[go: up one dir, main page]

WO2017076947A1 - Procédé de préparation d'acide furan-2,5-dicarboxylique - Google Patents

Procédé de préparation d'acide furan-2,5-dicarboxylique Download PDF

Info

Publication number
WO2017076947A1
WO2017076947A1 PCT/EP2016/076510 EP2016076510W WO2017076947A1 WO 2017076947 A1 WO2017076947 A1 WO 2017076947A1 EP 2016076510 W EP2016076510 W EP 2016076510W WO 2017076947 A1 WO2017076947 A1 WO 2017076947A1
Authority
WO
WIPO (PCT)
Prior art keywords
furfural
hydroxymethyl
starting material
hmf
material mixture
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.)
Ceased
Application number
PCT/EP2016/076510
Other languages
English (en)
Inventor
Richard Dehn
Holger WERHAN
Svenia DÜFERT
René BACKES
Alvaro GORDILLO
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Publication of WO2017076947A1 publication Critical patent/WO2017076947A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen

Definitions

  • the present invention relates to a process for preparing furan-2,5-dicarboxylic acid.
  • the present invention is defined in the appending claims. Furthermore, preferred configurations and aspect of the present invention are apparent from the detailed description herein below.
  • HMF 5-(Hydroxymethyl)furfural
  • FDCA furan-2,5-dicarboxylic acid
  • PET relies on ethylene and p-xylene which are usually obtained starting from of oil, natural gas or coal, i.e. from fossil fuels.
  • PET polyethylene terephthalate
  • terephthalic acid a compound used in the production of polyethylene terephthalate, PET
  • PET is based on ethylene and p-xylene which are usually obtained starting from of oil, natural gas or coal, i.e. from fossil fuels.
  • bio-based routes to ethylene e.g. dehydration of bio-ethanol
  • bio-based routes to ethylene are operated on commercial scale a straightforward access to bio-terephthalic acid remains difficult.
  • FDCA is the best bio-based alternative to terephthalic acid (for further information see: Lichtenthaler, F.W., "Carbohydrates as Organic Raw Materials” in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2010).
  • HMF is a versatile platform chemical. Alkoxymethylfurfurals, 2,5-furandicarboxylic acid, 5- hydroxymethylfuroic acid, bishydroxymethylfuran, 2,5-dimethylfuran, and the diether of HMF are furan derivatives with a high potential in fuel and/or polymer applications.
  • HMF HMF
  • FDCA can be co-polymerized with mono-ethylene glycol to give polyethylene furanoate (PEF), a polyester with properties similar to PET.
  • FDCA is usually obtained starting from fructose and/or other hexoses via a catalyzed, preferably acid-catalyzed, dehydration to key intermediate 5-(hydroxymethyl)furfural (HMF) followed by oxidation to FDCA.
  • HMF 5-(hydroxymethyl)furfural
  • carbohydrates preferably a mixture comprising 5-(hydroxymethyl)furfural (HMF) is prepared by subjecting a material mixture, comprising one, two or more compounds selected from the group consisting of hexoses (monomeric hexose molecules, e.g. fructose), oligosaccharides comprising hexose units, and polysaccharides comprising hexose units, to reaction conditions so that a mixture comprising HMF, water and by-products (for example, levulinic acid and formic acid) results.
  • hexoses monomeric hexose molecules, e.g. fructose
  • oligosaccharides comprising hexose units
  • polysaccharides comprising hexose units
  • oligo- and/or polysaccharides are usually depolymerised, and subsequently the resulting monosaccharides, e.g. monomeric hexose molecules, are converted into HMF.
  • Hexoses, oligosaccharides and polysaccharides are typically selected from the group consisting of fructose, glucose, and cellulose.
  • oligo- or polysaccharides are usually converted into monomeric hexose molecules by hydrolytic cleavage of the ether bonds connecting the different hexose units in an oligo- or polysaccharide molecule (e.g. cellulose).
  • depolymerization is conducted by using a catalyst, preferably in a one-pot-procedure.
  • a hydro- philic solvent is used (in particular water), e.g. in order to increase the amount of dissolved cellulose thus increasing the yield per process run.
  • a heterogeneous catalyst in order to facilitate post-synthetic workup.
  • an aqueous solution is used as a solvent, sometimes comprising 50 wt.-% of water or more, based on the total weight of the depolymerization mixture used.
  • Monosaccharides produced or provided are typically subjected to a dehydration process, wherein the monomeric hexose molecule is typically transferred by isomerisation (via e.g. ketone-enol tautomerization) into its ketone form which is subsequently converted into its ring form.
  • the formed ring-closed hexose molecules are typically dehy- drated (and optionally further isomerised) resulting in a mixture comprising HMF, byproducts (e.g. di-HMF) and water.
  • HMF byproducts
  • water causes undesirable by-products due to hydrolysis of the formed HMF as described above (for example, humins, levulinic acid and formic acid).
  • derivates of HMF as esters of HMF or as ethers of HMF do not to the same extent suffer from such side reactions.
  • HMF In contrast to the isolation of derivates of HMF, the isolation of HMF from such aqueous mixtures is challenging since HMF often undergoes side-reactions, e.g. hydrolysis (see scheme below).
  • the (crude) mixture comprising HMF and water is usually contaminated with byproducts to a certain degree and separation of HMF from the by-products is not possible with justifiable effort.
  • depolymerization or dehydration step also apply to a process for preparing furan-2,5-dicarboxylic acid according to the present invention as described in detail hereinbelow.
  • the successive steps of de- polymerization and dehydration can be used to prepare a starting material mixture as employed according to the present invention.
  • WO 2008/054804 A2 relates to "Hydroxymethyl furfural oxidation methods" (title). It is disclosed that a high solubility of FDCA in an acetic acid/water mixture (volume ratio 40:60) is achieved, compared to the solubility in pure water (cf. paragraph [0058]).
  • WO 2013/033081 A2 discloses a "process for producing both biobased succinic acid and 2,5-furandicarboxylic acid” (title).
  • WO 201 1/043661 A1 relates to a "Method for the preparation of 2,5-furandicarboxylic acid and for the preparation of the dialkyl ester of 2,5-furandicarboxylic acid" (title).
