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WO2025087759A1 - Extraction de composés organiques - Google Patents

Extraction de composés organiques Download PDF

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Publication number
WO2025087759A1
WO2025087759A1 PCT/EP2024/079155 EP2024079155W WO2025087759A1 WO 2025087759 A1 WO2025087759 A1 WO 2025087759A1 EP 2024079155 W EP2024079155 W EP 2024079155W WO 2025087759 A1 WO2025087759 A1 WO 2025087759A1
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WO
WIPO (PCT)
Prior art keywords
medium
clostridium
extraction
aqueous medium
organic product
Prior art date
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PCT/EP2024/079155
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English (en)
Inventor
Thomas Haas
Martin DEMLER
Henrick Jens RICKMEIER
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Evonik Operations GmbH
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Evonik Operations GmbH
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Publication of WO2025087759A1 publication Critical patent/WO2025087759A1/fr
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D11/00—Solvent extraction
    • B01D11/04—Solvent extraction of solutions which are liquid
    • B01D11/0492—Applications, solvents used
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/86—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by liquid-liquid treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/48—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
    • 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

Definitions

  • the invention relates to a method for extracting organic compounds from an aqueous medium using an extraction medium.
  • W02009059228 discloses a process for recovering acetic acid from a wood extract comprising: providing an aqueous wood extract containing acetic acid and dissolved hemicellulose containing uronic acid; providing a water insoluble solvent containing an extractant for the acetic acid; contacting the wood extract with the solvent and extractant in order to extract the acetic acid from the wood extract; and recovering the acetic acid from the solvent and extractant, wherein the extractant for acetic acid may comprise trioctylphosphine oxide.
  • US4705894 discloses a process for the recovery of a carboxylic acid selected from the group consisting of citric acid, malic acid, tartaric acid and oxalic acid from fermentation broths with an extractant being a mixture of trialkyl phosphine oxides having a total of 15 to 27 carbon atoms.
  • a well-known process for preparing and extracting alkanoic acids involves the hydrolysis and decarboxylation of malonic esters.
  • the malonic ester is saponified using aqueous sodium hydroxide to result in the formation of an aqueous solution of disodium salt and ethanol.
  • the salt solution is then treated with a strong mineral acid to produce a mineral acid sodium salt and to precipitate the solid dicarboxylic acid.
  • salting-out extraction is also commonly used for extracting organic compounds such as alkanoic acids.
  • This method uses a system composed of ethanol and ammonium sulfate.
  • the system parameters influencing the extraction efficiency include tie line length, phase volume ratio, acid concentration, temperature, system pH and the like.
  • WO 2021/018717 and WO 2019/158683 teach methods of extracting aliphatic alcohols and alkanoic acids respectively using an alkane and a trialkyl-phosphine-oxide.
  • these methods though simple, are still inefficient in producing high yield. Accordingly, there is a need in the art for not only a simple extraction method but one that is versatile for extracting any targeted organic products from an aqueous medium and for one that results in a higher yield of the targeted organic product than currently possible with the methods known in the art.
  • the present invention solves the problems above by providing a means of extracting organic compounds/ products from an aqueous solution that is not only more efficient and cheaper than the current methods available in the art but also results in a higher yield of the desired organic product.
  • the present invention also provides a means of extracting the organic product that can be used in conjunction with a biotechnological method of producing the organic product.
  • a method of extracting at least one dissolved organic product from an aqueous medium into an extraction medium comprising: a) contacting the extraction medium with the aqueous medium to form a resultant mixture; and b) allowing the extraction medium and aqueous medium to settle forming no visible droplets in the resultant mixture during the extraction, wherein the extraction medium comprises at least one trialkyl-phosphine-oxide and at least one alkane and the resultant mixture is shaken at a suitable velocity to produce no visible droplets.
  • the extraction method according to any aspect of the present invention allows for an increase in yield relative to the amount of extractants used.
  • less than 50% by weight of extraction medium may be used to extract the same amount of organic products as if only pure alkanes were used. Therefore, with a small volume of extraction medium, a larger yield of organic products may be extracted.
  • the extraction medium is also not harmful to microorganisms.
  • the extraction medium according to any aspect of the present invention may be present when the organic product is biotechnologically produced. Further, the organic product may be easily separated from the extraction solvent and the extraction solvent may be recycled.
  • the two liquids, the aqueous medium with the organic product (the target product) and the extraction medium are brought into contact with one another.
  • the two liquids are allowed to rest or settle into two separate layers and maintained as such so that no droplets are formed or at least the minimum number of droplets formed as possible in the liquids.
