WO2013096998A1 - Process for the production of a mixture of 2,4- furandicarboxylic acid and 2,5- furandicarboxylic acid (fdca) via disproportionation reaction, mixture of 2,4-fdca and 2, 5 - fdca obtainable thereby, 2, 4 - fdca obtainable thereby and use of 2,4- fdca - Google Patents
Process for the production of a mixture of 2,4- furandicarboxylic acid and 2,5- furandicarboxylic acid (fdca) via disproportionation reaction, mixture of 2,4-fdca and 2, 5 - fdca obtainable thereby, 2, 4 - fdca obtainable thereby and use of 2,4- fdca Download PDFInfo
- Publication number
- WO2013096998A1 WO2013096998A1 PCT/BR2011/000502 BR2011000502W WO2013096998A1 WO 2013096998 A1 WO2013096998 A1 WO 2013096998A1 BR 2011000502 W BR2011000502 W BR 2011000502W WO 2013096998 A1 WO2013096998 A1 WO 2013096998A1
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- WIPO (PCT)
- Prior art keywords
- fdca
- mixture
- producing
- route according
- disproportionation
- Prior art date
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- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 32
- 230000008569 process Effects 0.000 title claims abstract description 28
- 238000007323 disproportionation reaction Methods 0.000 title claims abstract description 26
- 239000000203 mixture Substances 0.000 title claims description 32
- 238000004519 manufacturing process Methods 0.000 title abstract description 12
- JOTDFEIYNHTJHZ-UHFFFAOYSA-N furan-2,4-dicarboxylic acid Chemical compound OC(=O)C1=COC(C(O)=O)=C1 JOTDFEIYNHTJHZ-UHFFFAOYSA-N 0.000 title description 6
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000002253 acid Substances 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 5
- 229920000728 polyester Polymers 0.000 claims abstract description 5
- 150000002148 esters Chemical class 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims description 24
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 18
- 239000011541 reaction mixture Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- -1 transition metal salts Chemical class 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000002198 insoluble material Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- 229910000027 potassium carbonate Inorganic materials 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 6
- 229920002521 macromolecule Polymers 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 description 11
- 238000005481 NMR spectroscopy Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 239000010931 gold Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 4
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 4
- 235000012141 vanillin Nutrition 0.000 description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- HHWWWZQYHPFCBY-UHFFFAOYSA-N methyl 6-oxopyran-3-carboxylate Chemical compound COC(=O)C=1C=CC(=O)OC=1 HHWWWZQYHPFCBY-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- HDCRDACZYDHUQX-UHFFFAOYSA-M sodium;furan-2-carboxylate Chemical compound [Na+].[O-]C(=O)C1=CC=CO1 HDCRDACZYDHUQX-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- LZFNKJKBRGFWDU-UHFFFAOYSA-N 3,6-dioxabicyclo[6.3.1]dodeca-1(12),8,10-triene-2,7-dione Chemical compound O=C1OCCOC(=O)C2=CC=CC1=C2 LZFNKJKBRGFWDU-UHFFFAOYSA-N 0.000 description 1
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- AETGYSUEDWYSME-UHFFFAOYSA-N 5-methoxycarbonylfuran-2-carboxylic acid Chemical compound COC(=O)C1=CC=C(C(O)=O)O1 AETGYSUEDWYSME-UHFFFAOYSA-N 0.000 description 1
- WJEKCCOEKJGSGX-UHFFFAOYSA-N 5-methoxycarbonylfuran-3-carboxylic acid Chemical compound COC(=O)C1=CC(C(O)=O)=CO1 WJEKCCOEKJGSGX-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical compound [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 230000003334 potential effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002311 subsequent effect Effects 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
- C08G63/181—Acids containing aromatic rings
Definitions
- the present invention refers to the production of 2,4-furandicar- boxylic acid (2,4-FDCA) through the disproportionation route, using as base 0 compounds oxidation products of furfural.
- This invention also refers to the mixture comprising 2,5-FDCA and 2,4-FDCA as a result of a disproportionation route and the use of 2,4-FDCA as a monomer or comonomer to produce macromolecules.
- the article also describes one example of a 2,4-FDCA based polyester.
- the melting point of that polymer is lower than that of 2,5-FDCA based ones, but the data supplied are excessively limited to draw any conclusion about the potential properties of that resin.
- Andrisano et al reported that the potassium salt of furoic acid when heated up to 250-300°C in nitrogen atmosphere, undergoes decarbox- ylation to furan with simultaneous carboxylation at the 5- position to dipotas- sium 2,5 furandicarboxylate.
- the objective of this invention is to provide a route to synthesize 2,4-FDCA in a 2-step process from cheap biomass (products derived from furfural), with elevated yield and absence of toxic byproducts.