  • a method is disclosed "for the preparation of 2,5-furan dicarboxylic acid comprising the step of contacting a feed comprising a compound selected from the group consisting of 5- hydroxymethylfurfural ("HMF"), an ester of 5-hydroxymethylfurfural, 5-methylfurfural, 5- (chloromethyl)furfural, 5-methylfuroic acid, 5-(chloromethyl)furoic acid, 2,5-dimethylfuran and a mixture of two or more of these compounds with an oxidant in the presence of an oxidation catalyst at a temperature higher than 140 °C" (see abstract).
  • the oxidation catalyst comprises cobalt, manganese and/or a source of bromine (see claims 3 and 4).
  • WO 2009/030512 A2 relates to "hydroxymethylfurfural ethers and esters prepared in ionic liquids" (title).
  • a method is disclosed "for the manufacture of an ether or ester of 5- hydroxymethylfurfural by reacting a hexose-containing starting material or HMF with an alcohol or an organic acid dissolved into an ionic liquid, using a metal chloride as catalyst" (see claim 1 ).
  • US 2012/0271060 A1 discloses a "method for preparation of 2,5-furandicarboxylic acid and for the preparation of the dialkyl ester of 2,5-furandicarboxylic acid" (Title).
  • the method comprises "contacting a feed comprising a compound selected from the group consisting of 5-hydroxymethylfurfural ("HMF"), an ester of 5-hydroxymethyl-furfural, 5- methylfurfural, 5-(chloromethyl)furfural, 5-methylfuroic acid, 5-(chloromethyl)furoic acid, 2,5-dimethylfuran and a mixture of two or more of these compounds with an oxidant in the presence of an oxidation catalyst at a temperature higher than 140° C. (see claim 1 ).
  • HMF 5-hydroxymethylfurfural
  • WO 2014/014979 relates to a process to produce a carboxylic acid composition.
  • the process comprises oxidizing at least one oxidizable compound in an oxidizable raw material stream in the presence of an oxidizing gas stream, solvent stream, and at least one catalyst system.
  • HMF route in the scheme below.
  • these side reactions are catalyzed by acids and therefore are catalyzed by the same catalysts that are typically present under the reaction conditions chosen for dehy- drating carbohydrates, in particular said material mixture, comprising one, two or more compounds selected from the group consisting of hexoses (monomeric hexose molecules, e.g.
  • HMF fructose
  • oligosaccharides comprising hexose units oligosaccharides comprising hexose units
  • polysaccharides comprising hexose units to give HMF.
  • HMF ester route oligosaccharides comprising hexose units
  • HMF ether route polysaccharides comprising hexose units
  • Typical derivatives of HMF which are produced as an intermediate product in the overall production process finally leading to FDCA and, if appropriate, PEF and other compounds, are esters of 5-(hydroxymethyl)furfural and 5-(alkoxymethyl)furfurals (as well as other ethers of 5-(hydroxymethyl)furfural).
  • esters of 5-(hydroxymethyl)furfural and 5-(alkoxymethyl)furfurals and/or other ethers of 5-(hydroxymethyl)furfural can be present in an intermediate product mixture .
  • these derivatives of HMF are typically produced in admixture with HMF (which is present as a by-product).
  • the derivatives of HMF produced typically are meant to be used as a starting material in a subsequent oxidation step in order to produce FDCA.
  • HMF is present in admixture with said derivatives of HMF, and therefore there is a need in industry for the identification of oxidation conditions in which both, the derivative of HMF and HMF itself, are oxidized to FDCA in a high yield.
  • the "HMF route” typically involves a dehydration of carbohydrates in water (not preferred according to the present invention, see below)
  • the "HMF ester route” typically involves a dehydration of carbohydrates in the presence of one or more compounds selected from the group consisting of organic acids, anhydrides of organic acids and esters of organic acids
  • the "HMF ether route” typically involves a dehydration of carbohydrates in the presence of an aliphatic alcohol.
  • a first aspect it was an object of the present invention to provide an improved process for preparing furane-2,5-dicarboxylic acid which avoids or at least alleviates disadvantages of the processes known today (and as stated above) and which can be operated in an economically advantageous manner.
  • Preferred processes to be specified according to further aspects should favourably convert a starting material mixture comprising 5-(hydroxymethyl)furfural (HMF), as well as esters of 5-(hydroxymethyl)furfural and/or ethers of 5- (hydroxymethyl)furfural (preferably 5-(alkoxymethyl)furfurals) to FDCA, with a high yield, and be capable of converting said starting material mixture to FDCA at high selectivities compared to processes known in the prior art.
  • HMF 5-(hydroxymethyl)furfural
  • esters of 5-(hydroxymethyl)furfural and/or ethers of 5- (hydroxymethyl)furfural preferably 5-(alkoxymethyl)furfurals
  • T R1 temperature in the range T R1 of from 1 10 to 140 °C, preferably in the range of from 120 to 140 °C, so that an amount of said 5-(hydroxymethyl)furfural (HMF) present in the starting material mixture is oxidised to furan-2,5- dicarboxylic acid and a first product mixture results comprising furan-2,5- dicarboxylic acid and an unreacted amount of said one or more second reactants, and
  • step (c) subjecting the first product mixture obtained in step (b) or a mixture obtained
  • Esters of 5-(hydroxymethyl)furfural (compound 2) used as a second reactant in the process of the present invention are represented by the following formula:
  • R1 is hydrogen a branched, cyclic or linear alkyl radical, a branched, cyclic or linear alkenyl radical, an aryl radical, an aralkyl radical, or an alkaryl radical, having a total number of carbon atoms in the range of from 1 to 18, preferably 1 to 13, more preferably 1 to 10, even more preferably 1 to 7.
  • Ethers of 5-(hydroxymethyl)furfural (compound 3) used as a second reactant in the process of the present invention are represented by the following formula:
  • R2 is a branched, cyclic or linear alkyl radical (i.e. compound 3 is a 5- (alkoxymethyl)furfural), a branched, cyclic or linear alkenyl radical, an aryl radical, an aralkyl radical, or an alkaryl radical, having a total number of carbon atoms in the range of from 1 to 18, preferably 1 to 13, more preferably 1 to 10, eve more preferably 1 to 7.
  • Furan-2,5-dicarboxylic acid (compound 4) is represented by the formula:
  • the polishtotal number" of carbon atoms in a specified radical is the total number in the radical including any substituents. I.e., when counting the total number of carbon atoms in a branched radical the carbon atoms in the substituent are also counted.
  • step (b) the term “first oxidation reactions” indicates conditions causing HMF to react so that furan-2,5-dicarboxylic acid is generated.
