Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
  • C07C45/78—Separation; Purification; Stabilisation; Use of additives
  • C07C45/786—Separation; Purification; Stabilisation; Use of additives by membrane separation process, e.g. pervaporation, perstraction, reverse osmosis
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
  • C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms
  • C07C49/17—Saturated compounds containing keto groups bound to acyclic carbon atoms containing hydroxy groups

Definitions

• the present invention relates to a process for obtaining acetoin from a medium comprising it, the process comprising a step of dehydration by pervaporation using a hydrophilic membrane.
• This process makes it possible to isolate and purify acetoin satisfactorily, both from the point of view of quality and yield. In addition, it eliminates the use of solvents and avoids the generation of impurities.
• Acetoin (3-hydroxybutanone) is a chiral organic molecule with the formula C4H8O2 belonging to the class of hydroxylated ketones and comprising two enantiomeric forms.
• Acetoin includes two functional groups, a hydroxyl group and a carbonyl group, which make it particularly reactive and prone to decomposition, particularly into acetaldehyde.
• Acetoin is found in trace amounts in many foods, including grapes, raspberries, apples, bananas, corn, honey and coffee. This molecule is also present in certain cheeses or certain meats. Finally, this molecule is also a synthetic intermediate in the sugar metabolism of certain microorganisms.
• Acetoin is, along with diacetyl (2,3-butanedione), one of the molecules that gives butter its characteristic flavor. It can be used as a flavoring agent.
• Acetoin is frequently used particularly in the food industry, particularly in the areas of dairy products, drinks, bakery, pastries and pastries, to give a “butter flavor” to products. including.
• regulations require the use of acetoin with a high degree of purity, for example at least 95% (see EC Regulation No. 1334/2008).
• Acetoin is also used in other fields, particularly in the fields of perfumery, pharmacy and tobacco. Acetoin can be obtained from chemical synthesis processes or biological processes.
• Chemical synthesis processes can use, for example, 2,3-butanedione and 2,3-butanediol as raw materials.
• Biological processes can use wild microorganisms, selected microorganisms or recombinant microorganisms.
• Recombinant microorganisms are known which do not naturally produce acetoin or produce it at too low a yield and/or as a synthesis intermediate.
• recombinant microorganisms have been obtained from the following microorganisms: Bacillus subtilis, Bacillus pumilus, Bacillus methanolicus, Bacillus licheniformis, Corynebacterium glutamicum, Escherichia coli, Lactococcus lactis, Saccharomyces cerevisiae and Serratia marcescens.
• the quantity and quality of the product obtained may not be sufficient, particularly for use in the food industry and pharmacy.
• a medium can be obtained comprising impurities, in particular acetoin by-products, organic residues (biomass) if obtained with a biological process, as well as other molecules. It is therefore necessary to isolate and purify acetoin from the medium containing it.
• a number of purification techniques are known, for example distillation, liquid-liquid extraction or salting-out extraction.
• the effectiveness of these techniques, in particular distillation, can be limited by the fact that acetoin forms an azeotropic mixture with water, the separation then being hampered or limited as soon as the liquid phase and the gas phase reach the same water/acetoin composition.
• the invention firstly relates to a process for obtaining acetoin from a medium to be treated, the process comprising a step of dehydration by pervaporation using a hydrophilic membrane, to obtain a dehydrated medium comprising at least 70 % acetoin, by total weight of the treated medium.
• the hydrophilic membrane is selected from the group consisting of hydrophilic polymeric membranes, hydrophilic inorganic membranes, hydrophilic two-dimensional material-based membranes, hydrophilic mixed matrix membranes, or membranes derived therefrom.
• the hydrophilic membrane is a hydrophilic silica-based membrane or a hydrophilic membrane derived therefrom.
• the hydrophilic silica-based membrane is obtained from organoalkoxysilane precursors.
• an underpressure of -700.10 5 mPa or more is applied at the permeation surface of the hydrophilic membrane.
• the dehydration step is carried out in the absence of solvents and/or inorganic salts.
• the method comprises a step of pretreatment of the medium to be treated implemented, before the step of dehydration, by a technique selected from the group consisting of centrifugation, front filtration, microfiltration and nanofiltration.
• the method comprises a posttreatment step of the treated medium implemented, after the dehydration step, by distillation.
• the medium comprising acetoin is obtained by a biological process carried out using recombinant microorganisms.
• the recombinant microorganisms are yeasts belonging to the genus Saccharomyces.
• the invention secondly concerns acetoin, obtained from the process described opposite.
• the invention thirdly concerns the use of a hydrophilic membrane, as described opposite, to obtain acetoin.
• the present invention makes it possible to meet the needs expressed above.
• the inventors demonstrated that acetoin can be isolated and purified satisfactorily, both in terms of quality and yield, by selecting hydrophilic membranes.