- 2,5-FDCA and 2,4- FDCA monomers might generate a synergic effect such as that of ethylene terephthalate and ethylene isophthalate in the macromolecular structure and properties of PET such as crystallization and melting point.
- the objective of this invention is to provide a process for producing a mixture of 2,4-FDCA and 2,5-FDCA by subjecting furoic acid salts to a disproportionation reaction, catalysed by metal salts, comprising the steps of:
- the object of this invention also comprises the mixture of 2,5- FDCA and 2,4-FDCA as a result of a disproportionation route, the 2,4-FDCA obtained by the disproportionation reaction process and the use of 2,4-FDCA to synthesize chemical compounds which can be polymerized such as esters is also object of this invention.
- Fig. 1 Disproportionation reaction undergone by the K-furoate generating the mixture of dicarboxylic acids precursors (which will further be acidified) and furan.
- Fig. 2 H NMR analysis showing the three protons for furoate in equal ratio, without any other signal besides the NMR solvent, confirming that the furfural had been converted completely and selectively into sodium fu- roate.
- the objective of this invention is to provide a process for producing a mixture of 2,4-FDCA and 2,5-FDCA by subjecting furoic acid salts to a disproportionation reaction (see Figure 1 ), catalyzed by metal salts, comprising the steps of:
- the furfural oxidation of the first step is made in the presence of Au/TiO 2 catalyst.
- the Au/TiO2 is optimized for this reaction.
- Furfural, Au/TiO2 and NaOH in water was charged into the reactor and pressurized with oxygen (3x10 5 Pa of O 2 ) and stirred at 600rpm and at 50°C for 3-5h.
- the furoic acid product is further converted to a furoic acid salt, which can be potassium, sodium, cesium and preferably potassium. Other renewable sources can be used to produce the furoates.
- the furoic acid salt and a metal salt catalyst are then heated un- der stirring for an interval ranging from 1 h to 5.5h, preferably 5h.
- the temperature of the system ranges from 220 °C to 280 °C, preferably 260 °C (salt bath temperature not the internal temperature.)
- the catalyst is chosen from transition metal salts, alkaline earth metal salts, preferably FeCI 2 , Cdl 2 , Zn(OTf) 2 or ZnCI 2 . When the FeCI 2 catalyst is used, the reactive mixture is placed under a slight flow of N 2 .
- ZnCI 2 (20 mole%) was found to be active (best) and the results obtained are comparable or more even better than the Cdl 2 catalyst which has been screened as the best catalyst by Andrisano for the disproportionation reaction of K-Furoate.
- the reaction was stopped after the specified time and cooled down to room temperature in 2 h.
- the furan is collected via a Dean-Stark trap and a C0 2 -aceton-ice bath. After cooling, water is added and the black insoluble material is filtered off and upon acidification the 2,5-FDCA was collected.
- 12 N HCI is used to acidify the reaction mixture until reaches pH 1. 2,5-FDCA is precipitated out immediately from the reaction mixture.
- NMR analysis shows that there is a high degree of K-furoate conversion which al- lows to precise the amount of 2,4-FDCA in the product mixture.
- the diacid obtained with the present invention may be useful to produce chemical compounds which can be useful monomers to the polymer industry and other industries such as solvents, lubricants or plasticizers in- dustry. Furthermore, these 2,4-FDCA based compounds can be used to produce polyesters.
- Example 1 Procedure for preparing furoic acid from furfural: Oxidation of furfural
- Furfural (3.00 grammes, 31.22 mmol) was dissolved in 40 ml wa- ter.
- One equivalent (31.75 mmol; 1 .02 eq) of base (NaOH) and 0.012 grammes of Au/TiO2 catalyst (ex-Strem-Autek; 1 .2 wt % Au, Au particle size 2-3 nm) were added to the furfural solution in water.
- the 100ml reaction vessel (Biichi glasuster picoclave) was closed and overhead stirring was applied. Oxygen pressure (303974,99 Pa of O 2 ) was applied to the reaction mixture.
- the reaction mixture was put at 50 °C.
- This reaction demonstrates the efficiency in obtaining furoate salts from furfural, that can serve as input for the subsequent disproportionation reaction.
