.09 Gum [%] 4 3.5 3.2 0.20% Ca [ppm] 4.9 11 11 96.2 2,2-dimethylpropane- Mg [ppm] 2.6 5.1 4.9 1,3-diol + 0.5 U/g PLA1 P [ppm] 15 29 27 FFA [%] 0.96 0.91 Gum [%] 4.3 4 3.5 0.20% Ca [ppm] 8.7 5.1 10 96.3 butane-2,3-diol + Mg [ppm] 5.1 2.5 4.3 0.5 U/g PLA1 P [ppm] 28 14 26 FFA [%] Gum [%] 4 4 3.7 0.20% Ca [ppm] 16 7.7 13 96.3 propane-1,2-diol + Mg [ppm] 6.9 3.4 5.6 0.5 U/g PLA1 P [ppm] 39 18 31 FFA [%] 1.08 Gum [%] 4.3 4 3.5

[0148] The results show that a series of additives can increase the oil yield in enzymatic soybean oil degumming with phospholipase 1, and the chosen dosage of 0.2% gives the greatest increase in the oil yield of 0.5% in the case of use of 2-methylpentane-2,4-diol and hexane-1,2-diol.

[0149] Some additives, especially 1-octanol, 3-heptanol, 2,3-dimethylpropane-1,3-diol, butane-2,3-diol and propane-1,2-diol also lead to acceleration of the reaction compared to the enzymatic degumming without additives, recognizable especially from the P values of the oil after 10 minutes. One example of this is the additive 2,2-dimethylpropane-1,3-diol, the use of which lowers the P value after 10 minutes to 15 ppm compared to 57 ppm of P in the case of enzymatic degumming without additive.

TABLE-US-00019 TABLE 19 relating to example 7: Enzymatic degumming of rapeseed oil without and with addition of solubilizers Rapeseed oil Oil 10 30 60 yield Experiment min. miru min. [%] Partial neutralization Ca [ppm] 5.6 5.1 4 94.5 with 0.5 U/g PLA1 Mg [ppm] 1.4 1.3 0.9 (standard degumming) P [ppm] 12 13 7 FFA [%] 1.44 1.66 Gum [%] 5.3 5.3 5.0 0.20% Ca [ppm] 15 11 9.6 94.4 1-octanol + Mg [ppm] 2.6 1.8 1.4 0.5 U/g PLA1 P [ppm] 19 15 11 FFA [%] 1.22 1.37 Gum [%] 5.5 5 4.7 0.20% Ca [ppm] 13 10 8.2 94.5 3-heptanol + Mg [ppm] 2.1 1.6 1.2 0.5 U/g PLA1 P [ppm] 18 14 10 FFA [%] 1.18 1.53 Gum [%] 5.5 5.3 5.0 0.20% Ca [ppm] 6.8 4.9 4.4 94.5 heptane-1,7-diol + Mg [ppm] 1.3 1.3 1 0.5 U/g PLA1 P [ppm] 9.7 12 7.5 FFA [%] 1.34 1.53 Gum [%] 5 5.4 5 0.20% Ca [ppm] 6.3 4.9 4.2 94.6 2-methylpentane-2,4- Mg [ppm] 1.2 1 0.9 diol + 0.5 U/g PLA1 P [ppm] 7.7 7.2 7 FFA [%] 1.45 1.68 Gum [%] 5.4 5.4 5.3 0.20% Ca [ppm] 5.6 4.5 4.1 94.4 propane-1,2-diol + Mg [ppm] 1.2 0.9 1.1 0.5 U/g PLA1 P [ppm] 9.1 6.3 7.2 FFA [%] 1.32 1.69 Gum [%] 5.5 5.5 5.1

[0150] It is found that the additives have a different effect on the enzymatic degumming of rapeseed oil with PLAT than soybean oil. It is also possible to identify additives of the invention that exhibit positive effects with regard to the reduction in the P values and ion values. This is the case especially with the use of 2-methylpentane-2,4-diol and propane-1,2-diol.

