WO2019014393A1 - Nouveaux procédés de préparation d'acide 2,5-furandicarboxylique - Google Patents

Nouveaux procédés de préparation d'acide 2,5-furandicarboxylique Download PDF

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Publication number
WO2019014393A1
WO2019014393A1 PCT/US2018/041707 US2018041707W WO2019014393A1 WO 2019014393 A1 WO2019014393 A1 WO 2019014393A1 US 2018041707 W US2018041707 W US 2018041707W WO 2019014393 A1 WO2019014393 A1 WO 2019014393A1
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Prior art keywords
acid
reaction mixture
sugar derivative
halide salt
consist
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PCT/US2018/041707
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English (en)
Inventor
James M. Longmire
Stanley Herrmann
Eric L. Dias
Henricus Johannes Cornelis DEN OUDEN
Staffan Torssell
Ruja SHRESTHA
Gary M. Diamond
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Stora Enso Oyj
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Publication of WO2019014393A1 publication Critical patent/WO2019014393A1/fr

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    • 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

  • aspects of the present disclosure relate to processes for preparing 2,5- furandicarboxylic acid from various substrates, including C 6 -aldaric acids and lactones of C 6 - aldaric acids.
  • FDCA 2,5-furandicarboxylic acid
  • FDCA and its derivatives have many commercial applications.
  • FDCA and its derivatives have the potential to displace aromatic dicarboxylic acids such as terephthalic and isophthalic acid.
  • FDCA and its derivatives are also useful in the production of other commodity chemicals.
  • FDCA may be hydrogenated to adipic acid, which is utilized in the production of nylon.
  • Aromatic dicarboxylic acids are used for the production of polyesters and polyamides in the scale of tens of millions of tons per year.
  • FDCA can be produced by direct oxidation of 5-hydroxymethylfurfural (HMF) with nitric acid, though with low selectivity and yield.
  • FDCA and its esters can be produced by oxidation of mono- or dialkoxymethylfurfural in the presence of a homogeneous catalytic system that is similar to the system used in terephthalic acid production (Co/Mn/Br) and results a maximum total yield of furandicarboxylics (with FDCA as a major constituent) of 82%.
  • the present disclosure is directed to a process for producing
  • FDCA 2.5- furandicarboxylic acid
  • the sugar derivative substrate can be a homogeneous sugar derivative substrate or the sugar derivative substrate can be a heterogeneous sugar derivative substrate.
  • the sugar derivative substrate can be selected from the group consisting of glucaric acid, glucaric acid dilactone, 1,4-glucaric acid monolactone, 3,6-glucaric acid monolactone, sodium glucarate, potassium glucarate, calcium glucarate, galactaric acid, 1,4-galactaric acid monolactone, 3,6-galactaric acid monolactone, sodium galactarate, potassium galactarate, calcium galactrate, mannaric acid, mannaric acid dilactone, 1,4-mannaric acid monolactone,
  • the Bronsted acid can selected from the group consisting of hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, phosphoric acid, methanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, acetic acid, and trifluoracetic acid.
  • the Bronsted acid can be selected from the group consisting of hydrochloric acid, hydrobromic acid, sulfuric acid, and methanesulfonic acid.
  • the halide salt can be a metal halide or a tetraalkylammonium halide.
  • the metal halide can be selected from the group consisting of FeBr 2 , FeBr 3 , FeCl 2 , FeCl 3 , CuBr, CuBr 2 , CuCl, CuCl 2 , ZnCl 2 , ZnBr 2 , NiCl 2 , NiBr 2 , NaCl, NaBr, Nal, LiBr, LiCl, CaCl 2 , CaBr 2 , MgCl 2 , MgBr 2 , KC1, KBr, and KI.
  • the metal halide salt can be selected from the group consisting of FeBr 2 , FeCl 2 , CuBr 2 , CuCl 2 , ZnCl 2 , ZnBr 2 , NiCl 2 , NiBr 2 , LiBr, LiCl, CaCl 2 , CaBr 2 , MgCl 2 , and MgBr 2 .
  • the metal halide salt can be CaBr 2 and the Bronsted acid can be hydrobromic acid.
  • the metal halide salt can be CaBr 2 and the Bronsted acid can be hydrochloric acid.
  • the metal halide salt can be CaBr 2 and the Bronsted acid can be methanesulfonic acid.
  • the metal halide salt can be CaBr 2 and the Bronsted acid can be sulfuric acid.
  • the metal halide salt can be MgBr 2 and the Bronsted acid can be hydrobromic acid.
  • the metal halide salt can be MgBr 2 and the Bronsted acid can be methanesulfonic acid.
  • the metal halide can be MgBr 2 and the Bronsted acid can be sulfuric acid.
  • the metal halide can be LiBr and the Bronsted acid can be hydrobromic acid.
  • the metal halide can be LiBr and the Bronsted acid can be methanesulfonic acid.
  • the metal halide salt can be ZnCl 2 and the Bronsted acid can be hydrochloric acid.
  • the tetraalkylammonium halide can be selected from the group consisting of tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, tetrabutylammonium chloride, and tetrabutylammonium bromide.
  • the tetraalkylammonium halide salt can be tetraethylammonium bromide and the Bronsted acid can be methanesulfonic acid.
  • the water-miscible organic solvent can be selected from the group consisting of 1,4-dioxane, tetrahydrofuran, sulfolane, a glyme, N-methyl-2-pyrrolidone, methyl ethyl ketone, dimethyl foimamide, and dimethyl sulfoxide.
  • the water-miscible organic solvent can be 1,4-dioxane or sulfolane.
  • the glyme can be selected from the group consisting of 1,2-dimethoxyethane, ethyl glyme, diethylene glycol dimethyl ether, ethyl diglyme, triglyme, butyl diglyme, tetraglyme, and a polyglyme.
  • the reaction mixture can be pressurized to a pressure ranging from 15-500 psi, 25-500 psi, 50-500 psi, 100-500 psi, 200-500 psi, 300-500 psi, or 400-500 psi or can be within a range defined by any two of the aforementioned pressures.
  • the concentration of the sugar derivative substrate can be in the range from 0.01 M to 10.0 M.
  • the concentration of acid can range from between 0.01-10.0 M, 0.02-5.0 M, 0.05-2.0 M, 0.10-1.0 M, 0.15-1.0 M, 0.20-1.0 M, 0.2-1.25 M, 0.4-1.25 M, 0.5- 1.0 M, or 0.6-1.25 M, or can be within a range defined by any two of the aforementioned concentrations.
  • the concentration of Bronsted acid can be in the range from 0.05 M to 10.0 M.
  • the concentration of acid can range from between 0.05-10.0 M, 0.10-5.0 M, 0.2-4.0 M, or 0.4-3.0 M, or can be within a range defined by any two of the aforementioned concentrations.
  • the concentration of halide salt can range from between 0.01-3.0 M, 0.05- 2.0 M, 0.1-1.0 M, or 0.2-0.5 M, or can be within a range defined by any two of the aforementioned concentrations.
  • the concentration of halide salt can be at least 0.1 M.
  • the concentration of halide salt can be less than 2.0 M, or less than 1.5 M, or less than 1 M, or less than 0.75 M, or less than 0.5 M but not zero.
  • the process can further comprise adding water to the reaction mixture.
  • concentration of water can range from between 0.01- 20.0 M, 0.01- 10.0 M, 0.1-5.0 M, or 0.2-1.0 M, or can be within a range defined by any two of the aforementioned concentrations.
  • the process can further comprise adding alcohol to the reaction mixture.
  • the alcohol can be selected from the group consisting of n-butanol, sec-butanol, isobutanol, 1-pentanol, 2-pentanol, 2-(2-chloroethoxy) ethanol), ethoxyethanol, and cyclohexanol.
  • the concentration of alcohol can range from between 0.01-1.0 M, 0.1-l.OM, or 0.5-1.0M, or can be within a range defined by any two of the aforementioned concentrations.
  • the process can comprise the step of pressurizing the reaction mixture with one or more gasses selected from the group consisting of nitrogen, argon, helium, and carbon dioxide.
  • the process can comprise the step of heating the reaction mixture.
  • the reaction mixture can be heated to a temperature range from between 90-200 °C, 110-160 °C, 110-180 °C, 70-150 °C, 80-150 °C, 90-150 °C, 100-150 °C, 110-150 °C, 120-150 °C, 130-150 °C, or 140-150 °C or within a range defined by any two of the aforementioned temperatures.
  • the reaction mixture can be heated to a temperature of 90 °C.
  • the reaction mixture can be heated to a temperature of 120 °C.
  • the reaction mixture can be heated to a temperature of 140 °C or 160 °C.
  • the reaction mixture can be heated for 1 min. to 24 hours, 1 min.
  • the reaction mixture is heated to a temperature of 90-200 °C, 110-160 °C, or 110-180 °C, preferably 130-160 °C, for time period of 1 min. to 24 hours, 1 min. to 3 hours, or 1 min.
  • the concentration of sugar derivative substrate can range from between 0.05-10.0 M, 0.10-5.0 M, 0.2-4.0 M, or 0.4-3.0 M, or can be within a range defined by any two of the aforementioned concentrations.
  • the process for producing FDCA can result in formation of 2-furoic acid.
  • the process for producing FDCA may utilize dioxane as the water- miscible organic solvent, and the process can further comprise: forming a 2-haloethoxy ethanol; and reacting the 2-haloethoxy ethanol with FDCA to form a mono- or di-ester of FDCA.
  • the process can further comprise hydrolyzing the FDCA ester with a base to form an FDCA salt.
  • the base can be selected from the group consisting of NaOH, KOH, LiOH, Ca(OH) 2 , and CsOH.
  • the process for producing FDCA can further comprise preparing the sugar derivative substrate from lignocellulosic material by subjecting the lignocellulosic material to hydrolysis conditions followed by oxidation conditions to produce a sugar derivative substrate.
  • the hydrolysis of the lignocellulosic material can produce a sugar derivative substrate comprising a mixture of C 6 -aldaric acids.
  • the lignocellulosic material may comprise a compound selected from the group consisting of cellulose, hemicellulose, and lignin.
  • the yield of FDCA for the process can be at least 60%, or at least 70%, or at least 80%, or at least 90%, or at least 95%, or at least 98%, or at least 99% or within a range defined by any two of the aforementioned percentages.
  • the yield of FDCA can be at least 60%, or at least 70%, or at least 80%, or at least 90%, or at least 95%, or at least 98%, or at least 99% or within a range defined by any two of the aforementioned percentages.
  • the process for producing FDCA can produce FDCA and additional impurities.
  • the amount of FDCA relative to the additional impurities can be at least 60%, or at least 65%, or at least 70%, or at least 75%, or at least 80%, or at least 85%, or at least 90%, or at least 91%, or at least 92%, or at least 93%, or at least 94%, or at least 95%, or at least 96%, or at least 97%, or at least 98%, or at least 99% by weight percent, or within any range defined by the aforementioned weight percents.
  • the molar ratio of FDCA to 2-furoic acid can be least 5:1, or at least 6:1 or at least 7:1, or at least 8:1, or at least 9:1, or at least 10:1, or at least 15:1, or at least 20:1, or at least 25:1, or at least 30:1, or at least 35:1, or at least 40:1, or at least 45:1, or at least 50:1, or within any range defined by the aforementioned molar ratios.
  • the process for producing FDCA can further comprise steps of isolating, crystalizing, or decolorizing said FDCA.
  • the present disclosure is directed to reaction mixture comprising: a sugar derivative substrate; a water-miscible organic solvent; a halide salt; and a Bronsted acid.
  • the reaction mixture can further comprise FDCA.
  • the sugar derivative substrate can be a homogenous sugar derivative substrate.
  • the sugar derivative substrate can be a heterogeneous sugar derivative substrate.
  • the sugar derivative substrate can be selected from the group consisting of: glucaric acid and salts and lactones thereof; galactaric acid and salts and lactones thereof; and mannaric acid and salts and lactone thereof; or a mixture thereof.
  • the sugar derivative substrate can be selected from the group consisting of glucaric acid, glucaric acid dilactone, 1,4-glucaric acid monolactone, 3,6-glucaric acid monolactone, sodium glucarate, potassium glucarate, calcium glucarate, galactaric acid, 1,4-galactaric acid monolactone, 3,6-galactaric acid monolactone, sodium galctarate, potassium galactarate, calcium galactarate, mannaric acid, mannaric acid dilactone, 1,4-mannaric acid monolactone, 3,6-mannaric acid monolactone, sodium mannarate, potassium mannarate, calcium mannarate, or a mixture thereof.
  • the sugar derivative substrate can be glucaric acid, or a salt or lactone thereof.
  • the sugar derivative substrate can be galactaric acid, or a salt or lactone thereof.
  • the sugar derivative substrate can be mannaric acid, or a salt or lactone thereof.
  • the sugar derivative substrate can be glucaric acid dilactone.
  • the sugar derivative substrate can be mannaric acid dilactone.
  • the concentration of sugar derivative substrate in the mixture can range from between 0.05-10.0 M, 0.10-5.0 M, 0.2-4.0 M, or 0.4-3.0 M, or can be within a range defined by any two of the aforementioned concentrations.
  • the water-miscible organic solvent can be selected from the group consisting of 1,4-dioxane, tetrahydrofuran, sulfolane, a glyme, N-methyl-2-pyrrolidone, methyl ethyl ketone, dimethyl foimamide, and dimethyl sulfoxide.
  • the water-miscible organic solvent can be 1,4-dioxane or sulfolane.
  • the Bronsted acid can be selected from the group consisting of hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, phosphoric acid, methanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, acetic acid, and trifluoracetic acid.
  • the concentration of the acid in the mixture can range from between 0.05- 10.0 M, 0.10-5.0 M, 0.2-4.0 M, or 0.4-3.0 M, or within a range defined by any two of the aforementioned concentrations.
  • the halide salt can be a metal halide or a tetraalkylammonium halide.
  • the metal halide can be selected from the group consisting of FeBr 2 , FeBr 3 , FeCl 2 , FeCl 3 , CuBr, CuBr 2 , CuCl, CuCl 2 , ZnCl 2 , ZnBr 2 , NiCl 2 , NiBr 2 , NaCl, NaBr, Nal, LiBr, LiCl, CaCl 2 , CaBr 2 , MgCl 2 , MgBr 2 , KC1, KBr, and KI.
  • the metal halide salt can be selected from the group consisting of FeBr 2 , FeCl 2 , CuBr 2 , CuCl 2 , ZnCl 2 , ZnBr 2 , NiCl 2 , NiBr 2 , LiBr, LiCl, CaCl 2 , CaBr 2 , MgCl 2 , and MgBr 2 .
  • the metal halide salt can be CaBr 2 and the Bronsted acid can be hydrobromic acid.
  • the metal halide salt can be CaBr 2 and the Bronsted acid can be hydrochloric acid.
  • the metal halide salt can be CaBr 2 and the Bronsted acid can be methanesulfonic acid.
  • the metal halide salt can be CaBr 2 and the Bronsted acid can be sulfuric acid.
  • the metal halide salt can be MgBr 2 and the Bronsted acid can be hydrobromic acid.
  • the metal halide salt can be MgBr 2 and the Bronsted acid can be methanesulfonic acid.
  • the metal halide can be MgBr 2 and the Bronsted acid can be sulfuric acid.