  • the phrase ‘to settle forming almost no droplets in the resultant mixture’ according to any aspect of the present invention refers to the step or process of allowing the two liquids, which have been brought in contact with each other, to rest and come to a formation of perhaps two separate layers with the minimum number of droplets formed as possible in both liquids.
  • the two liquids, the aqueous medium and extraction medium once brought into contact with one another are given time to form their separate layers and are not mixed or stirred to reduce the number of droplets formed in the two mediums.
  • the two mediums thus have almost no droplets formed in them. Particularly, no visible droplets are seen in the two mediums. With almost no droplets present in both mediums, no emulsion is formed or present.
  • the two mediums appear not to form an emulsion or no emulsion appears to be formed.
  • the reduced formation of emulsions results in a better extraction yield of the organic product.
  • the resultant mixture is shaken at a suitable velocity, preferably not stirred, to produce no visible droplets.
  • a suitable velocity may be to produce no visible droplets in the resultant mixture.
  • extraction is carried out using droplets where constant stirring, particularly at high velocity creates droplets, in the aqueous medium, which are then used to extract the organic compounds/ products.
  • no droplets are formed and the extraction is carried out using layers which is not only more efficient than the traditional method but also simpler.
  • the extraction medium and the aqueous medium are kept separate and are not mixed up.
  • the almost no visible formation of droplets is a result of the two mediums according to any aspect of the present invention not being mixed or stirred, particularly not regularly mixed or the mediums are only minimally mixed.
  • the step of bringing the two mediums in contact with one another, where they are both mixed there may be no further step of mixing or stirring the mediums, especially not during the extraction phase.
  • the lack of regular mixing or minimal mixing results in almost no droplets or at least no visible droplets being formed. This may then result in almost no emulsion being formed.
  • extraction medium according to any aspect of the present invention is added to or brought into contact with the aqueous medium containing the organic product that is to be extracted.
  • the extraction medium may be added to an aqueous medium comprising the organic product.
  • the organic product is being produced in the aqueous medium and the extraction medium is added to the aqueous medium from the onset of production of organic product or once the concentration of organic product has reached a point where it can be extracted.
  • the extraction medium may be present as the organic product is being produced in the aqueous medium.
  • the organic product present according to any aspect of the present invention may be selected from the group consisting of nitro compounds, sulfides, sulfites, alkenes, alkynes, aromatic compounds, carboxylic acids, dicarboxylic acids, hydroxycarboxylic acids, carboxylic acid esters, hydroxycarboxylic acid esters, alcohols, aldehydes, ketones, amines and amino acids.
  • the organic product may be a substituted or unsubstituted compound.
  • the organic product may be at least one alkanoic acid. More in particular, the organic product comprises at least hexanoic acid.
  • the organic product may be already present in the aqueous medium prior to the extraction step (a).
  • the organic product is produced in the aqueous solution during step (a). That is to say, the extraction solvent is added to the aqueous medium where the organic product is being produced.
  • the method according to any aspect of the present invention may be a method of extracting at least one isolated dissolved organic product from an aqueous medium.
  • An isolated organic product may refer to at least one organic product that may be separated from the medium where the organic product has been produced.
  • the alkanoic acid and/or ester thereof may be produced in an aqueous medium (e.g. fermentation medium where the organic product is produced by specific cells from a carbon source).
  • the isolated organic product may refer to the organic product extracted from the aqueous medium.
  • the extracting step allows for the separation of excess water from the aqueous medium thus resulting in a formation of a mixture containing the extracted organic product.
  • the extracting medium may also be referred to as the ‘extraction medium’ or ‘organic solvent’.
  • the extraction medium may be used for extracting/ isolating the organic product produced according to any method of the present invention from the aqueous medium wherein the organic product was originally produced. At the end of the extracted step, excess water from the aqueous medium may be removed thus resulting in the extraction medium containing the extracted organic product thereof.
  • the extraction medium may comprise a combination of compounds that may result in an efficient means of extracting the organic compound from the aqueous medium.
  • the extraction medium may comprise: (i) at least alkane comprising at least 12 carbon atoms, and (ii) at least one molecule trialkyl-phosphine oxide (TAPO).
  • the organic solvent according to any aspect of the present invention may efficiently extract the organic compound into the alkane- alkyl-phosphine oxide extracting medium.
  • This organic solvent of a mixture of alkyl-phosphine oxides and at least one alkane may be considered suitable in the method according to any aspect of the present invention as the mixture works efficiently in extracting the desired organic product in the presence of a fermentation medium.
