WO2023104316A1 - Extraction de polyhydroxyalcanoates à partir d'une biomasse et leurs utilisations - Google Patents

Extraction de polyhydroxyalcanoates à partir d'une biomasse et leurs utilisations Download PDF

Info

Publication number
WO2023104316A1
WO2023104316A1 PCT/EP2021/085203 EP2021085203W WO2023104316A1 WO 2023104316 A1 WO2023104316 A1 WO 2023104316A1 EP 2021085203 W EP2021085203 W EP 2021085203W WO 2023104316 A1 WO2023104316 A1 WO 2023104316A1
Authority
WO
WIPO (PCT)
Prior art keywords
pha
hydroxybutyrate
biomass
butyl
solvent
Prior art date
Application number
PCT/EP2021/085203
Other languages
English (en)
Inventor
Roger Marti
Florian DARDANO
Luce ALBERGATI
Ricardo SILVESTRE
Manfred Zinn
Véronique AMSTUTZ
Nils HANIK
Original Assignee
Hes-So Valais-Wallis
Hes-So Fribourg
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 Hes-So Valais-Wallis, Hes-So Fribourg filed Critical Hes-So Valais-Wallis
Priority to PCT/EP2021/085203 priority Critical patent/WO2023104316A1/fr
Publication of WO2023104316A1 publication Critical patent/WO2023104316A1/fr

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91Polymers modified by chemical after-treatment
    • C08G63/912Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/03Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/18Organic compounds containing oxygen
    • C10L1/19Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00Liquid carbonaceous fuels
    • C10L1/10Liquid carbonaceous fuels containing additives
    • C10L1/14Organic compounds
    • C10L1/22Organic compounds containing nitrogen
    • C10L1/222Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/224Amides; Imides carboxylic acid amides, imides
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00Use of additives to fuels or fires for particular purposes
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00Components of fuel compositions
    • C10L2200/04Organic compounds
    • C10L2200/0407Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0415Light distillates, e.g. LPG, naphtha
    • C10L2200/0423Gasoline
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10LFUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2270/00Specifically adapted fuels
    • C10L2270/02Specifically adapted fuels for internal combustion engines
    • C10L2270/023Specifically adapted fuels for internal combustion engines for gasoline engines