  • the metal halide can be LiBr and the Bronsted acid can be hydrobromic acid.
  • the metal halide can be LiBr and the Bronsted acid can be methanesulfonic acid.
  • the metal halide salt can be ZnCl 2 and the Bronsted acid can be hydrochloric acid.
  • the tetraalkylammonium halide can be selected from the group consisting of tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, tetrabutylammonium chloride, and tetrabutylammonium bromide.
  • the tetraalkylammonium halide salt can be tetraethylammonium bromide and the Bronsted acid can be methanesulfonic acid.
  • the water-miscible organic solvent can be selected from the group consisting of 1,4-dioxane, tetrahydrofuran, sulfolane, a glyme, N-methyl-2-pyrrolidone, methyl ethyl ketone, dimethyl formamide, and dimethyl sulfoxide.
  • the water-miscible organic solvent can be 1,4-dioxane or sulfolane.
  • the glyme can be selected from the group consisting of 1,2-dimethoxyethane, ethyl glyme, diethylene glycol dimethyl ether, ethyl diglyme, triglyme, butyl diglyme, tetraglyme, and a polyglyme.
  • the concentration of halide salt in the mixture can range from between 0.01-3.0 M, 0.05-0.2 M, 0.1-1.0 M, or 0.2-0.5 M, or can be within a range defined by any two of the aforementioned concentrations.
  • the concentration of halide salt can be at least 0.1 M.
  • the concentration of halide salt can be less than 2.0 M, or less than 1.5 M, or less than 1 M, or less than 0.75 M, or less than 0.5 M but not zero.
  • the reaction mixture can further comprise water.
  • concentration of water in the mixture can range from between 0.01-20.0 M, 0.01- 10.0 M, 0.1-5.0 M, or 0.2- 1.0 M, or can be within a range defined by any two of the aforementioned concentrations.
  • the reaction mixture can further comprise an alcohol.
  • the alcohol can be selected from the group consisting of n-butanol, sec-butanol, isobutanol, 1-pentanol, 2- pentanol, 2-(2-chloroethoxy) ethanol), ethoxyethanol, and cyclohexanol.
  • the concentration of alcohol ranges from between 0.01-1.0 M, 0.1-l.OM, or 0.5-1.0M, or within a range defined by any two of the aforementioned concentrations.
  • the reaction mixture can comprise compounds derived from the hydrolysis of cellulose, hemicellulose, or lignin.
  • the reaction mixture can comprise 2-furoic acid.
  • Figure 1A depicts 2,5-furandicarboxylic acid (FDCA) and 2-furoic acid (2-FA) yields in sulfolane using a variety of halide salts and and in the absence of a Bronsted acid.
  • FDCA 2,5-furandicarboxylic acid
  • 2-FA 2-furoic acid
  • Figure IB depicts FDCA and 2-FA yields in sulfolane in the presence of HBr as a Bronsted acid using a variety of halide salts.
  • Figure 1C depicts FDCA and 2-FA yields in sulfolane in the presence of HC1 as a Bronsted acid using a variety of halide salts.
  • Figure ID depicts FDCA and 2-FA yields in sulfolane in the presence of H 2 S0 4 as a Bronsted acid using a variety of halide salts.
  • Figure IE depicts FDCA and 2-FA yields in sulfolane in the presence of MsOH as a Bronsted acid using a variety of halide salts.
  • Figure IF depicts FDCA and 2-FA yields in sulfolane in the presence of F3CSO3H as a Bronsted acid using a variety of halide salts.
  • Figure 2A depicts FDCA selectivity versus conversion for glucaric acid dilactone (GADL) substrate in sulfolane using a variety of halide salts and and in the absence of a Bronsted acid.
  • GADL glucaric acid dilactone
  • Figure 2B depicts FDCA selectivity versus conversion for GADL substrate in sulfolane in the presence of HBr as a Bronsted acid using a variety of halide salts.
  • Figure 2C depicts FDCA selectivity versus conversion for GADL substrate in sulfolane in the presence of HC1 as a Bronsted acid using a variety of halide salts.
  • Figure 2D depicts FDCA selectivity versus conversion for GADL substrate in the presence of H 2 S0 4 as a Bronsted acid using a variety of halide salts.
  • Figure 2E depicts FDCA selectivity versus conversion for GADL substrate in the presence of MsOH as a Bronsted acid using a variety of halide salts.
  • Figure 2F depicts FDCA selectivity versus conversion for GADL substrate in the presence of F3CSO3H as a Bronsted acid using a variety of halide salts.
  • Figure 3A depicts FDCA yield from GADL in sulfolane with Bronsted acid concentrations in the range of about 7 M to about 6 M using a variety of halide salts.
  • Figure 3B depicts FDCA yield from GADL in sulfolane with Bronsted acid concentrations of about 5 M using a variety of halide salts.
  • Figure 3C depicts FDCA yield from GADL in sulfolane with Bronsted acid concentrations of about 4 M using a variety of halide salts.
  • Figure 3D depicts FDCA yield from GADL in sulfolane with Bronsted acid concentrations of about 3 M using a variety of halide salts.
  • Figure 3E depicts FDCA yield from GADL in sulfolane with Bronsted acid concentrations of about 2 M using a variety of halide salts.
  • Figure 3F depicts FDCA yield from GADL in sulfolane with Bronsted acid concentrations in the range of about 1 M to about 0 M using a variety of halide salts.
  • Figure 4 depicts FDCA yield from GADL in sulfolane as a function of halide salt and Bronsted acid concentrations at different temperatures.
  • Figure 5 depicts the mass balance and yields of 2-FA from the reaction of GADL sugar derivative substrate in sulfolane.
  • Figure 6 depicts FDCA yield and conversion from GADL with CaBr 2 and H 2 S0 4 selected as the halide salt and Bronsted acid, respectively in sulfolane at different H 2 0 concentrations.
  • Figure 7 depicts a comparison of FDCA yield from GADL with CaBr 2 or MgBr 2 in sulfolane using different sources of Bronsted acid and different H 2 0 concentrations.
  • Figure 8 depicts FDCA yield from GADL with CaBr 2 or MgBr 2 in sulfolane as a function of the ratio of halide salt concentration to acid concentration at different H 2 0 concentrations.
  • Figure 9 depicts the mass balance and yields of 2-FA from the reaction of GADL sugar derivative substrate with CaBr 2 or MgBr 2 in sulfolane at different H 2 0 concentrations.
  • Figure 10 depicts FDCA yield and selectivity using GADL as the sugar derivative substrate in sulfolane.
  • Figure 11 A depicts FDCA selectivity as a function of the ratio of halide concentration to proton concentration as well as FDCA yield versus conversion of GADL sugar derivative substrate using CaBr 2 as a halide salt.
  • Figure 1 IB depicts FDCA selectivity as a function of the ratio of halide concentration to proton concentration as well as FDCA yield versus conversion of GADL sugar derivative substrate using LiBr as a halide salt.
  • Figure 11C depicts FDCA selectivity as a function of the ratio of halide concentration to proton concentration as well as FDCA yield versus conversion of GADL sugar derivative substrate using MgBr 2 as a halide salt.
  • Figure 1 ID depicts FDCA selectivity as a function of the ratio of halide concentration to proton concentration as well as FDCA yield versus conversion of GADL sugar derivative substrate in the absence of a halide salt.
  • Figure 12 depicts yields of 2-FA and mass balance using GADL as the sugar derivative substrate in sulfolane in HC1 and HBr systems as a function of the ratio of halide salt concentration to acid concentration.
  • Figure 13 depicts FDCA yield both as a function of Bronsted acid concentration and conversion of GADL in sulfolane when no halide salt is added to the reaction.
  • Figure 14 depicts the yield of FDCA versus conversion of GADL in dioxane using various Bronsted acids and in the absence of halide salts at a variety of water concentrations.
  • Figure 15 depicts the selectivity of FDCA formation from GADL versus the conversion of FDCA in dioxane using various Bronsted acids and in the absence of halide salts at a variety of water concentrations.
  • Figure 16 depicts the yield of FDCA versus conversion of GADL in NMP using various Bronsted acids and in the absence of halide salts at a variety of water concentrations.
  • Figure 17 depicts the selectivity of FDCA formation from GADL versus the conversion of FDCA in NMP using various Bronsted acids and in the absence of halide salts at a variety of water concentrations.
  • Figure 18 depicts the selectivity of FDCA formation from GADL in dioxane versus the concentration of TEAB added to the reaction mixture.
  • Figure 19 depicts the conversion of GADL in dioxane/HCl and dioxane/HBr versus the concentration of TEAB added to the reaction mixture.
  • Figure 20 depicts the yield of FDCA versus conversion of GADL in dioxane/HCl and a variety of water concentrations versus the concentration of TEAB added to the reaction mixture.
  • Figure 21 depicts the yield of 2-FA versus conversion of GADL in dioxane/HCl and a variety of water concentrations versus the concentration of TEAB added to the reaction mixture.
  • Figure 22 depicts the conversion of GADL in dioxane/HCl and a variety of water concentrations versus the concentration of TEAB added to the reaction mixture.
  • Figure 23 depicts the yield of FDCA from GADL in dioxane/HCl and a variety of water concentrations versus the concentration of TEAB added to the reaction mixture.
  • Figure 24 depicts the yield of 2-FA from GADL in dioxane/HCl and a variety of water concentrations versus the concentration of TEAB added to the reaction mixture.
  • Figure 25 depicts the yield of FDCA from GADL in dioxane/HCl and a variety of water concentrations versus the concentration of tetraethylammonium chloride (TEAC) added to the reaction mixture.
  • TEAC tetraethylammonium chloride
  • Figure 26 depicts the yield of 2-FA from GADL in dioxane/HCl and a variety of water concentrations versus the concentration of TEAC added to the reaction mixture
  • Figure 27 depicts the conversion of GADL, yields of FDCA and 2-FA and selectivity for FDCA in dioxane/HCl and TEAB versus the concentration of acid in the reaction mixture.
  • sucgar derivative substrate refers to a composition comprising one or more compounds selected from C 6 -aldaric acids, and/or lactones, esters and/or salts of C 6 -aldaric acids.
  • sugar derivative substrates include but are not limited to e.g., glucaric acid, sodium glucarate, potassium glucarate, calcium glucarate, glucaric acid 1,4-monolactone, glucaric acid 3,6-monolactone, glucaric acid dilactone, galactaric (mucic) acid, sodium galactarate, potassium galactarate, calcium galactarate, galactaric acid 1,4-monolactone, galactaric acid 3,6-monolactone, mannaric acid, sodium mannarate, potassium mannarate, calcium mannarate, mannaric acid 1,4- monolactone, mannaric acid 3,6-monolactone, and/or mannaric acid dilactone.
  • glucaric acid sodium glucarate, potassium glucarate, calcium glucarate, glucaric acid 1,4-monolactone, glucaric acid 3,6-monolactone, glucaric acid dilactone
  • the sugar derivative substrate may be homogenous or heterogenous.
  • a homogenous sugar derivative substrate contains a single species of a C 6 -aldaric acid, or a single species of a lactone, ester, or salt of a C 6 -aldaric acid.
  • a heterogenous sugar derivative substrate contains two or more species of C 6 -aldaric acids, or lactones, esters, or salts of C 6 -aldaric acid.
  • C 6 -aldaric acid refers to a compound having the formula HOOC-(CHOH) 4 -COOH, or a salt thereof.
  • Examples of C 6 -aldaric acids include glucaric acid, galctaric acid, mannaric acid and/or gularic acid.
  • C 6 -aldaric acids may be derived from sugars, and/or may be obtained, for example, by oxidation of aldoses.
  • Bronsted acids include but are not limited to e.g., hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, trifluoracetic acid, formic acid, methanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, and/or trifluoromethanesulfonic acid.
  • halide salt refers to an ionic compound composed of cations and halide anions (e.g., F “ , CI “ , Br “ , and ⁇ ).
  • Halide salts may have a metal cation, including, but not limited to e.g., Li + , Na + , K + , Ca 2+ , Mg 2+ , Cu 2+ , Cu 3+ , Fe 2+ , Fe 3+ , Zn 2+ , and/or Ni 2+ .
  • Halide salts may have a tetraalkylammonium cation of the formula NR-f 1" , where each R is independently selected from a C 1-8 alkyl.
  • Tetraalkylammonium halide salts include, but are not limited to e.g., tetramethylammonium, tetraethylammonium, and/or tetrabutylammonium.
  • Exemplary halide salts include but are not limited to e.g., LiCl, LiBr, Lil, NaCl, NaBr, Nal, KF, KC1, KBr, KI, CaCl 2 , CaBr 2 , MgCl 2 , MgBr 2 , CuCl, CuCl 2 , CuBr, CuBr 2 , FeCl 2 , FeCl 3 , FeBr 2 , FeBr 3 , ZnCl 2 , ZnBr 2 , NiCl 2 , NiBr 2 , tetramethylammonium choride, tetramethylammonium bromide, tetramethylammonium iodide, te
  • water-miscible organic solvent refers to a carbon-containing compound that forms a homogenous mixture when mixed with water at room temperature.
  • water-miscible organic solvents include but are not limited to e.g., 1,4-dioxane, tetrahydrofuran (THF), sulfolane, N-methyl-2-pyrrolidinone (NMP), dimethylfoimamide (DMF), dimethylsulfoxide (DMSO), methyl ethyl ketone, acetic acid, ethanol, «-propanol, 1,3 -propanediol, isopropanol, «-butanol, 1,2-butanediol, 1,3-butanediol, I, 4-butanediol, 1,5-pentanediol, acetonitrile, ethylene glycol, propylene glycol, pyridine, and/or a
  • glyme refers to alkyl ethers of ethylene glycol or propylene glycol.
  • examples of glymes include but are not limited to e.g., 1,2- dimethoxyethane, ethyl glyme, diethylene glycol dimethyl ether, ethyl diglyme, triglyme, butyldiglyme, tetraglyme, and/or a polyglyme.
  • the term "alcohol” refers to a compound comprising a Ci_ 20 straight, branched, or cyclic chain bearing one or more hydroxyl (-OH) groups.
  • the C 1-2 o chain may optionally comprise one or more C-C double or C-C triple bonds.
  • the Ci-2o chain may also be optionally substituted with one or more groups selected from halogens (e.g., -F, -CI, -Br, or -I), -O-Ci ⁇ oalkyl, and/or -O-Ci ⁇ ohaloalkyl.
  • alcohols include but are not limited to e.g., methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t- butyl alcohol, 2,2,2-trifluoroethanol, hexafluoro-2-propanol, cylcopentanol, cyclohexanol, methoxyethanol, ethoxyethanol, and/or 2-(2-chloroethoxy)ethan-l-ol (CEE).
  • CEE 2-(2-chloroethoxy)ethan-l-ol
  • lignocellulosic material refers to a composition comprising cellulose, hemicellulose, and/or lignin.
  • Lignocellulosic material may be derived from a variety of sources including, but not Umited to e.g., logs, whole tree chips, bark chips, hybrid poplar, hybrid willow, sawdust, pulp waste, paper pulp, soybeans, sugar beets, sugarcane, bagasse, corn, corn stover, switchgrass, wheat, plant biomass, agricultural waste, and/or plant-derived household waste.
  • the terms “comprise(s)” and “comprising” are to be interpreted as having an open-ended meaning. That is, the terms are to be interpreted synonymously with the phrases “having at least” or “including at least.”