  • the mixture of alkyl-phosphine oxides and at least one alkane may be considered to work better than any method currently known in the art for extraction of organic products as it does not require any special equipment to be carried out and it is relatively easy to perform with a high product yield.
  • the alkyl-phosphine oxide also known as a tri-alkyl-phosphine oxide (TAPO) used in the method according to any aspect of the present invention is selected from an alkyl-phosphine oxide of general formula 1 general formula 1 with R 1 , R 2 and R 3 selected from alkyl radicals, preferably linear alkyl radicals, containing 4 to 18, preferably 6 to 12, carbon atoms, with the proviso, that at least two of R 1 , R 2 and R 3 differ from each other.
  • TAPO tri-alkyl-phosphine oxide
  • the alkyl-phosphine oxide is selected from an alkyl-phosphine oxide of general formula 1 with R 1 , R 2 and R 3 selected from alkyl radicals, preferably linear alkyl radicals, containing 8 to 10, particularly 8 or 10, carbon atoms, more particularly with the proviso, that referring to all alkyl-phosphine oxide of general formula 1 contained in the extracting medium, the molar ratio of all alkyl radicals containing 8 and 10 carbon atoms is in the range of from 1.0:2.0 to 2.0:1.0, particularly from 1.0:1.5 to 1 .5:1 .0, even more particularly from 1 .0:1 .2 to 1 .2:1 .0.
  • the alkyl-phosphine oxide in the extracting medium in the method according to any aspect of the present invention is an alkyl- phosphine oxide of general formula 1 general formula 1 with R 1 , R 2 and R 3 selected from linear alkyl radicals with 6 to 12, carbon atoms and wherein one alkyl radical has 8 carbon atoms and the other 10 carbon atoms, with the proviso, that at least two of R 1 , R 2 and R 3 differ from each other.
  • the alkyl-phosphine oxide accounts for at least 50 wt.-%, particularly at least 80 wt.-%, even more particularly at least 90 wt.-%, the most particularly at least 97 wt.-%, of the total extracting medium.
  • the extracting medium according to any aspect of the present invention may further comprise other than the alkyl-phosphine oxide, a second organic component.
  • the second organic component contains at least 12 carbons.
  • the alkane may comprise at 12- 18 carbon atoms.
  • the second organic component is an alkane linear or branched that may be selected from the group consisting, tetradecane, pentadecane, hexadecane, heptadecane, octadecane and squalene or mixtures of alkanes such as white mineral oil (Fragoltherm-Q-32-N).
  • the second organic component may comprise of an aromatic hydrocarbon that may be selected from the group consisting, diisopropylbiphenyl, partly hydrogenated terphenyl, dibenzyltoluol and diisopropylnaphthalene or a mix of aromatic solvents such as Solvesso 200.
  • aromatic hydrocarbon that may be selected from the group consisting, diisopropylbiphenyl, partly hydrogenated terphenyl, dibenzyltoluol and diisopropylnaphthalene or a mix of aromatic solvents such as Solvesso 200.
  • an alcohol may be selected from the group consisting, oleyl alcohol, 2-octyldodecanol and 2-hexyldodecanol as the second organic component.
  • the weight ratio of the alkyl-phosphine oxide to alkane in the extracting medium preferably is between 1 :100 to 100:1. Even more in particular, the weight ratio of the alkyl-phosphine oxide to alkane may be selected within the range of from 1 :2 to 50:1 , more preferably from 1 :1 to 97:3. In the example, the alkane may be hexadecane and therefore the weight ratio of the alkyl-phosphine oxide to hexadecane may be about 97:3.
  • the extracting medium according to any aspect of the present invention may efficiently extract the organic product into the extracting medium.
  • This extracting medium of a mixture of at least one alkyl- phosphine oxide containing at least two different alkyl radicals per alkyl-phosphine oxide molecule, and at least one alkane may be considered suitable in the method according to any aspect of the present invention as the mixture works efficiently in extracting the desired organic product in the presence of the aqueous medium or aqueous production medium.
  • the alkane may be a straight or a branched alkane. In one example, the alkane may be a branched alkane and the branched alkane may be squalene.
  • the extracting medium of a mixture of at least one alkyl-phosphine oxide containing at least two different alkyl radicals per alkyl-phosphine oxide molecule and at least one partially hydrogenated aromatic hydrocarbon may be considered suitable in the method according to any aspect of the present invention as the mixture works efficiently in extracting the desired organic product in the presence of the aqueous production medium.
  • the mixture of at least one alkyl-phosphine oxide containing at least two different alkyl radicals per alkyl-phosphine oxide molecule and at least one partially hydrogenated aromatic hydrocarbon may be considered to work better than any method currently known in the art for extraction organic product as it does not require any special equipment to be carried out and it is relatively easy to perform with a high product yield.
