Fermented and esterified molasses

Abstract

The present invention relates to the sugar industry, in particular to a method for preparing a fermented molasses comprising at least one glycine betaine ester, said method comprising the steps of: (1) providing a fermented sugar beet molasses, (2) adding at least one acid to the fermented sugar beet molasses in an acid: glycine betaine molar ratio of 1-2.2, and (3) esterifying the acidified fermented molasses obtained in the preceding step by mixing with at least one alcohol. The present invention also relates to a fermented and esterified molasses comprising betaine esters, and to the use thereof for improving the surfactant and / or emulsifying properties of a composition.

Description

TECHNICAL FIELD

[0001] The present invention relates to the field of sugar industry, in particular to a new fermented molasses, to a process for its preparation, and to its use as an agent for improving the surface active and / or emulsifying properties of a composition. PRIOR ART

[0002] Glycine betaine (C5H 11 NO2) is a molecule from which a variety of derivatives can be obtained, which have a wide variety of applications, in particular in the field of surface active agents.

[0003] In particular, glycine betaine, also known as trimethylglycine, is a cheap natural substance which constitutes a choice of raw material for the preparation of surface active agents. For example, alkyl betaines or alkyl amido betaines are the most widely used.

[0004] Document WO 2015 / 078890 describes a composition of fatty esters of glycine betaine, esters of glycine betaine and esters of alkyl polyglucosides, which in particular comprises a structure of the alkyl polyglucoside type carrying a cationic group introduced by grafting of glycine betaine.

[0005] Document FR 2 869 913, for example, provides a way of obtaining esters or amides based on glycine betaine, obtained in the form of a crude reaction product or by washing the crude reaction product with an organic solvent.

[0006] Document WO 2013 / 188508 describes a composition containing cationic glycine betaine esters and / or amides. Betaine acid alkylene methanesulfonates and betaine base amino alkylene methanesulfonates form part of these esters and these amides. Glycine betaine esters and amides are used in said composition of cationic surface active agents with antimicrobial activity, and are presented as crude or semi-purified or purified mixtures, which are effective.

[0007] Document FR 3 082 52 describes a surface active agent composition comprising glycine betaine amide salts, alkyl ammonium salts, glycine betaine ester salts and glycine betaine.

[0008] Document FR 3 088 930 describes the use of a mixture comprising glycine betaine esters, obtained by reaction of glycine betaine with a fatty alcohol, for improving the surface active agent properties of a composition.

[0009] Despite the existence of many glycine betaine derivatives, there remains a need to provide other alternatives which can improve the surface active and / or emulsifying properties, in particular green solutions, which are environmentally friendly, as opposed to the solutions of petrochemical origin which are often used.

[0010] More typically, glycine betaine is a byproduct of the sugar industry and is found in beet molasses, accounting for about 5% to 7% by weight of the dry matter relative to the total dry matter weight of the beet molasses.

[0011] As mentioned above, glycine betaine is a suitable raw material for preparing surfactants.

[0012] To date, manufacturers have extracted glycine betaine directly from beet molasses using methods such as chromatography. The extracted glycine betaine is then concentrated and used specifically to obtain derivatives, as described above.

[0013] Document WO 2004 / 002938, for example, describes a method of chromatographic fractionation followed by nanofiltration, which can thus recover at least one fraction rich in glycine betaine from a starting solution containing betaine, such as a molasses solution.

[0014] Molasses is a substance known to those skilled in the art. It is a byproduct of sugar production from sugar beets and sugarcane in sugar mills, or of brown sugar production in refineries. Regardless of whether the sugar production method starts from sugarcane or sugar beets, after the crystallization stage, sugar is obtained on one hand, and molasses on the other.

[0015] Although used to extract glycine betaine, beet molasses is more commonly used in animal feed, mixed with straw or other cellulose feeds, but it can also be used as a binder in animal rations or to encourage animals to consume relatively unpalatable feeds.

[0016] As an alternative to animal husbandry, manufacturers also use molasses to produce "precious" products through fermentation. This is because molasses can be used as a substrate through fermentation mechanisms available to certain microorganisms, in particular yielding baker's yeast, ethanol, citric acid, glutamic acid, lysine, or antibiotics.