  • the term “comprising” means that the process includes at least the recited steps, but may include additional steps.
  • the term “comprising” means that the compound, composition or device includes at least the recited features or components, but may also include additional features or components.
  • Lignocellulosic material may be processed to produce a sugar derivative substrate.
  • the lignocellulosic material may be derived from one or more sources including but not limited to e.g., logs, whole tree chips, bark chips, hybrid poplar, hybrid willow, sawdust, pulp waste, paper pulp, soybeans, sugar beets, sugarcane, bagasse, corn, corn stover, switchgrass, wheat, plant biomass, agricultural waste, and/or plant-derived household waste.
  • lignocellulosic material may be subjected to hydrolysis conditions with or without separation (e.g., chromatographic separation) followed by oxidation conditions to produce a sugar derivative substrate.
  • hydrolysis conditions e.g., chromatographic separation
  • oxidation conditions e.g., oxidation conditions
  • Methods of converting lignocellulosic material to a sugar derivative substrate were previously described by Rennovia in WO2011/155964 to Murphy et al., which is hereby expressly incorporated herein by reference in its entirety. Additional methods for converting lignocellulosic material to a sugar derivative substrate have been described in EP3088377 and EP3088378, both to Marion et al., which are also hereby expressly incorporated by reference in their entireties.
  • the hydrolysis conditions for the lignocellulosic material are not limited to a specific method.
  • the lignocellulosic material may be subjected to chemical hydrolysis conditions. Chemical hydrolysis of lignocellulosic material may be readily achieved by treating the material with an aqueous acid, such as aqueous H 2 S0 4 or HC1.
  • aqueous acid such as aqueous H 2 S0 4 or HC1.
  • lignocellulosic material may be subjected to enzymatic hydrolysis conditions.
  • the lignocellulosic material is subjected to hydrolysis conditions that produces C 6 -aldoses.
  • the lignocellulosic material is subjected to hydrolysis conditions that produce glucose.
  • the hydrolyzed material may be oxidized to produce a sugar derivative substrate by any one of several available methods.
  • the hydrolyzed material is filtered to remove particulate matter before being subjected to oxidation conditions.
  • the hydrolyzed material is oxidized using nitric acid.
  • oxidation of the hydrolyzed material may be achieved by oxidizing an aqueous solution of the hydrolyzed material with oxygen in the presence of an oxidation catalyst.
  • the oxygen can be supplied to the reaction as air, oxygen enriched air, oxygen alone, or oxygen with other constituents substantially inert to the reaction.
  • the oxidation may comprise at least one noble metal, including but not limited to e.g., Au, Pt and/or Pd, and may further comprise a solid support, such as a carbon, ceria, titania or a zirconia support.
  • exemplary oxidation catalysts include Pd/C, Au-Pt/ZrC ⁇ 2 and/or Au-Pt/TiCh.
  • the oxidation catalysts are selected from the catalysts described by Rennovia in WO2011/155964 to Murphy et al.
  • the oxidation conditions are conducted in the presence of a base. In some embodiments, the oxidation conditions are conducted in the absence of added base.
  • the lignocellulosic material is subjected to hydrolysis conditions followed by oxidation conditions to produce C 6 -aldaric acids.
  • the resulting C 6 -aldaric acids may be converted to the corresponding lactones, esters, or salts by appropriate methods referenced by Rennovia in WO2011/155964 to Murphy et al.
  • lactones without wishing to be bound by theory, it is believed that various mono- and di-lactones are present in equilibrium with aldaric acids in aqueous solution.
  • the lignocellulosic material is subjected to hydrolysis conditions followed by oxidation conditions to produce glucaric acid.
  • the resulting glucaric acid may be converted to a corresponding lactone, ester, or salt by appropriate methods referenced by Rennovia in WO2011/155964 to Murphy et al.
  • the lignocellulosic material is subjected to hydrolysis to produce mannaric acid, which may subsequently be converted to a corresponding lactone, ester, or salt.
  • the present disclosure provides novel processes for producing 2,5-furandicarboxylic acid (FDCA).
  • the processes disclosed herein provide beneficial and advantageously high yields of FDCA.
  • the processes disclosed herein provide beneficial and advantageous selectivity of FDCA that minimizes the production of side-products.
  • the processes disclosed herein produce FDCA with minimal production of 2- furoic acid as a side product.
  • the processes disclosed herein use heterogeneous sugar derivative substrates to produce FDCA in high purity.
  • the processes disclosed herein produce FDCA in yields and purity sufficient for use in commercial production of commodity chemicals, such as the commercial production of polyesters, polyamides, and polyurethanes. .
  • the present disclosure provides a process for producing FDCA, the process comprising contacting a sugar derivative substrate with a Bronsted acid and a halide salt in the presence of a water-miscible organic solvent to form a reaction mixture producing FDCA.
  • a reaction mixture producing FDCA.
  • 2-furoic acid will be formed in the reaction mixture.
  • the conversion of a sugar derivative substrate comprising C 6 -aldaric acids (including e.g., esters and salts of C 6 -aldaric acids) to FDCA may occur via a Bronsted acid-catalyzed cyclodehydration of the C 6 -aldaric acids to produce FDCA, as shown in Scheme 1.
  • mono- and di-lactones of C 6 -aldaric acids may convert to the corresponding C 6 - aldaric acids in acidic solution, as shown in Scheme 2, which can then be converted to FDCA according to the cyclodehydration process shown in Scheme 1.
  • mono- and di-lactones of C 6 -aldaric acids may be converted directly to FDCA.
  • the conversion of sugar derivative substrates to FDCA in surprisingly high yield may be realized with various different halide salts and Bronsted acids, and may also be realized with various concentrations of halide salts and Bronsted acids.
  • the sugar derivative substrate may be a homogenous sugar derivative substrate. In some embodiments the sugar derivative substrate may be a heterogenous sugar derivative substrate. In some embodiments, the sugar derivative substrate may be a C 6 -aldaric acid, or a lactone, ester, or salt of a C 6 -aldaric acid. In some embodiments, the sugar derivative substrate may be glucaric acid, or a lactone, ester, or salt of glucaric acid. In one embodiment, the sugar derivative substrate may be glucaric acid. In one embodiment, the sugar derivative substrate may be sodium glucarate. In one embodiment, the sugar derivative substrate may be potassium glucarate.
  • the sugar derivative substrate may be calcium glucarate. In one embodiment, the sugar derivative substrate may be glucaric acid 1,4-monolactone. In one embodiment, the sugar derivative substrate may be glucaric acid 3,6-monolactone. In one embodiment, the sugar derivative substrate may be glucaric acid dilactone. In one embodiment, the sugar derivative substrate may be galactaric (mucic) acid. In one embodiment, the sugar derivative substrate may be sodium galactarate. In one embodiment, the sugar derivative substrate may be potassium galactarate. In one embodiment, the sugar derivative substrate may be calcium galactarate. In one embodiment, the sugar derivative substrate may be galactaric acid 1,4-monolactone.
  • the sugar derivative substrate may be galactaric acid 3,6-monolactone. In one embodiment, the sugar derivative substrate may be mannaric acid. In one embodiment, the sugar derivative substrate may be sodium mannarate. In one embodiment, the sugar derivative substrate may be potassium mannarate. In one embodiment, the sugar derivative substrate may be calcium mannarate. In one embodiment, the sugar derivative substrate may be mannaric acid 1,4-monolactone. In one embodiment, the sugar derivative substrate may be mannaric acid 3,6-monolactone. In one embodiment, the sugar derivative substrate may be mannaric acid dilactone. In one embodiment, the sugar derivative substrate may comprise a mixture of two or more of any of the aforementioned sugar derivative substrates.
  • the sugar derivative substrate may be present in the reaction at any concentration up to its solubility limit.
  • the concentration of sugar derivative substrate in the reaction mixture may be e.g., at least 0.01 M, at least 0.02 M, at least 0.05 M, at least 0.10 M, at least 0.15 M, at least 0.25 M, at least 0.30 M, at least 0.35 M, at least 0.40 M, at least 0.45 M, at least 0.50 M, at least 0.55 M, at least 0.60 M, at least 0.70 M, at least 0.80 M, at least 0.90 M, at least 1.0 M, at least 2.0 M, at least 3.0 M, at least 4.0 M, at least 5.0 M, at least 6.0 M, at least 7.0 M, at least 8.0 M, at least 9.0 M, or at least 10.0 M or may be within a range defined by any two of the aforementioned concentrations.
  • the concentration of sugar derivative substrate in the reaction mixture ranges from e.g., 0.01-10.0 M, 0.02-5.0 M, 0.05- 2.0 M, 0.10-1.0 M, 0.15-1.0 M, 0.20-1.0 M, 0.2-1.25 M, 0.4-1.25 M, 0.5-1.0 M, or 0.6-1.25 M, or may be within a range defined by any of two of the aforementioned concentrations.
  • the sugar derivative substrate may be present in the reaction mixture at a concentration of at least 0.20 M.
  • the sugar derivative substrate may be present in the reaction mixture at a concentration of e.g., at least 0.2 M, or at least 0.3 M, or at least 0.4 M, or at least 0.5 M, or at least 0.6 M, or at least 0.8 M, or at least 1.0 M, or at least 1.25 M, or at least 1.5 M or may be within a range defined by any two of the aforementioned concentrations.
  • the sugar derivative substrate may be present in the reaction mixture at in a concentration that ranges from between e.g., 0.2-2.0 M, 0.3-1.5 M, 0.4-1.25 M, 0.5-1.25 M, or 0.6-1.0 M, or may be within a range defined by any of two of the aforementioned concentrations.
  • Water-miscible organic solvents are suitable for use in the practice of the present disclosure. Without wishing to be bound by any particular theory, the water-miscible organic solvent is believed to facilitate the efficient conversion of the sugar derivative substrate to FDCA by both solubilizing the sugar derivative substrate and, at least to some extent, the Bronsted acid and halide salt.
  • the water-miscible organic solvent includes but is not limited to 1,4-dioxane, tetrahydrofuran (THF), sulfolane, dimethylfoimamide (DMF), dimethylsulfoxide (DMSO), methyl ethyl ketone, acetic acid, ethanol, «-propanol, 1,3 -propanediol, isopropanol, «-butanol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, acetonitrile, ethylene glycol, propylene glycol, pyridine, and/or a glyme.
  • the water-miscible organic solvent may comprise or consist of 1,4-dioxane. In one embodiment, the water-miscible organic solvent may comprise or consist of tetrahydrofuran (THF). In one embodiment, the water-miscible organic solvent may comprise or consist of sulfolane. In one embodiment, the water- miscible organic solvent may comprise or consist of N-methyl-2-pyrrolidinone (NMP). In one embodiment, the water-miscible organic solvent does not comprise NMP. In one embodiment, the water-miscible organic solvent may comprise or consist of dimethylfoimamide (DMF). In one embodiment, the water-miscible organic solvent may comprise or consist of dimethylsulfoxide (DMSO).
  • THF tetrahydrofuran
  • the water-miscible organic solvent may comprise or consist of sulfolane.
  • NMP N-methyl-2-pyrrolidinone
  • the water-miscible organic solvent does not comprise NMP.
  • the water-miscible organic solvent may comprise or consist of methyl ethyl ketone. In one embodiment, the water-miscible organic solvent may comprise or consist of acetic acid. In one embodiment, the water-miscible organic solvent may comprise or consist of ethanol. In one embodiment, the water-miscible organic solvent may comprise or consist of «-propanol. In one embodiment, the water-miscible organic solvent may comprise or consist of 1,3-propanediol. In one embodiment, the water-miscible organic solvent may comprise or consist of isopropanol. In one embodiment, the water-miscible organic solvent may comprise or consist of «-butanol.
  • the water-miscible organic solvent may comprise or consist of 1,2-butanediol. In one embodiment, the water-miscible organic solvent may comprise or consist of 1,3-butanediol. In one embodiment, the water-miscible organic solvent may comprise or consist of 1,4-butanediol. In one embodiment, the water-miscible organic solvent may comprise or consist of 1,5-pentanediol. In one embodiment, the water- miscible organic solvent may comprise or consist of acetonitrile. In one embodiment, the water-miscible organic solvent may comprise or consist of ethylene glycol. In one embodiment, the water-miscible organic solvent may comprise or consist of propylene glycol.
  • the water-miscible organic solvent may comprise or consist of pyridine. In some embodiments, the water-miscible organic solvent may comprise or consist of a glyme. In one embodiment, the glyme may comprise or consist of 1,2-dimethoxyethane. In one embodiment, the glyme may comprise or consist of ethyl glyme. In one embodiment, the glyme may comprise or consist of diethylene glycol dimethyl ether. In one embodiment, the glyme may comprise or consist of ethyl diglyme. In one embodiment, the glyme may comprise or consist of triglyme. In one embodiment, the glyme may comprise or consist of butyldiglyme.
  • the glyme may comprise or consist of tetraglyme. In one embodiment, the glyme may comprise or consist of a polyglyme. In some embodiments, the processes of the present disclosure may utilize a mixture comprising two or more of any of the aforementioned water-miscible organic solvents.
  • the processes of the present disclosure may be carried out using a variety of Bronsted acids.
  • the Bronsted acid may comprise or consist of hydrochloric acid.
  • the Bronsted acid may comprise or consist of hydrobromic acid.
  • the Bronsted acid may comprise or consist of hydroiodic acid.
  • the Bronsted acid may comprise or consist of sulfuric acid.
  • the Bronsted acid may comprise or consist of nitric acid.
  • the Bronsted acid may comprise or consist of phosphoric acid.
  • the Bronsted acid may comprise or consist of acetic acid.
  • the Bronsted acid may comprise or consist of trifluoracetic acid.
  • the Bronsted acid may comprise or consist of formic acid. In one embodiment, the Bronsted acid may comprise or consist of methanesulfonic acid (MsOH). In one embodiment, the Bronsted acid may comprise or consist of p-toluenesulfonic acid (p-TsOH). In one embodiment, the Bronsted acid may comprise or consist of benzenesulfonic acid. In one embodiment, the Bronsted acid may comprise or consist of trifluoromethanesulfonic acid (TfOH). In some embodiments, the processes of the present disclosure may be carried out utilizing a combination of two or more of the aforementioned Bronsted acids.
  • MsOH methanesulfonic acid
  • p-TsOH p-toluenesulfonic acid
  • TfOH trifluoromethanesulfonic acid
  • the processes of the present disclosure may be carried out utilizing a combination of two or more of the aforementioned Bronsted acids.
  • the Bronsted acid may be present in the reaction at any concentration up to its solubility limit.
  • the concentration of Bronsted acid in the reaction mixture may be at least e.g., 0.1 M, at least 0.2 M, at least 0.3 M, at least 0.4 M, at least 0.5 M, at least 0.6 M, at least 0.7 M, at least 0.8 M, at least 0.9 M, at least 1.0 M, at least 2.0 M, at least 3.0 M, at least 4.0 M, at least 5.0 M, at least 6.0 M, at least 7.0 M, at least 8.0 M, at least 9.0 M, or at least 10.0 M or a concentration that is within a range defined by any two of the aforementioned concentrations.
  • the concentration of Bronsted acid in the reaction mixture ranges from e.g., 0.1-10.0 M, 0.5-5.0 M, 1.0-4.0 M, or 2.0-3.0 M, or may be within a range defined by any of two of the aforementioned concentrations.