Definitions

  • the present invention pertains to the technical field of extracting PHA from biomass , in particular by means of solvents , and treating the extracted PHA to give a desired chemical intermediate .
  • the present invention further relates to using such intermediate as an additive for fuel .
  • the applied solvent is a key factor to improve both process efficiency and sustainability, especially on an industrial scale .
  • the solvents must be chosen carefully with regard to costs , health and safety considerations as well as environmental impact .
  • PHA and their intermediates have been envisaged for use as a biofuel .
  • PHA can be methyl esteri fied to become a biofuel .
  • Such an application extends the added value of PHA and, accordingly, improves the green footprint of such material .
  • the invention relates to a method of reacting polyhydroxyalkanoates ( PHA) to form an intermediate , comprising the steps of a) providing a reaction mixture comprising
  • reagent in particular an alcohol or an amine
  • a catalyst in a solvent comprising butyl 3-hydroxybutyrate; b) exposing the reaction mixture to elevated temperatures and/or elevated pressure, preferably temperatures of at least 90°C.
  • the PHA provided in step a) have been extracted from biomass ; particularly preferably have the PHA been extracted from biomass as is described hereinafter as a further aspect of the invention.
  • Another aspect of the invention relates to a method for extracting polyhydroxyalkanoates (PHA) from biomass, comprising the steps of a) combining a biomass containing PHA with a solvent to form a biomass liquor ; b) optionally : heating the biomass liquor to at least partially solubilize the PHA to form a PHA liquor ; c) recovering PHA from the PHA liquor; characterized in that the solvent used in step a) comprises butyl 3-hydroxybutyrate.
  • PHA polyhydroxyalkanoates
  • PHA polyhydroxyalkanoates
  • Ri, R2, R3, R4, R5, and Re are independently a hydrogen atom, a halogen atom or a hydrocarbon radical.
  • a hydrocarbon radical contains at least one carbon atom.
  • a hydrocarbon radical can be saturated or unsaturated, substituted or unsubstituted, branched or straight chained, and/or cyclic or acyclic.
  • substituted hydrocarbon radicals include halo-substituted hydrocarbon radicals, hydroxysubstituted hydrocarbon radicals, nitrogen-substituted hydrocarbon radicals, and oxygen-substituted hydrocarbon radicals.
  • hydrocarbon radicals include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, and decyl.
  • the units may be the same, as in a homopolymer, or be selected from two or more different units, as in a copolymer or terpolymer.
  • a block copolymer is also encompassed by the term.
  • the PHA can include one or more units, for example 10-100'000 units, preferably 100-30'000 units of the above Formula I.
  • the polymers typically have a molecular weight above 270 Dalton, for example 10'000 to 3'000'000 Dalton.
  • biomass e.g., bacterial biomass, yeast biomass, fungal biomass, microalgal biomass, archeal biomass
  • Bio- mass-derived PHA can be formed, for example, via enzymatic polymerization of the monomer units.
  • the biomass can be formed of one or more of a variety of entities.
  • Such entities include, for example, microbial strains for producing PHAs (e.g., Alcali- genes eutrophus/Cuprlavldus necator, Alcaligenes la- tus/ Azohydromonas lata, Rhodospirillum rubrum, Halomonas bluephagenesis , Azetobacter , Aeromonas , Comamonas , Pseudomonas') , Archaea (e.g., species of Bacillus, Halobacterium, Natronococ- cus, Natronobacterium, Halorubrum, Haloquadratum, Halococcus , Haloterrigena , Natrialba , Haloarcula , and Halo f erax) , and recombinant strains, genetically engineered organisms, preferably containing recombinant plasmids or introduced gene sequences on the chromosome, for producing PHAs (e.g
  • the PHA is isolated from plant biomass derived from plants such as sugar cane, switchgrass, soybean, cotton, coconuts, groundnuts, rapeseed, sunflower seed, olive, palm, sesame seed, linseed, castor, safflower seed, tobacco and potato.
  • plant biomass derived from plants such as sugar cane, switchgrass, soybean, cotton, coconuts, groundnuts, rapeseed, sunflower seed, olive, palm, sesame seed, linseed, castor, safflower seed, tobacco and potato.
  • transgenic plants are used as a source for PHA.
  • Transgenic plant derived PHA polymers or their derivatives can be processed and separated from plant biomass in commercially useful forms.
