WO2019121876A1 - Vinasse as a fermentation medium - Google Patents

Vinasse as a fermentation medium Download PDF

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Publication number
WO2019121876A1
WO2019121876A1 PCT/EP2018/085779 EP2018085779W WO2019121876A1 WO 2019121876 A1 WO2019121876 A1 WO 2019121876A1 EP 2018085779 W EP2018085779 W EP 2018085779W WO 2019121876 A1 WO2019121876 A1 WO 2019121876A1
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Prior art keywords
vinasse
fermentation
molasses
sugar
pulp
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PCT/EP2018/085779
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French (fr)
Inventor
Jérémy PESSIOT
Nicolas SORDET
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Afyren
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Publication of WO2019121876A1 publication Critical patent/WO2019121876A1/en

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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P13/00—Preparation of nitrogen-containing organic compounds
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P13/00—Preparation of nitrogen-containing organic compounds
    • C12P13/005—Amino acids other than alpha- or beta amino acids, e.g. gamma amino acids
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats
    • C12P7/6409—Fatty acids

Definitions

  • the present invention relates to the production of organic molecules chosen from organic acids, organic acid derivatives and amino acids, in particular organic acids by anaerobic fermentation of molasses and / or pulp, residues of the sugar industry, in which the molasses and / or the pulp are fermented in an aqueous medium which contains vinasse.
  • Vinasse is a residue of the distillation of alcoholic liquids and especially of the sugar industry. In the manufacture of sugar, by-products of manufacture molasses are often recycled by alcoholic fermentation, for the recovery of ethanol by distillation. Vinasse is one of the residues of this distillation.
  • vinasse is generally considered a toxic medium for microorganisms.
  • the cognac vinasse can be recycled by fermentation with Sporoblomyces to produce flavors.
  • the vinasse is used mixed with waste, such as organic fractions of household waste, or peat, for the production of biogas.
  • waste such as organic fractions of household waste, or peat
  • it is a question of selecting optimized yeast strains capable of growing on toxic media. including the vinasse, or to set up processes for the recovery and recycling of vinasses for the production of ethanol.
  • the vinasses are spread as fertilizer in the neighboring fields of sugar factories to avoid overly expensive transport. It is also used as a feedstock for processing in complex fertilizer manufacturing processes (WO 2017/132742, CN 106398962). The vinasse is dried to keep only the dry matter, according to more or less complex processes for the production of biogas (EP 0 057 152). Others propose their use for a chemical transformation with catalysts for preparing methacrylic acid.
  • the inventors have now understood that the use of vinasse as a culture medium for the anaerobic digestion of molasses and / or pulp in a process for the production of organic acids makes it possible to improve the acid yield, in addition to the improvement the economic recovery of the sugar industry when the molasses of sugar beet or cane, and the pulp and vinasse used in the process are all residues of the sugar industry.
  • the present invention relates to the use of vinasse alone or as a mixture with water as a culture medium for the anaerobic fermentation of molasses and / or pulp in a process for the production of organic molecules, in particular preferably organic acids. of fatty organic acids.
  • the invention also relates to a method for preparing organic molecules chosen from organic acids, organic acid derivatives and amino acids comprising the steps a) of anaerobic fermentation of molasses and / or pulp in aqueous fermentation medium, b ) recovering a fermentation juice from the fermentation must and c) isolating the organic molecules from the fermentation juice, wherein the aqueous fermentation medium comprises vinasse.
  • the purpose of the fermentation process is to produce organic acids, more particularly fatty organic acids, such as acetic, butyric, isobutyric, propionic, valeric, isovaleric, hexanoic, heptanoic and octanoic acids, and mixtures thereof.
  • organic acids more particularly fatty organic acids, such as acetic, butyric, isobutyric, propionic, valeric, isovaleric, hexanoic, heptanoic and octanoic acids, and mixtures thereof.
  • the invention relates to an improvement of anaerobic molasses and / or pulp fermentation processes in a process for producing organic molecules such as organic acids, in particular fatty organic acids, derivatives of these organic acids such as polyhydroxyalkanoates or esters, or amino acids, by the use of vinasse, alone or in admixture with water as an aqueous fermentation medium for the anaerobic fermentation step.
  • organic molecules such as organic acids, in particular fatty organic acids, derivatives of these organic acids such as polyhydroxyalkanoates or esters, or amino acids
  • the purpose of the fermentation process is to produce organic acids, more particularly fatty organic acids, such as acetic, butyric, propionic, isobutyric, valeric and isovaleric acids. hexanoic, heptanoic and octanoic and their mixtures.
  • Vinasse is an alcoholic distillation residue that includes water and solid residues, a complex mixture of organic and inorganic residues. Its composition and in particular its dry matter content will depend on its origin, be it a residue of wine distillation, as a by-product of the production of cognac, for example, or a distillation residue of solid fermentation product, for the preparation of spirits such as rum, grape marc, vodka, whiskey, or residues of the sugar industry used for the production of industrial ethanol.
  • the vinasse residue of the sugar industry comes from both sugarcane processing and sugar beet processing.
  • the vinasse employed is a residue of the sugar industry.
  • vinasses can be presented in several forms depending on their concentration in dry matter, known as light, pre-concentrated or concentrated vinasse.