  • the extracting medium according to any aspect of the present invention in combination with alkane or partially hydrogenated aromatic solvent is also not toxic for microorganisms.
  • contacting means bringing about direct contact between the aqueous medium and the extraction medium according to any aspect of the present invention.
  • the aqueous medium and the extraction medium may be in different compartments and brought together in a single compartment.
  • step (b) according to any aspect of the present invention, the extraction medium and aqueous medium are allowed to settle forming almost no droplets in the resultant mixture during the extraction.
  • the aqueous medium and the extraction medium are left to stand for a time sufficient to form no droplets and to extract the organic product from the aqueous medium into the organic medium.
  • a skilled person may be capable of determining the amount of time needed to reach distribution equilibrium and the right bubble agglomeration that may be needed to optimize the extraction process.
  • the time needed may be dependent on the amount of organic product that may be extracted.
  • the time needed to extract the organic product from the aqueous medium into the extraction medium may only take a few minutes.
  • the time for extraction is equivalent to the time of fermentation.
  • the ratio of the extraction medium used to the amount of organic product to be extracted may vary depending on how quick the extraction is to be carried out.
  • the amount of extraction medium is equal to the amount of aqueous medium comprising the organic product.
  • the two phases are separated using any means known in the art.
  • the two phases may be separated using a separation funnel or simple decantation.
  • the separation of the organic solvent from the organic product may be carried out using distillation in view of the fact that some organic products distill at a significantly lower boiling point than the extracting medium.
  • a skilled person may be able to select the best method of separating the extraction medium from the desired organic product depending on the characteristics of the organic product desired to be extracted.
  • Step (b) preferably ends with the extraction medium made available again to be recycled or reused.
  • the aqueous medium is at least one fermentation medium comprising at least one microorganism.
  • the microorganisms capable of producing the organic product may be cultivated with any culture media, substrates, conditions, and processes generally known in the art for culturing bacteria. This allows for the organic product to be produced using a biotechnological method.
  • appropriate growth medium, pH, temperature, agitation rate, inoculum level, and/or aerobic, microaerobic, or anaerobic conditions are varied.
  • the conditions in the container e.g.
  • the method according to any aspect of the present invention may be carried out in an aqueous medium with a pH between 5 and 8, or 5.5 and 7.
  • the pressure may be between 1 and 10 bar.
  • the microorganisms may be cultured at a temperature ranging from about 20° C to about 80° C. In one example, the microorganism may be cultured at 37° C.
  • the aqueous medium may comprise any nutrients, ingredients, and/or supplements suitable for growing the microorganism or for promoting the production of the organic product.
  • the aqueous medium may comprise at least one of the following: carbon sources, nitrogen sources, such as an ammonium salt, yeast extract, or peptone; minerals; salts; cofactors; buffering agents; vitamins; and any other components and/or extracts that may promote the growth of the bacteria.
  • the culture medium to be used must be suitable for the requirements of the particular strains.
  • the method of extraction of the organic product according to any aspect of the present invention may be used together with any biotechnological method of producing the organic product.
  • This is especially advantageous as usually during the fermentation process to produce organic product using biological methods, the organic product would be left to collect in the aqueous medium and after reaching certain concentrations in the fermentation medium, the very target product (organic product) may inhibit the activity and productivity of the microorganism. This thus limits the overall yield of the fermentation process.
  • the alkanoic acids and/or ester thereof are extracted as they are produced thus reducing end-product inhibition drastically.
  • the method according to any aspect of the present invention is also more efficient and cost effective than the traditional methods of removing organic products, particularly from a fermentation method as they are produced, as there is no primary reliance on distillation and/or a precipitation for recovering of the organic products. Distillation or precipitation process may lead to higher manufacturing costs, lower yield, and higher waste products therefore reducing the overall efficiency of the process.
  • the method according to any aspect of the present invention attempts to overcome these shortcomings.
  • the number of droplets in the resultant mixture is almost not visible.
  • the number of droplets is about 0.1 %, 0.05, 0.15, 0.2, 0.25, or 0.3 of the total volume of medium. Even more in particular, the number of droplets is about 0.1% of the total volume of medium.
  • Any method known in the art may be used to measure the number of droplets in the medium. More in particular, the method used to measure the number of droplets may be the naked eye or a microscope and manual counting.
  • the microorganism according to any aspect of the present invention is at least one acetogenic bacteria or at least one microorganism for carbon chain elongation or a combination thereof.