  • the Bronsted acid may be present in the reaction mixture at a concentration of e.g., at least 0.50 M.
  • the Bronsted acid may be present in the reaction mixture at a concentration of e.g., at least 0.5 M, or at least 1.0 M, or at least 1.5 M, or at least 2.0 M, or at least 3.0 M, or at least 3.5 M, or at least 4.0 M, or at least 4.5 M, or at least 5.0 M, or at least 4.5 M, or at least 5.0 M, or at least 4.5 M, or at least 5.0 M, or at least 4.5 M, or at least 5.0 M, or at least 4.5 M, or at least 5.0 M, or at least 4.5 M, or at least 5.0 M, or at least 4.5 M, or at least 5.0 M, or at least 4.5 M, or at least 5.0 M, or at least 4.5 M, or at least 5.0 M, or at least 4.5 M, or at least 5.0 M, or at least 5.5 M, or at least 6.0 M, or at least 6.5 M, or at least 7.0 M, or at least 7.5 M, or at least 8.0 M, or at least
  • the Bronsted acid may be present in the reaction mixture at a concentration that ranges from between 0.5-10.0 M, 1.0-5.0 M, 1.5-4.0 M, 2.0-4.0 M, or 2.0-6.0 M, or may be within a range defined by any of two of the aforementioned concentrations.
  • the processes of the present disclosure may be carried out using a variety of halide salts.
  • the halide salt may comprise or consist of a metal halide salt.
  • the metal halide salt may comprise or consist of LiCl.
  • the metal halide salt may comprise or consist of LiBr.
  • the metal halide salt may comprise or consist of Lil.
  • the metal halide salt may comprise or consist of NaCl. In one embodiment, the metal halide salt may comprise or consist of NaBr. In one embodiment, the metal halide salt may comprise or consist of Nal. In one embodiment, the metal halide salt may comprise or consist of KF. In one embodiment, the metal halide salt may comprise or consist of KC1. In one embodiment, the metal halide salt may comprise or consist of KBr. In one embodiment, the metal halide salt may comprise or consist of KI. In one embodiment, the metal halide salt may comprise or consist of CaCl 2 . In one embodiment, the metal halide salt may comprise or consist of CaBr 2 .
  • the metal halide salt may comprise or consist of MgCl 2 . In one embodiment, the metal halide salt may comprise or consist of MgBr 2 . In one embodiment, the metal halide salt may comprise or consist of CuCl. In one embodiment, the metal halide salt may comprise or consist of CuCl 2 . In one embodiment, the metal halide salt may comprise or consist of CuBr. In one embodiment, the metal halide salt may comprise or consist of CuBr 2 . In one embodiment, the metal halide salt may comprise or consist of FeCl 2 . In one embodiment, the metal halide salt may comprise or consist of FeCl 3 . In one embodiment, the metal halide salt may comprise or consist of FeBr 2 .
  • the metal halide salt may comprise or consist of FeBr 3 . In one embodiment, the metal halide salt may comprise or consist of ZnCl 2 . In one embodiment, the metal halide salt may comprise or consist of ZnBr 2 . In one embodiment, the metal halide salt may comprise or consist of NiCl 2 . In one embodiment, the metal halide salt may comprise or consist of NiBr 2 . In some embodiments, the halide salt may comprise or consist of a tetraalkylammonium halide salt. In one embodiment, the tetraalkylammonium salt may comprise or consist of tetramethylammonium choride.
  • the tetraalkylammonium salt may comprise or consist of tetramethylammonium bromide. In one embodiment, the tetraalkylammonium salt may comprise or consist of tetramethylammonium iodide. In one embodiment, the tetraalkylammonium salt may comprise or consist of tetraethylammonium chloride. In one embodiment, the tetraalkylammonium salt may comprise or consist of tetraethylammonium bromide. In one embodiment, the tetraalkylammonium salt may comprise or consist of tetraethylammonium iodide.
  • the tetraalkylammonium salt may comprise or consist of tetrabutylammonium chloride. In one embodiment, the tetraalkylammonium salt may comprise or consist of tetrabutylammonium bromide. In one embodiment, the tetraalkylammonium salt may comprise or consist of tetrabutylammonium iodide. In some embodiments, the processes of the present disclosure may utilize hydrates of any of the aforementioned halide salts. In some embodiments, the processes of the present disclosure may utilize two or more of any of the aforementioned halide salts.
  • the halide salt may be present in the reaction at any concentration up to its solubility limit.
  • the concentration of halide salt in the reaction mixture may be e.g., at least 0.01 M, at least 0.02 M, at least 0.05 M, at least 0.10 M, at least 0.15 M, at least 0.25 M, at least 0.30 M, at least 0.35 M, at least 0.40 M, at least 0.45 M, at least 0.50 M, at least 0.60 M, at least 0.70 M, at least 0.80 M, at least 0.90 M, at least 1.0 M, at least 1.2 M, at least 1.5 M, at least 2.0 M, at least 2.5 M, or at least 3.0 M or within a range defined by any two of the aforementioned concentrations.
  • the concentration of halide salt in the reaction mixture ranges from e.g., 0.01-3.0 M, 0.05-2.0 M, 0.10-1.0 M, or 0.20-0.50 M, or may be within a range defined by any of two of the aforementioned concentrations.
  • the halide salt may be present in the reaction mixture at a concentration of e.g., at least 0.20 M.
  • the halide salt may be present in the reaction mixture at a concentration of e.g., at least 0.2 M, or at least 0.3 M, or at least 0.4 M, or at least 0.5 M, or at least 0.6 M, or at least 0.8 M, or at least 1.0M, or at least 1.2 M, or at least 1.25 M, or at least 1.5 M or within a range defined by any two of the aforementioned concentrations.
  • the halide salt may be present in the reaction mixture at a concentration that ranges from e.g., between 0.2-2.0 M, 0.3-1.5 M, 0.4-1.2 M, 0.4-1.25 M, 0.5-1.25 M, or 0.6-1.0 M, or may be within a range defined by any of two of the aforementioned concentrations.
  • the halide salt may be present in the reaction mixture at a concentration of at least 0.1 M.
  • the halide slat may be present in the reaction mixture at a concentration of less than 2.0 M, or less than 1.5 M, or less than 1.3 M, or less than 1 M, or less than 0.75 M, or less than 0.5 M but not zero.
  • the processes of the present disclosure may be particularly sensitive to both the concentration of halide salt present and to the molar ratio of sugar derivative substrate to the halide salt.
  • the molar ratio of sugar derivative substrate to halide salt may be present in the reaction mixture in a molar ratio of e.g., 5:1 to 1:5, for example 4.5:1 or 4:1 or 3.5:1 or 3:1 or 2.75:1 or 2.5:1 or 2:1 or 1:75:1 or 1.5:1 or 1.25:1 or 1:1 or 1:1.25 or 1:1.5 or 1:1.75 or 1:2 or 1:2.25 or 1:2.5 or 1:2.75 or 1:3 or 1:3.5 or 1:4 or 1:4.5, or within any range defined by any two of the aforementioned molar ratios.
  • the Bronsted acid may comprise or consist of hydrochloric acid and the halide salt may comprise or consist of LiCl.
  • the Bronsted acid may comprise or consist of hydrochloric acid and the halide salt may comprise or consist of LiBr.
  • the Bronsted acid may comprise or consist of hydrochloric acid and the halide salt may comprise or consist of NaCl.
  • the Bronsted acid may comprise or consist of hydrochloric acid and the halide salt may comprise or consist of Nal. In some embodiments, the Bronsted acid may comprise or consist of hydrochloric acid and the halide salt may comprise or consist of KC1. In some embodiments, the Bronsted acid may comprise or consist of hydrochloric acid and the halide salt may comprise or consist of KBr. In some embodiments, the Bronsted acid may comprise or consist of hydrochloric acid and the halide salt may comprise or consist of KI. In some embodiments, the Bronsted acid may comprise or consist of hydrochloric acid and the halide salt may comprise or consist of CaCl 2 .
  • the Bronsted acid may comprise or consist of hydrochloric acid and the halide salt may comprise or consist of CaBr 2 . In some embodiments, the Bronsted acid may comprise or consist of hydrochloric acid and the halide salt may comprise or consist of MgCl 2 . In some embodiments, the Bronsted acid may comprise or consist of hydrochloric acid and the halide salt may comprise or consist of MgBr 2 . In some embodiments, the Bronsted acid may comprise or consist of hydrochloric acid and the halide salt may comprise or consist of CuCl. In some embodiments, the Bronsted acid may comprise or consist of hydrochloric acid and the halide salt may comprise or consist of CuCl 2 .
  • the Bronsted acid may comprise or consist of hydrochloric acid and the halide salt may comprise or consist of CuBr. In some embodiments, the Bronsted acid may comprise or consist of hydrochloric acid and the halide salt may comprise or consist of CuBr 2 . In some embodiments, the Bronsted acid may comprise or consist of hydrochloric acid and the halide salt may comprise or consist of FeCl 2 . In some embodiments, the Bronsted acid may comprise or consist of hydrochloric acid and the halide salt may comprise or consist of FeCl 3 . In some embodiments, the Bronsted acid may comprise or consist of hydrochloric acid and the halide salt may comprise or consist of FeBr 2 .
  • the Bronsted acid may comprise or consist of hydrochloric acid and the halide salt may comprise or consist of FeBr 3 .
  • the Bronsted acid may comprise or consist of hydrochloric acid and the halide salt may comprise or consist of ZnCl 2 .
  • the Bronsted acid may comprise or consist of hydrochloric acid and the halide salt may comprise or consist of NiCl 2 .
  • the Bronsted acid may comprise or consist of hydrochloric acid and the halide salt may comprise or consist of NiBr 2 .
  • the Bronsted acid may comprise or consist of hydrochloric acid and the halide salt may comprise or consist of tetramethylammonium chloride.
  • the Bronsted acid may comprise or consist of hydrochloric acid and the halide salt may comprise or consist of tetramethylammonium bromide. In some embodiments, the Bronsted acid may comprise or consist of hydrochloric acid and the halide salt may comprise or consist of tetramethylammonium iodide. In some embodiments, the Bronsted acid may comprise or consist of hydrochloric acid and the halide salt may comprise or consist of tetraethylammonium chloride. In some embodiments, the Bronsted acid may comprise or consist of hydrochloric acid and the halide salt may comprise or consist of tetraethylammonium bromide.
  • the Bronsted acid may comprise or consist of hydrochloric acid and the halide salt may comprise or consist of tetraethylammonium iodide. In some embodiments, the Bronsted acid may comprise or consist of hydrochloric acid and the halide salt may comprise or consist of tetrabutylammonium chloride. In some embodiments, the Bronsted acid may comprise or consist of hydrochloric acid and the halide salt may comprise or consist of tetrabutylammonium bromide. In some embodiments, the Bronsted acid may comprise or consist of hydrochloric acid and the halide salt may comprise or consist of tetrabutylammonium iodide.
  • the Bronsted acid may comprise or consist of methanesulfonic acid and the halide salt may comprise or consist of LiCl.
  • the Bronsted acid may comprise or consist of methanesulfonic acid and the halide salt may comprise or consist of LiBr.
  • the Bronsted acid may comprise or consist of methanesulfonic acid and the halide salt may comprise or consist of NaCl.
  • the Bronsted acid may comprise or consist of methanesulfonic acid and the halide salt may comprise or consist of Nal. In some embodiments, the Bronsted acid may comprise or consist of methanesulfonic acid and the halide salt may comprise or consist of KC1. In some embodiments, the Bronsted acid may comprise or consist of methanesulfonic acid and the halide salt may comprise or consist of KBr. In some embodiments, the Bronsted acid may comprise or consist of methanesulfonic acid and the halide salt may comprise or consist of KI. In some embodiments, the Bronsted acid may comprise or consist of methanesulfonic acid and the halide salt may comprise or consist of CaCl 2 .
  • the Bronsted acid may comprise or consist of methanesulfonic acid and the halide salt may comprise or consist of CaBr 2 . In some embodiments, the Bronsted acid may comprise or consist of methanesulfonic acid and the halide salt may comprise or consist of MgCl 2 . In some embodiments, the Bronsted acid may comprise or consist of methanesulfonic acid and the halide salt may comprise or consist of MgBr 2 . In some embodiments, the Bronsted acid may comprise or consist of methanesulfonic acid and the halide salt may comprise or consist of CuCl.
  • the Bronsted acid may comprise or consist of methanesulfonic acid and the halide salt may comprise or consist of CuCl 2 . In some embodiments, the Bronsted acid may comprise or consist of methanesulfonic acid and the halide salt may comprise or consist of CuBr. In some embodiments, the Bronsted acid may comprise or consist of methanesulfonic acid and the halide salt may comprise or consist of CuBr 2 . In some embodiments, the Bronsted acid may comprise or consist of methanesulfonic acid and the halide salt may comprise or consist of FeCl 2 .
  • the Bronsted acid may comprise or consist of methanesulfonic acid and the halide salt may comprise or consist of FeCl 3 . In some embodiments, the Bronsted acid may comprise or consist of methanesulfonic acid and the halide salt may comprise or consist of FeBr 2 . In some embodiments, the Bronsted acid may comprise or consist of methanesulfonic acid and the halide salt may comprise or consist of FeBr 3 . In some embodiments, the Bronsted acid may comprise or consist of methanesulfonic acid and the halide salt may comprise or consist of ZnCl 2 .
  • the Bronsted acid may comprise or consist of methanesulfonic acid and the halide salt may comprise or consist of NiCl 2 . In some embodiments, the Bronsted acid may comprise or consist of methanesulfonic acid and the halide salt may comprise or consist of NiBr 2 . In some embodiments, the Bronsted acid may comprise or consist of methanesulfonic acid and the halide salt may comprise or consist of tetramethylammonium choride. In some embodiments, the Bronsted acid may comprise or consist of methanesulfonic acid and the halide salt may comprise or consist of tetramethylammonium bromide.
  • the Bronsted acid may comprise or consist of methanesulfonic acid and the halide salt may comprise or consist of tetramethylammonium iodide. In some embodiments, the Bronsted acid may comprise or consist of methanesulfonic acid and the halide salt may comprise or consist of tetraethylammonium chloride. In some embodiments, the Bronsted acid may comprise or consist of methanesulfonic acid and the halide salt may comprise or consist of tetraethylammonium bromide.
  • the Bronsted acid may comprise or consist of methanesulfonic acid and the halide salt may comprise or consist of tetraethylammonium iodide. In some embodiments, the Bronsted acid may comprise or consist of methanesulfonic acid and the halide salt may comprise or consist of tetrabutylammonium chloride. In some embodiments, the Bronsted acid may comprise or consist of methanesulfonic acid and the halide salt may comprise or consist of tetrabutylammonium bromide. In some embodiments, the Bronsted acid may comprise or consist of methanesulfonic acid and the halide salt may comprise or consist of tetrabutylammonium iodide.
  • the Bronsted acid may comprise or consist of sulfuric acid and the halide salt may comprise or consist of LiCl.
  • the Bronsted acid may comprise or consist of sulfuric acid and the halide salt may comprise or consist of LiBr.
  • the Bronsted acid may comprise or consist of sulfuric acid and the halide salt may comprise or consist of NaCl.
  • the Bronsted acid may comprise or consist of sulfuric acid and the halide salt may comprise or consist of Nal.