- Example 2 Process for production of a mixture of 2,4-FDCA and
- Example 3 Process for production of a mixture of 2,4-FDCA followed by 2,5-FDCA isolation
- the reaction crude mixture (2,4-FDCA, 2,5-FDCA, 2-Furoic acid and Cdl 2 ) was subjected to soxhlet extraction using acetone for 8 h. After cooling to room temperature, acetone insoluble white crystalline powder was analyzed by NMR which showed no proton signals. The acetone soluble part was recovered and the solvent was evaporated under reduced pressure in the rotatory evaporator. NMR analysis showed the presence of 2,4-FDCA, 2,5-FDCA and 2-Furoic acid in the crude mixture. The mixture was then stirred vigorously with chloroform for 10 min at room temperature and filtered. This process was repeated until 2-furoic acid was completely removed from the mixture.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Furan Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Polyesters Or Polycarbonates (AREA)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/BR2011/000502 WO2013096998A1 (en) | 2011-12-29 | 2011-12-29 | Process for the production of a mixture of 2,4- furandicarboxylic acid and 2,5- furandicarboxylic acid (fdca) via disproportionation reaction, mixture of 2,4-fdca and 2, 5 - fdca obtainable thereby, 2, 4 - fdca obtainable thereby and use of 2,4- fdca |
| BR112014016185-2A BR112014016185B1 (pt) | 2011-12-29 | 2011-12-29 | Processo para a produção de uma mistura de ácido 2,4-furandicarboxílico e ácido 2,5-furandicarboxílico |
| US14/368,676 US9284290B2 (en) | 2011-12-29 | 2011-12-29 | Process for the production of the mixture 2,4 furandicarboxylic acid (FDCA) and 2,5 furandicarboxylic acid via disproportionation reaction |
| EP11811513.8A EP2797907B1 (en) | 2011-12-29 | 2011-12-29 | Process for the production of a mixture of 2,4- furandicarboxylic acid and 2,5- furandicarboxylic acid (FDCA) via disproportionation reaction, mixture of 2,4-FDCA and 2,5-FDCA obtainable thereby, 2,4-FDCA obtainable thereby and use of 2,4-FDCA |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/BR2011/000502 WO2013096998A1 (en) | 2011-12-29 | 2011-12-29 | Process for the production of a mixture of 2,4- furandicarboxylic acid and 2,5- furandicarboxylic acid (fdca) via disproportionation reaction, mixture of 2,4-fdca and 2, 5 - fdca obtainable thereby, 2, 4 - fdca obtainable thereby and use of 2,4- fdca |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2013096998A1 true WO2013096998A1 (en) | 2013-07-04 |
Family
ID=45528853
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/BR2011/000502 WO2013096998A1 (en) | 2011-12-29 | 2011-12-29 | Process for the production of a mixture of 2,4- furandicarboxylic acid and 2,5- furandicarboxylic acid (fdca) via disproportionation reaction, mixture of 2,4-fdca and 2, 5 - fdca obtainable thereby, 2, 4 - fdca obtainable thereby and use of 2,4- fdca |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US9284290B2 (pt-pt) |
| EP (1) | EP2797907B1 (pt-pt) |
| BR (1) | BR112014016185B1 (pt-pt) |
| WO (1) | WO2013096998A1 (pt-pt) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104059037A (zh) * | 2014-03-25 | 2014-09-24 | 浙江理工大学 | 一种制备2,5-呋喃二甲酸的方法 |
| CN106554338A (zh) * | 2015-09-30 | 2017-04-05 | 中国科学院宁波材料技术与工程研究所 | 一种糠酸制备2,5-呋喃二甲酸的方法 |
| WO2017158106A1 (fr) * | 2016-03-16 | 2017-09-21 | Universite De Lille 1 Sciences Et Technologies | Procede de preparation d'acide furoïque |
| EP3235848A1 (en) | 2016-04-18 | 2017-10-25 | Stichting Wageningen Research | Furan dicarboxylate copolyesters |
| WO2018002291A1 (fr) | 2016-07-01 | 2018-01-04 | Centre National De La Recherche Scientifique | Procédé de préparation de l'acide 2,5-furane dicarboxylique (fdca) à partir de dérivés de pentoses |
| CN108299354A (zh) * | 2017-01-12 | 2018-07-20 | 中国科学院宁波材料技术与工程研究所 | 一种2,5-呋喃二甲酸或其酯化物的制备方法 |
| WO2019214576A1 (zh) * | 2018-05-10 | 2019-11-14 | 中国科学院长春应用化学研究所 | 2，5-呋喃二甲酸的制备方法 |
