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WO2025176454A1 - Procédé de séparation d'hexaméthylène diamine d'une solution aqueuse obtenue à partir d'un procédé de fermentation microbienne - Google Patents

Procédé de séparation d'hexaméthylène diamine d'une solution aqueuse obtenue à partir d'un procédé de fermentation microbienne

Info

Publication number
WO2025176454A1
WO2025176454A1 PCT/EP2025/052801 EP2025052801W WO2025176454A1 WO 2025176454 A1 WO2025176454 A1 WO 2025176454A1 EP 2025052801 W EP2025052801 W EP 2025052801W WO 2025176454 A1 WO2025176454 A1 WO 2025176454A1
Authority
WO
WIPO (PCT)
Prior art keywords
hmda
aqueous solution
pressure
monovalent alcohol
distillation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2025/052801
Other languages
English (en)
Inventor
Mathias LEIMBRINK
Jonas KRAUSE
Emrah ALTUNTEPE
Jürgen BAUSA
Thomas WALTERMANN
Connor GALLEHER
Bo Chen
Iman SAFARI
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Genomatica Inc
Original Assignee
Covestro Deutschland AG
Genomatica Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Covestro Deutschland AG, Genomatica Inc filed Critical Covestro Deutschland AG
Publication of WO2025176454A1 publication Critical patent/WO2025176454A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/82—Purification; Separation; Stabilisation; Use of additives
    • C07C209/84—Purification