• hydrophilic membranes By using such membranes, only water and hydrophilic compounds migrate through the membrane into the permeate (filtrate), while acetoin remains in the retentate (treated medium), resulting in gradual and satisfactory dehydration of the membrane. acetoin.
• This pervaporation dehydration technique also makes it possible to overcome the separation constraints associated with the formation of azeotropic mixtures.
• liquid-liquid extraction technique has the disadvantage of being carried out with solvents, for example ethyl acetate, used in large quantities. Furthermore, disadvantageously, the inventors have demonstrated that this technique leads to the formation of impurities, for example methyl allyl acetate, a reaction product between acetoin and ethyl acetate. Finally, this technique does not make it possible to obtain acetoin that can be labeled “natural”.
• hydrophilic membrane makes it possible to obtain a process with improved performance compared to a process using an organophilic membrane, i.e. say a higher yield and a higher degree of dehydration and those although water is initially the majority in the medium.
• Figure 1 represents a graph of the concentration of acetoin and water (% by weight) in the retentate as a function of time (min).
• Figure 2 represents a graph concerning the concentration of acetoin in the retentate (% by weight) and the underpressure at the level of the permeation surface (.10 5 mPa) as a function of time (min).
• the present invention relates to a process for obtaining acetoin from a medium comprising it (medium to be treated), the process comprising a step of dehydration by pervaporation using a hydrophilic membrane.
• the dehydration step consists of bringing the medium to be treated into contact with a first surface of the hydrophilic membrane and applying underpressure at the level of the permeation surface (second surface) of the hydrophilic membrane.
• the underpressure applied at the permeation surface of the hydrophilic membrane is -700.10 5 mPa or more, preferably from -300.10 5 to -0.1.10 5 mPa, very preferably from -100.10 5 to -10 5 mPa.
• the underpressure is defined in relation to the pressure at the surface in contact with the medium to be dehydrated.
• the temperature applied to the power supply is 150°C or less, preferably 5 to 100°C, very preferably 30 to 90°C.
• a permeate is therefore gradually formed comprising the water and the hydrophilic compounds having migrated through the hydrophilic membrane (medium to be eliminated), while the residual medium, comprising acetoin, forms the retentate (treated medium).
• hydrophilic membrane we mean a membrane which preferentially allows permeate, water and hydrophilic molecules to pass through.
• the hydrophilic membrane can be chosen from the group consisting of hydrophilic polymeric membranes, hydrophilic inorganic membranes, membranes based on hydrophilic two-dimensional membranes, mixed-matrix membranes. hydrophilic membranes) or the hydrophilic membranes derived therefrom; preferably the hydrophilic membrane is an inorganic membrane or a hydrophilic membrane which is derived therefrom.
• the hydrophilic inorganic membrane can be chosen from the group consisting of membranes based on hydrophilic zeolites, membranes based on hydrophilic silica, membranes with a hydrophilic metal-organic framework (MOF) membranes, membranes with a hydrophilic covalent organic framework (COF) membranes or hydrophilic membranes derived therefrom; preferably the hydrophilic inorganic membrane is a membrane based on hydrophilic silica or a hydrophilic membrane derived therefrom; very preferably the hydrophilic inorganic membrane is a hydride membrane based on hydrophilic silica.
• Silica-based hydride membranes are indifferently called organic-inorganic silica membranes, organosilica membranes or organosilica hydrid membranes. ").
• the hydrophilic silica-based hydride membrane may be chosen from the group consisting of hydrophilic pendant-type organosilica membranes or bridged-type silica-based hydride membranes. organosilica membranes”) hydrophilic; preferably hydrophilic bridged silica-based hydride membranes.
• organosilica membranes hydrophilic; preferably hydrophilic bridged silica-based hydride membranes.
• Hybrid membranes based on silica are known (see the review by X. Ren entitled “Organosilica-based membranes in gas and liquid-phase separation”, Membranes, 2019, 9, 107; the work entitled “Pervaporation, vapor permeation and membrane distillation - Principles and applications”, Ed.
• Hybrid membranes based on bridged silica can be obtained from organoalkoxysilane precursors (monomers), that is to say alkoxysilane precursors comprising organic groups.
• the organoalkoxysilane precursor can be chosen from organoalkoxysilane precursors comprising one, two, three or more silica atoms.
• the organoalkoxysilane precursor comprising a silica atom may be chosen from the group consisting of methyltrimethoxysilane (MTMS), methyltriethoxysilane (MTES), phenyltriethoxysilane (PhTES), hydroxymethyl(triethoxy)silane (HMTES), 3-aminopropylriethoxysilane (APTES) and their mixtures.