  • the method according to the invention can be used indifferently with these different types of vinasse. In general, depending on the method of obtaining the dry matter content of unconcentrated and concentrated vinasse is respectively between 1 and 15% and between 15 and 65%.
  • Vinasse can be used alone or mixed with water as an aqueous fermentation medium.
  • the volume ratio water / vinasse is between 0/100 and 5/95 advantageously between 90/10 and 30/70.
  • the dry matter content from the vinasse in the aqueous fermentation medium will be between 3% and 70% and more preferably between 15 and 60%.
  • the vinasse employed in the aqueous fermentation medium is a residue of the sugar processing sugar beet industry and the water / vinasse volume ratio is between 90/10 and 30. / 70.
  • the aqueous fermentation medium consists of water and vinasse, according to the proportions described above.
  • This fermentation medium can be supplemented with vitamins, yeast extract, buffers, or any other adjuvant for optimizing fermentation performance.
  • the fermentation step a) will generally be carried out in mesophilic and anaerobic mode in a stirred fermenter.
  • the culture mode can be continuous or discontinuous.
  • the molasses or pulp used for fermentation are preferably residues of the sugar industry, in particular sugar cane or sugar beet processing, preferably sugar beet pulp or sugar beet pulp. sugar beet or sugar cane.
  • the molasses and the pulp can be used together in the same fermenter, in all proportions, or separately in different fermentors.
  • pulp and / or molasses are the only sources of carbon for anaerobic fermentation.
  • the culture medium comprises
  • the culture medium comprises
  • Anaerobic fermentation is generally carried out with microorganisms alone or in mixtures, including in particular cellulotytic or proteolytic microorganisms such as Bacteroides and Clostridia.
  • the anaerobic fermentation is carried out by the seeding of the culture medium with an inoculum which comes from the anaerobic fermentation of molasses and / or pulp.
  • This inoculum which is a mixture of microorganisms can be obtained by the fermentation of small amounts of molasses and / or pulp under anaerobic conditions, or can come from the fermentation must obtained in step a) of a process according to the invention. invention implemented previously.
  • step b the recovery is at the end of fermentation according to usual separation techniques to remove solid residues present in the fermentation must, for example by centrifugation, centrifugal decantation, etc.
  • Step c) of isolation of organic acids is generally by extraction, precipitation and / or distillation. These steps are carried out on the fermentation juice, optionally concentrated after removal of at least a portion of the water, and optionally with the addition of an organic solvent to promote partitioning of different acids.
  • extraction methods described in applications WO 2015/0536683, WO 2014/100424.
  • Other methods of acid precipitation isolation of potassium or ammonia salts with a strong acid and recovery of organic acids in the drying vapors of the precipitated salts prior to their separation by distillation are also described in PCT / EP2018 / 083122 and US 16 / 205,983 filed on 11/30/2018, the contents of which are incorporated herein by reference.
  • PCT / EP2018 / 083122 and US 16 / 205,983 filed on 11/30/2018, the contents of which are incorporated herein by reference.
  • organic acid derivatives and the amino acids can be obtained by chemical and / or enzymatic transformation of the previously isolated organic acids, according to usual methods known to those skilled in the art.
  • the fermentation juice can come from a single fermentation must or can be a mixture of several fermentation juices from several fermentation musts, if necessary after concentration. In this case, each fermentation must can come independently of the fermentation of pulp or molasses or a mixture of pulp and molasses.
  • molasses, pulp and vinasse are residues of the sugar processing industry of the same raw material, in particular sugar cane or sugar beet. More preferably, molasses and pulp are sugar beet molasses and sugar beet pulp, and vinasse is a residue of the sugar beet processing industry, also known as sugar beet vinasse. sugar ".
  • pulp, molasses and vinasse come from the same refinery producing sugar by transformation of sugar cane or sugar beet, in particular sugar beet.
  • the substrate used here consists of sugar beet pulps.
  • the fermentation juices are analyzed and a fermentation yield of organic acids (acetic, propionic, isobutyric, butyric, isovaleric, valeric and caproic acid) is deduced from 31% for the fermenter n ° 1 and 37% for the fermenter. # 2.
  • the same fermentation is carried out in a third industrial fermenter but there is no addition of vinasse to the fermentation medium. In this case, at the end of fermentation at the same time, this time a fermentation yield of 28% organic acids is observed.

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Abstract

The present invention relates to the production of organic acids by anaerobic fermentation of molasses and/or pulp, residues of the sugar industry, in which the molasses and/or the pulp are fermented in an aqueous medium containing vinasse.

Description

VINASSE COMME MILIEU DE FERMENTATION  VINASSE AS A MEDIUM OF FERMENTATION
DOMAINE DE L'INVENTION FIELD OF THE INVENTION
La présente invention concerne la production de molécules organiques choisies parmi les acides organiques, les dérivés d’acides organiques et les acides aminés, en particulier d’acides organiques par fermentation anaérobie de mélasse et/ou de pulpe, résidus de l’industrie sucrière, dans lequel la mélasse et/ou la pulpe sont mises à fermenter dans un milieu aqueux qui contient de la vinasse.  The present invention relates to the production of organic molecules chosen from organic acids, organic acid derivatives and amino acids, in particular organic acids by anaerobic fermentation of molasses and / or pulp, residues of the sugar industry, in which the molasses and / or the pulp are fermented in an aqueous medium which contains vinasse.