Definitions

  • the present invention relates to a method for separating hexamethylene diamine from an aqueous solution originating from a microbial fermentation process.
  • Hexamethylene diamine (HDA, HMDA, or hexane-i,6-diamine)
  • HDA Hexamethylene diamine
  • HMDA hexane-i,6-diamine
  • PA66 Polyamide-6.6
  • PA66 is generated from hexamethylene diamine and adipic acid.
  • Another important use is the phosgenation of HMDA to the corresponding diisocyanate, which can then be converted in further steps into polyurethanes, polyureas or polyisocyanurates.
  • HMDA is first of all generated as a mixture with water, and the mixture is then processed into pure diamine. Recovering a diamine from the aqueous fermentation medium can be carried out as disclosed in EP 2684867 At, for example, after most of the cell components have been removed.
  • a method for the production of pentamethylene diamine is disclosed, in which the diamine is extracted in a liquid phase extraction process from the aqueous phase that has optionally been concentrated by distillation beforehand.
  • extractants non-halogen aliphatic solvents, preferably straight chain alcohols with 4 to 7 carbon atoms, are recommended. These extractants must subsequently be separated from the product again by distillation.
  • the distillation processes to concentrate the aqueous raw product or to isolate the pentamethylene diamine from the extract the use of one or more distillation columns and a pressure of between 0.1 kPa and normal pressure is described in each case.
  • Biotechnological production processes are also known for the production of hexamethylene diamine.
  • US 20170369913 Al discloses extraction with various extractants and distillation of hexamethylene diamine (which has been produced by biological means).
  • a method for separating hexamethylene diamine (HMDA) from an aqueous solution comprising the steps: a) providing an HMDA-containing aqueous solution, wherein said aqueous solution is a fermentation broth, b) extracting the HMDA-containing aqueous solution with a monovalent alcohol having 4 to 8 carbon atoms, c) obtaining an HMDA-containing alcoholic phase, and d) distilling the HMDA-containing alcoholic phase at a pressure of 1-1000 mbar and separating the HMDA from the monovalent alcohol.
  • HMDA hexamethylene diamine
  • the HMDA-containing aqueous solution is a fermentation broth.
  • a “fermentation broth” as referred to in the present application is an aqueous composition which originates from a microbial fermentation process.
  • This microbial fermentation process is, preferably, a process, wherein microorganisms, preferably bacteria, are provided with one or more organic compounds that are converted to HMDA by the metabolic activity of said microorganisms.
  • a suitable fermentation broth must comprise a range of nutrients such as amino acids or vitamins in order to support the activity of the microorganisms, it is clear that the aqueous solution must comprise organic compounds in addition to HMDA.
  • said aqueous solution additionally comprises at least one compound selected from the group consisting of (i) acetate, (ii) lactate, (iii) glutamate, (iv) ammonium and (v) y-aminobutyric acid.
  • Acetate is a short-chain fatty acid which originates from a multitude of aerobic as well anaerobic metabolic pathways in microorganisms, e.g. butyric acid fermentation or by cleavage of acetyl-coenzyme A.
  • Lactate is a product of glycolysis.
  • Glutamate is a proteinogenic amino acid. Ammonium is found in many fermentation broths as source of nitrogen. It may also be released during amino acid metabolism, y-aminobutyric acid is produced by a multitude of microorganisms such as certain Lactobacilli or yeasts.
  • Acetate is preferably present in a concentration range between i and 4,000 mg/L, more preferably 200 and 3,000 mg/L and most preferably 750 to 2,500 mg/L.
  • Lactate is preferably present in a concentration range between 1 and 400 mg/L, more preferably 5 and 200 mg/L and most preferably 10 to too mg/L.
  • Glutamate is preferably present in a concentration range between 10 and 1,000 mg/L, more preferably 50 and 600 mg/L and most preferably 75 to 250 mg/L.
  • Ammonium is preferably present in a concentration range between 1 and 200 mg/L, more preferably 5 and 120 mg/L and most preferably 10 to 80 mg/L.
  • y-aminobutyric acid is preferably present in a concentration range between 300 and 4,000 mg/L, more preferably 500 and 3,000 mg/L and most preferably 700 to 2,000 mg/L.
  • the present application does not relate to the separation of HMDA from an aqueous solution, if the HMDA originates from the depolymerization of a polymer.
  • aqueous solution is not the product of a microbial fermentation process but from the chemical process used for the depolymerization.
  • the HMDA is preferably present in uncharged form. This is typically the case at a pH of at least 11.5. Therefore, the HMDA-containing aqueous solution in method step a) preferably has a pH of at least 11.5, more preferably 12.0..
  • the monovalent alcohol may be selected from the group consisting of i-pentanol, 1- hexanol, 1-heptanol or mixtures thereof.
  • the HMDA-containing alcoholic phase may be distilled in step d) at a pressure of 50- 800 mbar, 100-600 mbar, or 150-400 mbar.
  • HMDA-containing alcoholic phase may be distilled in step d) with a single distillation column.
  • step b) maybe carried out using an extraction column and/or a mixer-settler, having 3 to 15 theoretical stages.
  • the expressions “comprising”, “including” or “containing” mean preferably “consisting substantially of’ and particularly preferably “consisting of’.
  • “Extraction” in the present case is understood to mean a separation process consisting of the separation of a substance from a matrix, wherein in the present case substance and matrix are both liquids to result in a liquid-liquid extraction. Two immiscible phases are combined to separate a solute from one phase into the other, according to the relative solubility in each of the phases. Suitable extraction devices for the liquid-liquid extraction are well known in the art.
  • distillation in the present case is understood to mean a thermal separation process used to recover evaporable substances, preferably liquids, from a composition. These separated vapors are subsequently precipitated, usually by condensation.
  • the term encompasses in particular repeated evaporation and condensation using a column (distillation column) with a plurality of separating stages. Processes of this kind in which several distillation steps are arranged in a series in a column should strictly speaking be called rectification, but will nevertheless likewise be referred to herein as distillation for the purpose of simplification. The advantage of these processes is the powerful separating effect and the possibility of operating the plant continuously.
  • a “distillation apparatus” is accordingly an apparatus which is suitable for performing a thermal separation process of this kind, i.e.
  • evaporators for example sieve plate columns, packed columns, packed-bed columns, bubble cap tray columns or even single-stage evaporators such as, for example, falling film evaporators, thin-film evaporators, flash evaporators, multiphase helical-coil evaporators, or natural or forced circulation evaporators.
  • an HMDA-containing aqueous solution is provided.
  • the weight ratio of HMDA and water can be freely chosen, e.g., the HMDA can be present at a maximum amount of about 50 wt.-%, based on the total weight of water and HMDA, to allow efficient extraction of the HMDA from a respective concentrated HMDA-containing aqueous solution.
  • the skilled person may choose a minimum amount of the HMDA of about 0.1 wt.-%, based on the total weight of water and HMDA, and may choose a maximum amount of the diamine depending on the HMDA and temperature used as long as a two phase system may still be achieved when mixed with the monovalent alcohol extractant.