  • step (c) the term “second oxidation conditions” indicates conditions causing the one or more second reactants selected from the group consisting of esters of 5- (hydroxymethyl)furfural and ethers of 5-(hydroxymethyl)furfural (preferably 5- (alkoxymethyl)furfural) to react so that furan-2,5-dicarboxylic acid is generated.
  • Step (c) comprises subjecting the first product mixture obtained in step (b) or a mixture obtained from the first product mixture obtained in step (b) by additional treatment steps to second oxidation conditions (as specified above or below and in the claims).
  • the first product mixture obtained in step (b) is directly used in step (c), i.e. there are no additional treatment steps for making and obtaining a mixture from said first product mixture.
  • said first product mixture is transformed into a mixture for use in step (c) by one or more additional treatment steps which are preferably selected from the group consisting of removing material from the first product mixture and adding material to the first product mixture.
  • steps (b) and (c) are conducted in the same reactor thus decreasing the complexity of the reactor design of the overall process.
  • steps (b) and (c) are conducted in the same reactor thus decreasing the complexity of the reactor design of the overall process.
  • steps (b) and (c) in two or more separate reactors in series, (in contrast to step-by-step synthesis).
  • steps (b) and (c) are conducted in several separate reactors.
  • the oxidation agent in steps (b) and/or (c) is preferably an oxygen containing gas, more preferably air or any other gas mixture comprising N 2 and 0 2 .
  • oxygen refers to molecular oxygen (0 2 )
  • oxygen gas refers to a gas substantially consisting of molecular oxygen (0 2 ).
  • the invention is inter alia based on the surprising discovery that when oxidising a starting material mixture comprising HMF(first reactant) and one or more compounds selected from the group consisting of esters of HMF and ethers of 5-(hydroxymethyl)furfural (compounds of formula 3, see above, preferably 5-(alkoxymethyl)furfurals) (second reactants) the maximum yield of FDCA is obtained when the oxidation is started at a (lower) temperature T R i in the range of from 1 10 to 140 °C and is then increased to a (higher) tem- perature T R2 in the range of from 140 to 200 °C (T R1 ⁇ T R2 ).
  • the reactant HMF is oxidised at a high reaction rate to give FDCA.
  • the second reactant(s) do not react to a significant amount (neither to FDCA nor to any by-products), i.e. their respective reaction rate is low.
  • the temperature is increased to temperature range T R2 and the rate of the oxidation reactions for the second reactant(s) is significantly increased so that they are oxidised to FDCA at an increased rate.
  • step (b) is kept in the range of from 120 to 135 °C, preferably from 125 to 135 °C, for at least 75 % of the duration (e.g. residence time) of step (b) and/or the temperature in step (c) is kept in the range of from 145 °C to 190 °C for at least 75 % of the duration (e.g. residence time) of step (c).
  • step (b) and step (c) Maintaining the reaction temperature for step (b) and step (c) in the temperature ranges as described above for a preferred process results in a more selective conversion of HMF to FDCA in step (b) and in a more selective conversion of the one or more second reac- tants to FDCA in step (c). Thus, the overall yield to FDCA is increased.
  • step (b) is at least conducted until 80 %, preferably until 90%, of said 5-(hydroxymethyl)furfural (HMF) present in the starting material mixture has been reacted to furan-2,5-dicarboxylic acid and by-products.
  • step (b) is at least conducted until 80 %, preferably until 90%, of said 5-(hydroxymethyl)furfural (HMF) present in the starting material mixture has been reacted to furan-2,5-dicarboxylic acid and by-products.
  • step (b) is conducted for a residence time in the range of from 10 to 120 minutes, preferably for a residence time in the range of from 30 to 100 minutes and/or step (c) is conducted for a residence time in the range of from 10 to 120 minutes, pref- erably for a residence time in the range of from 30 to 100 minutes.
  • step (c) is conducted for a residence time in the range of from 10 to 120 minutes, pref- erably for a residence time in the range of from 30 to 100 minutes.
  • a too short residence time is disadvantageous since no high yields in FDCA can be obtained (for step (b) and/or step (c)).
  • step (a) a too long residence time is disadvantageous since the overall selectivity towards FDCA is decreased with time due to decomposition of FDCA.
  • a process of the invention can be conducted in batch, semi-batch or continuous mode.
  • the skilled person would select the most favourable reactor design depending on the exact composition of the starting material mixture prepared or provided in step (a). Due to the limited thermal stability of the starting material mixture prepared or provided in step (a), back-mixed reactor concepts with low stationary concentrations of first and second reactants and oxidation intermediates are preferred.
  • suitable reactors include stirred tank reactors operated in semi-batch or continuous mode, or any other type of reactor with at least partial recycling of the effluent to the reaction zone, e.g. tubular reactors with external loop.
  • stirred tank reactor operated in semi-batch mode with gradually increasing temperature e.g. by using a temperature ramp
  • a cascade of two or more con- tinuously stirred tank reactors with gradually increasing temperature e.g. by using a temperature ramp.
  • step (i) in step (b) the concentrations of one or more compounds selected from the group consisting of 5-(hydroxymethyl)furfural (HMF) second reactants selected from the group consisting of esters of 5-(hydroxy- methyl)furfural and ethers of 5-(hydroxymethyl)furfural (preferably 5- (alkoxymethyl)furfurals), furan-2,5-dicarboxylic acid and/or the conversion of the oxidation agent, preferably oxygen, are monitored and
  • reaction conditions are changed from the reaction conditions of step (b) to the reaction conditions of step (c) if one or more of said concentrations and/or said conversion of the oxidation agent monitored, preferably oxygen, reach a predetermined value.
  • the skilled person will predetermine said value in view of the starting concentrations of HMF (first reactant) and the second reactants and/or on the basis of the oxidation agent chosen (preferably oxygen (0 2 ) is used as an oxidation agent).