ETAT DE LA TECHNIQUE  STATE OF THE ART
La vinasse est un résidu de la distillation des liquides alcooliques et notamment de l’industrie sucrière. Dans la fabrication du sucre, les sous-produits de fabrication que sont les mélasses sont souvent recyclés par fermentation alcoolique, pour la récupération d’éthanol par distillation. La vinasse est un des résidus de cette distillation.  Vinasse is a residue of the distillation of alcoholic liquids and especially of the sugar industry. In the manufacture of sugar, by-products of manufacture molasses are often recycled by alcoholic fermentation, for the recovery of ethanol by distillation. Vinasse is one of the residues of this distillation.
Le recyclage de la vinasse pose un problème industriel particulier pour ces industries du sucre et de l’alcool, car il s’agit d’un produit complexe avec beaucoup d’eau et des sels minéraux de composition variable, dont le transport et le traitement sont souvent trop onéreux pour sa valorisation. La vinasse est généralement considérée comme un milieu toxique pour les microorganismes.  The recycling of vinasse poses a particular industrial problem for these sugar and alcohol industries because it is a complex product with a lot of water and mineral salts of varying composition, including transport and processing. are often too expensive for its valuation. Vinasse is generally considered a toxic medium for microorganisms.
De par sa teneur en matières organiques et en sels, certains se sont penchés sur la possibilité d’employer directement ces vinasses comme substrats de fermentation pour la production d’alcools ou de produits à haute valeur ajoutée. Pour la demande FR 2 777 571 , la vinasse de cognac peut être recyclée par fermentation avec des Sporoblomyces pour produire des arômes. Pour la demande FR 1 516 540, la vinasse est employée en mélange avec des déchets, comme les fractions organiques d’ordures ménagères, ou de la tourbe noire, pour la production de biogaz. Pour les demandes FR 3 953 857, FR 2 608 170 et US 2002/155583 et pour l’article de Fadel & al., (2014), il s’agit de sélectionner des souches de levures optimisées capables de croître sur des milieux toxiques, dont la vinasse, ou encore de mettre en place des procédés de récupération et recyclage des vinasses pour la production d’éthanol.  Because of their organic matter and salt content, some have looked into the possibility of directly using these vinasse as fermentation substrates for the production of alcohols or high added value products. For the application FR 2 777 571, the cognac vinasse can be recycled by fermentation with Sporoblomyces to produce flavors. For the application FR 1 516 540, the vinasse is used mixed with waste, such as organic fractions of household waste, or peat, for the production of biogas. For the applications FR 3,953,857, FR 2,608,170 and US 2002/155583 and for the article by Fadel et al., (2014), it is a question of selecting optimized yeast strains capable of growing on toxic media. , including the vinasse, or to set up processes for the recovery and recycling of vinasses for the production of ethanol.
Certains ont également étudié l’utilisation de la vinasse pour la production d’une biomasse de champignons filamenteux pour l’alimentation des poissons (Nair R & al., 2016).  Some have also studied the use of vinasse for the production of filamentous fungi biomass for fish feed (Nair R & al., 2016).
Aujourd’hui, les vinasses sont épandues comme engrais dans les champs voisins des sucreries pour éviter des transports trop onéreux. Elle est également employée comme matière première pour être transformée dans des procédés complexes de fabrication d’engrais (WO 2017/132742 ; CN 106398962). La vinasse est séchée pour ne conserver que la matière sèche, selon des procédés plus ou moins complexes pour la production de biogaz (EP 0 057 152). D’autres proposent leur utilisation pour une transformation chimique avec des catalyseurs pour préparer de l’acide méthacrylique. Today, the vinasses are spread as fertilizer in the neighboring fields of sugar factories to avoid overly expensive transport. It is also used as a feedstock for processing in complex fertilizer manufacturing processes (WO 2017/132742, CN 106398962). The vinasse is dried to keep only the dry matter, according to more or less complex processes for the production of biogas (EP 0 057 152). Others propose their use for a chemical transformation with catalysts for preparing methacrylic acid.
On connaît des procédés de préparation d’acides organiques par fermentation anaérobie de biomasse (C. Granda 2014), en particulier de mélasses ou de pulpes en milieux aqueux (Cavalcante & al., 2017 ; Raveendran & al., 2016 ; WO 2016/135396 ; WO 2016/135397 ; WO 2016/012701 ; WO 2017/013335 ; WO 2015/0536683 ; WO 2014/100424 ; WO 2010/047815).  Methods for the preparation of organic acids by anaerobic fermentation of biomass (C. Granda 2014), in particular molasses or pulps in aqueous media are known (Cavalcante et al., 2017; Raveendran & al., 2016; WO 2016 / WO 2016/013701; WO 2017/013335; WO 2015/0536683; WO 2014/100424; WO 2010/047815).
Les inventeurs ont maintenant compris que l’utilisation de vinasse comme milieu de culture pour la fermentation anaérobie de mélasse et/ou de pulpe dans un procédé de production d’acides organiques permettait d’améliorer le rendement en acides, en plus de l’amélioration du rendement économique de valorisation de l’industrie sucrière quand la mélasse de betterave ou de canne à sucre, et les pulpes et vinasses employées dans le procédé sont toutes des résidus de l’industrie sucrière.  The inventors have now understood that the use of vinasse as a culture medium for the anaerobic digestion of molasses and / or pulp in a process for the production of organic acids makes it possible to improve the acid yield, in addition to the improvement the economic recovery of the sugar industry when the molasses of sugar beet or cane, and the pulp and vinasse used in the process are all residues of the sugar industry.