[0017] Conversely, the fermentation process uses molasses to produce a large amount of liquid fermentation residue. This liquid fermentation residue corresponds to "fermented" molasses.

[0018] Because microorganisms consume the components, fermented molasses is generally considered a useless fermentation residue and is primarily upgraded to fertilizer in the agricultural sector.

[0019] Fermented molasses is not considered a product of choice for manufacturers in order to extract glycine betaine because its extraction requires a large amount of water and because of the cost of the chromatographic equipment used for the extraction.

[0020] However, given the amount of fermented molasses produced annually, there is a need to provide new methods for upgrading this fermentation residue, which has so far been considered unattractive, and advantageously, to provide greener alternatives to petrochemical-derived surfactants.

[0021] Therefore, the applicant company's contribution lies in being able to achieve this dual purpose by providing a new preparation method using fermented molasses as a starting material.

[0022] SUMMARY

[0023] Therefore, the present invention relates to a method for preparing fermented molasses containing at least one glycine betaine ester, the method comprising the following stages:

[0024] 1) Provide fermented beet molasses,

[0025] 2) Add at least one acid to the fermented beet molasses at an acid / glycine betaine molar ratio of 1-2.2.

[0026] 3) The acidified fermented molasses obtained in the aforementioned stage is esterified by mixing with at least one alcohol.

[0027] The present invention also relates to fermented and esterified molasses containing betaine esters, and its use for improving the surfactant and / or emulsifying properties of the composition. DETAILED DESCRIPTION

[0029] As mentioned above, fermented molasses is considered to be fermented residue primarily used in agriculture and animal husbandry for application as fertilizer or in animal feed.

[0030] Therefore, the present invention provides a new method for upgrading fermented molasses through the following approach.

[0031] Therefore, the first subject of the present invention relates to a method for preparing fermented molasses containing at least one glycine betaine ester, said method comprising the following stages:

[0032] 1) Provide fermented beet molasses,

[0033] 2) Add at least one acid to the fermented beet molasses at an acid / glycine-betaine molar ratio of 1-2.2.

[0034] 3) The acidified fermented molasses obtained in the aforementioned stage is esterified by mixing with at least one alcohol.

[0035] Surprisingly, the applicant company has discovered that fermented beet molasses can be used for esterification to obtain at least one glycine betaine ester.

[0036] Fermented beet molasses primarily contains water. This characteristic has, to date, constituted a prohibitive technological limitation on its direct use as a reaction medium for obtaining betaine esters.

[0037] This is because the large amount of water prevents those skilled in the art from carrying out any esterification reaction, and also hinders the amount of glycine betaine present in beet molasses during esterification fermentation.

[0038] Therefore, contrary to technical precedent and to date in the field of surfactants, the applicant company has demonstrated that glycine betaine esters can be obtained directly from glycine betaine without the need for extraction and by using fermented molasses as a reaction medium.

[0039] This is because, in the specific field of surfactants, manufacturers mainly focus on extracting glycine betaine from beet molasses, and then subjecting the extracted glycine betaine to different reactions to obtain betaine derivatives, especially glycine betaine esters.

[0040] Furthermore, as mentioned above, fermented molasses is not a suitable product for large-scale extraction of glycine betaine due to the large amount of water required for its extraction.

[0041] By providing a preparation method that allows for the direct esterification of glycine betaine in fermented molasses without prior extraction, thereby obtaining glycine betaine ester, the applicant company deviates from the conventional practices in the field of surfactants.

[0042] Then, the fermented molasses containing one or more glycine betaine esters obtained at the end of the method according to the invention can be used directly to improve the surfactant and / or emulsifying properties of the composition.

[0043] Fully advantageously, the preparation method according to the invention thus makes it possible to utilize and recover a portion of the large volume of fermented molasses produced by the manufacturer by carrying out in-situ esterification of glycine betaine still present in the fermented molasses.

[0044] Therefore, the preparation method according to the present invention provides an upgraded method for fermenting molasses and obtains a new co-product that has particularly advantageous applications in improving the emulsifying and / or surfactant properties of the composition.

[0045] The preparation method of the present invention includes a first stage of providing fermented beet molasses.

[0046] As described above, fermented molasses is a byproduct of molasses obtained through fermentation by bacteria, yeast, or fungi, which allows the production of "valuable" products such as baker's yeast, ethanol, or citric acid and glutamic acid.