  • the cells are brought into contact with a carbon source which includes monosaccharides (such as glucose, galactose, fructose, xylose, arabinose, or xylulose), disaccharides (such as lactose or sucrose), oligosaccharides, and polysaccharides (such as starch or cellulose), one-carbon substrates and/or mixtures thereof. More in particular, the cells are brought into contact with a carbon source comprising CO and/or CO2 to produce an organic product. With respect to the source of substrates comprising carbon dioxide and/or carbon monoxide, a skilled person would understand that many possible sources for the provision of CO and/or CO2 as a carbon source exist.
  • monosaccharides such as glucose, galactose, fructose, xylose, arabinose, or xylulose
  • disaccharides such as lactose or sucrose
  • oligosaccharides such as starch or cellulose
  • polysaccharides such
  • the carbon source of the present invention any gas or any gas mixture can be used which is able to supply the microorganisms with sufficient amounts of carbon, so that acetate and/or ethanol, may be formed from the source of CO and/or CO2.
  • the microorganism may use synthesis gas, CO2, CO, combinations thereof or any other carbon source as a substrate for the organic product production.
  • acetogenic bacteria refers to a microorganism which is able to perform the Wood-Ljungdahl pathway and thus is able to convert CO, CO2 and/or hydrogen to acetate.
  • These microorganisms include microorganisms which in their wild-type form do not have a WoodLjungdahl pathway, but have acquired this trait as a result of genetic modification.
  • Such microorganisms include but are not limited to E. coli cells. These microorganisms may be also known as carboxydotrophic bacteria.
  • acetogenic bacteria 21 different genera of the acetogenic bacteria are known in the art (Drake et al., 2006), and these may also include some Clostridia (Drake & Kusel, 2005). These bacteria are able to use carbon dioxide or carbon monoxide as a carbon source with hydrogen as an energy source (Wood, 1991). Further, alcohols, aldehydes, carboxylic acids as well as numerous hexoses may also be used as a carbon source (Drake et al., 2004). The reductive pathway that leads to the formation of acetate is referred to as acetyl-CoA or Wood-Ljungdahl pathway.
  • the acetogenic bacteria may be selected from the group consisting of Acetoanaerobium notera (ATCC 35199), Acetonema longum (DSM 6540), Acetobacterium carbinolicum (DSM 2925), Acetobacterium malicum (DSM 4132), Acetobacterium species no. 446 (Morinaga et al., 1990, J. Biotechnol., Vol. 14, p.
  • DSM 521 formerly Clostridium thermoaceticum
  • DSM 1974 Oxobacter pfennigii
  • DM 13326 Sporomusa ovata
  • DM 2662 Sporomusa silvacetica
  • DSM 2875 Sporomusa termitida
  • DSM 4440 Thermoanaerobacter kivui
  • the strain ATCC BAA-624 of Clostridium carboxidivorans may be used. Even more in particular, the bacterial strain labelled "P7" and "P11" of Clostridium carboxidivorans as described for example in U.S. 2007/0275447 and U.S. 2008/0057554 may be used. Another particularly suitable bacterium may be Clostridium ljungdahlii.
  • strains selected from the group consisting of Clostridium ljungdahlii PETC, Clostridium ljungdahlii ERI2, Clostridium ljungdahlii COL and Clostridium ljungdahlii 0-52 may be used in the conversion of synthesis gas to the organic product. These strains for example are described in WO 98/00558, WO 00/68407, ATCC 49587, ATCC 55988 and ATCC 55989.
  • the chain elongating bacteria may be selected from the group consisting of Clostridium kluyveri (DSM 555), C.carboxidivorans (DSM 15243), Megasphaera cerevisiae (ATCC 43254; DSM 20462), Pseudoram ibacter alactolyticus (ATCC 23263; DSM 3980;), Eubacterium pyruvativorans (ATCC BAA- 574), Acinetobacter sp.
  • the chain elongating bacteria may be selected from the group consisting of Clostridium kluyveri (DSM 555), and C.carboxidivorans (DSM 15243).
  • the overall efficiency, alkanoic acid and/or ester thereof productivity and/or overall carbon capture of the method of the present invention may be dependent on the stoichiometry of the CO2, CO, and H2 in the continuous gas flow.
  • the continuous gas flows applied may be of composition CO2 and H2.
  • concentration range of CO2 may be about 10-50 %, in particular 33 % by volume and H2 would be within 44 % to 84 %, in particular, 64 to 66.04 % by volume.
  • the continuous gas flow can also comprise inert gases like N2, up to a N2 concentration of 50 % by volume.
  • Mixtures of sources can be used as a carbon source.