Example 8 Partial Neutralization and Enzymatic Degumming with Addition of Polyglycols

[0151] Using the reaction conditions in example 7, the effect of a polyglycol on citric acid degumming with partial neutralization and enzymatic degumming was examined (reaction variants 3 and 4). For this purpose, a polyglycol B11/50 was used. This is an ethylene oxide-propylene oxide monobutyl ether wherein the ethylene oxide and propylene oxide groups are randomly distributed (mean molar mass: 1300 g/mol and HLB value: 9.58). The compound was purchased from Clariant Produkte (Deutschland) GmbH in Gendorf.

[0152] For this purpose, a soybean oil with the following characterization data was used:

TABLE-US-00020 TABLE 20 Characterization data of the soybean oils used Crude soybean oil Ca content [ppm] 172 Mg content [ppm] 129 P content [ppm] 800 FFA content [%] 0.99

[0153] For the experiments with the partial neutralization, the procedure was as described in example 5 (reaction variant 3); for the experiments on enzymatic degumming, the procedure was as described in example 7 (reaction variant 4). Only the addition of water was reduced from 2.5% to 2%. In the experiments with additive, 0.2% by weight of additive was used in each case, based on the oil.

[0154] The results of the studies are shown in the following table:

TABLE-US-00021 TABLE 21 Results of the degumming with ethylene oxide-propylene oxide monobutyl ether as solubilizer in the partial neutralization of crude soybean oil and in the enzymatic degumming of crude soybean oil Soybean oil Oil 10 30 60 yield Experiment min. min. min. [%] Partial neutralization Ca [ppm] 29 23 21 95.7 Reference measurement Mg [ppm] 20 15 13 P [ppm] 134 104 88 FFA [%] 0.81 0.94 Gum [%] 2.8 3.2 3.7 Partial neutralization Ca [ppm] 13 17 18 95.5 with addition of Mg [ppm] 6.6 7 7 ethylene oxide- P [ppm] 42 43 40 propylene oxide FFA [%] 0.87 0.87 monobutyl ether Gum [%] 3.6 3.9 3.8 Partial neutralization + Ca [ppm] 14 13 8.8 96 0.5 U/g PLA1 Mg [ppm] 8 7.9 4.6 P [ppm] 48 45 21 FFA [%] 0.85 0.93 Gum [%] 4.8 4.0 3.5 Partial neutralization + Ca [ppm] 11 5.9 4.6 96.4 0.5 U/g PLA1 Mg [ppm] 4.5 2.9 2.3 with addition of P [ppm] 27 19 15 ethylene oxide- FFA [%] 0.98 1.12 propylene oxide Gum [%] 4.1 3.2 2.9 monobutyl ether

[0155] The results indicate the effect of the polyglycol of the invention on the oil degumming. The partial neutralization without subsequent use of phospholipase does not increase the oil yield, but the values of P, Ca and Mg are distinctly reduced after 10 min and also after 30 min and 60 min of reaction time compared to the comparative measurement.

[0156] In the enzymatic oil degumming, the addition of the additive leads both to an increase in the oil yield and to significant lowering of the values for P, Ca and Mg in the oil compared to the comparative measurements without additives at 20 min, 30 min and 60 min. The rise in the FFA value with the additive documents the higher conversion of the phospholipase after 10 min and 60 min.

Example 9 Aqueous Degumming with Citric Acid According to Reaction Variant 5

[0157] According to reaction variant 5, a crude soybean oil having the following starting contents was used: phosphorus 860 ppm, calcium 63 ppm, magnesium 60 ppm and a content of free fatty acids of 0.45%.