[0047] Fermented molasses can usually be obtained from beet molasses or sugarcane molasses.

[0048] According to the present invention, the fermented molasses is obtained from beet molasses because cane molasses does not contain glycine betaine. Therefore, the fermented molasses of the present invention is fermented beet molasses.

[0049] Preferably, fermented beet molasses is obtained by fermenting beet molasses with yeast.

[0050] According to one specific implementation, fermented beet molasses can also be a mixture of fermented beet molasses and fermented sugarcane molasses. In such a mixture, glycine betaine is then provided by the fermented beet molasses.

[0051] According to this specific embodiment, the mixture may contain up to 70% by weight of fermented beet molasses, up to 80% by weight of fermented beet molasses, up to 90% by weight of fermented beet molasses, and in fact even up to 95% by weight of fermented beet molasses. The remainder consists of fermented sugarcane molasses.

[0052] As mentioned above, fermented molasses contains primarily water, specifically more than 90% by weight relative to its total weight. This significant amount of water has, to date, constituted a technical barrier preventing manufacturers from using it in esterification reactions.

[0053] Advantageously, fermented molasses can be concentrated to reduce the amount of water and obtain a higher dry matter content.

[0054] According to one specific embodiment, fermented molasses can be concentrated until a dry matter content of 45%-80% is obtained. Preferably, the dry matter content of the fermented molasses is 50%-75%, particularly 55%-65%, for example, about 60%.

[0055] According to another specific embodiment, the fermented beet molasses supplied in the first stage of the method is desalted fermented molasses. For example, desalination can be performed by adding sulfuric acid to precipitate potassium sulfate (K2SO4), sodium sulfate (Na2SO4), magnesium sulfate (MgSO4), and calcium sulfate (CaSO4) salts.

[0056] Advantageously, desalination allows for an increase in the proportion of organic matter and glycine betaine in fermented molasses relative to the total dry matter.

[0057] Traditionally, fermented beet molasses can also be defined by the distribution of its nitrogenous components and its amino acid profile, either intended for use as fertilizer or for animal feed.

[0058] Therefore, the fermented molasses according to the present invention can exhibit the following distribution of nitrogenous substances:

[0059] - Total amino acid nitrogen determined by the Kjeldahl method: 25%-50% of total nitrogen

[0060] - Betaine nitrogen: 40%-50% of total nitrogen

[0061] - Ammonia nitrogen: 2%-3% of total nitrogen.

[0062] The preparation method of the present invention then includes a stage of adding at least one acid to fermented molasses, wherein the acid / glycine betaine molar ratio is 1-2.2.

[0063] Those skilled in the art can determine the amount of glycine betaine present in fermented molasses using known methods, so as to add acid to it according to the required molar ratio.

[0064] Therefore, the acidification step is performed to lower the pH of the fermented beet molasses to below the pK of glycine betaine and carboxylic acid present in the molasses. a It is done in the form of values.

[0065] Therefore, acidified fermented molasses exhibits a pH of 1.1-1.7, preferably 1.2-1.6.

[0066] According to a specific implementation plan, the acid used is sulfuric acid or methanesulfonic acid.

[0067] The third stage of the method according to the invention consists of a stage in which acidified fermented molasses is esterified by mixing with at least one alcohol.

[0068] This mixing stage uses at least one alcohol, either a single alcohol or a mixture of alcohols.

[0069] The alcohol is used in an excess amount relative to glycine betaine. Therefore, it is advantageous to add the alcohol at an alcohol / glycine betaine molar ratio of 1-2.5, preferably 1.5-2.3.

[0070] According to this stage, mixing is carried out under conditions that allow for the esterification reaction between the carboxylic acid functional group of glycine betaine, which is contained in acidified fermented molasses, and at least one alcohol used.

[0071] In other words, this stage allows for the extraction of betaine esters from glycine betaine, which is present in fermented and acidified beet molasses.

[0072] Esterification is a reaction well known to those skilled in the art. Therefore, to obtain such a reaction, the mixing conditions can be easily adjusted by those skilled in the art.

[0073] For example, the mixture of acidified fermented molasses and at least one alcohol according to the present invention can be refluxed at a temperature of 100°C-120°C for 2-3 hours.