  • a reducing agent for example hydrogen may be supplied together with the carbon source.
  • this hydrogen may be supplied when the C and/or CO2 is supplied and/or used.
  • the hydrogen gas is part of the synthesis gas present according to any aspect of the present invention.
  • additional hydrogen gas may be supplied.
  • a carbon source comprising CO and/or CO2 contacts the cells in a continuous gas flow.
  • the continuous gas flow comprises synthesis gas.
  • composition and flow rates of the streams may be necessary to monitor the composition and flow rates of the streams at relevant intervals.
  • Control of the composition of the stream can be achieved by varying the proportions of the constituent streams to achieve a target or desirable composition.
  • the composition and flow rate of the blended stream can be monitored by any means known in the art.
  • the system is adapted to continuously monitor the flow rates and compositions of at least two streams and combine them to produce a single blended substrate stream in a continuous gas flow of optimal composition, and means for passing the optimised substrate stream to the fermenter.
  • an aqueous solution or “medium” comprises any solution comprising water, mainly water as solvent that may be used to keep the cell according to any aspect of the present invention, at least temporarily, in a metabolically active and/or viable state and comprises, if such is necessary, any additional substrates.
  • the person skilled in the art is familiar with the preparation of numerous aqueous mediums, usually referred to as media that may be used to keep and/or culture the cells, for example LB medium in the case of E.coli, ATCC1754-Medium may be used in the case of C.ljungdahlii. It is advantageous to use as an aqueous solution a minimal medium, i.e.
  • M9 medium may be used as a minimal medium.
  • the cells are incubated with the carbon source sufficiently long enough to produce the desired product. For example for at least 1 , 2, 4, 5, 10 or 20 hours.
  • the temperature chosen must be such that the cells according to any aspect of the present invention remains catalytically competent and/or metabolically active, for example 10 to 42 °C, preferably 30 to 40 °C, in particular, 32 to 38 °C in case the cell is a C.ljungdahlii cell.
  • the aqueous medium according to any aspect of the present invention also includes the medium in which the organic product is produced. It mainly refers to a medium where the solution comprises substantially water.
  • the aqueous medium in which the cells are used to produce the organic product is the very medium which contacts the extraction medium for extraction of the organic product.
  • the mixture of the microorganism and the carbon source according to any aspect of the present invention may be employed in any known bioreactor or fermenter to carry out any aspect of the present invention.
  • the complete method according to any aspect of the present invention that begins with the production of the organic product and ends with the extraction of the organic product takes place in a single container. There may therefore be no separation step between the step of producing the organic product and the step of extracting the organic product. This saves time and costs.
  • the microorganism may be grown in the aqueous medium and in the presence of the extraction medium. The method according to any aspect of the present invention thus provides for a one pot means of producing the organic product.
  • a further step of separation may be carried out to remove the organic product. Any separation method known in the art such as using a funnel, column, distillation and the like may be used. The remaining extraction medium and/or the cells may then be recycled.
  • the extraction process may take place as a separate step and/or in another pot.
  • the extracting medium according to any aspect of the present invention may be added to the fermentation medium or the fermentation medium may be added to a pot comprising the extracting medium.
  • the desired the organic product may then be extracted by any separation method known in the art such as using a funnel, column, distillation and the like.
  • the remaining extracting medium may then be recycled.
  • Another advantage of the method is that the extracting medium may be recycled. Therefore, once the organic product is separated from extraction medium, the extraction medium can be recycled and reused, reducing waste.
  • an extraction medium comprising at least one trialkyl-phosphine-oxide and at least one alkane for extracting at least one liquid organic product from an aqueous medium into an extraction medium, wherein the extraction medium forms no visible droplets when in contact with the aqueous medium.
  • the liquid organic product is hexanoic acid.
  • the homoacetogenic bacterium Clostridium autoethanogenum was cultivated together with the chain elongating bacterium Clostridium kluyveri in a coculture on synthesis gas in a mineral medium with potassium thioacetate as reduced sulfur source.
  • the cultivation was carried out under anaerobic conditions in a pressure-resistant stainless steel bubble column loop reactor.
  • the cultivation was run at 37°C and an overpressure of 2 bar as a continuous fermentation with continuous feeding of 300 L/h of a mixture of water, substrates, salts, trace elements and vitamins.
  • the pH was automatically hold at 5.80 with ammonia feeding.
  • the outlet stream of 300 L/h out of the fermenter was for 98,2% as permeate with cell retention and for 1 ,8% as purge without cell retention.
  • the gas was discharged into the medium through a sparger with a ventilation rate of - 1000 L/h as a gas mixture of 62,5% H2 and 37,5% CO2.