  • the skilled person wishes to monitor the concentration of HMF in the mixture present in step (b) the skilled person starts from the starting concentration of HMF and calculates a (lower) concentration of HMF corresponding to a predetermined conversion.
  • the skilled person will typically consider the amount or concentration of oxygen in an outlet gas stream containing oxygen assuming that no conversion takes place (maximum oxygen concentration in the outlet gas stream), and he will consider the amount or concentration of oxygen in the inlet oxidation gas stream.
  • the skilled person will typically consider how in a given reaction apparatus the outlet stream composition will change when the oxidation agent (e.g. molecular oxy- gen (0 2 )) is not anymore converted in the reaction mixture but remains unreacted.
  • the oxygen concentration in the outlet gas stream is lower in comparison to the situation towards the end of the oxidation of HMF.
  • the concentration of the oxidation agent in the outlet gas stream will increase and enter a concentration range indicating that no further oxygen conversion takes place in the reaction mixture upon which, for example, the temperature can be increased to temperature range T R2 .
  • the concentration of small amounts of carbon monoxide or carbon dioxide gas in the outlet gas stream which often corresponds to the selectivity to FDCA and therewith also to the overall yield to FDCA.
  • the concentration of HMF or of the one or more second reactants or of the FDCA produced in the one or more reactors used for the process for preparing furan-2,5-dicarboxylic acid is advantageous to measure the concentration of HMF or of the one or more second reactants or of the FDCA produced in the one or more reactors used for the process for preparing furan-2,5-dicarboxylic acid.
  • step (b) and/or (c) the temperature in the respective mixture is increased stepwise or as a temperature ramp.
  • step (a) it is advantageous to increase the temperature in step (b) and/or (c) stepwise or as a temperature ramp thus increasing the overall yield of the reaction.
  • step (a) Also preferred is a process as described above or below, wherein in step (a)
  • a starting material mixture comprising 5-(hydroxymethyl)furfural (HMF) as a first reactant and one or more second reactants selected from the group consisting of esters of 5-(hydroxymethyl)furfural is prepared by dehydration of carbohydrates in the presence of one or more compounds selected from the group consisting of organic acids, anhydrides of organic acids and esters of organic acids or
  • step (a-eth) a starting material mixture comprising 5-(hydroxymethyl)furfural (HMF) as a first reactant and one or more second reactants selected from the group consisting of ethers of 5-(hydroxymethyl)furfural (preferably 5-(alkoxymethyl)furfurals) is prepared by dehydration of carbohydrates in the presence of an aliphatic alcohol as a solvent.
  • the dehydration of carbohydrates in step (a-est) or in step (a-eth) is preferably an acid- catalyzed dehydration.
  • Starting material mixtures as described above in step (a-est) or in step (a-eth) are conveniently produced by converting renewably raw materials (e.g. carbohydrates as fructose or glucose) into HMF and are thus a readily available and environmentally friendly source of HMF.
  • renewably raw materials e.g. carbohydrates as fructose or glucose
  • step (a) Also preferred is a process as described above or below, wherein in said starting material mixture prepared or provided in step (a)
  • (r-eth)the molar ratio of 5-(hydroxymethyl)furfural (HMF) to ethers of 5- (hydroxymethyl)furfural (preferably 5-(alkoxymethyl)furfurals) is in the range of from 1 : 1 to 1 : 100, preferably in the range of from 1 :2 to 1 :50.
  • step (a) the total amount of 5-(hydroxymethyl)furfural (HMF) is in the range of from 0.3 wt.-% to 30 wt.-%, preferably in the range of from 5 wt.- % to 15 wt, based on the total weight of the reaction mixture.
  • HMF 5-(hydroxymethyl)furfural
  • step (a) the total amount of ethers of 5- (hydroxymethyl)furfural (preferably 5-(alkoxymethyl)furfurals) and esters of 5-(hydroxy- methyl)furfural is in the range of from 5 wt.-% to 50 wt.-%, preferably in the range of from 10 wt.-% to 30 wt, based on the total weight of the reaction mixture. If HMF is present in a significant amount in said starting material mixture provided or prepared in step (a), the overall yield to FDCA is increased in a process for preparing FDCA as described herein above or below in comparison to processes known in the prior art.
  • step (b) subjecting said starting material mixture to first oxidation conditions comprises contacting the starting material mixture with oxygen in the presence of a catalyst system comprising cobalt, manganese and bromine and/or in step (c) subjecting said first product mixture obtained in step (b) or the mixture obtained from the first product mixture obtained in step (b) by additional treatment steps to second oxidation conditions comprises contacting the starting material mixture with oxygen in the presence of a catalyst system comprising cobalt, manganese and bromine.
  • a catalyst system comprising cobalt, manganese and bromine as described above is used in step (b) and/or step (c) preferably-the total amount of cobalt is in the range of from 0.01 wt.-% to 5 wt.-%, preferably in the range of from 0.1 wt.-% to 1 wt.-%, based on the on the total weight of the starting material mixture prepared or provided in step (a), and/or - the total amount of manganese is in the range of from 0.01 wt.-% to 5 wt.-%, preferably in the range of from 0.1 wt.-% to 1 wt.-%, based on the on the total weight of the starting material mixture prepared or provided in step (a), and/or the total amount of bromine is in the range of from 0.01 wt.-% to 5 wt.-%, preferably in the range of from 0.1 wt.-% to 1 wt.-%, based
  • step (b) and step (c) reduces the complexity of the reactor design and the corresponding costs.
  • step (b) the starting material mixture comprises a saturated organic acid having 2 to 6 carbon atoms (i.e. a total number of carbon atoms in the range of from 2 to 6) as a solvent, preferably acetic acid.
  • step (c) the first product mixture comprises a saturated organic acid having 2 to 6 carbon atoms (i.e. a total number of carbon atoms in the range of from 2 to 6) as a solvent, preferably acetic acid.
  • Saturated organic acids as specified in the aspect above are preferred solvents for a process for preparing FDCA since they dissolve HMF, esters of 5-(hydroxymethyl)furfural and ethers of 5-(hydroxymethyl)furfural (preferably used are 5-(alkoxymethyl)furfurals) in large quantities.