  • the Bronsted acid may comprise or consist of sulfuric acid and the halide salt may comprise or consist of KC1.
  • the Bronsted acid may comprise or consist of sulfuric acid and the halide salt may comprise or consist of KBr. In some embodiments, the Bronsted acid may comprise or consist of sulfuric acid and the halide salt may comprise or consist of KI. In some embodiments, the Bronsted acid may comprise or consist of sulfuric acid and the halide salt may comprise or consist of CaCl 2 . In some embodiments, the Bronsted acid may comprise or consist of sulfuric acid and the halide salt may comprise or consist of CaBr 2 . In some embodiments, the Bronsted acid may comprise or consist of sulfuric acid and the halide salt may comprise or consist of MgCl 2 .
  • the Bronsted acid may comprise or consist of sulfuric acid and the halide salt may comprise or consist of MgBr 2 .
  • the Bronsted acid may comprise or consist of sulfuric acid and the halide salt may comprise or consist of CuCl.
  • the Bronsted acid may comprise or consist of sulfuric acid and the halide salt may comprise or consist of CuCl 2 .
  • the Bronsted acid may comprise or consist of sulfuric acid and the halide salt may comprise or consist of CuBr.
  • the Bronsted acid may comprise or consist of sulfuric acid and the halide salt may comprise or consist of CuBr 2 .
  • the Bronsted acid may comprise or consist of sulfuric acid and the halide salt may comprise or consist of FeCl 2 . In some embodiments, the Bronsted acid may comprise or consist of sulfuric acid and the halide salt may comprise or consist of FeCl 3 . In some embodiments, the Bronsted acid may comprise or consist of sulfuric acid and the halide salt may comprise or consist of FeBr 2 . In some embodiments, the Bronsted acid may comprise or consist of sulfuric acid and the halide salt may comprise or consist of FeBr 3 . In some embodiments, the Bronsted acid may comprise or consist of sulfuric acid and the halide salt may comprise or consist of ZnCl 2 .
  • the Bronsted acid may comprise or consist of sulfuric acid and the halide salt may comprise or consist of NiCl 2 . In some embodiments, the Bronsted acid may comprise or consist of sulfuric acid and the halide salt may comprise or consist of NiBr 2 . In some embodiments, the Bronsted acid may comprise or consist of sulfuric acid and the halide salt may comprise or consist of tetramethylammonium choride. In some embodiments, the Bronsted acid may comprise or consist of sulfuric acid and the halide salt may comprise or consist of tetramethylammonium bromide.
  • the Bronsted acid may comprise or consist of sulfuric acid and the halide salt may comprise or consist of tetramethylammonium iodide. In some embodiments, the Bronsted acid may comprise or consist of sulfuric acid and the halide salt may comprise or consist of tetraethylammonium chloride. In some embodiments, the Bronsted acid may comprise or consist of sulfuric acid and the halide salt may comprise or consist of tetraethylammonium bromide. In some embodiments, the Bronsted acid may comprise or consist of sulfuric acid and the halide salt may comprise or consist of tetraethylammonium iodide.
  • the Bronsted acid may comprise or consist of sulfuric acid and the halide salt may comprise or consist of tetrabutylammonium chloride. In some embodiments, the Bronsted acid may comprise or consist of sulfuric acid and the halide salt may comprise or consist of tetrabutylammonium bromide. In some embodiments, the Bronsted acid may comprise or consist of sulfuric acid and the halide salt may comprise or consist of tetrabutylammonium iodide.
  • the Bronsted acid may comprise or consist of hydrobromic acid and the halide salt may comprise or consist of LiCl.
  • the Bronsted acid may comprise or consist of hydrobromic acid and the halide salt may comprise or consist of LiBr.
  • the Bronsted acid may comprise or consist of hydrobromic acid and the halide salt may comprise or consist of NaCl.
  • the Bronsted acid may comprise or consist of hydrobromic acid and the halide salt may comprise or consist of Nal.
  • the Bronsted acid may comprise or consist of hydrobromic acid and the halide salt may comprise or consist of KC1.
  • the Bronsted acid may comprise or consist of hydrobromic acid and the halide salt may comprise or consist of KBr. In some embodiments, the Bronsted acid may comprise or consist of hydrobromic acid and the halide salt may comprise or consist of KI. In some embodiments, the Bronsted acid may comprise or consist of hydrobromic acid and the halide salt may comprise or consist of CaCl 2 . In some embodiments, the Bronsted acid may comprise or consist of hydrobromic acid and the halide salt may comprise or consist of CaBr 2 . In some embodiments, the Bronsted acid may comprise or consist of hydrobromic acid and the halide salt may comprise or consist of MgCl 2 .
  • the Bronsted acid may comprise or consist of hydrobromic acid and the halide salt may comprise or consist of MgBr 2 .
  • the Bronsted acid may comprise or consist of hydrobromic acid and the halide salt may comprise or consist of CuCl.
  • the Bronsted acid may comprise or consist of hydrobromic acid and the halide salt may comprise or consist of CuCl 2 .
  • the Bronsted acid may comprise or consist of hydrobromic acid and the halide salt may comprise or consist of CuBr.
  • the Bronsted acid may comprise or consist of hydrobromic acid and the halide salt may comprise or consist of CuBr 2 .
  • the Bronsted acid may comprise or consist of hydrobromic acid and the halide salt may comprise or consist of FeCl 2 . In some embodiments, the Bronsted acid may comprise or consist of hydrobromic acid and the halide salt may comprise or consist of FeCl 3 . In some embodiments, the Bronsted acid may comprise or consist of hydrobromic acid and the halide salt may comprise or consist of FeBr 2 . In some embodiments, the Bronsted acid may comprise or consist of hydrobromic acid and the halide salt may comprise or consist of FeBr 3 . In some embodiments, the Bronsted acid may comprise or consist of hydrobromic acid and the halide salt may comprise or consist of ZnCl 2 .
  • the Bronsted acid may comprise or consist of hydrobromic acid and the halide salt may comprise or consist of NiCl 2 . In some embodiments, the Bronsted acid may comprise or consist of hydrobromic acid and the halide salt may comprise or consist of NiBr 2 . In some embodiments, the Bronsted acid may comprise or consist of hydrobromic acid and the halide salt may comprise or consist of tetramethylammonium choride. In some embodiments, the Bronsted acid may comprise or consist of hydrobromic acid and the halide salt may comprise or consist of tetramethylammonium bromide.
  • the Bronsted acid may comprise or consist of hydrobromic acid and the halide salt may comprise or consist of tetramethylammonium iodide. In some embodiments, the Bronsted acid may comprise or consist of hydrobromic acid and the halide salt may comprise or consist of tetraethylammonium chloride. In some embodiments, the Bronsted acid may comprise or consist of hydrobromic acid and the halide salt may comprise or consist of tetraethylammonium bromide. In some embodiments, the Bronsted acid may comprise or consist of hydrobromic acid and the halide salt may comprise or consist of tetraethylammonium iodide.
  • the Bronsted acid may comprise or consist of hydrobromic acid and the halide salt may comprise or consist of tetrabutylammonium chloride. In some embodiments, the Bronsted acid may comprise or consist of hydrobromic acid and the halide salt may comprise or consist of tetrabutylammonium bromide. In some embodiments, the Bronsted acid may comprise or consist of hydrobromic acid and the halide salt may comprise or consist of tetrabutylammonium iodide.
  • the processes of the present carrying out the processes of the present disclosure it may be desirable to carry out the reaction with a particular molar ratio of Bronsted acid to halide salt in the reaction mixture.
  • the molar ratio of Bronsted acid to halide salt may be in the range of e.g., 20:1 to 1:20, for example 20:1, 19:1, 18:1, 17:1, 16:1, 15:1, 14:1, 13:1, 12:1, 11:1, 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, or 1:20, or within any range defined by any two of the aforementioned molar ratios.
  • the molar ratio of Bronsted acid to halide salt may be 20:1. In some embodiments, the molar ratio of Bronsted acid to halide salt may be 17.5:1. In some embodiments, the molar ratio of Bronsted acid to halide salt may be 14:1. In some embodiments, the molar ratio of Bronsted acid to halide salt may be 9:1.
  • hydrochloric acid and ZnCl 2 may be present in the reaction mixture in a molar ratio ranging from e.g., 5:1 to 20:1, or 8:1 to 18:1, or 10:1 to 15:1, or within any range defined by any two of the aforementioned molar ratios.
  • the molar ratio of methanesulfonic acid to CaBr 2 may be present in the reaction mixture in a molar ratio of 3:1 to 1:3, for example 2.75:1 or 2.5:1 or 2:1 or 1:75:1 or 1.5:1 or 1.25:1 or 1:1 or 1:1.25 or 1:1.5 or 1:1.75 or 1:2 or 1:2.25 or 1:2.5 or 1:2.75, or within any range defined by any two of the aforementioned molar ratios.
  • the molar ratio of methanesulfonic acid to LiBr may be present in the reaction mixture in a molar ratio of 3:1 to 1:3, for example 2.75:1 or 2.5:1 or 2:1 or 1:75:1 or 1.5:1 or 1.25:1 or 1:1 or 1:1.25 or 1:1.5 or 1:1.75 or 1:2 or 1:2.25 or 1:2.5 or 1:2.75, or within any range defined by any two of the aforementioned molar ratios.
  • Bronsted acid and halide salt may be desired in connection with using a specific solvent.
  • the water-miscible organic solvent comprises or consists of 1,4-dioxane
  • the Bronsted acid comprises or consists of HC1
  • the halide salt comprises or consists of ZnCl 2 .
  • water-miscible organic solvent comprises or consists of 1,4-dioxane
  • the Bronsted acid comprises or consists of HC1
  • the halide salt comprises or consists of ZnBr 2 .
  • water-miscible organic solvent comprises or consists of 1,4- dioxane
  • the Bronsted acid comprises or consists of HC1
  • the halide salt comprises or consists of CaBr 2 .
  • water-miscible organic solvent comprises or consists of 1,4-dioxane
  • the Bronsted acid comprises or consists of HC1
  • the halide salt comprises or consists of NaBr.
  • the water-miscible organic solvent comprises or consists of sulfolane
  • the Bronsted acid comprises or consists of MsOH
  • the halide salt comprises or consists of LiBr.
  • the water-miscible organic solvent comprises or consists of sulfolane
  • the Bronsted acid comprises or consists of MsOH
  • the halide salt comprises or consists of CaBr 2 .
  • the water-miscible organic solvent comprises or consists of sulfolane
  • the Bronsted acid comprises or consists of HC1
  • the halide salt comprises or consists of CaBr 2 .
  • the water-miscible organic solvent comprises or consists of sulfolane
  • the Bronsted acid comprises or consists of H 2 S0 4
  • the halide salt comprises or consists of CaBr 2
  • the water- miscible organic solvent comprises or consists of sulfolane
  • the Bronsted acid comprises or consists of HBr
  • the halide salt comprises or consists of LiBr.
  • the processes of the present disclosure may be carried out by optionally including water in the reaction mixture.
  • the amount of water included in the reaction mixture is the residual amount of water present in the water-miscible organic solvent.
  • water may be added to the reaction mixture.
  • the concentration of water in the reaction mixture may be e.g., at least 0.01 M, at least 0.02 M, at least 0.05 M, at least 0.10 M, at least 0.15 M, at least 0.25 M, at least 0.30 M, at least 0.35 M, at least 0.40 M, at least 0.45 M, at least 0.50 M, at least 0.60 M, at least 0.70 M, at least 0.80 M, at least 0.90 M, at least 1.0 M, at least 1.5 M, at least 2.0 M, at least 2.5 M, or at least 3.0 M or within a range defined by any two of the aforementioned concentrations.
  • the concentration of water in the reaction mixture ranges from e.g., 0.01-3.0 M, 0.05-2.0 M, 0.10-1.0 M, or 0.20-0.50 M, or may be within a range defined by any of two of the aforementioned concentrations.
  • the water may be present in the reaction mixture at a concentration of at least 0.20 M.
  • the water may be present in the reaction mixture at a concentration of e.g., at least 0.2 M, or at least 0.3 M, or at least 0.4 M, or at least 0.5 M, or at least 0.6 M, or at least 0.8 M, or at least 1.0M, or at least 1.25 M, or at least 1.5 M or within a range defined by any two of the aforementioned concentrations.
  • the water may be present in the reaction mixture at a concentration that ranges from e.g., between 0.2-2.0 M, 0.3-1.5 M, 0.4-1.25 M, 0.5-1.25 M, or 0.6-1.0 M, or may be within a range defined by any of two of the aforementioned concentrations.
  • the processes of the present disclosure may be carried out by optionally including water in the reaction mixture.
  • the amount of water included in the reaction mixture is the residual amount of water present in the water-miscible organic solvent.
  • water may be added to the reaction mixture.
  • the concentration of water in the reaction mixture may be e.g., at least 0.01 M, at least 0.02 M, at least 0.05 M, at least 0.10 M, at least 0.15 M, at least 0.24 M, at least 0.25 M, at least 0.30 M, at least 0.35 M, at least 0.40 M, at least 0.45 M, at least 0.50 M, at least 0.60 M, at least 0.70 M, at least 0.80 M, at least 0.90 M, at least 1.0 M, at least 1.5 M, at least 2.0 M, at least 2.5 M, at least 3.0 M, at least 3.5 M, at least 4.0 M, at least 4.5 M, at least 5.0 M, at least 6.0 M or within a range defined by any two of the aforementioned concentrations.
  • the concentration of water in the reaction mixture ranges from e.g., 0.01-6.0 M, 0.02-5.0 M, 0.03-3.0 M, 0.05-2.0 M, 0.10-1.0 M, or 0.20-0.50 M, or may be within a range defined by any of two of the aforementioned concentrations.
  • the water may be present in the reaction mixture at a concentration of at least 0.20 M.
  • the water may be present in the reaction mixture at a concentration of e.g., at least 0.2 M, or at least 0.3 M, or at least 0.4 M, or at least 0.5 M, or at least 0.6 M, or at least 0.8 M, or at least 1.0M, or at least 1.25 M, or at least 1.5 M, or at least 3.0 M, or at least 5.0 M, or at least 6.0 M or within a range defined by any two of the aforementioned concentrations.
  • the water may be present in the reaction mixture at a concentration that ranges from e.g., between 0.2-5.0 M, 0.3-2.0 M, 0.4-1.5 M, 0.5-1.25 M, 0.6-1.25 M, or 0.8-1.0 M, or may be within a range defined by any of two of the aforementioned concentrations.
  • the processes of the present disclosure may be carried out by optionally including an alcohol in the reaction mixture.
  • the alcohol may comprise or consist of methanol.
  • the alcohol may comprise or consist of ethanol.
  • the alcohol may comprise or consist of n-propanol.
  • the alcohol may comprise or consist of isopropanol.
  • the alcohol may comprise or consist of n-butanol. In one embodiment, the alcohol may comprise or consist of 2-(2-chloroethoxy)ethan-l-ol (CEE). In some embodiments, the processes of the present disclosure may utilize two or more of any of the aforementioned alcohols.
  • the concentration of alcohol in the reaction mixture may be e.g., at least 0.01 M, at least 0.02 M, at least 0.05 M, at least 0.10 M, at least 0.15 M, at least 0.25 M, at least 0.30 M, at least 0.35 M, at least 0.40 M, at least 0.45 M, at least 0.50 M, at least 0.60 M, at least 0.70 M, at least 0.80 M, at least 0.90 M, or at least 1.0 M or within a range defined by any two of the aforementioned concentrations.