  • the media feed consisted of 0.004 g/L Mg-acetate x 4 H2O, 0.164 g/L Na-acetate, 0.016 g/L Ca-acetate, 0.245 g/l K-acetate, 0.107 mL/L H3PO4 (8.5%), 0.35 mg/L Co-acetate, 1 .245 mg/L Ni-acetate x 4 H2O, 20 pg/L d-biotin, 20 pg/L folic acid, 10 pg/L pyridoxine-HCI, 50 pg/L thiamine-HCI, 50 pg/L Riboflavin, 50 pg/L nicotinic acid, 50 pg/L Ca-pantothenate, 50 pg/L Vitamin B12, 50 pg/L p-aminobenzoate, 50 pg/L lipoic acid, 2.109 mg/L (NH4)2Fe(SO4)2 x 6 H2O
  • the culture was previously inoculated with cells from fresh cultures of C.autoethanogenum and C.kluyveri and was already running since > 32.000 h full continuously as stable coculture at an optical density (ODeoonm) of - 14.8.
  • Fresh medium was continuously feeded into the reactor and fermentation broth continuously removed from the reactor with a dilution rate of 2.8 d -1 During cultivation several 5 mL samples were taken to determinate ODeoonm, pH und product formation. The determination of the product concentrations was performed by semiquantitative 1 H-NMR spectroscopy. As an internal quantification standard sodium trimethylsilylpropionate (T(M)SP) was used.
  • the steady state concentration of the educts and products in the reactor were about 1.6 g/L ethanol, 1.6 g/L acetate, 1 .3 g/L butyrate and 3.5 g/L hexanoate.
  • the fermentation broth was filtered through a cell retention ceramic membrane to get a clear, cell free supernatant. This supernatant was used for further extraction experiments.
  • Clostridium kluyveri The bacterium Clostridium kluyveri was cultivated in a co culture with Clostridium autoethanogenum for the biotransformation of ethanol and acetate to hexanoic acid.
  • the aqueous phase was overlayed with a mixture of Fragoltherm Q-32-N with trialkylphosphineoxide (TAPO). All cultivation steps were carried out under anaerobic conditions, the preculture in a stainless steel bubble column loop reactor and the main culture in a pressure-resistant glass bottle that can be closed airtight with a butyl rubber stopper.
  • TAPO trialkylphosphineoxide
  • the homoacetogenic bacterium Clostridium autoethanogenum was cultivated together with the chain elongating bacterium Clostridium kluyveri in a coculture on synthesis gas in a mineral medium.
  • the cultivation was carried out under anaerobic conditions in a pressure-resistant stainless steel bubble column loop reactor.
  • the cultivation was run at 37°C and an overpressure of 2 bar as a continuous fermentation with continuous feeding of 300 L/h of a mixture of water, substrates, salts, trace elements and vitamins.
  • the pH was automatically hold at 5.80 with ammonia feeding.
  • the outlet stream of 300 L/h out of the fermenter was for 98,2% as permeate with cell retention and for 1 ,8% as purge without cell retention.
  • the gas was discharged into the medium through a sparger with a ventilation rate of - 1000 L/h as a gas mixture of 62,5% H2 and 37,5% CO2.
  • the media feed consisted of 0.004 g/L Mg-acetate x 4 H2O, 0.164 g/L Na-acetate, 0.016 g/L Ca-acetate, 0.245 g/l K-acetate, 0.107 mL/L H3PO4 (8.5%), 0.35 mg/L Co-acetate, 1 .245 mg/L Ni-acetate x 4 H2O, 20 pg/L d-biotin, 20 pg/L folic acid, 10 pg/L pyridoxine-HCI, 50 pg/L thiamine-HCI, 50 pg/L Riboflavin, 50 pg/L nicotinic acid, 50 pg/L Ca-pantothenate, 50 pg/L Vitamin B12, 50 pg/L p-aminobenzoate, 50 pg/L lipoic acid, 2.109 mg/L (NH4)2Fe(SO4)2 x 6 H2O
  • the culture was previously inoculated with cells from fresh cultures of C. autoethanogenum and C. kluyveri and was already running since > 30.000 h full continuously as stable coculture at an optical density (ODeoonm) of ⁇ 14.
  • Fresh medium was continuously feeded into the reactor and fermentation broth continuously removed from the reactor with a dilution rate of 2.8 d 1 .