  • the formed intermediate is an ester, preferably an alkanoic acid ester.
  • alkanoic esters include methyl 3- hydroxybutyrate, ethyl 3-hydroxybutyrate, methyl 3- hydroxypropionate, ethyl 3-hydroxypropionate, methyl 4- hydroxybutyrate, ethyl 4-hydroxybutyrate, propyl 3- hydroxybutyrate, propyl 4-hydroxybutyrate, isopropyl 3- hydroxybutyrate, isopropyl 4-hydroxybutyrate, butyl 3- hydroxybutyrate, butyl 4-hydroxyvalerate, derivatives of poly (3- hydroxypropionate) , etc.
  • Treating a PHA to form an ester includes combining the PHA with an alcohol and - optionally - a catalyst, and exposing the PHA to elevated temperature and/or elevated pressure.
  • Preferable alcohols include methanol, ethanol, propanol, isopropanol, and/or butanol, preferably n- butanol .
  • the formed intermediate may be an amide, preferably an alkenoic acid amide.
  • alkenoic acid amides include N-methyl 3-hydroxybutyramide, N-ethyl 3- hydroxybutyramide, N-methyl 4-hydroxybutyramide, N-ethyl 4- hydroxybutyramide, N-hydroxyethyl 4-hydroxybutyramide, N-methyl 4-hydroxyvaleramide, derivatives of poly ( 3-hydroxypropionate, etc.
  • Treating a PHA to form an amide includes combining the PHA with an amine (e.g. a primary, a secondary amine, such as ammonia, methyl amine, ethyl amine, pyrrolidone) and using elevated temperature and/or pressure.
  • an amine e.g. a primary, a secondary amine, such as ammonia, methyl amine, ethyl amine, pyrrolidone
  • solvent comprising butyl 3-hydroxybutyrate
  • solvent such as an alcohol, mixed with an amount of cosolvent of the Formula II
  • the reaction temperature can be chosen in a moderate range, such as 90° to 220°C, more preferably 100° to 150°C, even more preferably 115° to 135°C.
  • an elevated pressure e.g., 2 to 14 bar, preferably 5 to 10 bar
  • the temperature can be raised correspondingly, for example to temperatures above 135°C, preferably 140-160°C.
  • the reaction can be performed even under atmospheric pressure.
  • the yield obtainable under such conditions is well above 60%, preferably above 70%, typically even above 80%, with a good degree of purity.
  • comparable yields can usually be achieved only under difficult reaction conditions, i.e. higher temperatures and/or pressures, or after long reaction times.
  • the elevated temperatures for forming an amide are typically lower, e.g., between 50 to 90°C.
  • the PHA provided in step a) are extracted from biomass, preferably extracted by a method as described hereinafter. It is particularly preferred that the PHA in step a) is provided as a pretreated substance, having a purity of > 90%, measured by gas chromatography of methanolised PHA or by weight loss determination after dissolution/precipitation cycle. Most preferably, the PHA in step a) is provided as pure poly (3- hydroxybutyrate ) .
  • PHB poly ( 3-hydroxybutyrate )
  • Formula III a structure comprising repeating monomer units of the Formula III, preferably, a homopolymer comprising repeating monomer units of the above Formula III.
  • the monomer typically has a stereocenter ( A-conf iguration) , giving the following Formula IV:
  • R- and S- conf igurations may be obtained if the polymer is obtained by way of chemical synthesis. It is possible to directly react a biomass comprising a relevant PHB content with an alcohol or an amine in order to form an intermediate. But the method as described above has turned out to give particularly high yields if purified PHA or preferably PHB is provided as a starting material.
  • the catalyst used in step a) is a Broensted acidic ionic liquid, preferably 1- methyl-3- ( 3-sulfopropyl ) -imidazolium hydrogen sulphate ( [HSO3- pmimJHSO .
  • suitable catalysts include sulfuric acid, para-toluene sulfonic acid, hydrochloric acid, and phosphoric acid (protic catalysts) , but also aprotic catalysts including certain transesterification catalysts (e.g., metal-containing transesterification catalysts such as tin compounds, but also titanium, zinc compounds and clays are possible) .
  • enzymes such as Candida antarctica lipase B
  • Broensted acidic ionic liquids are suitable due to their thermal stability, reusability, and miscibility with organic compounds.
  • Methyl-! ⁇ 3-sulfopropyl ) -imidazolium hydrogen sulphate ( [HSO3- pmimJHSO of the Formula V has turned out to be particularly suitable for the ease of recycling for subsequent reactions.
  • FeCls or FeC12 can be used as a catalyst.