  • step (a) (a-est) a starting material mixture comprising 5-(hydroxymethyl)furfural (HMF) as a first reactant and one or more second reactants selected from the group consisting of esters of 5-(hydroxymethyl)furfural is prepared by catalyzed dehydration of carbohydrates in the presence of one or more compounds selected from the group consisting of organic acids, anhydrides of organic acids and esters of organic acids, in said starting material mixture prepared in step (a)
  • HMF 5-(hydroxymethyl)furfural
  • step (r-est) the molar ratio of 5-(hydroxymethyl)furfural (HMF) to esters of 5-(hydroxy- methyl)furfural is in the range of from 1 : 1 to 1 : 100, preferably in the range of from 1 :2 to 1 :50
  • step (b) subjecting said starting material mixture to first oxidation conditions comprises contacting the starting material mixture with oxygen in the presence of a catalyst system comprising cobalt, manganese and bromine
  • step (c) subjecting said first product mixture obtained in step (b) or the mixture obtained from the first product mixture obtained in step (b) by additional treatment steps to second oxidation conditions comprises contacting the starting material mixture with oxygen in the presence of a catalyst system comprising cobalt, manganese and bromine.
  • step (b) and step (c) the same catalyst system is used, and the starting material mixture comprises a saturated organic acid having 2 to 6 carbon atoms (i.e. a total number of carbon atoms in the range of from 2 to 6) as a solvent, preferably acetic acid.
  • the second reactant is selected from the group consisting of esters of 5-(hydroxymethyl)furfural.
  • step (a) (a-eth) a starting material mixture comprising 5-(hydroxymethyl)furfural (HMF) as a first reactant and one or more second reactants selected from the group consisting of ethers of 5-(hydroxymethyl)furfural (preferably 5-(alkoxymethyl)furfurals) is prepared by dehydration of carbohydrates in the presence of an aliphatic alcohol as a solvent.
  • step (a) a starting material mixture comprising 5-(hydroxymethyl)furfural (HMF) as a first reactant and one or more second reactants selected from the group consisting of ethers of 5-(hydroxymethyl)furfural (preferably 5-(alkoxymethyl)furfurals) is prepared by dehydration of carbohydrates in the presence of an aliphatic alcohol as a solvent.
  • step (r-eth) the molar ratio of 5-(hydroxymethyl)furfural (HMF) to ethers of 5- (hydroxymethyl)furfural (preferably 5-(alkoxymethyl)furfurals) is in the range of from 1 : 1 to 1 : 100, preferably in the range of from 1 :2 to 1 :50
  • step (b) subjecting said starting material mixture to first oxidation conditions comprises contacting the starting material mixture with oxygen in the presence of a catalyst system comprising cobalt, manganese and bromine
  • step (c) subjecting said first product mixture obtained in step (b) or the mixture obtained from the first product mixture obtained in step (b) by additional treatment steps to second oxidation conditions comprises contacting the starting material mixture with oxygen in the presence of a catalyst system comprising cobalt, manganese and bromine.
  • step (b) and step (c) the same catalyst system is used, and the starting material mixture comprises a saturated organic acid having 2 to 6 carbon atoms (i.e. a total number of carbon atoms in the range of from 2 to 6) as a solvent, preferably acetic acid.
  • a saturated organic acid having 2 to 6 carbon atoms (i.e. a total number of carbon atoms in the range of from 2 to 6) as a solvent, preferably acetic acid.
  • the second reactant is selected from the group consisting of esters of 5-(hydroxymethyl)furfural and ethers of 5- (hydroxymethyl)furfural (preferably 5-(alkoxymethyl)furfurals).
  • the first product mixture obtained in step (b) comprises 5-(hydroxymethyl)furfural (HMF) in a molar amount below 20 %, preferably below 10 %, even more preferably below 5 % of the molar amount present in said starting material mixture furan-2,5-dicarboxylic acid in a molar amount above 75 % of the molar amount of 5-(hydroxymethyl)furfural (HMF) present in said starting material mixture.
  • HMF 5-(hydroxymethyl)furfural
  • the person skilled in the art identifies the corresponding reaction conditions by, e.g., a small series of pre-experiments. For example, in such a series of pre-experiments, he changes the reaction temperature ranges (T R1 and/or T R2 ) and the corresponding residence time and measures the molar amount of HMF and/or the molar amount of FDCA in the first product mixture obtained in step (b).
  • step (b) preferably comprises
  • reaction temperature ranges T R1 or T R2
  • residence time measures the molar amount of HMF and/or the molar amount of FDCA in the first product mixture obtained in step (b) and respectively in step (c).
  • one, two or more of said second reactants selected from the group consisting of esters of 5-(hydroxy- methyl)furfural and ethers of 5-(hydroxymethyl)furfural (preferably 5- (alkoxymethyl)furfurals) are selected from the group consisting of 5- (acetoxymethyl)furfural (5-AMF), 5-(formyloxymethyl)furfural, 5-(ethoxymethyl)furfural (5- EMF), 5-(methoxymethyl)furfural (5-MMF).
  • esters of 5-(hydroxymethyl)furfural and ethers of 5-(hydroxymethyl)furfural are more conveniently oxidised to FDCA than other esters of 5-(hydroxymethyl)furfural or other ethers of 5-(hydroxymethyl)furfural.
  • Liquid products were analyzed using quantitative HPLC on an Agilent 1 100 instrument using a Waters XBridge BEH C18 (5 ⁇ 3x150 mm) column equipped with a UV detector.
  • Comparative example C1 (temperature: 130 °C):
  • a 1.2 L stirred-tank reactor equipped with reflux condenser, baffles and disk stirrer is charged with a catalyst mixture comprising glacial acetic acid (570 mL), Co(OAc) 2 (4.4 g), Mn(OAc) 2 (300 mg) and hydrobromic acid (4.4 g of a 48 wt.-% solution in water).
  • the autoclave is pressurized to 10 bar with nitrogen, the stirrer is started (1200 rpm) and the catalyst mixture is heated to 130 °C. Once the reaction temperature is reached, the off- gas valve is opened and a constant flow of air (200 NL/h) (as an example of an oxidation agent according to the invention) is passed through the reactor.
  • the starting material mixture as prepared is then dosed into the reactor comprising the catalyst mixture over a period of 90 min, wherein the temperature of 130 °C was maintained during dosing.
  • the starting material mixture used mimics a starting material mix- ture prepared by dehydration of carbohydrates in the presence of an aliphatic alcohol as a solvent, wherein the aliphatic alcohol as a solvent was exchanged by acetic acid after the preparation of the starting material mixture (corresponding to step (a-eth) as described herein above).