[0158] The crude oil was subjected to pre-conditioning with the aid of aqueous citric acid (1000 ppm) and then neutralized to pH 7 to 8 with aqueous sodium hydroxide solution (1 mol/L). Subsequently, various concentrations of propane-1,2-diol (0.05-0.2% by weight of propanediol) were added and stirring was continued. In a comparison, a sample without propane-1,2-diol (standard degumming) was stirred. The oil/water ratio (by weight) was 98.5:1.5. Samples were taken regularly (see table 22). At the end of the reaction, the gum phase was centrifuged off and the oil yield was determined via mass weighing.

[0159] The results are summarized in table 22. It can clearly be seen that an increasing concentration of propane-1,2-diol leads to a decrease in the calcium (Ca), magnesium (Mg) and phosphorus (P) ions. In the standard degumming of the soybean oil, the following ion values were achieved after a reaction time of one hour: Ca: 4.7 ppm; Mg: 3.7 ppm and P: 42 ppm. After a reaction time of one hour, the following ion values were achieved with 0.2% by weight propane-1,2-diol: Ca: 1.1 ppm; Mg: 0.69 ppm and P: 10 ppm. In addition, the oil yield increases with propane-1,2-diol from 95.5 to 95.8% by weight. The values were confirmed in repeat determinations. It was thus shown that the oil degumming is more effective and a higher oil yield is achieved as a result of the addition of propane-1,2-diol.

TABLE-US-00022 TABLE 22 Degumming with different concentrations of propane- 1,2-diol in comparison with standard degumming Test 10 min. 60 min. Oil yield [%] Standard Ca [ppm] 7.6 4.7 95.5 degumming Mg [ppm] 6.5 3.7 P [ppm] 77 42 FFA [%] 0.11 0.16 0.05% Ca [ppm] 1.5 2.2 95.5 propane-1,2- Mg [ppm] 1.2 1.8 diol P [ppm] 12 20 FFA [%] 0.07 0.15 0.1% Ca [ppm] 1.6 2.2 95.6 propane-1,2- Mg [ppm] 1.2 1.7 diol P [ppm] 12 18 FFA [%] 0.08 0.12 0.2% Ca [ppm] 1.6 1.1 95.8 propane-1,2- Mg [ppm] 1.2 0.9 diol P [ppm] 13 10 FFA [%] 0.11 0.15

Example 10: Enzymatic Degumming According to Reaction Variant 6

[0160] According to reaction variant 6, a crude soybean oil with the following starting contents was used: phosphorus 860 ppm, calcium 63 ppm, magnesium 60 ppm and a content of free fatty acids of 0.45%. The crude oil was subjected to pre-conditioning by means of aqueous citric acid (1000 ppm) and was then neutralized to pH 4-5 with aqueous sodium hydroxide solution (1 mol/L). A phospholipase A1 (PLA1) from Thermomyces lanuginosus and various concentrations of propane-1,2-diol (0.05 to 0.2% by weight) were then added according to reaction variant 6 and stirring was continued. As comparison, a sample without propane-1,2-diol (PLA1 standard degumming) was stirred. The oil/water ratio (weight) was 98.5:1.5. Samples were taken at regular intervals (see table 23). At the end of the reaction, the gum phase was removed by centrifugation and the oil yield was determined via mass weighing.

[0161] The results are summarized in table 23. It can clearly be seen that an increasing concentration of propane-1,2-diol leads to an increased oil yield and that the use, for example, of 0.2% by weight propane-1,2-diol+PLA1 permits a further increase by approximately 1% degummed soybean oil. The values were confirmed in repeat determinations. It was thus shown that the oil degumming is more effective and a higher oil yield is achieved as a result of the addition of propane-1,2-diol.