  • FeCl 3 or FeC12 has turned out to give partic- ularly high yields in a method as described above.
  • the catalyst can, however, be advantageously used also on a more general level in an method of reacting polyhydroxyalkanoates (PHA) to form an intermediate comprising the steps of a) providing a reaction mixture comprising
  • reagent in particular an alcohol or an amine
  • the catalyst has shown to deliver particularly high yields well above 70%, e.g., of butyl 3-hydroxybutyrate, even when used under moderate reaction conditions (atmospheric pressure, temperatures between 90 and 140°C) .
  • the solvent used for the reaction comprises at least 5 wt-% of butyl 3-hydroxybutyrate, preferably 8 to 50 wt-% of butyl 3-hydroxybutyrate, more preferably 10 to 40 wt-% of butyl 3-hydroxybutyrate.
  • the solvent used for the reaction comprises at least 5 wt-% of butyl 3-hydroxybutyrate, preferably 8 to 50 wt-% of butyl 3-hydroxybutyrate, more preferably 10 to 40 wt-% of butyl 3-hydroxybutyrate.
  • amounts > 40 wt-% are likewise possible. However, such amounts are not preferable from an economical point of view.
  • the invention includes a method for extracting polyhydroxyalkanoates (PHA) from biomass, comprising the steps of a) combining a biomass containing PHA with a solvent to form a biomass liquor; b) optionally : heating the biomass liquor to at least partially solubilize the PHA to form a PHA liquor ; c) recovering PHA from the PHA liquor; characterized in that the solvent used in step a) comprises butyl 3-hydroxybutyrate.
  • PHA polyhydroxyalkanoates
  • steps a) to c) can be perfomed simultaneously or sequentially.
  • the above described method is particularly suitable for the extraction of short chain length PHA (scl PHA) .
  • short chain length PHA is understood hereinafter PHA of the above Formula I, wherein n is zero, one, two, three or four.
  • the biomass provided in step a) comprises a high amount of poly ( 3-hydroxybutyrate ) (PHB) , preferably a PHB content of > 80%.
  • PHB poly ( 3-hydroxybutyrate )
  • Most particularly preferred is the method for the extraction of poly ( A-3-hydroxybutyrate) .
  • Short chain length PHA (scl PHA) , and most typically poly(A-3- hydroxybutyrate ) , are often isolated from plant biomass derived from, e.g., sugar cane, switchgrass, soybean, cotton, coconuts, groundnuts, rapeseed, sunflower seed, olive, palm, sesame seed, linseed, castor, safflower seed, tobacco, potato, and algae. Such plants may be transgenic or wild type. Extraction of short chain length PHA places high demands on the performance of extraction solvent, due to the relatively high polarity of the polymer. The superior performance of butyl 3-hydroxybutyrate is more pronounced when used for extraction of short chain length PHA. For example, a quantitative extraction can be performed in comparatively short time under mild reaction conditions.
  • the PHA in step c) is recovered from the PHA liquor by filtration.
  • the biomass residues e.g. cell debris
  • the filter cake may be dissolved once more in solvent, e.g., a different solvent, and filtered for increasing the PHA yield.
  • the PHA may be recovered by precipitating the PHA from the solution using an anti-solvent such as methanol or ethanol or through other methods such as sedimentation, re-suspension, centrifugation, cooling, solvent evaporation and combinations thereof.
  • butyl 3-hydroxybutyrate of the Formula IT has turned out to be particularly suitable for the purposes of extraction.
  • Butyl 3-hydroxybutyrate can be used as an extraction solvent in steps a) and subsequently step b) .
  • the biomass can be suspended in the solvent in a ratio of 1-2 g per 100 ml, and the extraction can be performed at temperatures of 50° to 140°C, preferably 55° to 90°C, even at atmospheric pressure, to give a quantitative yield.
  • the solvent used in step a) comprises at least 5 wt-% of butyl 3-hydroxybutyrate, preferably 8 to 50 wt-% of butyl 3-hydroxybutyrate, more preferably 10 to 40 wt-% of butyl 3-hydroxybutyrate.
  • the solvent used in step a) comprises at least 5 wt-% of butyl 3-hydroxybutyrate, preferably 8 to 50 wt-% of butyl 3-hydroxybutyrate, more preferably 10 to 40 wt-% of butyl 3-hydroxybutyrate.
  • amounts > 40 wt-% are likewise possible. However, such amounts are not preferable from a commercial point of view.
  • step b) the biomass liquor is heated to temperatures of 50 to 140°C, preferably 55° to 90°C, at atmospheric pressure. High yields are thus obtainable even after short extraction periods. It is preferred that the biomass containing PHA is provided as a dry biomass .