  • a 1.2 L stirred-tank reactor equipped with reflux condenser, baffles and disk stirrer is charged with a catalyst mixture comprising glacial acetic acid (570 mL), Co(OAc) 2 (4.4 g), Mn(OAc) 2 (300 mg) and hydrobromic acid (4.4 g of a 48 wt.-% solution in water).
  • the autoclave is pressurized to 10 bar with nitrogen, the stirrer is started (1200 rpm) and the catalyst mixture is heated to 160 °C. Once the reaction temperature is reached, the off- gas valve is opened and a constant flow of air (200 NL/h) (as an example of an oxidation agent according to the invention) is passed through the reactor.
  • the starting material mixture as prepared is then dosed into the reactor comprising the catalyst mixture over a period of 90 min, wherein the temperature of 160 °C was maintained during dosing.
  • the starting material mixture used mimics a starting material mix- ture prepared by dehydration of carbohydrates in the presence of an aliphatic alcohol as a solvent, wherein the aliphatic alcohol as a solvent was exchanged by acetic acid after the preparation of the starting material mixture (corresponding to step (a-eth) as described herein above).
  • a 1.2 L stirred-tank reactor equipped with reflux condenser, baffles and disk stirrer is charged with a catalyst mixture comprising glacial acetic acid (570 mL), Co(OAc) 2 (4.4 g), Mn(OAc) 2 (300 mg) and hydrobromic acid (4.4 g of a 48 wt.-% solution in water).
  • the autoclave is pressurized to 10 bar with nitrogen, the stirrer is started (1200 rpm) and the catalyst mixture is heated to 150 °C. Once the reaction temperature is reached, the off- gas valve is opened and a constant flow of air (200 NL/h) (as an example of an oxidation agent according to the invention) is passed through the reactor.
  • the starting material mixture as prepared is then dosed into the reactor comprising the catalyst mixture over a period of 90 min, wherein a temperature of 150 °C was maintained during dosing.
  • the starting material mixture used mimics a starting material mixture prepared by dehydration of carbohydrates in the presence of an aliphatic alcohol as a solvent, wherein the aliphatic alcohol as a solvent was exchanged by acetic acid after the preparation of the starting material mixture (corresponding to step (a-eth) as described herein above).
  • the first product mixture obtained is subjected to second oxidation conditions in the range of from above 150 to approximately 170 °C by increasing the temperature of the first product mixture, with a temperature ramp of 2 K/min, so that the temperature of 170 °C is reached after 10 minutes.
  • second oxidation conditions in the range of from above 150 to approximately 170 °C by increasing the temperature of the first product mixture, with a temperature ramp of 2 K/min, so that the temperature of 170 °C is reached after 10 minutes.
  • reaction mixture is allowed to further react for 30 min at 170 °C.
  • step (c) At least a fraction of said unreacted amount of 5-MMF and oxidation intermediates (DFF, FFCA, HFCA) present in the first product mixture is oxidized resulting in a second product mixture comprising furan-2,5-dicarboxylic acid.
  • the air-flow is stopped and replaced by a nitrogen flow and the second product mixture is cooled to room temperature.
  • Solid reaction products of the second product mixture are isolated by filtration, subse- quently washed with acetic acid and water, and dried under vacuum.
  • the thus obtained solid reaction products comprising FDCA and FDCA-monomethylester are analyzed using quantitative NMR (see analysis below, item (i)).
  • Residual quantities of FDCA and the monomethylester of FDCA in the liquid phase of the second product mixture are analyzed using quantitative LC-chromatography (see analysis below, item (ii)).
  • Example E1 (according to the invention; "temperatures 130 °C, 160 °C”): A 1.2 L stirred-tank reactor equipped with reflux condenser, baffles and disk stirrer is charged with a catalyst mixture comprising glacial acetic acid (570 mL), Co(OAc) 2 (4.4 g), Mn(OAc) 2 (300 mg) and hydrobromic acid (4.4 g of a 48 wt.-% solution in water). The autoclave is pressurized to 10 bar with nitrogen, the stirrer is started (1200 rpm) and the catalyst mixture is heated to 130 °C. Once the reaction temperature is reached, the off- gas valve is opened and a constant flow of air (200 NL/h) (as an example of an oxidation agent according to the invention) is passed through the reactor.
  • a constant flow of air 200 NL/h
  • a solution of 5-(hydroxymethyl)furfural (5-HMF; 33.6 g, 267 mmol) and 5- (methoxymethyl)furfural (5-MMF; 33.6 g, 240 mmol) in acetic acid (155 g) is prepared as a starting material mixture.
  • the starting material mixture as prepared is then dosed into the reactor comprising the catalyst mixture over a period of 90 min, wherein the temperature of 130 °C was maintained during dosing.
  • the starting material mixture used mimics a starting material mixture prepared by dehydration of carbohydrates in the presence of an aliphatic alcohol as a solvent, wherein the aliphatic alcohol as a solvent was exchanged by acetic acid after the preparation of the starting material mixture (corresponding to step (a-eth) as described herein above).
  • the first product mixture obtained is subjected to second oxidation conditions in the range of from above 140 to approximately 160 °C by increasing the temperature of the first product mixture obtained in step (b), with a temperature ramp of 2 K/min, so that the temperature of 160 °C is reached after 15 minutes.
  • second oxidation conditions in the range of from above 140 to approximately 160 °C by increasing the temperature of the first product mixture obtained in step (b), with a temperature ramp of 2 K/min, so that the temperature of 160 °C is reached after 15 minutes.
  • reaction mixture is allowed to further react for 30 min at 160 °C.
  • step (c) At least a fraction of said unreacted amount of 5-MMF and oxidation intermediates (DFF, FFCA, HFCA) present in the first product mixture is oxidized resulting in a second product mixture comprising furan-2,5-dicarboxylic acid.
  • the yield of FDCA can be calculated by formula (I) n + n
  • n H MF and n M MF are the molar amounts of the starting materials used.
  • the yield of FDCA-monomethylester can be calculated by formula (II) n + n
  • n H MF and n M MF are the molar amounts of the starting materials used.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Furan Compounds (AREA)