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| DK3283470T3 (da) * | 2015-04-14 | 2023-12-11 | Du Pont | Processer til fremstilling af 2,5-furandicarboxylsyre og derivater deraf |
| EP3402787A4 (en) | 2016-01-13 | 2019-11-27 | Stora Enso Oyj | PROCESS FOR THE PREPARATION OF 2,5-FURANDIC ACETIC ACID AND INTERMEDIATES AND DERIVATIVES THEREOF |
| CN107082872A (zh) * | 2016-04-27 | 2017-08-22 | 杨第伦 | 新型正极材料π‑体系甲酸盐及其制备方法 |
| CN114751881B (zh) * | 2017-01-12 | 2024-09-20 | 中国科学院宁波材料技术与工程研究所 | 一种呋喃二羧酸化合物的制备方法 |
| KR102117340B1 (ko) * | 2017-03-21 | 2020-06-01 | 한국생산기술연구원 | 알칼리금속-아졸라이드계 촉매를 이용한 2,5-퓨란디카르복실산의 제조방법 |
| KR102568266B1 (ko) | 2017-07-12 | 2023-08-17 | 스토라 엔소 오와이제이 | 정제된 2,5-푸란디카르복실산 경로 생성물 |
| US10844031B2 (en) * | 2018-11-16 | 2020-11-24 | Iowa State University Research Foundation, Inc. | Green, copper-catalyzed disproportionation of aromatic and heteroaromatic carboxylates to dicarboxylates |
| CN109574963B (zh) * | 2018-12-21 | 2021-06-25 | 厦门大学 | 一种糠酸酯类化合物的合成方法 |
| KR102278268B1 (ko) * | 2019-11-22 | 2021-07-16 | 한국화학연구원 | 5-알콕시메틸퍼퓨랄로부터 2,5-퓨란디카르복실산 제조방법 |
| EP4578851A2 (en) | 2020-02-06 | 2025-07-02 | The Board of Trustees of the Leland Stanford Junior University | Carbonate-promoted carboxylation at high rates |
| AU2021279456A1 (en) | 2020-05-29 | 2022-12-15 | Braskem S.A. | Production and use of plasticizers based on 2,4-isomer of furandicarboxylic acid diesters |
| MX2023001730A (es) * | 2020-08-12 | 2023-05-18 | Archer Daniels Midland Co | Purificacion del ester dimetilico del acido 2,5-furandicarboxilico y otros productos esterificados. |
| US12018119B2 (en) | 2021-01-29 | 2024-06-25 | Braskem S.A. | Copolyesters of 2,4-FDCA with increased crystallization control |
| US20230002363A1 (en) | 2021-06-16 | 2023-01-05 | Braskem S.A. | Furanic diglycidyl ethers and esters and use thereof |
| US11708343B2 (en) | 2021-07-16 | 2023-07-25 | Kse, Inc. | Method and integrated process for the carboxylation of furan derived carboxylic acids to 2,5-furandicarboxylic acid |
| CN116283849B (zh) * | 2023-03-15 | 2025-03-18 | 上海沃凯生物技术有限公司 | 2,5-呋喃二甲酸的制备方法 |
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- 2011-12-29 US US14/368,676 patent/US9284290B2/en active Active
- 2011-12-29 WO PCT/BR2011/000502 patent/WO2013096998A1/en active Application Filing
- 2011-12-29 EP EP11811513.8A patent/EP2797907B1/en not_active Not-in-force
- 2011-12-29 BR BR112014016185-2A patent/BR112014016185B1/pt active IP Right Grant
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104059037A (zh) * | 2014-03-25 | 2014-09-24 | 浙江理工大学 | 一种制备2,5-呋喃二甲酸的方法 |
| CN106554338A (zh) * | 2015-09-30 | 2017-04-05 | 中国科学院宁波材料技术与工程研究所 | 一种糠酸制备2,5-呋喃二甲酸的方法 |
| WO2017158106A1 (fr) * | 2016-03-16 | 2017-09-21 | Universite De Lille 1 Sciences Et Technologies | Procede de preparation d'acide furoïque |
| FR3048969A1 (fr) * | 2016-03-16 | 2017-09-22 | Univ De Lille 1 Sciences Et Tech | Procede de preparation d'acide furoique |
| US10961212B2 (en) | 2016-03-16 | 2021-03-30 | Université de Lille | Furoic acid preparation method |
| EP3235848A1 (en) | 2016-04-18 | 2017-10-25 | Stichting Wageningen Research | Furan dicarboxylate copolyesters |
| WO2018002291A1 (fr) | 2016-07-01 | 2018-01-04 | Centre National De La Recherche Scientifique | Procédé de préparation de l'acide 2,5-furane dicarboxylique (fdca) à partir de dérivés de pentoses |
| CN108299354A (zh) * | 2017-01-12 | 2018-07-20 | 中国科学院宁波材料技术与工程研究所 | 一种2,5-呋喃二甲酸或其酯化物的制备方法 |
| WO2019214576A1 (zh) * | 2018-05-10 | 2019-11-14 | 中国科学院长春应用化学研究所 | 2，5-呋喃二甲酸的制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2797907A1 (en) | 2014-11-05 |
| US20150119588A1 (en) | 2015-04-30 |
| US9284290B2 (en) | 2016-03-15 |
| BR112014016185A8 (pt) | 2017-12-19 |
| BR112014016185A2 (pt) | 2017-06-13 |
| BR112014016185B1 (pt) | 2019-02-12 |
| EP2797907B1 (en) | 2015-08-26 |
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