  • the PHA or preferably PHB may have been prewashed .
  • the method as described above is for producing a biofuel and comprises the steps of a ) providing a reaction mixture comprising polyhydroxyalkanoates ( PHA) ; an alcohol , in particular methanol , ethanol , ( iso- ) propanol , butanol or a mixture thereof ; optionally : a catalyst ; in a solvent comprising butyl 3-hydroxybutyrate ; b ) exposing the reaction mixture to elevated temperatures and/or elevated pressure , preferably temperatures of at least 90 ° C ; and c ) combining the substance resulting in step b ) with a chemical fuel .
  • PHA polyhydroxyalkanoates
  • an alcohol in particular methanol , ethanol , ( iso- ) propanol , butanol or a mixture thereof
  • b exposing the reaction mixture to elevated temperatures and/or elevated pressure , preferably temperatures of at
  • the term “bulchemical fuel” is understood a fuel selected from the group of gasoline , diesel , and alcohol fuel .
  • the alcohol fuel is selected from the group consisting of ethanol , n-propanol and n- butanol .
  • PHA which is esteri fied by the method as described above can be reacted in a particularly ef ficient way into an additive for fuel , due to the excellent dissolvability of PHA in butyl 3-hydroxybutyrate .
  • PHA after having been used as a bioplastic, PHA can be turned into an additive for a fuel , whereby the application value of PHA is further increased .
  • the PHA provided in the reac- tion mixture of step a) may be contained in biomass and/or may have been extracted from biomass, preferably by a method as described above.
  • the PHA provided in step a) are contained in biomass and/or in an object made from PHA-based plastic.
  • the biomass may be an active sludge from waste water treatment. It can be directly dissolved in butyl 3-hydroxybutyrate ; however, one or more optional iso- lation/purif ication steps may proceed the esterification reaction.
  • the PHA may e.g., be present as a waste object made from PHA plastic, hence having an even better environmental impact due to the chain of applications.
  • PHB and more preferably poly ( .R-3-hydroxybutyrate ) , is provided in step a) of the method.
  • PHB are contained in biomass and/or in an object made from PHA plastic.
  • PHB is preferred not only due to their abundancy as a product of biomass synthesis. Also, PHB provides good combustion heat when admixed to a chemical fuel, and offers interesting commercial prospects.
  • the invention further relates to the use of butyl 3- hydroxybutyrate as an additive for a chemical fuel, preferably in a ratio of 5 to 40 wt-%, preferably 10 to 30 wt-%, of the total resulting fuel.
  • butyl 3-hydroxybutyrate is readily miscible with chemical fuels, in particular gasoline or diesel.
  • Fig 1 Diagram of measured torque over timing advance in engine tests for pure gasoline (SP98) , 20% Butyl 3-hydroxybutyrate blend, 20% Methyl 3- hydroxybutyrate blend and 20% n-Butanol blend, respectively;
  • Fig 2 Diagram of measured power over engine speed in engine tests for pure gasoline (SP98) , 20% butyl 3- hydroxybutyrate blend, 20% methyl 3- hydroxybutyrate blend and 20% n-butanol blend, respectively;
  • Fig 3 Diagram of measured torque over fuel-air equivalence ratio in engine tests for pure gasoline (SP98) , 20% butyl 3-hydroxybutyrate blend, 20% Methyl 3-hydroxybutyrate blend and 20% n-Butanol blend, respectively;
  • Fig 4 Diagram of measured engine efficiency relative to pure gasoline (SP98) over engine speed in engine tests for 20% butyl 3-hydroxybutyrate blend, 20% methyl 3-hydroxybutyrate blend and 20% n-butanol blend, respectively.
  • distillation residue was reused as catalyst without further treatment for the next synthesis.
  • the apparatus was flushed three times with argon.
  • the reactive mixture was mechanically mixed with a half-moon shaped PTFE stirrer.
  • the jacket was heated in order to reach a T r of 115°C (solvent reflux) for 24 h. Then, the reaction mixture was cooled down to room temperature, filtered in order to eliminate the PHB residues and transferred in a 100 mL single neck round bottom flask connected to a distillation apparatus. N-Butanol was evap- orated in a vacuum ( T j 60°C, 30 mbar) .
  • Example 3 Butyl 3-hydroxybutyrate from pure PHB at atmospheric pressure by using FeCla as a catalyst