Abstract

La présente invention concerne un procédé de préparation d'acide furan-2,5-dicarboxylique comprenant les étapes suivantes : (a) de préparation ou fourniture d'un mélange matériau de départ comprenant du 5-(hydroxyméthyl)furfural (HMF) comme premier réactif et un ou plusieurs seconds réactifs sélectionnés dans le groupe constitué des esters de 5-(hydroxyméthyl)furfural et des éthers de 5-(hydroxyméthyl)furfural, (b) de soumission dudit mélange matériau de départ aux premières conditions d'oxydation à une température située dans la plage TR1 de 110 à 140°C de sorte qu'une quantité dudit 5-(hydroxyméthyl)furfural (HMF) présent dans le mélange matériau de départ est oxydée en acide furan-2,5-dicarboxylique et qu'un premier mélange de produits résulte comprenant de l'acide furan-2,5-dicarboxylique et une quantité n'ayant pas réagi desdits un ou plusieurs seconds réactifs, et (c) de soumission du premier mélange de produits obtenu dans l'étape (b) ou du mélange obtenu à partir du premier mélange de produits obtenu dans l'étape (b) par des étapes de traitement supplémentaires aux secondes conditions d'oxydation à une température accrue dans la plage TR2 de plus de 140 à 200°C de sorte que ladite au moins une fraction de ladite quantité n'ayant pas réagi desdits un ou plusieurs seconds réactifs présents dans le premier mélange de produits est oxydée et un second mélange de produits résulte comprenant de l'acide furan-2,5-dicarboxylique.
PCT/EP2016/076510 2015-11-04 2016-11-03 Procédé de préparation d'acide furan-2,5-dicarboxylique Ceased WO2017076947A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP15193069.0 2015-11-04
EP15193069 2015-11-04

Publications (1)

Publication Number Publication Date
WO2017076947A1 true WO2017076947A1 (fr) 2017-05-11

Family

ID=54427625

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2016/076510 Ceased WO2017076947A1 (fr) 2015-11-04 2016-11-03 Procédé de préparation d'acide furan-2,5-dicarboxylique

Country Status (1)

Country Link
WO (1) WO2017076947A1 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10259797B2 (en) 2015-11-04 2019-04-16 Basf Se Process for preparing a mixture comprising 5-(hydroxymethyl) furfural and specific HMF esters
EP3498699A1 (fr) 2017-12-13 2019-06-19 Basf Se Procédé de chromatographie pour la purification de dérivés du furfural
US10428039B2 (en) 2015-11-04 2019-10-01 Basf Se Process for preparing furan-2,5-dicarboxylic acid
US10618873B2 (en) 2016-02-01 2020-04-14 Basf Se Method for producing C4-C15 lactams
US10774034B2 (en) 2017-05-03 2020-09-15 Basf Se Process for the conversion of ethylene oxide to monoethanolamine and ethylenediamine employing a zeolite
CN112638888A (zh) * 2018-06-25 2021-04-09 伊士曼化工公司 用于生产5-(烷氧基羰基)呋喃-2-甲酸（acfc）的氧化方法
US11091425B2 (en) 2016-11-30 2021-08-17 Basf Se Process for the conversion of ethylene glycol to ethylenediamine employing a zeolite catalyst
US11104637B2 (en) 2016-11-30 2021-08-31 Basf Se Process for the conversion of monoethanolamine to ethylenediamine employing a copper-modified zeolite of the MOR framework structure
CN113826808A (zh) * 2021-09-27 2021-12-24 佛山科学技术学院 一种清除5-羟甲基糠醛的方法及其在食品加工中的应用
US11440895B2 (en) 2018-06-25 2022-09-13 Eastman Chemical Company Oxidation process to produce 5-(alkoxycarbonyl)furan-2-carboxylic acids (ACFC)
US11787774B2 (en) 2019-09-05 2023-10-17 Eastman Chemical Company Efficient process for producing 5-(alkoxycarbonyl)-furan-2-carboxylic acids

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080103318A1 (en) 2006-10-31 2008-05-01 Lilga Michael A Hydroxymethyl Furfural Oxidation Methods
WO2009030512A2 (fr) 2007-09-07 2009-03-12 Furanix Technologies B.V. Éthers et esters d'hydroxyméthylfurfural préparés dans des liquides ioniques
WO2011043661A1 (fr) 2009-10-07 2011-04-14 Furanix Technologies B.V. Procédé de préparation d'acide 2,5-furane dicarboxylique et de préparation de l'ester dialkylique d'acide 2,5-furane dicarboxylique
US8242293B2 (en) 2006-03-10 2012-08-14 Furanix Technologies B.V. Method for the synthesis of organic acid esters of 5-hydroxymethylfurfural and their use
US20120283452A1 (en) 2009-10-07 2012-11-08 Furanix Technologies B.V. Method for the preparation of 2,5-furandicarboxylic acid and esters thereof
WO2012161968A1 (fr) 2011-05-24 2012-11-29 Eastman Chemical Company Procédé d'oxydation pour produire un produit d'acide carboxylique brut et/ou purifié
WO2013033081A2 (fr) 2011-08-31 2013-03-07 The University Of Kansas Procédé pour la production à la fois d'acide succinique et d'acide 2,5-furandicarboxylique biosourcés
WO2014014979A1 (fr) 2012-07-20 2014-01-23 Eastman Chemical Company Procédé d'oxydation pour obtenir un produit d'acide carboxylique purifié par déplacement de solvant et post-oxydation