  • the concentration of water in the reaction mixture ranges from e.g., 0.01-1.0 M, 0.02-1.0 M, 0.05-1.0 M, 0.10- 1.0M, or 0.10-0.50 M, or may be within a range defined by any of two of the aforementioned concentrations.
  • the alcohol may be present in the reaction mixture at a concentration of at least 0.02 M.
  • the alcohol may be present in the reaction mixture at a concentration of e.g., at least 0.1 M, or at least 0.2 M, or at least 0.3 M, or at least 0.4 M, or at least 0.5 M, or at least 0.6 M, or at least 0.8 M, or at least 1.0M or within a range defined by any two of the aforementioned concentrations.
  • the alcohol may be present in the reaction mixture at in a concentration that ranges from e.g., between 0.1-1.0 M, 0.2-0.6 M, or 0.3-0.5 M, or may be within a range defined by any of two of the aforementioned concentrations.
  • the dehydration of the sugar derivative substrate is typically carried out at an elevated temperature.
  • the dehydration is carried out at a temperature in the range from or any number in between e.g., 60°C to 200°C, such as e.g., 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 180, 190, or 200 °C or within a range defined by any two of the aforementioned temperatures.
  • the dehydration of the sugar derivative substrate is carried out at a temperature in the range from or any number in between e.g., 60°C to 180°C, or in the range from or any number in between 70°C to 160°C such as e.g., 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, or 180 °C or within a range defined by any two of the aforementioned temperatures.
  • the dehydration of the sugar derivative substrate may be carried out while pressuring the reaction mixture.
  • the dehydration of the sugar derivative substrate may be performed in a vessel pressurized with a gas.
  • the gas comprises or consists of nitrogen.
  • the gas comprises or consists of argon.
  • the gas comprises or consists of helium.
  • the gas comprises or consists of carbon dioxide.
  • the reaction mixture will be pressurized to a pressure ranging from or any number in between e.g., 15-500 psi.
  • the reaction mixture is pressurized to a pressure in the range from or any number in between e.g., 15-500 psi, 25-400 psi, 50-400 psi, 100-300 psi, 150-250 psi, or 250-350 psi, or within a range defined by any two of the aforementioned pressures.
  • the dehydration of the sugar derivative substrate is typically carried out for a time period ranging from or any time frame in between 1 h to 7 days.
  • the dehydration of the sugar derivative is carried out for a time in the range of e.g., 1 h and 96 h or any number in between 1 h to 96 h, such as e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 28, 32, 36, 40, 44, 48, 52, 56, 60, 64, 68, 72, 76, 80, 84, 88, 92 or 96 h, or within a range defined by any two of the aforementioned times.
  • the dehydration of the sugar derivative substrate is typically carried out for a time period ranging from or any time frame in between 0.5 h to 7 days.
  • the dehydration of the sugar derivative is carried out for a time in the range of e.g., 0.5 h and 96 h or any number in between 0.5 h to 96 h, such as e.g., 0.5, 1, 2, 3, 4, 5,
  • the dehydration of the sugar derivative substrate is typically carried out for a time period ranging from or any time frame in between 1 min to 7 days.
  • the dehydration of the sugar derivative is carried out for a time in the range of e.g., 1 min and 24 h or any number in between 1 min and 24 h, such as e.g., 1, 2, 3, 4, 5, 6,
  • the process for producing FDCA may comprise or consist of a reaction mixture comprising or consisting of a sugar derivative substrate comprising or consisting of a substrate selected from the group of glucaric acid dilactone, glucaric acid 1,4-monolactone, and/or potassium glucarate; a Bronsted acid selected from the group of HC1, HBr, MsOH, and/or H 2 S0 4 ; a halide salt selected from the group of ZnBr 2 , ZnCl 2 , NaBr, LiBr, MgBr 2 , and/or CaBr 2 ; and a water-miscible organic solvent that comprises or consists of sulfolane.
  • the water-miscible organic solvent may comprise water at a concentration ranging from or any number in between 0-2.5 M.
  • the temperature of the reaction mixture may range from or any number in between 90-120 °C. In some embodiments, the temperature of the reaction mixture may range from or any number in between 90-200 °C. In some embodiments, the temperature of the reaction mixture may range from or any number in between 110-180 °C or 110-160 °C. In some embodiments, the temperature of the reaction mixture may be 130-160 °C.
  • the reaction may proceed for a time ranging from or any number in between 3- 24 h. In some embodiments, the reaction may proceed for a time ranging from or any number in between 1 min to 3 h.
  • the reaction may proceed for a time ranging from or any number in between 1 min to 24 h.
  • the reaction mixture is heated to a temperature of 90-200 °C, 110-160 °C, or 110-180 °C, preferably 130- 160 °C, for time period of 1 min. to 24 hours, 1 min. to 3 hours, or 1 min. to 0.5 hours, preferably 1 min., 2 min., 3 min., 4 min., 5 min., 6 min., 7 min., 8 min., 9 min., or 10 min., or for a time that is within a range defined by any two of the aforementioned times.
  • the process for producing FDCA may comprise or consist of a reaction mixture including a sugar derivative substrate at a molar concentration in the range from or any number in between 0.1-3.5 M and the sugar derivative substrate comprises or consists of a substrate selected from the group of glucaric acid dilactone, glucaric acid 1,4-monolactone, and/or potassium glucarate; a Bronsted acid at a molar concentration in the range of from or any number in between 0.2-3.6 M and the Bronstead acid is selected from the group of HC1, HBr, MsOH, and/or H 2 S0 4 ; a halide salt at a molar concentration in the range of from or any number in between 0.1-3 M and the halide salt is selected from the group of ZnBr 2 , ZnCl 2 , NaBr, LiBr, MgBr 2 , and/or CaBr 2 ; and a water- miscible organic solvent that comprises or consists of
  • the water-miscible organic solvent may comprise water at a concentration ranging from or any number in between 0-2.5 M.
  • the temperature of the reaction mixture may range from or any number in between 90-120 °C. In some embodiments, the temperature of the reaction mixture may range from or any number in between 90-200 °C. In some embodiments, the temperature of the reaction mixture may range from or any number in between 110-180 °C. In some embodiments, the temperature of the reaction mixture may be 160 °C.
  • the reaction may proceed for a time ranging from or any number in between 3- 24 h. In some embodiments, the reaction may proceed for a time ranging from or any number in between 1 min to 3 h.
  • the reaction may proceed for a time ranging from or any number in between 1 min to 24 h.
  • the reaction mixture is heated to a temperature of 90-200 °C, 110-160 °C, or 110-180 °C, preferably 130- 160 °C, for time period of 1 min. to 24 hours, 1 min. to 3 hours, or 1 min. to 0.5 hours, preferably 1 min., 2 min., 3 min., 4 min., 5 min., 6 min., 7 min., 8 min., 9 min., or 10 min., or for a time that is within a range defined by any two of the aforementioned times.
  • the process for producing FDCA may comprise or consist of a reaction mixture comprising or consisting of a sugar derivative substrate comprising or consisting of a substrate selected from the group of glucaric acid dilactone, glucaric acid 1,4-monolactone, and/or potassium glucarate; a Bronsted acid selected from the group of HC1, HBr, MsOH, and/or H 2 S0 4 ; a halide salt selected from the group of ZnBr 2 , ZnCl 2 , NaBr, LiBr, MgBr 2 , and/or CaBr 2 ; and a water-miscible organic solvent that comprises or consists of sulfolane.
  • the water-miscible organic solvent may comprise water at a concentration ranging from or any number in between 0-6.0 M. In some embodiments, the water-miscible organic solvent may comprise water at a concentration at 5.0 M. In some embodiments, the temperature of the reaction mixture may range from or any number in between 90-150 °C. In some embodiments, the temperature of the reaction mixture may be 140 °C. In some embodiments, the temperature of the reaction mixture may range from or any number in between 90-200 °C. In some embodiments, the temperature of the reaction mixture may range from or any number in between 110-180 °C. In some embodiments, the temperature of the reaction mixture may be 160 °C.
  • the reaction may proceed for a time ranging from or any number in between 0.5-24 h. In some embodiments, the reaction may proceed for a time of 1 h. In some embodiments, the reaction may proceed for a time ranging from or any number in between 1 min to 3 h. In some embodiments, the reaction may proceed for a time ranging from or any number in between 1 min to 24 h. In some embodiments, the reaction mixture is heated to a temperature of 90-200 °C, 110-160 °C, or 110-180 °C, preferably 130-160 °C, for time period of 1 min. to 24 hours, 1 min. to 3 hours, or 1 min.
  • the process for producing FDCA may comprise a reaction mixture comprising or consisting of a sugar derivative substrate comprising or consisting of glucaric acid dilactone; a Bronsted acid selected from the group of HC1 and/or MsOH; a halide salt selected from the group of ZnCl 2 , LiBr, and/or CaBr 2 ; and a water- miscible organic solvent that comprises sulfolane.
  • the water-miscible organic solvent may comprise water.
  • the temperature of the reaction mixture may range from or any number in between 90-120 °C. In some embodiments, the temperature of the reaction mixture may range from or any number in between 90-200 °C.
  • the temperature of the reaction mixture may range from or any number in between 110-180 °C. In some embodiments, the temperature of the reaction mixture may be 160 °C. In some embodiments, the reaction may proceed for a time ranging from or any number in between 3-24 h. In some embodiments, the reaction may proceed for a time ranging from or any number in between 1 min to 3 h. In some embodiments, the reaction may proceed for a time ranging from or any number in between 1 min to 24 h. In some embodiments, the reaction mixture is heated to a temperature of 90-200 °C, 110-160 °C, or 110-180 °C, preferably 130-160 °C, for time period of 1 min. to 24 hours, 1 min.
  • the process for producing FDCA may comprise or consist of a reaction mixture comprising or consisting of a sugar derivative substrate at a molar concentration in the range from or any number in between 1-3.5 M and the sugar derivative substrate comprises or consists of glucaric acid dilactone; a Bronsted acid at a molar concentration in the range of from or any number in between 0.2-1.6 M and the Bronstead acid is selected from the group of HC1 and/or MsOH; a halide salt at a molar concentration of approximately 2 M and the halide salt is selected from the group of ZnCl 2 , LiBr, and/or CaBr 2 ; and a water-miscible organic solvent that comprises or consists of sulfolane.
  • the water-miscible organic solvent may comprise water at a concentration ranging from or any number in between 0.2-0.4 M.
  • the temperature of the reaction mixture may range from or any number in between 90-120 °C. In some embodiments, the temperature of the reaction mixture may range from or any number in between 90-200 °C. In some embodiments, the temperature of the reaction mixture may range from or any number in between 110-180 °C. In some embodiments, the temperature of the reaction mixture may be 160 °C.
  • the reaction may proceed for a time ranging from or any number in between 3-24 h. In some embodiments, the reaction may proceed for a time ranging from or any number in between 1 min to 3 h.
  • the reaction may proceed for a time ranging from or any number in between 1 min to 24 h.
  • the reaction mixture is heated to a temperature of 90-200 °C, 110-160 °C, or 110-180 °C, preferably 130-160 °C, for time period of 1 min. to 24 hours, 1 min. to 3 hours, or 1 min. to 0.5 hours, preferably 1 min., 2 min., 3 min., 4 min., 5 min., 6 min., 7 min., 8 min., 9 min., or 10 min., or for a time that is within a range defined by any two of the aforementioned times.
  • the process for producing FDCA may comprise or consist of a reaction mixture comprising or consisting of a sugar derivative substrate that comprises or consists of a substrate selected from the group of glucaric acid dilactone, glucaric acid 1,4-monolactone, and/or potassium glucarate; a Bronsted acid selected from the group of HC1 and/or HBr; a halide salt selected from the group of ZnBr 2 , ZnCl 2 , NaBr, LiBr, MgBr 2 , and/or CaBr 2 ; and a water-miscible organic solvent that comprises or consists of 1,4- dioxane.
  • the water-miscible organic solvent may comprise water at a concentration ranging from or any number in between 0-2.5 M.
  • the temperature of the reaction mixture may range from or any number in between 90-120 °C. In some embodiments, the temperature of the reaction mixture may range from or any number in between 90-200 °C. In some embodiments, the temperature of the reaction mixture may range from or any number in between 110-180 °C. In some embodiments, the temperature of the reaction mixture may be 160 °C.
  • the reaction may proceed for a time ranging from or any number in between 3-24 h. In some embodiments, the reaction may proceed for a time ranging from or any number in between 1 min to 3 h.
  • the reaction may proceed for a time ranging from or any number in between 1 min to 24 h.
  • the reaction mixture is heated to a temperature of 90-200 °C, 110-160 °C, or 110-180 °C, preferably 130-160 °C, for time period of 1 min. to 24 hours, 1 min. to 3 hours, or 1 min. to 0.5 hours, preferably 1 min., 2 min., 3 min., 4 min., 5 min., 6 min., 7 min., 8 min., 9 min., or 10 min., or for a time that is within a range defined by any two of the aforementioned times.
  • the process for producing FDCA may comprise or consist of a reaction mixture comprising or consisting of a sugar derivative substrate at a molar concentration in the range from or any number in between 0.1-3.5 M and the sugar derivative substrate comprises or consists of a substrate selected from the group of glucaric acid dilactone, glucaric acid 1,4-monolactone, and/or potassium glucarate; a Bronsted acid at a molar concentration in the range of from or any number in between 0.2-3.6 M and the Bronstead acid is selected from the group of HC1 and/or HBr; a halide salt at a molar concentration in the range of from or any number in between 0.1-3 M and the halide salt is selected from the group of ZnBr 2 , ZnCl 2 , NaBr, LiBr, MgBr 2 , and/or CaBr 2 ; and a water- miscible organic solvent that comprises or consists of 1,4-diox
  • the water-miscible organic solvent may comprise water at a concentration ranging from or any number in between 0-2.5 M.
  • the temperature of the reaction mixture may range from or any number in between 90-120 °C. In some embodiments, the temperature of the reaction mixture may range from or any number in between 90-200 °C. In some embodiments, the temperature of the reaction mixture may range from or any number in between 110-180 °C. In some embodiments, the temperature of the reaction mixture may be 160 °C.
  • the reaction may proceed for a time ranging from or any number in between 3-24 h. In some embodiments, the reaction may proceed for a time ranging from or any number in between 1 min to 3 h.
  • the reaction may proceed for a time ranging from or any number in between 1 min to 24 h.
  • the reaction mixture is heated to a temperature of 90-200 °C, 110-160 °C, or 110-180 °C, preferably 130-160 °C, for time period of 1 min. to 24 hours, 1 min. to 3 hours, or 1 min. to 0.5 hours, preferably 1 min., 2 min., 3 min., 4 min., 5 min., 6 min., 7 min., 8 min., 9 min., or 10 min., or for a time that is within a range defined by any two of the aforementioned times.
  • the process for producing FDCA may comprise or consist of a reaction mixture comprising or consisting of a sugar derivative substrate comprising or consisting of glucaric acid dilactone; a Bronsted acid comprising or consisting of HC1; a halide salt selected from the group of ZnCl 2 , LiBr, and/or CaBr 2 ; and a water- miscible organic solvent that comprises or consists of 1,4-dioxane.