EXPOSE DE L'INVENTION  SUMMARY OF THE INVENTION
La présente invention concerne l’utilisation de vinasse seule ou en mélange avec de l’eau comme milieu de culture pour la fermentation anaérobie de mélasse et/ou de pulpe dans un procédé de production de molécules organiques, en particulier d’acides organiques de préférence d’acides organiques gras.  The present invention relates to the use of vinasse alone or as a mixture with water as a culture medium for the anaerobic fermentation of molasses and / or pulp in a process for the production of organic molecules, in particular preferably organic acids. of fatty organic acids.
L’invention concerne aussi un procédé de préparation de molécules organiques choisies parmi les acides organiques, les dérivés d’acides organiques et les acides aminés comprenant les étapes a) de fermentation anaérobie de mélasse et/ou de pulpe en milieu de fermentation aqueux, b) de récupération d’un jus de fermentation à partir du moût de fermentation et c) d’isolation des molécules organiques à partir du jus de fermentation, dans lequel le milieu de fermentation aqueux comprend de la vinasse.  The invention also relates to a method for preparing organic molecules chosen from organic acids, organic acid derivatives and amino acids comprising the steps a) of anaerobic fermentation of molasses and / or pulp in aqueous fermentation medium, b ) recovering a fermentation juice from the fermentation must and c) isolating the organic molecules from the fermentation juice, wherein the aqueous fermentation medium comprises vinasse.
De manière avantageuse et préférée, le procédé de fermentation a pour objet de produire des acides organiques, plus particulièrement des acides organiques gras, comme les acides acétique, butyrique, isobutyrique, propionique, valérique, isovalérique, hexanoïque, heptanoïque et octanoïque et leurs mélanges.  Advantageously and preferably, the purpose of the fermentation process is to produce organic acids, more particularly fatty organic acids, such as acetic, butyric, isobutyric, propionic, valeric, isovaleric, hexanoic, heptanoic and octanoic acids, and mixtures thereof.
DESCRIPTION DETAILLEE DE L'INVENTION  DETAILED DESCRIPTION OF THE INVENTION
L’invention concerne une amélioration des procédés de fermentation anaérobie de mélasse et/ou de pulpe dans un procédé de production de molécules organiques telles que des acides organiques, en particuliers d’acides organiques gras, des dérivés de ces acides organiques comme des polyhydroxyalkanoates ou des esters, ou encore des acides aminés, par l’emploi de vinasse, seule ou en mélange avec de l’eau comme milieu de fermentation aqueux pour l’étape de fermentation anaérobie.  The invention relates to an improvement of anaerobic molasses and / or pulp fermentation processes in a process for producing organic molecules such as organic acids, in particular fatty organic acids, derivatives of these organic acids such as polyhydroxyalkanoates or esters, or amino acids, by the use of vinasse, alone or in admixture with water as an aqueous fermentation medium for the anaerobic fermentation step.
De manière avantageuse et préférée, le procédé de fermentation a pour objet de produire des acides organiques, plus particulièrement des acides organiques gras, comme les acides acétique, butyrique, propionique, isobutyrique, valérique, isovalérique, hexanoïque, heptanoïque et octanoïque et leurs mélanges. Advantageously and preferably, the purpose of the fermentation process is to produce organic acids, more particularly fatty organic acids, such as acetic, butyric, propionic, isobutyric, valeric and isovaleric acids. hexanoic, heptanoic and octanoic and their mixtures.
La vinasse est un résidu de distillation alcoolique qui comprend de l’eau et des résidus solides, mélange complexe de résidus organiques et inorganiques. Sa composition et notamment sa teneur en matières sèches dépendra de son origine, qu’il s’agisse d’un résidu de distillation de vin, comme sous-produit de la production de cognac, par exemple, ou d’un résidu de distillation de produit de fermentation solide, pour la préparation de spiritueux comme le rhum, le marc de raisin, la vodka, le whisky, ou encore les résidus de l’industrie sucrière employés pour la production d’éthanol industriel. Dans ce cas, la vinasse résidu de l’industrie sucrière provient tant de la transformation de la canne à sucre que de la betterave à sucre. Selon un mode préféré de réalisation de l’invention, la vinasse employée est un résidu de l’industrie sucrière.  Vinasse is an alcoholic distillation residue that includes water and solid residues, a complex mixture of organic and inorganic residues. Its composition and in particular its dry matter content will depend on its origin, be it a residue of wine distillation, as a by-product of the production of cognac, for example, or a distillation residue of solid fermentation product, for the preparation of spirits such as rum, grape marc, vodka, whiskey, or residues of the sugar industry used for the production of industrial ethanol. In this case, the vinasse residue of the sugar industry comes from both sugarcane processing and sugar beet processing. According to a preferred embodiment of the invention, the vinasse employed is a residue of the sugar industry.