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8242293B2 (en) 2006-03-10 2012-08-14 Furanix Technologies B.V. Method for the synthesis of organic acid esters of 5-hydroxymethylfurfural and their use
US20080103318A1 (en) 2006-10-31 2008-05-01 Lilga Michael A Hydroxymethyl Furfural Oxidation Methods
WO2008054804A2 (fr) 2006-10-31 2008-05-08 Battelle Memorial Institute Procédés d'oxydation d'hydroxyméthyl furfural
WO2009030512A2 (fr) 2007-09-07 2009-03-12 Furanix Technologies B.V. Éthers et esters d'hydroxyméthylfurfural préparés dans des liquides ioniques
WO2011043661A1 (fr) 2009-10-07 2011-04-14 Furanix Technologies B.V. Procédé de préparation d'acide 2,5-furane dicarboxylique et de préparation de l'ester dialkylique d'acide 2,5-furane dicarboxylique
US20120271060A1 (en) 2009-10-07 2012-10-25 Furanix Technologies B.V. Method for the preparation of 2,5-furandicarboxylic acid and for the preparation of the dialkyl ester of 2,5-furandicarboxylic acid
US20120283452A1 (en) 2009-10-07 2012-11-08 Furanix Technologies B.V. Method for the preparation of 2,5-furandicarboxylic acid and esters thereof
WO2012161968A1 (fr) 2011-05-24 2012-11-29 Eastman Chemical Company Procédé d'oxydation pour produire un produit d'acide carboxylique brut et/ou purifié
US20120302772A1 (en) 2011-05-24 2012-11-29 Eastman Chemical Company Oxidation process to produce a crude and/or purified carboxylic acid product
WO2013033081A2 (fr) 2011-08-31 2013-03-07 The University Of Kansas Procédé pour la production à la fois d'acide succinique et d'acide 2,5-furandicarboxylique biosourcés
WO2014014979A1 (fr) 2012-07-20 2014-01-23 Eastman Chemical Company Procédé d'oxydation pour obtenir un produit d'acide carboxylique purifié par déplacement de solvant et post-oxydation

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Methodology and scope of metal/bromide autoxidation of hydrocarbons", CATALYSIS TODAY, vol. 23, 1995, pages 69 - 158
LICHTENTHALER, F.W.: "Ullmann's Encyclopedia of Industrial Chemistry", 2010, WILEY-VCH VERLAG GMBH & CO. KGAA, article "Carbohydrates as Organic Raw Materials"

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10259797B2 (en) 2015-11-04 2019-04-16 Basf Se Process for preparing a mixture comprising 5-(hydroxymethyl) furfural and specific HMF esters
US10428039B2 (en) 2015-11-04 2019-10-01 Basf Se Process for preparing furan-2,5-dicarboxylic acid
US10618873B2 (en) 2016-02-01 2020-04-14 Basf Se Method for producing C4-C15 lactams
US11091425B2 (en) 2016-11-30 2021-08-17 Basf Se Process for the conversion of ethylene glycol to ethylenediamine employing a zeolite catalyst
US11104637B2 (en) 2016-11-30 2021-08-31 Basf Se Process for the conversion of monoethanolamine to ethylenediamine employing a copper-modified zeolite of the MOR framework structure
US10774034B2 (en) 2017-05-03 2020-09-15 Basf Se Process for the conversion of ethylene oxide to monoethanolamine and ethylenediamine employing a zeolite
EP3498699A1 (fr) 2017-12-13 2019-06-19 Basf Se Procédé de chromatographie pour la purification de dérivés du furfural
CN112638888A (zh) * 2018-06-25 2021-04-09 伊士曼化工公司 用于生产5-(烷氧基羰基)呋喃-2-甲酸（acfc）的氧化方法
US11236199B2 (en) * 2018-06-25 2022-02-01 Eastman Chemical Company Oxidation process to produce 5-(alkoxycarbonyl)furan-2-carboxylic acids (ACFC)
US11440895B2 (en) 2018-06-25 2022-09-13 Eastman Chemical Company Oxidation process to produce 5-(alkoxycarbonyl)furan-2-carboxylic acids (ACFC)
US11655334B2 (en) 2018-06-25 2023-05-23 Eastman Chemical Company Oxidation process to produce 5 methyl 5-methylfuran-2-carboxylate (MMFC)
CN112638888B (zh) * 2018-06-25 2024-04-02 伊士曼化工公司 用于生产5-(烷氧基羰基)呋喃-2-甲酸（acfc）的氧化方法
US11787774B2 (en) 2019-09-05 2023-10-17 Eastman Chemical Company Efficient process for producing 5-(alkoxycarbonyl)-furan-2-carboxylic acids
CN113826808A (zh) * 2021-09-27 2021-12-24 佛山科学技术学院 一种清除5-羟甲基糠醛的方法及其在食品加工中的应用
CN113826808B (zh) * 2021-09-27 2024-02-06 佛山科学技术学院 一种清除5-羟甲基糠醛的方法及其在食品加工中的应用

Similar Documents

Publication Publication Date Title
WO2017076947A1 (fr) Procédé de préparation d'acide furan-2,5-dicarboxylique
US10745369B2 (en) Processes for producing 2,5-furandicarboxylic acid and derivatives thereof and polymers made therefrom
CN102666521B (zh) 2，5-呋喃二甲酸和2，5-呋喃二甲酸的二烷基酯的制备方法
JP5441914B2 (ja) テレフタル酸組成物及びその製造方法
Amarasekara et al. NaOH catalyzed condensation reactions between levulinic acid and biomass derived furan-aldehydes in water
US10385033B2 (en) Process for preparing furan-2,5-dicarboxylic acid
CA2902493C (fr) Procede de fabrication d'acide 2,5-furan-dicarboxylique
US9238635B2 (en) Method for producing 5-hydroxymethylfurfural
US20170137363A1 (en) Method for producing muconic acids and furans from aldaric acids
KR101715169B1 (ko) 2,5-푸란디카르복실산의 제조 방법
Zhang et al. A facile and effective method for preparation of 2.5-furandicarboxylic acid via hydrogen peroxide direct oxidation of 5-hydroxymethylfurfural
JP2014515037A5 (fr)
Ban et al. Production of 2, 5-furandicarboxylic acid by optimization of oxidation of 5-methyl furfural over homogeneous Co/Mn/Br catalysts
KR20180080260A (ko) 푸란-2,5-디카르복실산을 제조하는 방법
CN108473455A (zh) 用于制备包含5-(羟基甲基)糠醛和特定的hmf酯的混合物的方法
Pedersen et al. Scalable synthesis of hydroxymethyl alkylfuranoates as stable 2, 5-furandicarboxylic acid precursors
CN119948018A (zh) 呋喃衍生物的氧化
BR112012008163B1 (pt) Método para a preparação de ácido 2,5-furanodicarboxílico e para a preparação de éster dialquílico de ácido 2,5-furanodicarboxílico

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: 16790369

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16790369

Country of ref document: EP

Kind code of ref document: A1