FERMENTED AND ESTERIFIED MOLASSES

Abstract

A method for preparing a fermented molasses including at least one glycine betaine ester, the method includes the steps of (1) providing a fermented beet molasses, (2) adding, into this fermented beet molasses, at least one acid in an acid: glycine betaine molar ratio between 1 and 2.2 and (3) esterifying the acidified fermented molasses obtained in the preceding step by mixing with at least one alcohol. Also, a fermented and esterified molasses including betaine esters and the use thereof for improving the surfactant and/or emulsifying properties of a composition.

Claims

1-8. (canceled)

9. A process for the preparation of fermented molasses comprising at least one glycine betaine ester, said process comprising the following stages of: 1) provision of a fermented beet molasses, 2) addition, to said fermented beet molasses, of at least one acid according to an acid/glycine betaine molar ratio of between 1 and 2.2, 3) esterification of the acidified fermented molasses obtained in the preceding stage by mixing with at least one alcohol.

10. The process as claimed in claim 9, wherein the fermented beet molasses is a mixture of fermented beet molasses and fermented cane molasses.

11. The process as claimed in claim 9, wherein the alcohol is mixed with the acidified fermented molasses according to an alcohol/glycine betaine molar ratio of between 1 and 2.5.

12. The process as claimed in claim 9, wherein the alcohol is chosen from ethanol, glycerol, lauryl alcohol (dodecan-1-ol), isoamyl alcohol (3-methylbutan-1-ol), oleyl alcohol, stearyl alcohol, fusel alcohols and their mixtures, preferably from ethanol, oleyl alcohol and lauryl alcohol.

13. The process as claimed in claim 9, further comprising, after the esterification stage 3), a stage of centrifugation and concentration of the supernatant to a dry matter content of from 50% to 80%.

14. The process as claimed in claim 9, wherein the fermented beet molasses supplied according to the first stage is a fermented and demineralized molasses.

15. A fermented and esterified beet molasses comprising one or more glycine betaine esters.

16. A method for improving surfactant and/or emulsifying properties of a composition, comprising adding the fermented molasses of claim 15 to the composition.

Description

FIGURES

[0092] FIG. 1 .sup.1H NMR spectrum (CDCl.sub.3) of a solution of fermented molasses supplemented with glycine betaine.

[0093] FIG. 2 .sup.1H NMR spectrum (CDCl.sub.3) of a diethyl ether fraction containing lauryl betainate ester.

[0094] FIG. 3 .sup.1H NMR spectrum (CDCl.sub.3) of fermented molasses esterified with lauryl alcohol in the presence of H.sub.2SO.sub.4.

[0095] FIG. 4 Superimposition of .sup.1H NMR spectra. A: .sup.1H NMR spectrum (CDCl.sub.3) of the liquid phase of the fermented molasses esterified with an oleyl alcohol; B: .sup.1H NMR spectrum of a diethyl ether solution containing lauryl betainate; C: .sup.1H NMR spectrum (CDCl.sub.3) of a fermented molasses esterified with a lauryl alcohol in the presence of H.sub.2SO.sub.4 (control); D: .sup.1H NMR spectrum (CDCl.sub.3) of a solution of fermented molasses supplemented with glycine betaine (control); E: .sup.1H NMR spectrum (CDCl.sub.3) of the gel phase of the fermented molasses esterified with oleyl alcohol.

EXAMPLES

Example 1: Preparation of Glycine Betaine Ester from Lauryl Alcohol (C.SUB.12.)

[0096] The fermented molasses used for this example is a demineralized molasses exhibiting the following characteristics: [0097] pH 3, [0098] 78% by weight of dry matter, with respect to the total dry matter, [0099] approximately 19% by weight of glycine betaine, with respect to the total weight of the fermented molasses.

[0100] An amount of this fermented molasses is acidified with constant stirring in a 250 ml round-bottomed flask with 2.4 molar equivalents of sulfuric acid (96% concentrated) with respect to the glycine betaine. The combined mixture is homogenized.

[0101] The lauryl alcohol is subsequently added to the round-bottomed flask according to an alcohol/glycine betaine molar ratio of 1.5 and the combined mixture is again homogenized.

[0102] The round-bottomed flask is placed under a hot rotary evaporator (90 C.) and under reduced pressure (100 mbar) with stirring from 100 to 150 rpm.

[0103] After 3 hours, the reaction is halted by immersing the round-bottomed flask in ice-cold water.

[0104] At the end of the reaction, the fermented and esterified molasses comprising glycine betaine esters exhibits a homogeneous appearance.

[0105] In order to confirm the presence of glycine betaine ester in the fermented and esterified molasses, a .sup.1H NMR analysis in deuterated chloroform (CDCl.sub.3) is carried out and the result is compared with control solutions.

[0106] The solutions analyzed by .sup.1H NMR are shown below: [0107] 1: Fermented beet molasses enriched in glycine betaine (control), [0108] 2: Diethyl ether solution containing lauryl betainate ester (control), [0109] 3: Fermented molasses esterified with lauryl alcohol in the presence of H.sub.2SO.sub.4.