Ces vinasses peuvent se présenter sous plusieurs formes selon leur concentration en matière sèche, connues sous les noms de vinasse légère, pré-concentrée ou concentrée. Le procédé selon l’invention peut être mis en oeuvre indifféremment avec ces différents types de vinasses. De manière générale, selon le mode d’obtention la teneur en matière sèche des vinasses non concentrées et concentrées est respectivement comprise entre 1 et 15% et entre 15 et 65%.  These vinasses can be presented in several forms depending on their concentration in dry matter, known as light, pre-concentrated or concentrated vinasse. The method according to the invention can be used indifferently with these different types of vinasse. In general, depending on the method of obtaining the dry matter content of unconcentrated and concentrated vinasse is respectively between 1 and 15% and between 15 and 65%.
La vinasse peut être employée seule ou en mélange avec de l’eau comme milieu de fermentation aqueux. Le rapport volumique eau/vinasse est compris entre 0/100 et 5/95 avantageusement compris entre 90/10 et 30/70.  Vinasse can be used alone or mixed with water as an aqueous fermentation medium. The volume ratio water / vinasse is between 0/100 and 5/95 advantageously between 90/10 and 30/70.
L’homme du métier saura déterminer un rapport eau/vinasse adapté au procédé de fermentation, notamment en fonction de la teneur en matière sèche de la vinasse. De manière avantageuse, la teneur en matière sèche provenant de la vinasse dans le milieu de fermentation aqueux sera comprise entre 3% et 70% et plus préférentiellement entre 15 et 60%.  Those skilled in the art will be able to determine a water / vinasse ratio suitable for the fermentation process, in particular as a function of the dry matter content of the vinasse. Advantageously, the dry matter content from the vinasse in the aqueous fermentation medium will be between 3% and 70% and more preferably between 15 and 60%.
Selon un mode préféré de réalisation de l’invention, la vinasse employée dans le milieu aqueux de fermentation est un résidu de l’industrie sucrière de transformation de la betterave à sucre et le rapport volumique eau/vinasse est compris entre 90/10 et 30/70.  According to a preferred embodiment of the invention, the vinasse employed in the aqueous fermentation medium is a residue of the sugar processing sugar beet industry and the water / vinasse volume ratio is between 90/10 and 30. / 70.
Selon un mode particulier de réalisation de l’invention, le milieu aqueux de fermentation consiste en de l’eau et de la vinasse, selon les proportions décrites précédemment. Ce milieu de fermentation peut être complémenté avec des vitamines, de l’extrait de levure, des tampons, ou tout autre adjuvant permettant une optimisation des performances de fermentation.  According to a particular embodiment of the invention, the aqueous fermentation medium consists of water and vinasse, according to the proportions described above. This fermentation medium can be supplemented with vitamins, yeast extract, buffers, or any other adjuvant for optimizing fermentation performance.
L’homme du métier connaît bien les procédés de préparation de molécules organiques par fermentation anaérobie de mélasse et ou de pulpe, comprenant en particulier les étapes a) de fermentation anaérobie de mélasse et/ou de pulpe en milieu de fermentation aqueux, b) de récupération d’un jus de fermentation à partir du moût de fermentation et c) d’isolation des molécules organiques à partir du jus de fermentation. Ces procédés et les conditions de mise en oeuvre des différentes étapes sont en particulier décrits dans les demandes de brevet WO 2016/135396, WO 2016/135397, WO 2016/012701 , WO 2017/013335, WO 2015/0536683, WO 2014/100424 et WO 2010/047815. Those skilled in the art are well acquainted with the processes for preparing organic molecules by anaerobic fermentation of molasses and or pulp, comprising in particular the steps a) of anaerobic fermentation of molasses and / or pulp in an aqueous fermentation medium, b) recovery of a fermentation juice from the fermentation must and c) insulation organic molecules from the fermentation juice. These methods and the conditions for carrying out the various steps are described in particular in patent applications WO 2016/135396, WO 2016/135397, WO 2016/012701, WO 2017/013335, WO 2015/0536683, WO 2014/100424. and WO 2010/047815.
L’étape a) de fermentation va généralement être mise en oeuvre en mode mésophile et anaérobie dans un fermenteur agité. Le mode de culture peut être continu ou discontinu.  The fermentation step a) will generally be carried out in mesophilic and anaerobic mode in a stirred fermenter. The culture mode can be continuous or discontinuous.
La mélasse ou la pulpe employées pour la fermentation sont de préférence des résidus de l’industrie sucrière, en particulier de transformation de la canne à sucre ou de la betterave à sucre, de préférence de la pulpe de betterave à sucre ou de la mélasse de betterave à sucre ou de canne à sucre.  The molasses or pulp used for fermentation are preferably residues of the sugar industry, in particular sugar cane or sugar beet processing, preferably sugar beet pulp or sugar beet pulp. sugar beet or sugar cane.
La mélasse et la pulpe peuvent être employées ensemble dans le même fermenteur, en toutes proportions, ou séparément dans des fermenteurs différents.  The molasses and the pulp can be used together in the same fermenter, in all proportions, or separately in different fermentors.
De manière préférentielle, pulpe et/ou mélasses sont les seules sources de carbone pour la fermentation anaérobie.  Preferably, pulp and / or molasses are the only sources of carbon for anaerobic fermentation.
Selon un mode particulier de réalisation, le milieu de culture comprend  According to a particular embodiment, the culture medium comprises
5 à 50% volumique de vinasse,  5 to 50% by volume of vinasse,
10’ à 50% volumique’ de pulpe, et  10 'to 50% by volume of pulp, and
0 à 85% volumique” d’eau.  0 to 85% by volume of water.