[0074] The alcohol used affects the betaine ester obtained. Those skilled in the art can select the alcohol or mixture of alcohols to obtain the desired betaine ester.

[0075] According to one specific embodiment, the alcohol used is selected from the group consisting of ethanol, glycerol, lauryl alcohol (dodecane-1-ol), isoamyl alcohol (3-methylbutane-1-ol), oleyl alcohol, stearyl alcohol, fusel alcohols, and mixtures thereof. Preferably, the alcohol is ethanol, oleyl alcohol, or lauryl alcohol.

[0076] Fuselols are a mixture of higher and lower alcohols, fatty alcohols, terpenes, and furfural. They are formed as metabolic byproducts through alcoholic fermentation.

[0077] According to another specific implementation, the alcohol used is a C3-C alcohol. 30 Chain-bound fatty alcohols, which may be saturated or unsaturated, such as octanol, nonanol, undecanool, dodecanool, or tridecanool.

[0078] According to this specific implementation, the esterification reaction between fermented molasses and fatty alcohols produces two distinct phases: a gel phase with a paste-like appearance containing glycine betaine esters, and a liquid phase containing excess unreacted fatty alcohols.

[0079] Therefore, the method according to the invention allows for the direct esterification of glycine betaine contained in fermented molasses using fermented molasses as a reaction medium, without the need for a prior extraction stage. At the end of the method, fermented and esterified molasses is thus obtained.

[0080] Therefore, the method according to the present invention can yield fermented beet molasses containing one or more glycine betaine esters and other carboxylic acid esters.

[0081] According to one specific embodiment, the method according to the invention includes a centrifugation stage when the esterification reaction has ended. Advantageously, when the fermented molasses used in the first stage according to the method is not desalted molasses, this centrifugation stage can remove precipitates and sulfate inorganic salts.

[0082] After centrifugation, the supernatant is recovered and then concentrated to obtain a dry matter content of 50%-80%, preferably 60%-70%.

[0083] According to one specific embodiment, the method according to the invention includes a recovery stage of glycine betaine ester. This recovery stage may be performed after the esterification stage or after the centrifugation stage.

[0084] According to this specific implementation plan, recycling can be advantageously carried out through extraction.

[0085] Another subject of the invention relates to fermented beet molasses, which is esterified and comprises one or more glycine betaine esters.

[0086] The fermented molasses is esterified because it contains one or more glycine betaine esters.

[0087] The fermented and esterified beet molasses containing one or more betaine esters according to the present invention can be obtained by the above method.

[0088] Another subject of the invention relates to the use of fermented and esterified beet molasses for improving the surfactant and / or emulsifying properties of compositions.

[0089] Because it contains cationic esters, the fermented and esterified beet molasses of the present invention can be used in any type of composition that conventionally uses cationic esters.

[0090] For example, the fermented and esterified beet molasses according to the present invention can be used as an antistatic agent in car wash compositions, as a foaming agent in liquid detergents, as a corrosion inhibitor in pipes, as an asphalt emulsion, as an antifungal agent and wetting agent in plant protection adjuvants, or also as a foaming agent and antistatic agent in shampoos.

[0091] Fermented molasses is used in addition to replacing, either entirely or partially, the petrochemical-derived emulsifiers and / or surfactants commonly used in the composition.

[0092] The fermented and esterified molasses according to the invention also covers a wide range of applications in the field of emulsification, such as in the petroleum industry, in the paint, pigment and varnish industry, or also in the construction and civil engineering industries.

[0093] The invention will be better understood with the aid of the following embodiments and accompanying drawings, which are merely illustrative and not intended to limit the scope of protection. Attached Figure Description

[0094] Figure 1

[0095] [ Figure 1 [Supplement with fermented molasses solution containing betaine] 1 1H NMR spectrum (CDCl3).

[0096] Figure 2

[0097] [ Figure 2 The diethyl ether fraction containing lauryl betaine 1 1H NMR spectrum (CDCl3).

[0098] Figure 3

[0099] [ Figure 3 Fermented molasses esterified with lauryl alcohol in the presence of H2SO4 11H NMR spectrum (CDCl3).