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Abstract

La présente invention concerne un procédé d'extraction d'au moins un produit organique liquide d'un milieu aqueux dans un milieu d'extraction, le procédé comprenant : a) la mise en contact du milieu d'extraction avec le milieu aqueux pour former un mélange résultant ; et b) le dépôt du milieu d'extraction et du milieu aqueux ne formant quasiment pas de gouttelettes dans le mélange résultant pendant l'extraction, le milieu d'extraction comprenant au moins un trialkyl-phosphine-oxyde et au moins un alcane.
PCT/EP2024/079155 2023-10-26 2024-10-16 Extraction de composés organiques Pending WO2025087759A1 (fr)

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Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4705894A (en) 1984-02-29 1987-11-10 Yuanfu Su Process for recovery of organic acids from aqueous solutions
WO1998000558A1 (fr) 1994-11-30 1998-01-08 Bioengineering Resources, Inc. Production biologique d'acide acetique a partir de gaz residuaires
WO2000068407A1 (fr) 1999-05-07 2000-11-16 Bioengineering Resources, Inc. Souches de clostridium produisant de l'ethanol a partir de gaz de combustion
JP2007082490A (ja) * 2005-09-22 2007-04-05 Toyota Central Res & Dev Lab Inc 有機酸の抽出発酵による生産方法及び該生産方法に用いる有機酸生産酵母
US20070275447A1 (en) 2006-05-25 2007-11-29 Lewis Randy S Indirect or direct fermentation of biomass to fuel alcohol
US20080057554A1 (en) 2006-08-31 2008-03-06 Huhnke Raymond L Isolation and characterization of novel clostridial species
WO2009059228A2 (fr) 2007-10-31 2009-05-07 University Of Maine System Board Of Trustees Récupération de l'acide acétique d'extraits de bois
US20140106421A1 (en) * 2012-10-15 2014-04-17 Industrial Technology Research Institute Methods Of Producing Carboxylic Acids And/Or Alcohols
WO2019158683A1 (fr) 2018-02-15 2019-08-22 Evonik Degussa Gmbh Extraction d'acides alcanoïques
WO2021018717A1 (fr) 2019-07-29 2021-02-04 Evonik Operations Gmbh Procédé d'extraction d'acide carbonique, d'acides aliphatiques, d'esters et d'alcools à partir d'un milieu aqueux

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4705894A (en) 1984-02-29 1987-11-10 Yuanfu Su Process for recovery of organic acids from aqueous solutions
WO1998000558A1 (fr) 1994-11-30 1998-01-08 Bioengineering Resources, Inc. Production biologique d'acide acetique a partir de gaz residuaires
WO2000068407A1 (fr) 1999-05-07 2000-11-16 Bioengineering Resources, Inc. Souches de clostridium produisant de l'ethanol a partir de gaz de combustion
JP2007082490A (ja) * 2005-09-22 2007-04-05 Toyota Central Res & Dev Lab Inc 有機酸の抽出発酵による生産方法及び該生産方法に用いる有機酸生産酵母
US20070275447A1 (en) 2006-05-25 2007-11-29 Lewis Randy S Indirect or direct fermentation of biomass to fuel alcohol
US20080057554A1 (en) 2006-08-31 2008-03-06 Huhnke Raymond L Isolation and characterization of novel clostridial species
WO2009059228A2 (fr) 2007-10-31 2009-05-07 University Of Maine System Board Of Trustees Récupération de l'acide acétique d'extraits de bois
US20140106421A1 (en) * 2012-10-15 2014-04-17 Industrial Technology Research Institute Methods Of Producing Carboxylic Acids And/Or Alcohols
WO2019158683A1 (fr) 2018-02-15 2019-08-22 Evonik Degussa Gmbh Extraction d'acides alcanoïques
WO2021018717A1 (fr) 2019-07-29 2021-02-04 Evonik Operations Gmbh Procédé d'extraction d'acide carbonique, d'acides aliphatiques, d'esters et d'alcools à partir d'un milieu aqueux

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KIEUN CHOI ET AL: "In Situ Biphasic Extractive Fermentation for Hexanoic Acid Production from Sucrose by Megasphaera elsdenii NCIMB 702410", APPLIED BIOCHEMISTRY AND BIOTECHNOLOGY, vol. 171, no. 5, 11 November 2013 (2013-11-11), pages 1094 - 1107, XP055095021, ISSN: 0273-2289, DOI: 10.1007/s12010-013-0310-3 *
MORINAGA ET, J. BIOTECHNOL., vol. 14, 1990, pages 187 - 194
SAKAI ET AL., BIOTECHNOL. LET., vol. 29, 2004, pages 1607 - 1612
SCHMIDT ET AL., CHEM. ENG. COMMUN., vol. 45, 1986, pages 61 - 73

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