• MTMS methyltrimethoxysilane
• MTES methyltriethoxysilane
• PhTES phenyltriethoxysilane
• HMTES hydroxymethyl(triethoxy)silane
• APTES 3-aminopropylriethoxysilane
• the organoalkoxysilane precursor comprising two silica atoms can be chosen from the group consisting of bis(triethoxysilyl)methane (BTESM), 1 -2-bis(triethoxysilyl)ethane (BTESE), 1,3-bis(triethoxysilyl)propane ( BTESP), 1,8-bis(triethoxysilyl)octane (BTESO), 1-2-Bis(triethoxysilyl)ethylene (BTESEthy), 1,2-bis(triethoxysilyl)acetylene (BTESA), 1,4- bis(triethoxysilyl)diacetylene (BTESDA), bis(trimethoxysilyl)norbornane (BTMS-Nor), 1,2-bis(triethoxysilyl)benzene (BTESB), 2,5-bis[2-triethoxysilyl)ethyl]-1 ,4-dioxane (BTES
• the organoalkoxysilane precursor can be chosen from the group consisting of TTESPT, TESE-POSS, MTMS, MTES, PhTES, HMTES, APTES, BTESM, BTESE, BTESP, BTESO, BTESEthy, BTESA, BTESDA, BTMS-Nor, BTESB, BTES-ED, BTESPA, BTES-Ac, BTPP, BTESMOU/BTESMPU, TTESPT, TESE-POSS and their mixtures; preferably the organoalkoxysilane precursor is chosen from the group consisting of BTESM, BTESE and their mixture; very preferably the organoalkoxysilane precursor is BTESE.
• the organic group can be used to functionalize the alkoxysilane precursors.
• Silica-based hydride membranes can be subject to additional treatment, for example with metals.
• Hydrophilic membranes are available commercially, for example under the name Hybsi® from Hybsi® (Pervatech®).
• the medium to be treated corresponds to the starting product (non-pretreated medium) or alternatively to the intermediate product (pretreated medium) having previously undergone a pretreatment step.
• the terms “medium”, “composition”, “solution” and “substrate” can be used interchangeably to designate the medium to be treated (and the treated medium if applicable).
• the medium to be treated may comprise from 2 to 50%, preferably from 6 to 30%, of acetoin, by total weight of the medium.
• the medium to be treated may comprise from 1 to 5%, or from 5 to 10%, or from 10 to 15%, or from 15 to 20%, or from 20 to 25%, or from 25 to 25%. 30%, or 30 to 35%, or 35 to 40%, or 40 to 45%, or 45 to 50%, of acetoin, by total weight of the medium.
• Acetoin can be present in the form of its enantiomer (3R)-3-hydroxybutanone (natural enantiomer), its enantiomer (3S)-3-hydroxybutanone or the mixture of these two enantiomers (including their racemic mixture).
• the medium to be treated is an aqueous medium.
• the medium to be treated may comprise at least 15%, preferably at least 45%, very preferably at least 65%, of water, by total weight of the medium.
• the medium to be treated can be obtained from a chemical synthesis process or from a biological process.
• the treated medium may comprise at least 70% (70 to 99%), preferably at least 80% (80 to 99%), very preferably at least 90% (90 to 99%), of acetoin, by weight. total middle.
• the dehydrated medium may comprise from 70 to 75%, or from 75 to 80%, or from 80 to 85%, or from 85 to 90%, or from 90 to 95%, or from 95 to 99 %, of acetoin, by total weight of the medium.
• the treated medium may comprise 30% or less (1 to 30%), preferably 20% or less (1 to 20%), very preferably 10% or less (1 to 20%), water. and additional compounds (impurities), by total weight of the medium.
• the dehydration step is carried out in the absence of solvents, for example ethyl acetate, methyl tert-butyl ether, butyl acetate, dimethyl carbonate, diethyl ether, diethyl carbonate, ethanol, methanol, acetone, isopropanol, acetonitrile, dichloromethane and/or chloroform.
• solvents for example ethyl acetate, methyl tert-butyl ether, butyl acetate, dimethyl carbonate, diethyl ether, diethyl carbonate, ethanol, methanol, acetone, isopropanol, acetonitrile, dichloromethane and/or chloroform.
• solvents for example ethyl acetate, methyl tert-butyl ether, butyl acetate, dimethyl carbonate, diethyl ether, diethyl carbonate, ethanol, methanol, acetone
• the dehydration step is carried out in the absence of inorganic salts, for example ammonium sulfate, magnesium sulfate, sodium sulfate, copper sulfate, calcium chloride, potassium hydrogen phosphate (dipotassium phosphate), potassium pyrophosphate, sodium carbonate and/or potassium carbonate.
• inorganic salts for example ammonium sulfate, magnesium sulfate, sodium sulfate, copper sulfate, calcium chloride, potassium hydrogen phosphate (dipotassium phosphate), potassium pyrophosphate, sodium carbonate and/or potassium carbonate.