Selon un autre mode particulier de réalisation de l’invention, le milieu de culture comprend  According to another particular embodiment of the invention, the culture medium comprises
5 à 80 % volumique de vinasse,  5 to 80% by volume of vinasse,
- 2’ à 20 % volumique’ de mélasse, et  - 2 'to 20% by volume of molasses, and
0 à 93% volumique” d’eau.  0 to 93% by volume of water.
La fermentation anaérobie est généralement mise en oeuvre avec des microorganismes seuls ou en mélanges, comprenant notamment des microorganismes cellulotytiques ou protéolytiques comme des Bacteroides et des Clostridia.  Anaerobic fermentation is generally carried out with microorganisms alone or in mixtures, including in particular cellulotytic or proteolytic microorganisms such as Bacteroides and Clostridia.
De préférence, la fermentation anaérobie est mise en oeuvre par l’ensemencement du milieu de culture par un inoculât qui provient de la fermentation anaérobie de mélasse et/ou de pulpe. Cet inoculât qui est un mélange de microorganismes peut être obtenu par la fermentation de petites quantités de mélasse et/ou de pulpe en conditions anaérobies, ou encore peut provenir du moût de fermentation obtenu à l’étape a) d’un procédé selon l’invention mis en oeuvre auparavant.  Preferably, the anaerobic fermentation is carried out by the seeding of the culture medium with an inoculum which comes from the anaerobic fermentation of molasses and / or pulp. This inoculum which is a mixture of microorganisms can be obtained by the fermentation of small amounts of molasses and / or pulp under anaerobic conditions, or can come from the fermentation must obtained in step a) of a process according to the invention. invention implemented previously.
Pour l’étape b), la récupération se fait en fin de fermentation selon des techniques usuelles de séparation pour éliminer les résidus solides présents dans le moût de fermentation par exemple par centrifugation, décantation centrifuge, etc.  For step b), the recovery is at the end of fermentation according to usual separation techniques to remove solid residues present in the fermentation must, for example by centrifugation, centrifugal decantation, etc.
L’étape c) d’isolation des acides organiques se fait généralement par extraction, précipitation et/ou distillation. Ces étapes sont mises en oeuvre sur le jus de fermentation, éventuellement concentré après élimination d’au moins une partie de l’eau, et le cas échéant avec l’ajout d’un solvant organique pour favoriser la partition des différents acides. On citera notamment les méthodes d’extraction décrites dans les demandes WO 2015/0536683, WO 2014/100424. D’autres méthodes d’isolation par précipitation acide des sels de potassium ou d’ammoniaque avec un acide fort et récupération des acides organiques dans les vapeurs de séchage des sels précipités avant leur séparation par distillation sont également décrites dans les demandes PCT/EP2018/083122 et US 16/205,983 déposées le 30/11/2018, dont le contenu est incorporé ici par référence. L’homme du métier connaît et saura choisir les moyens les mieux adaptés aux molécules organiques à isoler, cette étape n’étant pas limitante au regard de l’invention qui concerne d’abord l’étape a) de fermentation. Step c) of isolation of organic acids is generally by extraction, precipitation and / or distillation. These steps are carried out on the fermentation juice, optionally concentrated after removal of at least a portion of the water, and optionally with the addition of an organic solvent to promote partitioning of different acids. In particular, the extraction methods described in applications WO 2015/0536683, WO 2014/100424. Other methods of acid precipitation isolation of potassium or ammonia salts with a strong acid and recovery of organic acids in the drying vapors of the precipitated salts prior to their separation by distillation are also described in PCT / EP2018 / 083122 and US 16 / 205,983 filed on 11/30/2018, the contents of which are incorporated herein by reference. Those skilled in the art know and will be able to choose the most suitable means for the organic molecules to be isolated, this step not being limiting with regard to the invention which concerns first the fermentation step a).
Les dérivés d’acides organiques et les acides aminés peuvent être obtenus par transformation chimique et/ou enzymatique des acides organiques préalablement isolés, selon des méthodes usuelles connues de l’homme du métier.  The organic acid derivatives and the amino acids can be obtained by chemical and / or enzymatic transformation of the previously isolated organic acids, according to usual methods known to those skilled in the art.
Le jus de fermentation peut provenir d’un seul moût de fermentation ou peut être un mélange de plusieurs jus de fermentation provenant de plusieurs moûts de fermentation, le cas échéant après concentration. Dans ce cas, chaque moût de fermentation peut provenir indépendamment de la fermentation de pulpe ou de mélasse ou d’un mélange de pulpe et de mélasse.  The fermentation juice can come from a single fermentation must or can be a mixture of several fermentation juices from several fermentation musts, if necessary after concentration. In this case, each fermentation must can come independently of the fermentation of pulp or molasses or a mixture of pulp and molasses.
L’emploi de vinasse seule ou avec de l’eau comme milieu de fermentation aqueux ne vient pas modifier de manière substantielle ces conditions de mise en oeuvre des différentes étapes. En tout état de cause, l’homme du métier saura les adapter à la vue de ses connaissances générales sur ces procédés.  The use of vinasse alone or with water as aqueous fermentation medium does not substantially modify these conditions of implementation of the different steps. In any case, those skilled in the art will be able to adapt them to the view of their general knowledge of these processes.