[0100] Figure 4

[0101] [ Figure 4 ] 1 Superimposed ¹H NMR spectra. A: Liquid phase of fermented molasses esterified with oleyl alcohol. 1 HNMR spectrum (CDCl3); B: Ether solution containing lauryl betaine 1 H NMR spectrum; C: Fermented molasses esterified with lauryl alcohol in the presence of H2SO4 1 HNMR spectrum (CDCl3) (control); D: Fermented molasses solution supplemented with betaine 1 1H NMR spectrum (CDCl3) (control); E: gel phase of fermented molasses esterified with oleyl alcohol. 1 1H NMR spectrum (CDCl3). Detailed Implementation

[0102] Example 1: Preparation of glycine betaine ester from lauryl alcohol (C 12 )

[0103] The fermented molasses used in this embodiment is desalted molasses having the following characteristics:

[0104] -pH 3,

[0105] -Dry matter accounts for 78% by weight relative to total dry matter.

[0106] - Glycine betaine accounts for approximately 19% by weight relative to the total weight of fermented molasses.

[0107] In a 250 ml round-bottom flask, a certain amount of the fermented molasses was acidified with sulfuric acid (96% concentration) at a concentration of 2.4 molar equivalents relative to glycine betaine under temperature stirring. The combined mixture was then homogenized.

[0108] Subsequently, lauryl alcohol was added to the round-bottom flask at a molar ratio of 1.5 for alcohol to glycine betaine, and the combined mixture was homogenized again.

[0109] Place the round-bottom flask in a hot rotary evaporator (90°C) and stir at 100-150 rpm under reduced pressure (100 mbar).

[0110] Three hours later, the reaction was stopped by immersing the round-bottom flask in ice-cold water.

[0111] At the end of the reaction, the fermented and esterified molasses containing glycine betaine esters exhibited a homogeneous appearance.

[0112] To confirm the presence of glycine betaine esters in fermented and esterified molasses, an experiment was conducted in deuterated chloroform (CDCl3).1 HNMR analysis was performed, and the results were compared with those of the control solution.

[0113] pass 1 The solution analyzed by 1H NMR shows the following:

[0114] 1: Fermented beet molasses rich in glycine betaine (control).

[0115] 2: Ether solution containing lauryl betaine (control),

[0116] 3: Fermented molasses esterified with lauryl alcohol in the presence of H2SO4.

[0117] Each of solutions 1-3 1 The H NMR analysis results are shown in the figures. Figures 1-3 middle.

[0118] Figure 1 The control spectrum showed a characteristic peak of glycine betaine at 3.37 ppm.

[0119] Figure 2 The spectrum was also used as a reference to identify the characteristic peak of glycine betaine esterified with lauryl alcohol (lauryl betaine ester) at 3.51 ppm, as well as three peaks between 3.6 and 3.7 ppm, which are characteristic peaks of lauryl alcohol.

[0120] The spectrum obtained from fermented and esterified molasses showed a peak at approximately 3.5 ppm, confirming the presence of lauryl betaine ester. Furthermore, the absence of a characteristic peak at 3.37 ppm indicates that most of the glycine betaine reacted during the esterification process to form glycine betaine ester. Figure 3 ).

[0121] In summary, these results confirm that the method according to the invention enables the extraction of glycine betaine esters from fermented molasses, which is used directly as the reaction medium.

[0122] Example 2: Preparation of glycine betaine ester from oleyl alcohol (C 18 )

[0123] The fermented molasses used in this embodiment is desalted molasses having the following characteristics:

[0124] -pH 3,

[0125] -Dry matter accounts for 78% by weight relative to total dry matter.

[0126] - Glycine betaine accounts for approximately 19% by weight relative to the total weight of fermented molasses.

[0127] In a 250 ml round-bottom flask, under steady stirring, a certain amount of the fermented molasses was acidified with sulfuric acid (96% concentration) at an acid / glycine betaine molar ratio of 2, and then the combined mixture was homogenized.

[0128] Subsequently, oleyl alcohol was added to the round-bottom flask at an alcohol / glycine betaine molar ratio of 1.5, and the combined mixture was then homogenized again.

[0129] Place the round-bottom flask in a hot rotary evaporator (90°C) and stir at 100-150 rpm under reduced pressure (100 mbar).

[0130] Five hours later, the reaction was stopped by immersing the round-bottom flask in ice-cold water.

[0131] At the end of the reaction, the fermented and esterified molasses containing glycine betaine exists in two phases: a gel phase and a liquid phase.