TABLE-US-00023 TABLE 23 Degumming with different concentrations of propane-1,2- diol and PLA1 in comparison with PLA1 standard degumming Test 10 min. 60 min. Oil yield [%] 0.5 U/g PLA1 Ca [ppm] 0.5 0.5 95.8 standard Mg [ppm] 0.5 0.5 degumming P [ppm] 4.7 4.8 FFA [%] 0.15 0.31 Gum [%] 6.6 4.9 0.025% Ca [ppm] 1 0.3 96.2 propanediol + Mg [ppm] 0.9 0.3 0.5 U/g P [ppm] 10 3.6 PLA1 FFA [%] 0.26 0.45 Gum [%] 3.9 2.8 0.1% Ca [ppm] 0.9 1 96.6 propanediol + Mg [ppm] 0.9 1 0.5 U/g P [ppm] 7.5 9.6 PLA1 FFA [%] 0.20 0.32 Gum [%] 5.5 3.1 0.2% Ca [ppm] 1 0.3 96.8 propanediol + Mg [ppm] 0.9 0.3 0.5 U/g P [ppm] 10 3.6 PLA1 FFA [%] 0.26 0.45 Gum [%] 3.9 2.8

Example 11: Aqueous Degumming of Soybean Oil on the Pilot Scale

[0162] Within the scope of the degumming processes in oil refining on the industrial scale, the separation of the oil phase and the water phase is typically conducted in a continuous process, using disk separators according to the prior art. In order to rework this process, a pilot plant experiment was conducted, in which a disk separator was used, as is typically also used for industrial degumming processes (pilot scale).

[0163] For mixing of the crude oil with the aqueous phase, a plant for oil degumming on the scale of 100 to 120 kg of vegetable oil with a stirrer system, temperature-controlled jacketed reactor and with an IST 060-TRA-10 1 pump system comparable to industry was utilized. For the separation, an OSC 4 separator from GEA-Westfalia (Oelde) was used. Such a separator is characterized in that the filling with oil and emptying of the cleaned oil is continuous, while the heavy phase (water with vegetable oil gum or lecithin) is discontinuous, and occurs whenever the separator is filled with gum.

[0164] For the experiments, a crude soybean oil was utilized, the characterization data of which are compiled in the following table:

TABLE-US-00024 TABLE 24 Characterization data of the crude soybean oil used for the pilot plant experiments Content Unit Measurement FFA % 0.69 H.sub.2O (water by % 0.06 Karl Fischer - DIN 51777) P ppm 820 Fe ppm 33 Cu ppm <0.1 Ca ppm 120 Mg ppm 94 Na ppm 2 Al ppm 20

[0165] 100-120 kg of the crude soybean oil in each case were first stirred with 2% by weight of water in the jacketed reactor at 60 C. for 60 minutes and then subjected to a phase separation with the disk separator. This experiment served as a comparative example for a standard separation. Analogously, in a second variant, 0.2% by weight (based on the mass of the oil used) of propane-1,2-diol, a solubilizer of the invention, was added to the water used for the degumming.

[0166] With regard to the separation, the following procedure was followed in both cases:

[0167] The volume flow rate was fixed at 100 L/h for all experiments, and the backpressure of the light phase to 3.5 bar. The time interval between the partial emptying operations was defined as a variable parameter.

[0168] After stirring time of 60 minutes with the aqueous phase, the mixture was heated to 80 C. for 10 min. Subsequently, the separator containing the reaction mixture was preheated until the first partial emptying, then set to the defined parameters (volume flow rate and backpressure) until the second partial emptying. During this time, the separated oil was run into a separate vessel and determined. The mass of the heavy phase was also determined separately. Then the second partial emptying was followed by the switch to the actual separation vessel.

[0169] Until the third partial emptying, the separator was again set to a constant separation. This includes the heating of the separator and the checking of the clarity of the light phase in the sightglass. Exactly within the interval after the third partial emptying until the fourth partial emptying, two samples were taken at the tap at the sightglass window from the clear-running liquid every minute. The first sample was for the determination of the ions; the second sample was a centrifuge tube sample for determination of the proportion of the heavy phase in the separated oil. For this purpose, centrifugation was effected at 4000 rpm in a laboratory centrifuge for four minutes after sampling.

[0170] Sampling and sample analysis always followed after the third partial emptying, in order to prevent effects of the startup of the separation on the results. The interval chosen for sampling was one minute.