Selon un mode préféré de réalisation de l’invention, la mélasse, la pulpe et la vinasse, sont des résidus de l’industrie sucrière de transformation d’une même matière première, en particulier de canne à sucre ou de betterave à sucre. Plus préférentiellement, la mélasse et la pulpe sont de la mélasse de betterave à sucre et de la pulpe de betterave à sucre et la vinasse est un résidu de l’industrie sucrière de transformation de la betterave à sucre, également appelée « vinasse de betterave à sucre ».  According to a preferred embodiment of the invention, molasses, pulp and vinasse are residues of the sugar processing industry of the same raw material, in particular sugar cane or sugar beet. More preferably, molasses and pulp are sugar beet molasses and sugar beet pulp, and vinasse is a residue of the sugar beet processing industry, also known as sugar beet vinasse. sugar ".
Selon un mode préféré de réalisation de l’invention, pulpe, mélasse et vinasse proviennent de la même raffinerie de production de sucre par transformation de canne à sucre ou de betterave à sucre, en particulier de betterave à sucre.  According to a preferred embodiment of the invention, pulp, molasses and vinasse come from the same refinery producing sugar by transformation of sugar cane or sugar beet, in particular sugar beet.
EXEMPLES EXAMPLES
Exemple 1 : Production d’Acides par Fermentation de Mélasses de Betteraves Example 1 Production of Acids by Fermentation of Beet Molasses
Dans deux fermenteurs industriels (noté fermenteur n°1 et fermenteur n°2) on procède à la fermentation anaérobie mésophile de coproduits organiques dérivés de l’industrie sucrière : des mélasses de betteraves à sucre. Ces moûts de fermentation dont le pH est régulé à la potasse sont additionnés de vinasses de sucreries à une teneur en matière sèche de 7,6% et représentant 6% du volume final pour le fermenteur n°1 , et 12% du volume final pour le fermenteur n°2. Au bout de 144 heures de culture on analyse les jus de fermentation et on déduit un rendement de fermentation en acides organiques (acétique, propionique, isobutyrique, butyrique, isovalérique, valérique et caproïque) de 38% pour le fermenteur n°1 , et de 45% pour le fermenteur n°2. En parallèle, on réalise exactement la même fermentation dans un troisième fermenteur industriel mais il n’y a pas d’ajout de vinasse au milieu de fermentation. Dans ce cas, en fin de fermentation dans le même temps imparti, on observe cette fois un rendement de fermentation en acides organiques de 34%. In two industrial fermenters (denoted fermenter # 1 and fermenter # 2) the mesophilic anaerobic fermentation of organic co-products derived from the industry is carried out. sugar: molasses of sugar beet. These fermentation mashes whose pH is regulated with potash are added vinasse of sweets with a dry matter content of 7.6% and representing 6% of the final volume for the fermenter n ° 1, and 12% of the final volume for the fermenter n ° 2. After 144 hours of culture, the fermentation juices are analyzed and a fermentation yield of organic acids (acetic, propionic, isobutyric, butyric, isovaleric, valeric and caproic) is deduced from 38% for the fermenter No. 1, and 45% for the fermenter n ° 2. In parallel, the same fermentation is carried out in a third industrial fermenter but there is no addition of vinasse to the fermentation medium. In this case, at the end of fermentation at the same time, this time a fermentation yield of organic acids of 34% is observed.
Exemple 2 : Production d’Acides par Fermentation de Pulpes de Betteraves  Example 2 Acid Production by Fermentation of Beet Pulps
On réalise dans ce second exemple, le même mode opératoire que pour la fermentation de l’exemple 1 mais le substrat utilisé est ici constitué de pulpes de betteraves à sucre. En fin de fermentation on analyse les jus de fermentation et on déduit un rendement de fermentation en acides organiques (acétique, propionique, isobutyrique, butyrique, isovalérique, valérique et caproïque) de 31 % pour le fermenteur n°1 et 37% pour le fermenteur n°2. En parallèle, on réalise exactement la même fermentation dans un troisième fermenteur industriel mais il n’y a pas d’ajout de vinasse au milieu de fermentation. Dans ce cas, en fin de fermentation dans le même temps imparti, on observe cette fois un rendement de fermentation en acides organiques de 28%.  In this second example, the same procedure is carried out as for the fermentation of Example 1 but the substrate used here consists of sugar beet pulps. At the end of the fermentation the fermentation juices are analyzed and a fermentation yield of organic acids (acetic, propionic, isobutyric, butyric, isovaleric, valeric and caproic acid) is deduced from 31% for the fermenter n ° 1 and 37% for the fermenter. # 2. In parallel, the same fermentation is carried out in a third industrial fermenter but there is no addition of vinasse to the fermentation medium. In this case, at the end of fermentation at the same time, this time a fermentation yield of 28% organic acids is observed.