  • the source of the HMDA to be separated according to the method of the present invention is restricted to HMDA prepared by biotechnological means such as fermentation, enzymatic catalysis, or whole cell bio-catalysis.
  • biotechnological means such as fermentation, enzymatic catalysis, or whole cell bio-catalysis.
  • it is not HMDA obtained from recycling of polyamides or polyurethanes even in cases, where the HMDA used in the synthesis of said polymers was originally obtained by the biotechnological means defined above in this paragraph.
  • the HMDA-containing aqueous solution provided in step a) is extracted with a monovalent alcohol having 4 to 8 carbon atoms.
  • the monovalent alcohol must enable an efficient extraction of the HMDA. If too much water is carried over, the energy consumption of the distillation increases. Further, the monovalent alcohol must also be able to carry a high concentration of HMDA, so that the amount of alcohol required for the extraction of the HMDA is minimized as distillation of the alcohol requires energy.
  • the monovalent alcohol is not particularly restricted as long as it has 4 to 8 carbon atoms, and the monovalent alcohol may include all possible isomers.
  • the monovalent alcohol may be selected from i-butanol, i-butanol, sec-butanol, i-pentanol, 2-pentanol, 3- pentanol, neopentyl alcohol, i-hexanol, 2-hexanol, 3-hexanol, i-heptanol, 2-heptanol, 3- heptanol, 4-heptanol, i-octanol, 2-octanol, 3-octanol, 4-octanol, cyclopentanol, cyclohexanol, cycloheptanol or cyclooctanol or mixtures thereof.
  • the monovalent alcohol may be selected from 1- pentanol, i-hexanol, i-heptanol or mixtures thereof. In a more preferred embodiment of the present invention the monovalent alcohol maybe i-hexanol.
  • Step b) may be carried out by any suitable extracting device, which is known in the art. Extraction may be carried out using an extraction column and/or a mixture-settler, having 3 to 15 theoretical stages.
  • Extraction conditions are not limited, the extraction may be carried out at room temperature (2O-25°C) and/ or under ambient pressure. The higher the temperature the higher the partition coefficient, thus extraction efficiency is increased.
  • the extraction temperature is limited by the boiling temperature of water or the monovalent alcohol used as extractant.
  • the extraction may be carried out under ambient pressure.
  • a phase ratio, i.e., mass ratio, of alcohohwater can be from 0.1 to 1, 0.2 to 0.5 or 0.3 to 0.4.
  • an HMDA-containing alcoholic phase is obtained.
  • This HMDA-containing alcoholic phase is the organic phase obtained after extraction in step b).
  • the other phase is the aqueous phase.
  • HMDA has a higher solubility in the monovalent alcohol than in water, the HMDA will be concentrated in the organic alcoholic phase.
  • the HMDA-containing alcoholic phase may contain, besides HMDA and monovalent alcohol, also residual amounts of water.
  • HMDA-containing alcoholic phase (organic phase) maybe easily separated from the aqueous phase after extraction by means well known in the art.
  • the HMDA-containing alcoholic phase obtained in step c) is distilled at a pressure of 1-1,000 mbar, and, thus, the HMDA is separated from the monovalent alcohol and the optionally residual amounts of water. It was surprisingly found that the efficiency of the distillation step d) depends on the applied pressure as the equilibrium of vapor and liquid phases is highly pressuredependent.
  • a distillation device used in step d) is not limited, but any distillation device known in the art for such separation steps may be used.
  • the distillation device may be a single distillation column.
  • the single distillation column may have 5 to too, 10 to 60 or 20 to 50 theoretical stages.
  • i-hexanol is the monovalent alcohol
  • 20 or more theoretical stages e.g., 20 to 50 theoretical stages, may be used.
  • the distillation pressure may be from 100-1,000 mbar, 150-800 mbar, 150-700 mbar, 200-600 mbar, 200-500 mbar or 200-400 mbar. It is, thus, lower than the atmospheric pressure of 1,013 mbar.
  • the distillation pressure may be 200-400 mbar, the monovalent alcohol may be 1- hexanol.
  • the distillation pressure may be 200-400 mbar, the monovalent alcohol may be i-butanol
  • the monovalent alcohol used has a lower boiling point than the HMDA and is evaporated to the top of the distillation device, may be condensed and may then be removed from the distillation device and may be optionally reused as extractant.
  • HMDA typically has the higher boiling point and is, thus, concentrated at the bottom of the distillation device and may be removed therefrom for further processing.
  • the HMDA-containing aqueous solution may contain substances having higher or lower boiling points compared to HMDA.
  • Substances with lower boiling points compared to HMDA are, for example, apart from water, ammonia, etc.
  • gases such as nitrogen or carbon dioxide may be present in the composition in dissolved or bound form.
  • Fig. i is a graph illustrating the dependency of the ideal separation factor on temperature for a mixture of C6-diamine (HMDA) and different monovalent alcohols;
  • Fig. 2 is a graph illustrating the dependency of the ideal separation factor on the temperature for a mixture of C6-monoamine (hexaneamine) and different monovalent alcohols;
  • Fig. 3 is a graph illustrating the dependency of the ideal separation factor on the temperature for a mixture of a C6-diamine (HMDA) and different divalent alcohols;
  • Fig. 4 is a graph illustrating the dependency of the ideal separation factor on the temperature for a mixture of a C6-monoamine (hexaneamine) and different divalent alcohols;
  • Fig. 5 is a graph illustrating vapor-liquid equilibrium (VLE) data for a mixture of 1- hexanol and hexamethylene diamine; experimental data (data points) was generated with a circulating still - an isobaric dynamic method (here only data at 1000 mbar is shown). The ideal VLE of i-hexanol and hexamethylene diamine was calculated and an UNIFAC estimation was performed, as well. Experimental data was used to regress NRTL parameters. The calculation with NRTL using these parameters is also shown.
  • VLE vapor-liquid equilibrium
  • step d) of distilling the HMDA-containing alcoholic phase is the most essential step.
  • step d) of distilling the HMDA-containing alcoholic phase is the most essential step.
  • hexanediamine was used as diamine and hexanamine was used as monoamine.
  • the same findings as shown in Fig. 1-4 account also for C4 amines and diamines.
  • C4 to C6 monovalent and divalent alcohols are investigated in these studies as given in Fig. 1-4.
  • (Ideal) relative volatility For each example and comparative example of Fig. 1-4, a mixture of amine and alcohol was used to calculate, based on literature values, the (ideal) relative volatility (also referred to as separation factor) which is the ratio of the vapor pressures of the pure compounds of amine and alcohol at a given temperature, where the vapor pressure of the low-boiler is divided by the vapor pressure of the high-boiler.
  • Fig. 1-4 The separation factors for the respective mixtures are summarized in Fig. 1-4. From Fig. 1-4 it can be seen that the combinations of monovalent alcohols and diamines appear to behave in a totally unexpected manner. From basic textbook knowledge and also from the behavior of similar combinations (Fig. 2 to 4) it is always assumed that a separation gets easier with lowering the pressure (separation factor increases steadily with lowering the pressure - corresponds to lowering the temperature). But the separation factor of mixtures of monovalent alcohols and hexanediamine shows a specific maximum (this also accounts for putrescine in mixtures with C4 to C6 monovalent alcohols).
  • VLE vapor-liquid equilibrium