[0171] According to the instrument manufacturer, a separation can be described as good when the proportion of heavy phase in the clear-running liquid (separated oil) is 0.1% to 0.2% or better. The two processes were repeated, resulting in no significant differences in the measurement data.

[0172] The results with purely aqueous degumming and with addition of 0.2% by weight of propane-1-2-diol to the oil are shown in the two tables below and the figures, which show the analysis data based on the separated oil as a function of the separation time.

TABLE-US-00025 TABLE 25 Separation of the soybean oil on the pilot plant scale after the aqueous degumming Heavy phase in clear-running Ca [ppm] after Mg [ppm] after P [ppm] after Ca [ppm] after Mg [ppm] after P [ppm] after Time [min] liquid [%] separation separation separation centrifugation centrifugation centrifugation 3rd partial emptying 1 0.3 106 40 180 100 39 175 2 0.9 104 40 185 100 38 165 3 0.1 105 40 168 100 39 180 4 0.2 105 40 190 103 39 175 5 0.25 104 39 175 102 40 180 6 0.6 104 41 195 102 39 175 7 0.3 106 43 205 101 38 170 8 0.5 105 42 200 101 39 180 9 0.5 104 42 205 102 40 165 10 0.5 106 45 225 97 37 155 4th partial emptying 1 0.6 100 40 185 100 39 170

[0173] FIG. 3 shows the separation of the soybean oil on the pilot plant scale after the aqueous degumming (as per the data of table 25).

TABLE-US-00026 TABLE 26 Separation of the soybean oil on the pilot plant scale after the aqueous degumming with addition of 2.2% by weight of propane-1,2-diol Heavy phase in clear- Ca Mg P running [ppm] [ppm] [ppm] Ca [ppm] Mg [ppm] P [ppm] Time liquid after after after after after after [min] [%] separation separation separation centrifugation centrifugation centrifugation 3rd partial emptying 1 0.3 106 40 180 100 39 175 2 0.9 104 40 185 100 38 165 3 0.1 105 40 168 100 39 180 4 0.2 105 40 190 103 39 175 5 0.25 104 39 175 102 40 180 6 0.6 104 41 195 102 39 175 7 0.3 106 43 205 101 38 170 8 0.5 105 42 200 101 39 180 9 0.5 104 42 205 102 40 165 10 0.5 106 45 225 97 37 155 4th partial emptying 1 0.6 100 40 185 100 39 170

[0174] FIG. 4 shows the separation of the soybean oil on the pilot plant scale after the aqueous degumming with addition of 2.2% by weight of propane-1,2-diol (as per the data of table 26).

[0175] From the comparison of the content of the heavy phase of the separated oil (determined by the P content) as a function of the separation time, it is possible to make the following conclusions:

[0176] In the purely aqueous degumming, significant variations in the content of heavy phase occur from the start, which cannot be attributed to the separator becoming full. The upper limit with regard to the P content in the oil, defined on the industrial scale according to the separator manufacturer, is almost always exceeded after separation, and significant fluctuations occur.

[0177] The addition of propane-1,2-diol greatly improves the separation under the experimental conditions chosen. Within a period of up to 6 minutes, the proportion of the heavy phase in the separated oil remains very small and well below the upper limit of 0.2 weight. There is then a steep rise caused by the container for the gum in the separator becoming full. On the industrial scale, the separator would be emptied automatically here.

[0178] Indirectly, it is possible to infer a lower content of the gum in the oil and hence a higher oil yield through the use of propane-1,2-diol as additive from the profile of the content of heavy phase in the oil as a function of time, although exact quantification is not possible with these experimental data alone. If the first peak in the aqueous degumming is considered to be caused by process fluctuation because the content of heavy phase decreases below 0.2% by weight once again thereafter, the content of heavy phase remains above the limit of 0.2% from 4 minutes onward, meaning that the separator is then already filled with heavy phase. This situation occurs only after 7 minutes in the case of use of propane-1,2-diol.