  • the water-miscible organic solvent may comprise or consist of water.
  • the temperature of the reaction mixture may range from or any number in between 90-120 °C. In some embodiments, the temperature of the reaction mixture may range from or any number in between 90-200 °C.
  • the temperature of the reaction mixture may range from or any number in between 110-180 °C. In some embodiments, the temperature of the reaction mixture may be 160 °C. In some embodiments, the reaction may proceed for a time ranging from or any number in between 3-24 h. In some embodiments, the reaction may proceed for a time ranging from or any number in between 1 min to 3 h. In some embodiments, the reaction may proceed for a time ranging from or any number in between 1 min to 24 h. In some embodiments, the reaction mixture is heated to a temperature of 90-200 °C, 110-160 °C, or 110-180 °C, preferably 130-160 °C, for time period of 1 min. to 24 hours, 1 min.
  • the process for producing FDCA may comprise or consist of a reaction mixture comprising or consisting of a sugar derivative substrate at a molar concentration in the range from or any number in between 1-3.5 M and the sugar derivative substrate comprises or consists of glucaric acid dilactone; a Bronsted acid at a molar concentration in the range of from or any number in between 0.2-1.6 M and the Bronstead acid comprises or consists of HC1; a halide salt at a molar concentration of approximately 2 M and the halide salt is selected from the group of ZnCl 2 , LiBr, and/or CaBr 2 ; and a water-miscible organic solvent that comprises or consists of 1,4-dioxane.
  • the water-miscible organic solvent may comprise or consist of water at a concentration ranging from or any number in between 0.2-0.4 M.
  • the temperature of the reaction mixture may range from or any number in between 90-120 °C. In some embodiments, the temperature of the reaction mixture may range from or any number in between 90-200 °C. In some embodiments, the temperature of the reaction mixture may range from or any number in between 110-180 °C. In some embodiments, the temperature of the reaction mixture may be 160 °C.
  • the reaction may proceed for a time ranging from or any number in between 3-24 h. In some embodiments, the reaction may proceed for a time ranging from or any number in between 1 min to 3 h.
  • the reaction may proceed for a time ranging from or any number in between 1 min to 24 h.
  • the reaction mixture is heated to a temperature of 90-200 °C, 110-160 °C, or 110-180 °C, preferably 130-160 °C, for time period of 1 min. to 24 hours, 1 min. to 3 hours, or 1 min. to 0.5 hours, preferably 1 min., 2 min., 3 min., 4 min., 5 min., 6 min., 7 min., 8 min., 9 min., or 10 min., or for a time that is within a range defined by any two of the aforementioned times.
  • the process for producing FDCA may comprise or consist of a reaction mixture comprising or consisting of a sugar derivative substrate comprising or consisting of a substrate selected from the group of mannaric acid, mannaric acid dilactone, mannaric acid 1,4-monolactone, sodium mannarate, and/or potassium glucarate; a Bronsted acid selected from the group of HC1, HBr, MsOH, and/or H 2 S0 4 ; a halide salt selected from the group of ZnBr 2 , ZnCl 2 , NaBr, LiBr, MgBr 2 , and/or CaBr 2 ; and a water-miscible organic solvent that comprises or consists of sulfolane.
  • the water-miscible organic solvent may comprise water at a concentration ranging from or any number in between 0-2.5 M.
  • the temperature of the reaction mixture may range from or any number in between 90-120 °C. In some embodiments, the temperature of the reaction mixture may range from or any number in between 90-200 °C. In some embodiments, the temperature of the reaction mixture may range from or any number in between 110-180 °C. In some embodiments, the temperature of the reaction mixture may be 160 °C.
  • the reaction may proceed for a time ranging from or any number in between 3-24 h. In some embodiments, the reaction may proceed for a time ranging from or any number in between 1 min to 3 h.
  • the reaction may proceed for a time ranging from or any number in between 1 min to 24 h.
  • the reaction mixture is heated to a temperature of 90-200 °C, 110-160 °C, or 110-180 °C, preferably 130-160 °C, for time period of 1 min. to 24 hours, 1 min. to 3 hours, or 1 min. to 0.5 hours, preferably 1 min., 2 min., 3 min., 4 min., 5 min., 6 min., 7 min., 8 min., 9 min., or 10 min., or for a time that is within a range defined by any two of the aforementioned times.
  • the process for producing FDCA may comprise or consist of a reaction mixture comprising or consisting of a sugar derivative substrate, preferably a heterogeneous sugar derivative substrate, comprising or consisting of a substrate selected from the group of mannaric acid dilactone, glucaric acid dilactone, and/or galactaric acid; a Bronsted acid selected from the group of HC1, HBr, MsOH, and/or H 2 S0 4 ; a halide salt selected from the group of ZnBr 2 , ZnCl 2 , NaBr, LiBr, MgBr 2 , and/or CaBr 2 ; and a water- miscible organic solvent that comprises or consists of sulfolane.
  • a reaction mixture comprising or consisting of a sugar derivative substrate, preferably a heterogeneous sugar derivative substrate, comprising or consisting of a substrate selected from the group of mannaric acid dilactone, glucaric acid dilactone, and/or galactaric
  • the water-miscible organic solvent may comprise water at a concentration ranging from or any number in between 0-2.5 M.
  • the temperature of the reaction mixture may range from or any number in between 90-120 °C. In some embodiments, the temperature of the reaction mixture may range from or any number in between 90-200 °C. In some embodiments, the temperature of the reaction mixture may range from or any number in between 110-180 °C. In some embodiments, the temperature of the reaction mixture may be 160 °C.
  • the reaction may proceed for a time ranging from or any number in between 3- 24 h. In some embodiments, the reaction may proceed for a time ranging from or any number in between 1 min to 3 h.
  • the reaction may proceed for a time ranging from or any number in between 1 min to 24 h.
  • the reaction mixture is heated to a temperature of 90-200 °C, 110-160 °C, or 110-180 °C, preferably 130- 160 °C, for time period of 1 min. to 24 hours, 1 min. to 3 hours, or 1 min. to 0.5 hours, preferably 1 min., 2 min., 3 min., 4 min., 5 min., 6 min., 7 min., 8 min., 9 min., or 10 min., or for a time that is within a range defined by any two of the aforementioned times.
  • the process for producing FDCA may comprise or consist of a reaction mixture comprising or consisting of a sugar derivative substrate, preferably a heterogeneous sugar derivative substrate, comprising or consisting of a substrate selected from the group of mannaric acid dilactone, glucaric acid dilactone, and/or galactaric acid; a Bronsted acid selected from the group of HC1, HBr, MsOH, and/or H 2 S0 4 ; a halide salt selected from the group of ZnBr 2 , ZnCl 2 , NaBr, LiBr, MgBr 2 , and/or CaBr 2 ; and a water- miscible organic solvent that comprises or consists of sulfolane.
  • a reaction mixture comprising or consisting of a sugar derivative substrate, preferably a heterogeneous sugar derivative substrate, comprising or consisting of a substrate selected from the group of mannaric acid dilactone, glucaric acid dilactone, and/or galactaric
  • the water-miscible organic solvent may comprise water at a concentration ranging from or any number in between 0-6.0 M. In some embodiments, the water-miscible organic solvent may comprise water at a concentration of 5.0 M. In some embodiments, the temperature of the reaction mixture may range from or any number in between 90-150 °C. In some embodiments, the temperature of the reaction mixture may range from or any number in between 90-200 °C. In some embodiments, the temperature of the reaction mixture may range from or any number in between 110-180 °C. In some embodiments, the temperature of the reaction mixture may be 160 °C. In some embodiments, the temperature of the reaction mixture may be 140 °C.
  • the reaction may proceed for a time ranging from or any number in between 0.5-24 h. In some embodiments, the reaction may proceed for a time of 1 h. In some embodiments, the reaction may proceed for a time ranging from or any number in between 1 min to 3 h. In some embodiments, the reaction may proceed for a time ranging from or any number in between 1 min to 24 h. In some embodiments, the reaction mixture is heated to a temperature of 90-200 °C, 110-160 °C, or 110-180 °C, preferably 130-160 °C, for time period of 1 min. to 24 hours, 1 min. to 3 hours, or 1 min.
  • the yield of FDCA produced from the sugar derivative substrate in accordance with one or more of the processes described herein can be e.g., at least 60%, or at least 70%, or at least 80%, or at least 90% or at least 95%, or at least 98% or at least 99%. In some embodiments, the yield ranges from between 85-90%, 87-92%, 90-95%, 92-97%, 95- 98%, or 97-99%, or is within a range defined by any of two of the aforementioned percentages.
  • the FDCA produced from the sugar derivative substrate comprises or consists of e.g., from or any number in between 90 % to 99 % of FDCA by molar purity.
  • the molar purity of FDCA produced from the sugar derivative substrate can be at least 60%, or at least 70%, or at least 80%, or at least 90% or at least 95%, or at least 98% or at least 99% or within a range defined by any two of the aforementioned amounts.
  • the molar purity of FDCA produced from the sugar derivative substrate ranges from e.g., between 85-90%, 87-92%, 90-95%, 92- 97%, 95-98%, or 97-99%, or is within a range defined by any of two of the aforementioned percentages.
  • one or more of the processes for producing FDCA described herein may generate an amount of 2-furoic acid impurities in the FDCA product.
  • the amount of 2-furoic acid present in the FDCA product comprises less than about 5% 2-furoic acid by weight percent, or less than about 2% 2-furoic acid by weight percent, or less than about 1% 2-furoic acid by weight percent, or less than about 0.5% 2- furoic acid by weight percent.
  • the amount of 2-furoic acid present in the FDCA product comprises from or any number in between 0.05% to 5% 2- furoic acid by weight percent.
  • the amount of 2-furoic acid present in the FDCA product comprises from or any number in between 0.1% to 1% 2-furoic acid by weight percent. In still other embodiments, the amount of 2-furoic acid present in the FDCA product comprises from or any number in between 0.05 % to 0.5 % 2-furoic acid by weight percent. In some embodiments, the amount of 2-furoic acid present in the FDCA product comprises from or any number in between 0.5% to 1% 2-furoic acid by weight percent. In some embodiments, the amount of 2-furoic acid present in the FDCA product comprises from or any number in between 1% to 5% 2-furoic acid by weight percent.
  • one or more of the processes for producing FDCA described herein may generate impurities in the FDCA product.
  • the impurityies may comprise 2-furoic acid.
  • the one or more processes produce FDCA and additional impurities, wherein the amount of FDCA relative to the additional impurities is at least 60%, or at least 65%, or at least 70%, or at least 75%, or at least 80%, or at least 85%, or at least 90%, or at least 91%, or at least 92%, or at least 93%, or at least 94%, or at least 95%, or at least 96%, or at least 97%, or at least 98%, or at least 99% by weight percent, or within any range defined by the aforementioned weight percents.
  • one or more of the processes for producing FDCA described herein may generate impurities in the FDCA product.
  • the impurities may comprise 2-furoic acid.
  • the molar ratio of FDCA to 2- furoic acid i.e., the selectivity of the process for producing FDCA relative to 2-furoic acid
  • the selectivity of the process for producing FDCA relative to 2-furoic acid is least 5:1, or at least 6:1 or at least 7:1, or at least 8:1, or at least 9:1, or at least 10:1, or at least 15:1, or at least 20:1, or at least 25:1, or at least 30:1, or at least 35:1, or at least 40:1, or at least 45: 1, or at least 50: 1, or within any range defined by the aforementioned molar ratios.
  • a hydrolysis step subsequent to the cyclization and dehydration of the sugar derivative substrate may be desirable to perform a hydrolysis step subsequent to the cyclization and dehydration of the sugar derivative substrate in order to increase the yield of FDCA product.
  • the cyclization and dehydration of the sugar derivative substrate may result in the formation of FDCA esters depending on the reaction conditions. For instance, ester formation may be observed when solvents containing one or more ether groups or alcohol groups are utilized, or when one or more alcohols are included in the reaction mixture.
  • the Bronsted acid either alone or in combination with the halide salt in the reaction mixture, may result in the degradation of an ether solvent, resulting in the formation of an alcohol, which may then be subsequently reacted with carboxylic acid groups from the C 6 -aldaric acids in the sugar derivative substrate to form FDCA esters.
  • This process may occur when the water-miscible organic solvent in the reaction mixture is 1,4- dioxane and the Bronsted acid is, e.g., HC1.
  • Scheme 3 provides an illustrative example of how esters of FDCA may be formed in the presence of 1,4-dioxane (or any alcohol).
  • 1,4 dioxane may undergo protonation at the oxygen atom followed by subsequent substitution to form a 2-haloethoxy ethanol, such as 2-(2-chloroethoxy)ethan-l-ol (CEE).
  • the 2-haloethoxy ethanol (such as CEE) may then subsequently react to form esters with one or both of the carboxylic acid groups of the C 6 -aldaric acids present in the sugar derivate substrate to form mono- and di-esters of FDCA.
  • 2-haloethoxy ethanol (such as CEE) may react to form esters with one or both of the carboxylic acid groups of FDCA to form mono- and di-esters of FDCA.
  • a subsequent base hydrolysis step may then be desired to generate a salt of FDCA.
  • FDCA may then be regenerated via acidic workup. Similar formation of mono- and di-esters is not observed other solvents.
  • the conversion of C 6 -aldaric acids, or salts or lactone of C 6 -aldaric acids to FDCA in, e.g., sulfolane does not result in the formation of any appreciable quantities of FDCA esters.
  • Scheme 3 Formation of FDCA and esters in 1,4-dioxane
  • the hydrolysis step may be performed under basic conditions.
  • the base may comprise or consist of LiOH.
  • the base may comprise or consist of NaOH.
  • the base may comprise or consist of KOH.
  • the base may comprise or consist of CsOH.
  • the base may comprise or consist of Ca(OH) 2 .
  • the FDCA produced by one or more of the processes described herein may be purified from the reaction mixture.
  • Purification of the FDCA may comprise or consist of separating any heterogeneous solids that may have formed in the reaction mixture.
  • the reaction mixture may be further concentrated with respect to the soluble components by removal of a portion of the water-miscible organic solvent.
  • Water-miscible organic solvent solvent removal may comprise or consist of evaporation (e.g., by using an evaporator), or distillation.
  • the FDCA may also be purified by crystallization.
  • the present disclosure provides for a process for producing a crystalline FDCA the method comprising: providing a crystallization solution comprising FDCA and a crystallization solvent; initiating crystallization of FDCA; and producing FDCA crystals.
  • crystallization solvent refers to a solvent from which FDCA can be crystallized when conditions are imposed that cause a reduction in solubility of FDCA in the crystallization solvent (e.g., temperature reduction (cooling) or solvent removal).
  • the crystallization solvent may comprise or consist of water, an organic solvent, or a multi-component solvent comprising water and/or a water-miscible organic solvent and/or two or more organic solvent species. The crystallization process may directly follow the dehydration reaction.
  • the crystallization solution is typically a solution comprising FDCA and the dehydration solvent.
  • Crystallization may be performed by introducing a saturated (or super-saturated) solution of the FDCA reaction mixture in the dehydration solvent into a crystallizer in which the solution is subjected to crystallization conditions, and crystallization is initiated by, for example, lowering the temperature or concentrating the solution by solvent evaporation (i.e., solvent removal), or a combination of both.