• the method may include a step of pretreatment of the medium to be treated, implemented before the dehydration step.
• the medium to be treated is pretreated and the pretreated medium, thus obtained, is subsequently dehydrated.
• a pretreatment step can be implemented to eliminate suspended solids in the medium to be treated.
• a pretreatment step can be implemented when the acetoin is produced by a biological process and the medium to be treated therefore comprises biomass.
• the medium comprising acetoin is obtained from a biological process, it may comprise biomass.
• biomass we mean organic matter of bacterial or fungal, plant or animal origin, preferably organic matter of bacterial or fungal origin.
• the biomass may include whole microorganisms (living or dead), residues of these microorganisms (residues of nuclei, organelles, cytoplasm, membrane , etc.) and molecules produced by them (proteins, carbohydrates, lipids, etc.).
• the medium to be treated (not pretreated) may comprise from 1 to 20%, preferably from 1 to 10%, of dry biomass, by total weight of the medium.
• the pretreatment step can make it possible to eliminate at least 80%, preferably at least 90%, of the dry biomass contained in the medium to be dehydrated.
• the pretreatment step can be chosen by the techniques consisting of centrifugation, frontal filtration, microfiltration, ultrafiltration, nanofiltration or any other conventional clarification technique.
• the process may include a post-treatment step of the treated medium (retentate), carried out after the dehydration step.
• a post-treatment step can be implemented to increase the purity of the acetoin.
• the post-treatment step can be carried out by distillation.
• the process according to the invention is particularly advantageous, in that it makes it possible to overcome the difficulties encountered when carrying out direct distillation, due to the formation of an azeotropic water-acetoin mixture.
• the medium comprising acetoin can be obtained by a chemical synthesis process.
• the medium comprising acetoin can be obtained by a biological process.
• the biological process can be implemented using microorganisms, in particular wild microorganisms, selected microorganisms or recombinant microorganisms.
• Wild microorganisms are microorganisms that naturally produce acetoin at usable concentrations.
• the selected microorganisms are microorganisms with improved performance in terms of acetoin production.
• Recombinant microorganisms (genetically modified) - not naturally producing acetoin or producing it at too low a yield and/or as a synthesis intermediate - can be chosen from the group consisting of Bacillus subtilis, Bacillus pumilus, Bacillus methanolicus, Bacillus licheniformis, Corynebacterium glutamicum, Escherichia coli, Lactococcus lactis, Serratia marcescens and yeasts of the genus Saccharomyces; preferably a microorganism being a yeast of the Saccharomyces genus; very preferably Saccharomyces cerevisiae.
• the process according to the invention makes it possible to obtain a product comprising at least 70% acetoin, by total weight of the treated medium.
• Example according to the invention Process for obtaining acetoin by using a hydrophilic membrane
• Aqueous solution comprising 10% acetoin, by total weight of the aqueous solution
• Hybsi® AR membrane marketed by Hybsi® Dehydration device: PTU-044 device
• Vapor temperature Between 44 and 86°C
• the water content in the retentate and in the filtrate is measured by the Karl Fischer filtration method (KF titration).
• Acetoin content is measured by HPLC and/or gas chromatography.
• the objective of this process is to obtain the permeation of water from the medium to be treated through the hydrophilic membrane towards the permeate and as a corollary the dehydration of the acetoin (retentate).
• Figure 1 represents a graph regarding the concentration of acetoin and water (% by mass) in the retentate as a function of time (min)
• concentration of water white squares
• concentration of acetoin black circles
• the water concentration decreases to approximately 1.1%, by total weight of the retentate, while the acetoin concentration increases to approximately 77%, the difference corresponding to other organic residues. than acetoin.
• Comparative example Process for obtaining acetoin by using an organophilic membrane
• Materials Medium to be purified Aqueous solution comprising 10% acetoin, by total weight of the aqueous solution
• Organophilic membrane PDMS-FS membrane marketed by Pervatech®
• Permeate vacuum pressure from 20.10 5 mPa to 4.10 5 mPa
• the objective of this process is to obtain the permeation of acetoin from the medium comprising it through the organophilic membrane towards the filtration agent.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Water Supply & Treatment (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Separation Using Semi-Permeable Membranes (AREA)

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• 2022
  • 2022-04-15 FR FR2203539A patent/FR3134575B1/fr active Active
• 2023
  • 2023-04-13 EP EP23722431.6A patent/EP4508024A1/de active Pending
  • 2023-04-13 CN CN202380034069.3A patent/CN119156368A/zh active Pending
  • 2023-04-13 WO PCT/FR2023/050528 patent/WO2023198993A1/fr not_active Ceased
  • 2023-04-13 US US18/857,094 patent/US20250296907A1/en active Pending
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