  • reaction mixture was cooled down to room temperature, filtered in order to eliminate the PHB residues and transferred in a 2 L single neck round bottom flask connected to a distillation apparatus.
  • N-Butanol was evaporated in a vacuum (Tj 60°C, 30 mbar) .
  • the catalyst FeC12 520.1 mg, 0.0040 mol, 0.1 eq
  • n-butanol 54.5 mL, 0.60 mol, 15.0 eq
  • 3-hydroxybutyrate co-solvent 3.2 mL, 0.019 mol, 6% of the solvent/co-solvent solution
  • the apparatus was flushed three times with argon.
  • the reactive mixture is magnetically stirred.
  • the jacket was heated in order to reach a T r of 115°C (solvent reflux) for 24 h.
  • the reaction mixture was cooled down to room temperature, filtered in order to eliminate the catalyst and biomass residues, then transferred in a 50 mL single neck round bottom.
  • N-butanol was evaporated in a vacuum (Tj 60°C, 30 mbar) at the rotatory evaporator to give 4.02 g crude butyl 3-hydroxybutyrate (63% yield by NMR assay using 1,4- dimethoxybenzene as internal standard and corrected considering the initial addition of butyl 3-hydroxybutyrate as co-solvent) .
  • the solid part was dissolved in 100 mL of 1 , 1 , 1-3 , 3 , 3-hexaf luoro-2-propanol and filtered again in order to separate the extracted PHB from the biomass residues.
  • the obtained white solid was dried in an oven at 60 °C for 6 h (quantitative extraction, 1 g PHB) .
  • Example 6 Engine performance using M3HB and B3HB as a fuel additive .
  • Butyl 3-hydroxybutyrate (B3HB) was added to gasoline (SP98) to give an amount of 20 vol-% and was measured to have a density at 20°C of 0.78 g/mL and a combustion heat of 38'664 J/g.
  • M3HB Methyl-3- hydroxybutyrate
  • N-butanol was added to gasoline (SP98) to an amount of 20 vol-% and the fuel was measured to have a density at 20°C of 0.75 g/mL and a combustion heat of 40'416 J/g.
  • Fig 1 shows a plot of corrected measured torque ( [Nm] ) over timing advance ( [°] ) for pure gasoline (SP98) , 20% butyl 3- hydroxybutyrate blend, 20% methyl 3-hydroxybutyrate blend and 20% n-butanol blend respectively. Almost identical torque values were achieved for all fuels at 4000 rpm during optimisation of ignition timing.
  • Fig 2 shows a plot of measured corrected power ( [ kW ] ) over engine speed ( [rpm] ) for pure gasoline (SP98) , 20% butyl 3- hydroxybutyrate blend, 20% methyl 3-hydroxybutyrate blend and 20% n-butanol blend respectively. Almost identical power values were achieved for all fuels at full load.
  • Fig 3 shows a plot of corrected torque over fuel-air equivalence ratio for pure gasoline (SP98) , 20% butyl 3-hydroxybutyrate, 20 methyl 3-hydroxybutyrate and 20% n-butanol respectively. Similar torque values were achieved for all fuels at 4000 rpm. Nevertheless, it was found that on the test engine, the alternative fuel containing 20% B3HB had a higher minimum fuel-air equivalence ratio than the other fuel blends, i.e., it had to be slightly richer for the engine to maintain combustion.
  • Fig 4 shows a plot of engine efficiency (cylinder pressure) relative to pure gasoline (given in %) over variable engine speeds.
  • the cylinder pressures for all fuels were similar to those achieved with SP98, with maximum variations ranging from -1.7% to +8.2% compared to SP98.
  • the relative efficiency of the different fuel blends is slightly lower than that of standard SP98 fuel. This may be explained by the fact that the fuel blends have lower heating values (LHV/HHV) than pure commercial grade gasoline and the engine was designed specifically for such fuel.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Combustion & Propulsion (AREA)
  • Emergency Medicine (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne le domaine technique de l'extraction de PHA à partir d'une biomasse, en particulier au moyen de solvants, et le traitement du PHA extrait pour donner un intermédiaire souhaité. La présente invention concerne en outre l'utilisation d'un tel intermédiaire en tant qu'additif pour combustible. Pour l'une quelconque de ces applications, le solvant appliqué est un facteur important afin d'améliorer à la fois l'efficacité et la durabilité du processus, en particulier à l'échelle industrielle.
PCT/EP2021/085203 2021-12-10 2021-12-10 Extraction de polyhydroxyalcanoates à partir d'une biomasse et leurs utilisations WO2023104316A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/EP2021/085203 WO2023104316A1 (fr) 2021-12-10 2021-12-10 Extraction de polyhydroxyalcanoates à partir d'une biomasse et leurs utilisations