  • Solvent evaporation may be used to concentrate the solution to initiate crystallization, and may also be used to adjust the solvent composition to lower the solubility of FDCA.
  • the term "crystallization conditions" refers to an adjustment in temperature and/or adjustment in crystallization solution concentration and/or adjustment in crystallization solution composition that causes the initiation of crystallization of FDCA.
  • the initial temperature of the solution is typically in the range of from or any number in between 60°C to 180°C, such as e.g., 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, or 180 °C or within a range defined by any two of the aforementioned temperatures.
  • the initial temperature of the solution is in the range from or any number in between 70°C to 150°C such as e.g., 70, 80, 90, 100, 110, 120, 130, 140, or 150 °C or within a range defined by any two of the aforementioned temperatures.
  • the crystallization solution When the crystallization solution is cooled, it is typically cooled to a temperature that is at or below 60°C, such as e.g., equal to or less than 60, 50, 40, 30, 20, 10, 5, or 0 °C or within a range defined by any two of the aforementioned temperatures. More typically, it is cooled to a temperature at or below 50°C or at or below 40°C such as, e.g., equal to or less than 50, 40, 30, 20, 10, 5, or 0 °C or within a range defined by any two of the aforementioned temperatures.
  • Seed crystals of FDCA may be added to further promote the initiation of crystallization.
  • Other additives such as anti-foaming agents or crystallization aids, may be added to the crystallization solution to promote the crystallization process, and facilitate the formation of a suspension containing FDCA crystals.
  • Anti-foaming agents that are suitable for use in the practice of some of the alternatives described herein include, for example, silicones, surfactants, phosphates, alcohols, glycols, and/or stearates. Additives such as surfactants or electrolyte polymers may also influence the morphology and composition of the crystals formed.
  • FDCA crystals produced by the processes described herein can be separated from the solution (mother liquor) by centrifugation, filtration, and/or other suitable process for separating solids from liquids. The crystals can then be washed and dried using any suitable process known to those having ordinary skill in the art.
  • lignocellulosic material may be subjected to hydrolysis conditions followed by oxidation conditions to produce a sugar derivative substrate, and the resulting sugar derivative substrate may be contacted with a Bronsted acid and a halide salt in the presence of a water-miscible organic solvent to form a reaction mixture thereby producing FDCA.
  • the processes of the present disclosure may be carried out in batch, semi- batch, or continuous reactor format using reactors, such as, for example, fixed bed reactors, trickle bed reactors, slurry phase reactors, and/or moving bed reactors.
  • reactors such as, for example, fixed bed reactors, trickle bed reactors, slurry phase reactors, and/or moving bed reactors.
  • the relatively high solubilities of reactants and products (particularly, FDCA) in the water-miscible organic solvent facilitate the use of all such reactor formats, and particularly the fixed bed reactor format.
  • Salts including FeBr 2 (Alfa Aesar), FeBr 3 (Alfa Aesar), CaBr 2 (Alfa Aesar), CuBr (Sigma Aldrich), CuBr 2 (Alfa Aesar), CuCl (Sigma Aldrich), Et 4 NBr (Alfa Aesar), FeCl 3 (Sigma Aldrich), LiBr (Aldrich), Me 4 NBr (Alfa Aesar), Me 4 NCl (Acros Organics), NaBr (Aldrich), NiBr 2 (Alfa Aesar), ZnBr 2 (Alfa Aesar), ZnCl 2 (Sigma Aldrich), were transferred to 1.2 mL glass vials either as solids or by evaporation of a methanol solution containing the desired salt (0.1-0.5 mL) in a vacuum centrifuge (Genevac; 40-60 °C,
  • the glass vials were placed within a 96- well reactor insert (Symyx) and charged with a glass bead to aid with mixing and 0.25 mL of a dioxane solution containing 0.2-0.6 M glucaric acid dilactone (GADL; in-house preparation), 0-2.0 M H 2 0 (deionized (DI), 18.2 ⁇ -cm), and 2.0-3.9 M HC1 (supplied as a 4.0 M HC1 solution in dioxane from Sigma- Aldrich).
  • the reactor array was covered with a Teflon sheet, a silicone gasket sheet, and a Hastelloy-C gas diffusion plate each containing pinholes to allow gas diffusion.
  • the closed reactor array was sealed in a pressure vessel (Symyx), pressurized to 300 psi N 2 , heated to 120°C, and mixed with orbital shaking at a rate of 800 rpm for 3 h. After the desired reaction time, the pressure vessel was cooled to ambient temperature and vented. 0.75 mL of DMSO (BDH; 4-fold dilution) was added to each vial; the array was then sealed and inverted to mix. Each sample was then diluted 10-fold with a 0.25-1.2 M NaOH aqueous solution, mixed, and allowed to react for 0.5 h before a subsequent 5-fold dilution with DI H 2 0.
  • Example 1 A similar experimental procedure to Example 1 was used to test reaction solutions of 2.0 mL quantities. Salts, including Bu 4 NBr (Acros Organics), E NBr (Alfa Aesar), Me 4 NBr (Alfa Aesar), Me4NCl (Acros Organics), Me 4 NOAc (Acros Organics), NaBr (Aldrich), ZnCl 2 (Sigma Aldrich), were transferred as solids to 4.0 mL glass vials.
  • Salts including Bu 4 NBr (Acros Organics), E NBr (Alfa Aesar), Me 4 NBr (Alfa Aesar), Me4NCl (Acros Organics), Me 4 NOAc (Acros Organics), NaBr (Aldrich), ZnCl 2 (Sigma Aldrich)
  • the closed reactor array was sealed in a pressure vessel (Symyx), pressurized to 300 psi N 2 , heated to 90°C or 120°C, and mixed with orbital shaking at a rate of 500 rpm or 800 rpm for 17 h or 3 h, respectively.
  • the pressure vessel was cooled to ambient temperature and vented.
  • 2.0 mL of DMSO (BDH; 2-fold dilution) was then added to each vial, and the vials were capped and shaken. Each sample was then diluted another 2-fold with DMSO, followed by a 10-fold dilution with 0.5-1 M NaOH aqueous solution.
  • FDCA yields were also measured in GADL-alcohol-HCl-dioxane mixtures without salt present.
  • the alcohols used include n-butanol (Acros Organics) and 2- (2-chloroethoxy)ethanol (CEE; Acros Organics). These experiments were performed following the protocols outlined in Examples 1 and 2.
  • Example 3 Experiments using different starting substrates were performed according to the protocols outlined in Example 3.
  • the temperature of the silicone oil bath containing the reaction vessels was increased in a series of steps (50°C, 0.5 h; 70°C, 0.5 h; 90°C, 0.5 h) before reaching the reaction temperature (120°C, 3h) as opposed to placing the reaction vessels into the silicone oil bath preheated to the desired reaction temperature (Example 3).
  • the closed reactor array was sealed in a pressure vessel (Symyx), pressurized to 300 psi N 2 , heated to 100°C or 120°C, and mixed with orbital shaking at a rate of 500 rpm or 800 rpm for 17 h or 3 h, respectively.
  • the pressure vessel was cooled to ambient temperature and vented.
  • 2.0 mL of DMSO (BDH; 2-fold dilution) was then added to each vial, and the vials were capped and shaken. Each sample was then diluted another 2- fold with DMSO, followed by a 10-fold dilution with 0.05-1 M NaOH aqueous solution.
  • FDCA yields were also measured in GADL-mineral acid-sulfolane and GADL-mineral acid-H 2 0 mixtures without salt present, where mineral acids include: MsOH (Acros Organics), H 2 S0 4 (Sigma-Aldrich), HC1 (J.T. Baker), HBr (Alfa Aesar). These experiments were performed following the protocols outlined in Examples 1 and 2.
  • a 4-fold DMSO dilution was added and the vials were shaken. This was followed by a 2-fold DMSO dilution and a subsequent 10-fold dilution with 0.25 M NaOH aqueous solution; vials were then shaken and sat for 0.5 h at ambient temperature.
  • a Bronsted acid selected from HBr, HC1, H 2 S0 4 , MsOH and CF 3 S0 3 H (TfOH).
  • the vials were sealed and heated.
  • the reaction mixtures were stirred. After the reaction, the vials were cooled to ambient temperature.
  • the reactor was covered with a Teflon sheet, silicone gasket, Teflon sheet, and a stainless- steel diffusion plate each containing pinholes to allow gas diffusion.
  • the closed reactor array was sealed in a pressure vessel (Symyx), pressurized to 300 psi N 2 , heated to 100 °C, and mixed with orbital shaking at a rate of 500 rpm for 17 h. After the desired reaction time, the vials were cooled to ambient temperature. A 4-fold DMSO dilution was added and the vials were shaken.
  • the reactor was covered with a Teflon sheet, silicone gasket, Teflon sheet, and a stainless- steel diffusion plate each containing pinholes to allow gas diffusion.
  • the closed reactor array was sealed in a pressure vessel (Symyx), pressurized to 300 psi N 2 , heated to 120 °C, and mixed with orbital shaking at a rate of 800 rpm for 3 h. After the desired reaction time, the vials were cooled to ambient temperature. A 4-fold DMSO dilution was added and the vials were shaken.
  • the closed reactor array was sealed in a pressure vessel (Symyx), pressurized to 300 psi N 2 , heated to 120°C, and mixed with orbital shaking at a rate of 800 rpm for 3 h. After the desired reaction time, the pressure vessel was cooled to ambient temperature and vented. 0.75 mL of DMSO (BDH; 4-fold dilution) was added to each vial; the array was then sealed and inverted to mix. Each sample was then diluted 10-fold with a 0.25-1.2 M NaOH aqueous solution, mixed, and allowed to react for 0.5 h before a subsequent 5-fold dilution with DI H 2 0.
  • the closed reactor array was sealed in a pressure vessel (Symyx), pressurized to 300 psi N 2 , heated to 90°C, and mixed with orbital shaking at a rate of 500 rpm for 16 h. After the desired reaction time, the pressure vessel was cooled to ambient temperature and vented. 0.75 mL of DMSO (BDH; 4-fold dilution) was added to each vial; the array was then sealed and inverted to mix. Each sample was then diluted 10-fold with a 0.25-1.2 M NaOH aqueous solution, mixed, and allowed to react for 0.5 h before a subsequent 5-fold dilution with DI H 2 0.
  • DMSO DMSO
  • the vial was sealed and placed in a silicone oil bath pre-heated to 120 °C.
  • the reaction mixture was stirred at a rate of 400-500 rpm.
  • the vial was cooled to ambient temperature.
  • a 4-fold DMSO dilution was added and the vials were shaken. This was followed by a 10-fold dilution with 0.25 M NaOH aqueous solution; vials were then shaken and sat for 0.5 h at ambient temperature.
  • Table 16 show selected mixed aldaric acids/aldaric dilactones to furan-2,5-dicarboxylic acid (FDCA) dehydration reactions using methanesulfonic acid and hydrogen bromide.
  • Mixed alderic acids and aldaric dilactones may include mannaric acid dilactone (MADL), glucaric acid dilactone (GADL) and galactaric acid (GA).
  • Example 20 Dehydration of mannaric acid dilactone (MADL) to furan-2,5-dicarboxylic acid (FDCA) using methanesulfonic acid in 1.0 mL reaction mixture.
  • MADL mannaric acid dilactone
  • FDCA furan-2,5-dicarboxylic acid
  • Example 21 Dehydration of mannaric acid dilactone (MADL) to furan-2,5-dicarboxylic acid (FDCA) using hydrogen bromide in 1.0 mL reaction mixture.
  • MADL mannaric acid dilactone
  • FDCA furan-2,5-dicarboxylic acid
  • the vials were sealed and placed in a silicone oil bath pre-heated to a desired reaction temperature and allowed 0.083 h (or about 5 min) to reach reaction temperature.
  • the reaction mixtures were stirred at a rate of 600-1000 rpm.
  • the vials were cooled to ambient temperature.
  • a 3-fold DMSO dilution was added and the vials were shaken. This was followed by a 4-fold DMSO dilution and a subsequent 10-fold dilution with 0.06 M NaOH aqueous solution; vials were then shaken and sat for 0.5 h at ambient temperature.

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Abstract

La présente invention concerne des procédés de production d'acide 2,5-furandicarboxylique (FDCA) à partir de divers substrats, comprenant des acides C6-aldariques et des lactones d'acides C6-aldariques.
PCT/US2018/041707 2017-07-12 2018-07-11 Nouveaux procédés de préparation d'acide 2,5-furandicarboxylique WO2019014393A1 (fr)

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CN111606874A (zh) * 2020-05-28 2020-09-01 浙江恒澜科技有限公司 一种微波诱导强化和恒沸精馏除水组合技术制备2,5-呋喃二甲酸的方法与装置
CN113045522A (zh) * 2021-03-05 2021-06-29 浙江恒澜科技有限公司 一种氢卤酸和金属卤化物协同催化己糖二酸（盐）脱水环合制备2,5-呋喃二甲酸的方法
CN116003354A (zh) * 2022-12-27 2023-04-25 莆田达凯新材料有限公司 一种2,5呋喃二甲酸的结晶提纯方法
WO2023169517A1 (fr) * 2022-03-10 2023-09-14 江苏赛瑞克新材料科技有限公司 Procédé de préparation d'un composé d'acide 2,5-furandicarboxylique

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US6534680B1 (en) 1997-02-12 2003-03-18 Basf Aktiengesellschaft Dicarboxylic acid crystallizates
WO2000034211A1 (fr) 1998-12-04 2000-06-15 Bp Chemicals Limited Procede d'oligomerisation
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
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WO2014058859A2 (fr) * 2012-10-11 2014-04-17 Wisconsin Alumni Research Foundation Procédé pour convertir des monosaccharides en 5-(hydroxyméthyl)furfural (hmf) utilisant des solvants issus de biomasse
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WO2016168233A1 (fr) * 2015-04-14 2016-10-20 E I Du Pont De Nemours Procédés de production d'acide 2,5-furandicarboxylique et de ses dérivés, et polymères fabriqués à partir de ceux-ci
EP3088377A1 (fr) 2015-04-30 2016-11-02 Rhodia Operations Procédé pour la préparation d'un acide aldarique ou un sel de celui-ci
EP3088378A1 (fr) 2015-04-30 2016-11-02 Rhodia Operations Procédé pour la préparation d'un mélange d'acides aldariques, ou sels de ceux-ci
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CN111606874A (zh) * 2020-05-28 2020-09-01 浙江恒澜科技有限公司 一种微波诱导强化和恒沸精馏除水组合技术制备2,5-呋喃二甲酸的方法与装置
CN111606874B (zh) * 2020-05-28 2022-07-08 浙江恒逸石化研究院有限公司 一种微波诱导强化和恒沸精馏除水组合技术制备2,5-呋喃二甲酸的方法与装置
CN113045522A (zh) * 2021-03-05 2021-06-29 浙江恒澜科技有限公司 一种氢卤酸和金属卤化物协同催化己糖二酸（盐）脱水环合制备2,5-呋喃二甲酸的方法
WO2023169517A1 (fr) * 2022-03-10 2023-09-14 江苏赛瑞克新材料科技有限公司 Procédé de préparation d'un composé d'acide 2,5-furandicarboxylique
CN116003354A (zh) * 2022-12-27 2023-04-25 莆田达凯新材料有限公司 一种2,5呋喃二甲酸的结晶提纯方法

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