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de séparation d'hexaméthylène diamine (HMDA) d'une solution aqueuse, comprenant les étapes consistant à : a) fournir une solution aqueuse contenant HMDA, ladite solution aqueuse étant un bouillon de fermentation, b) extraire la solution aqueuse contenant HMDA avec un alcool monovalent ayant de 4 à 8 atomes de carbone, c) obtenir une phase alcoolique contenant HMDA, et d) distiller la phase alcoolique contenant HMDA à une pression de 1 à 1000 mbar et séparer HMDA de l'alcool monovalent.
PCT/EP2025/052801 2024-02-21 2025-02-04 Procédé de séparation d'hexaméthylène diamine d'une solution aqueuse obtenue à partir d'un procédé de fermentation microbienne Pending WO2025176454A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US202463555961P 2024-02-21 2024-02-21
US63/555,961 2024-02-21
EP24191183 2024-07-26
EP24191183.3 2024-07-26

Publications (1)

Publication Number Publication Date
WO2025176454A1 true WO2025176454A1 (fr) 2025-08-28

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PCT/EP2025/052801 Pending WO2025176454A1 (fr) 2024-02-21 2025-02-04 Procédé de séparation d'hexaméthylène diamine d'une solution aqueuse obtenue à partir d'un procédé de fermentation microbienne

Country Status (1)

Country Link
WO (1) WO2025176454A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2684867A1 (fr) 2011-03-09 2014-01-15 Mitsui Chemicals, Inc. Pentaméthylène diisocyanate, procédé de fabrication de pentaméthylène diisocyanate, composition de polyisocyanate, résine de polyuréthane et résine de polyurée
US20170369913A1 (en) 2014-12-23 2017-12-28 Genomatica, Inc. Method of producing & processing diamines

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2684867A1 (fr) 2011-03-09 2014-01-15 Mitsui Chemicals, Inc. Pentaméthylène diisocyanate, procédé de fabrication de pentaméthylène diisocyanate, composition de polyisocyanate, résine de polyuréthane et résine de polyurée
US20170369913A1 (en) 2014-12-23 2017-12-28 Genomatica, Inc. Method of producing & processing diamines

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