REFERENCES REFERENCES
- CN 106398962, EP 0 057 152, FR 1 516 540, FR 2 777 571 , WO 2010/047815, WO 2014/100424, WO 2015/0536683, WO 2016/012701, WO 2016/135396, WO  - CN 106398962, EP 0 057 152, FR 1 516 540, FR 2 777 571, WO 2010/047815, WO 2014/100424, WO 2015/0536683, WO 2016/012701, WO 2016/135396, WO
2016/135397, WO 2017/013335, WO 2017/132742  2016/135397, WO 2017/013335, WO 2017/132742
Cavalcante W. & al., Process Biochemistry, 2016, 54, 106-119  Cavalcante W. et al., Process Biochemistry, 2016, 54, 106-119
Fadel M. & al., African Journal of Biotechnology, 2014, 13 :47, 4390-4398  Fadel M. et al., African Journal of Biotechnology, 2014, 13: 47, 4390-4398
Granda C., Wordl Congress in Industrial Biotechnology and Bioprocessing,  Granda C., Wordl Congress in Industrial Biotechnology and Bioprocessing,
Philadelphia, Présentation le 14/05/2014  Philadelphia, Presentation on the 14/05/2014
Nair R. & al., Bioresource Technology, 2016, 221 , 469-476  Nair R. & al., Bioresource Technology, 2016, 221, 469-476
Raveendran & al., Renewable Energy, 2016, 98, 203-215  Raveendran & al., Renewable Energy, 2016, 98, 203-215

Claims

REVENDICATIONS
1. Procédé de production de molécules organiques choisies parmi les acides organiques, les dérivés d’acides organiques et les acides aminés comprenant les étapes a) de fermentation anaérobie de mélasse et/ou de pulpe en milieu de fermentation aqueux, b) de récupération d’un jus de fermentation à partir du moût de fermentation et c) d’isolation des molécules organiques à partir du jus de fermentation, caractérisé en ce que le milieu de fermentation aqueux comprend de la vinasse. A process for producing organic molecules selected from organic acids, organic acid derivatives and amino acids comprising the steps a) of anaerobic fermentation of molasses and / or pulp in an aqueous fermentation medium, b) recovery of a fermentation juice from the fermentation must and c) isolation of the organic molecules from the fermentation juice, characterized in that the aqueous fermentation medium comprises vinasse.
2. Procédé selon la revendication 1 , caractérisé en ce que la vinasse est un résidu de l’industrie sucrière de transformation de la canne à sucre ou de la betterave à sucre.  2. Method according to claim 1, characterized in that the vinasse is a residue of the sugar processing industry of sugar cane or sugar beet.
3. Procédé selon l’une des revendications 1 ou 2, caractérisé en ce que la mélasse, la pulpe et la vinasse sont des résidus de l’industrie sucrière de transformation de la canne à sucre ou de la betterave à sucre.  3. Method according to one of claims 1 or 2, characterized in that the molasses, pulp and vinasse are residues of the sugar processing industry of sugar cane or sugar beet.
4. Procédé selon l’une des revendications 1 à 3, caractérisé en ce que la mélasse est de la mélasse de betterave à sucre, la pulpe est de la pulpe de betterave à sucre et la vinasse est un résidu de l’industrie sucrière de transformation de la betterave à sucre.  4. Method according to one of claims 1 to 3, characterized in that the molasses is sugar beet molasses, the pulp is sugar beet pulp and vinasse is a residue of the sugar industry of sugar beet processing.
5. Procédé selon l’une des revendications 1 à 4, caractérisé en ce que le rapport volumique eau/vinasse est compris entre 0/100 et 5/95.  5. Method according to one of claims 1 to 4, characterized in that the volume ratio water / vinasse is between 0/100 and 5/95.
6. Procédé selon la revendication 5, caractérisé en ce que le rapport volumique eau/vinasse est compris entre 90/10 et 30/70  6. Method according to claim 5, characterized in that the volume ratio water / vinasse is between 90/10 and 30/70.
7. Utilisation de vinasse seule ou en mélange avec de l’eau comme milieu de culture pour la fermentation anaérobie de mélasse et/ou de pulpe dans un procédé de production de molécules organiques choisies parmi les acides organiques, les dérivés d’acides organiques et les acides aminés.  7. Use of vinasse alone or in admixture with water as a culture medium for the anaerobic digestion of molasses and / or pulp in a process for the production of organic molecules selected from organic acids, organic acid derivatives and amino acids.
8. Procédé selon l’une des revendications 1 à 6 ou utilisation selon la revendication 7, caractérisé en ce que les molécules organiques sont choisies parmi les acides organiques gras.  8. Method according to one of claims 1 to 6 or use according to claim 7, characterized in that the organic molecules are chosen from fatty organic acids.
9. Procédé ou utilisation selon la revendication 8, caractérisé en ce que les acides organiques gras sont choisis parmi les acides acétique, butyrique, isobutyrique, propionique, valérique, isovalérique, hexanoïque, heptanoïque et octanoïque et leurs mélanges.  9. Process or use according to claim 8, characterized in that the fatty organic acids are chosen from acetic, butyric, isobutyric, propionic, valeric, isovaleric, hexanoic, heptanoic and octanoic acids and mixtures thereof.
PCT/EP2018/085779 2017-12-19 2018-12-19 Vinasse as a fermentation medium WO2019121876A1 (en)

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CN110506833A (en) * 2019-09-11 2019-11-29 广西壮族自治区农业科学院 A method of Cultures of S. cerevisiae is produced using Chinese yam vinasse
CN112626136A (en) * 2021-01-15 2021-04-09 驻马店华中正大有限公司 Method for producing butyric acid by fermenting distiller's grain water

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