[0110] The results of the .sup.1H NMR analyses of each of the solutions 1 to 3 are respectively presented in FIGS. 1 to 3.

[0111] The control spectrum of FIG. 1 exhibits a peak at 3.37 ppm characteristic of glycine betaine.

[0112] The spectrum of FIG. 2 also serves as control and to identify the peak characteristic of glycine betaine esterified with lauryl alcohol (lauryl betainate) at 3.51 ppm, and also three peaks between 3.6 and 3.7 ppm which are characteristic of lauryl alcohol.

[0113] The spectrum obtained with the fermented and esterified molasses exhibits a peak at approximately 3.5 ppm and confirms the presence of the lauryl betainate ester. In addition, the absence of characteristic peak at 3.37 ppm makes it possible to say that the majority of the glycine betaine reacted during the esterification reaction to form the glycine betaine esters (FIG. 3).

[0114] Together, these results confirm that the process according to the invention makes it possible to obtain glycine betaine esters from fermented molasses, said fermented molasses being used directly as reaction medium.

Example 2: Preparation of Glycine Betaine Ester from Oleyl Alcohol (C.SUB.18.)

[0115] The fermented molasses used for this example is a demineralized molasses exhibiting the following characteristics: [0116] pH 3, [0117] 78% by weight of dry matter, with respect to the total dry matter, [0118] approximately 19% by weight of glycine betaine, with respect to the total weight of the fermented molasses.

[0119] An amount of this fermented molasses is acidified with sulfuric acid (96% concentrated) under constant stirring in a 250 ml round-bottomed flask according to an acid/glycine betaine molar ratio equal to 2, then the combined mixture is homogenized.

[0120] Subsequently, the oleyl alcohol is added to the round-bottomed flask according to an alcohol/glycine betaine molar ratio equal to 1.5, then the combined mixture is again homogenized.

[0121] The round-bottomed flask is placed under a hot rotary evaporator (90 C.) and under reduced pressure (100 mbar) with stirring from 100 to 150 rpm.

[0122] After 5 hours, the reaction is halted by immersing the round-bottomed flask in ice-cold water.

[0123] At the end of the reaction, the fermented and esterified molasses comprising glycine betaine esters exists in two phases, a gel phase and a liquid phase.

[0124] In order to confirm the presence of glycine betaine ester in the fermented and esterified molasses, .sup.1H NMR analyses are carried out on the different phases obtained and the results are compared with control solutions.

[0125] The solutions analyzed are listed below: [0126] A: Liquid phase of the fermented molasses esterified with an oleyl alcohol, [0127] B: Diethyl ether solution containing the lauryl betainate, [0128] C: Fermented molasses esterified with a lauryl alcohol (C.sub.12) in the presence of H.sub.2SO.sub.4 (control). [0129] D: Solution of fermented molasses supplemented in glycine betaine (control), [0130] E: Gel phase of the fermented and esterified molasses.

[0131] The results of the .sup.1H NMR analyses of each of the solutions A to E are presented in FIG. 4.

[0132] The spectrum D makes it possible to identify the position of the peak characteristic of glycine betaine at 3.37 ppm.

[0133] Glycine betaine esters exhibit substantially the same chemical shift whatever the alcohol used for the esterification. Consequently, the spectra B and C are used as controls with the characteristic peak of the lauryl betainate ester at 3.51 in order to identify the presence of the oleyl betainate ester.

[0134] The absence of the peak characteristic of glycine betaine on the spectra A and E indicates that it has been predominantly consumed within the fermented molasses during the esterification reaction to form the glycine betaine esters. The oleyl betaine esters are found only in the gel phase of the fermented and esterified molasses, as is evidenced by the presence of the peak at 3.51 ppm on the spectrum E, said peak being absent on the spectrum A of the liquid phase.

[0135] Again, the results confirm that it is possible to obtain glycine betaine esters from fermented molasses, said fermented molasses being used directly as reaction medium.

[0136] Thus, going against what has until now been accepted, the applicant company proves that it is possible to carry out an esterification reaction starting from fermented molasses, thus obtaining glycine betaine esters after addition of alcohol.

Example 3: Preparation of Glycine Betaine Ester from Fermented Molasses and Ethanol

[0137] A volume of fermented beet molasses is acidified with sulfuric acid down to pH 1.9.

[0138] The acidified fermented molasses is subsequently mixed either with 1.1 molar equivalents of ethanol, with respect to the glycine betaine, (mixture 1), or with 5% by weight of glycerol (mixture 2).

[0139] The two mixtures are refluxed at 110 C. for 2 h 30.

[0140] Subsequently, a centrifugation stage is carried out at 20 C. for 10 min at 8000 rev/min in order to remove the precipitates and the sulfate inorganic salts. The supernatant is recovered, then concentrated by evaporation until a dry matter of approximately 65% is obtained, and the presence of glycine betaine esters was confirmed by .sup.1H NMR measurements.