[0132] To confirm the presence of glycine betaine ester in fermented and esterified molasses, different phases were subjected to... 1 The results were analyzed by 1H NMR and compared with those of the control solution.

[0133] The solutions analyzed are shown below:

[0134] A: Liquid phase of fermented molasses esterified with oleyl alcohol

[0135] B: An ether solution containing lauryl betaine ester.

[0136] C: Using lauryl alcohol (C) in the presence of H2SO4 l2 Esterified fermented molasses (control).

[0137] D: Fermented molasses solution supplemented with glycine betaine (control).

[0138] E: The gel phase of fermented and esterified molasses.

[0139] Each of the solutions AE 1 The H NMR analysis results are shown in Figure 4 middle.

[0140] Spectrum D shows that the characteristic peak of glycine betaine is located at 3.37 ppm.

[0141] Regardless of the alcohol used for esterification, glycine betaine esters exhibit essentially the same chemical shift. Therefore, spectra B and C were used as controls, with the characteristic peak of lauryl betaine ester at 3.51, to identify the presence of oil-based betaine esters.

[0142] The absence of characteristic peaks for glycine betaine in spectra A and E indicates that it is primarily consumed in the fermented molasses during esterification to form glycine betaine esters. Oil-based betaine esters were found only in the gel phase of fermented and esterified molasses, as evidenced by the presence of a peak at 3.51 ppm in spectrum E, which is absent in spectrum A of the liquid phase.

[0143] Furthermore, the results confirmed that glycine betaine esters can be obtained from fermented molasses, which is used directly as the reaction medium.

[0144] Therefore, contrary to what has been accepted to date, the applicant company demonstrates that an esterification reaction can be initiated from fermented molasses to obtain glycine betaine ester after the addition of alcohol.

[0145] Example 3: Preparation of glycine betaine ester from fermented molasses and ethanol.

[0146] A certain volume of fermented beet molasses was acidified to pH 1.9 using sulfuric acid.

[0147] The acidified fermented molasses is then mixed with 1.1 molar equivalents of ethanol relative to glycine betaine (mixture 1), or with 5% by weight of glycerol (mixture 2).

[0148] The two mixtures were refluxed at 110°C for 2 hours.

[0149] Subsequently, a centrifugation stage of 8000 rpm for 10 minutes at 20°C was performed to remove precipitates and sulfate inorganic salts. The supernatant was recovered and then concentrated by evaporation until approximately 65% ​​dry matter was obtained. 1 1H NMR measurements confirmed the presence of glycine betaine ester.

Claims

1. A method for preparing fermented molasses containing at least one glycine betaine ester, the method comprising the following stages: 1) Provide fermented beet molasses, said fermented beet molasses containing glycine betaine, 2) Concentrate the fermented beet molasses until a dry matter content of 45%-80% is obtained. 3) At least one acid is added to the fermented beet molasses at an acid / glycine betaine molar ratio of 1-2.

2. 4) Esterification of the acidified fermented molasses obtained in the foregoing stage by mixing with at least one alcohol, wherein the alcohol and the acidified fermented molasses are mixed at an alcohol / glycine betaine molar ratio of 1-2.

5.

2. The method as described in claim 1, characterized in that, The alcohol is selected from ethanol, glycerol, lauryl alcohol (dodecane-1-ol), isoamyl alcohol (3-methylbut-1-ol), oleyl alcohol, stearyl alcohol, fusel alcohol, and mixtures thereof.

3. The method as described in claim 2, characterized in that, The alcohol is selected from ethanol, oleyl alcohol, and lauryl alcohol.

4. The method according to any one of claims 1-3, characterized in that, After the esterification stage 3), the method includes centrifuging the supernatant and concentrating the dry matter content from 50% to 80%.

5. The method according to any one of claims 1-3, characterized in that, The fermented beet molasses supplied in the first phase is a fermented and desalted molasses.

6. The fermented and esterified beet molasses obtained by the method according to any one of claims 1-5, wherein the fermented and esterified beet molasses comprises one or more glycine betaine esters.

7. Use of the fermented and esterified beet molasses as claimed in claim 6 or the fermented and esterified beet molasses obtained by the method according to any one of claims 1-5 for improving the surfactant and / or emulsifying properties of the composition.

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