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2021/085203 WO2023104316A1 (fr) 2021-12-10 2021-12-10 Extraction de polyhydroxyalcanoates à partir d'une biomasse et leurs utilisations

Publications (1)

Publication Number Publication Date
WO2023104316A1 true WO2023104316A1 (fr) 2023-06-15

Family

ID=78844892

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2021/085203 WO2023104316A1 (fr) 2021-12-10 2021-12-10 Extraction de polyhydroxyalcanoates à partir d'une biomasse et leurs utilisations

Country Status (1)

Country Link
WO (1) WO2023104316A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030158441A1 (en) 2001-12-18 2003-08-21 Luhua Zhong Methods of making intermediates from polyhydroxyalkanoates
EP2302021A1 (fr) * 2008-05-30 2011-03-30 Shantou University Applications de dérivés d acide gras hydroxy comme carburants et additifs de carburant
US8377151B2 (en) * 2006-07-19 2013-02-19 Zackery Allen McMurry Process for producing a renewable biofuel from waste water treatment plants

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030158441A1 (en) 2001-12-18 2003-08-21 Luhua Zhong Methods of making intermediates from polyhydroxyalkanoates
US8377151B2 (en) * 2006-07-19 2013-02-19 Zackery Allen McMurry Process for producing a renewable biofuel from waste water treatment plants
EP2302021A1 (fr) * 2008-05-30 2011-03-30 Shantou University Applications de dérivés d acide gras hydroxy comme carburants et additifs de carburant

Similar Documents

Publication Publication Date Title
US6709848B1 (en) Methods for isolating polyhydroxyalkanoates from plants
CN104496793B (zh) 长碳链二元羧酸的精制方法
Keenan et al. Production and characterization of poly‐β‐hydroxyalkanoate copolymers from Burkholderiacepacia utilizing xylose and levulinic acid
US8535399B2 (en) Use of hydroxyalkanoic acid derivatives as fuel additives
US7695532B2 (en) Process for making biodiesel from crude tall oil
Akaraonye et al. Poly (3‐hydroxybutyrate) production by Bacillus cereus SPV using sugarcane molasses as the main carbon source
US8143034B2 (en) Method for preparing long-chain hydroxyacids, diacids and oligomers and polymers thereof
Kessler et al. Production of microbial polyesters: fermentation and downstream processes
JP2007538132A (ja) 再生可能な供給原料からのポリ乳酸(pla)の生産のためのプロセス
Wang et al. Properties of a new gasoline oxygenate blend component: 3-Hydroxybutyrate methyl ester produced from bacterial poly-3-hydroxybutyrate
EP0973930A1 (fr) Extraction de pha a haute temperature au moyen de solvants pauvres en pha
WO1997015681A9 (fr) Procedes d'extraction de polyhydroxyalkanoates a partir de vegetaux
JP2005536608A (ja) 超分岐性、水溶性ポリエステルの製造方法
CN101065416A (zh) 单一溶剂的聚合物提取方法
Van Thuoc et al. Polyhydroxyalkanoate production from rice straw hydrolysate obtained by alkaline pretreatment and enzymatic hydrolysis using Bacillus strains isolated from decomposing straw
CN101892271A (zh) 发酵法生产聚羟基脂肪酸酯
WO2023104316A1 (fr) Extraction de polyhydroxyalcanoates à partir d'une biomasse et leurs utilisations
US20130123469A1 (en) Fractionation of proteins and lipids from microalgae
EP2732043A2 (fr) Procédé de séparation
CN113502305B (zh) 一种利用重组酰亚胺酶合成(r)-异丁基戊二酸单酰胺的方法
CA2954654A1 (fr) Nouveau procede de recuperation d'acide lactique
WO2021049910A1 (fr) Procédé de préparation d'un copolymère séquencé
CA2234965C (fr) Procedes d'extraction de polyhydroxyalkanoates a partir de vegetaux
WO2016143988A1 (fr) Procédé pour produire simultanément du biodiesel, de l'additif pour biodiesel, et du formate d'alkyle à partir de microalgues
CN113684231B (zh) 一种多液相酶法酯化合成酯类物质的方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21823929

Country of ref document: EP

Kind code of ref document: A1