CN116655566A - Method for synthesizing 2, 5-furandicarboxylic acid by one step through 2, 5-furandicarboxaldehyde without participation of oxygen - Google Patents
Method for synthesizing 2, 5-furandicarboxylic acid by one step through 2, 5-furandicarboxaldehyde without participation of oxygen Download PDFInfo
- Publication number
- CN116655566A CN116655566A CN202310631803.6A CN202310631803A CN116655566A CN 116655566 A CN116655566 A CN 116655566A CN 202310631803 A CN202310631803 A CN 202310631803A CN 116655566 A CN116655566 A CN 116655566A
- Authority
- CN
- China
- Prior art keywords
- sulfobutyl
- ionic liquid
- furandicarboxaldehyde
- synthesizing
- participation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 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 36
- 238000000034 method Methods 0.000 title claims abstract description 28
- PXJJKVNIMAZHCB-UHFFFAOYSA-N 2,5-diformylfuran Chemical compound O=CC1=CC=C(C=O)O1 PXJJKVNIMAZHCB-UHFFFAOYSA-N 0.000 title claims abstract description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000001301 oxygen Substances 0.000 title claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 19
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 13
- 239000002608 ionic liquid Substances 0.000 claims abstract description 49
- 150000002443 hydroxylamines Chemical class 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 238000010907 mechanical stirring Methods 0.000 claims abstract description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 53
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- -1 1-sulfobutyl-3-methylimidazole p-toluenesulfonate Chemical compound 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical group Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 8
- ZPAKGDVDAFOWRO-UHFFFAOYSA-N hydrogen sulfate 1-(3-methyl-1H-imidazol-3-ium-2-yl)butane-1-sulfonic acid Chemical compound OS([O-])(=O)=O.CCCC(c1[nH]cc[n+]1C)S(O)(=O)=O ZPAKGDVDAFOWRO-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 claims description 5
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- VUAHJJRJRAIMGU-UHFFFAOYSA-N 1-(3-methyl-1H-imidazol-3-ium-2-yl)butane-1-sulfonic acid trifluoromethanesulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)F.CCCC(c1[nH]cc[n+]1C)S(O)(=O)=O VUAHJJRJRAIMGU-UHFFFAOYSA-N 0.000 claims description 3
- ZNNXXAURXKYLQY-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole;sulfuric acid Chemical compound OS(O)(=O)=O.CCCCN1CN(C)C=C1 ZNNXXAURXKYLQY-UHFFFAOYSA-N 0.000 claims description 3
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005580 one pot reaction Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 3
- AOKJITQXBAPAJO-UHFFFAOYSA-N S(=O)(=O)(O)C(CCC)C1=NC=CN1C Chemical compound S(=O)(=O)(O)C(CCC)C1=NC=CN1C AOKJITQXBAPAJO-UHFFFAOYSA-N 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 14
- 239000007800 oxidant agent Substances 0.000 abstract description 5
- 230000001590 oxidative effect Effects 0.000 abstract description 5
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- PCSKKIUURRTAEM-UHFFFAOYSA-N 5-hydroxymethyl-2-furoic acid Chemical compound OCC1=CC=C(C(O)=O)O1 PCSKKIUURRTAEM-UHFFFAOYSA-N 0.000 description 4
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- SHNRXUWGUKDPMA-UHFFFAOYSA-N 5-formyl-2-furoic acid Chemical compound OC(=O)C1=CC=C(C=O)O1 SHNRXUWGUKDPMA-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Furan Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for synthesizing 2, 5-furandicarboxylic acid by one step from 2, 5-furandicarboxaldehyde without participation of oxygen. The method comprises the following steps: adding 2, 5-furan dicarboxaldehyde, ionic liquid, hydroxylamine salt and solvent into a closed reactor under nitrogen atmosphere, and reacting for 2-9 h at 60-150 ℃ under mechanical stirring to obtain the product 2, 5-furan dicarboxylic acid. The invention does not use oxygen as an oxidant, and has intrinsic safety; noble metal catalysts are not used, so that the cost is reduced; the target product has high selectivity and simple separation; the ionic liquid is easy to recycle and recycle.
Description
Technical Field
The invention belongs to the field of biomass conversion preparation chemicals, and particularly relates to a method for preparing 2, 5-furandicarboxylic acid from 2, 5-furandicarboxaldehyde.
Background
2, 5-furandicarboxylic acid (FDCA) is one of the most promising compounds among furans derivatives, and is evaluated by the United states chemical society as one of the twelve bio-platform molecules of greatest research value (Polymer Chemistry,2010,1 (3): 245-251). FDCA can be used to produce various biochemical substances, and because of its structure similar to terephthalic acid, it is often used as a renewable, green substitute for terephthalic acid for the synthesis of high performance polymers such as bio-based polyesters, nylons, and novel biodegradable copolyesters. In addition, FDCA can be used for producing petroleum-based polymer modifiers (RSC Advances,2018,8 (6): 3161-3177) such as degradable plastics, unsaturated resins and the like.
Currently, FDCA is mainly prepared by oxidation of 5-Hydroxymethylfurfural (HMF). The catalytic system mostly requires pure oxygen or air as an oxidant, and noble metals (such as gold, platinum, palladium and ruthenium) or non-noble metals (such as manganese, cobalt and cerium) as catalysts (Industrial)&Engineering Chemistry Research,2020,59 (11): 4895-4904; chemSuschem 2019,12 (12): 2715-2724). Han et al, at 10bar O with Pt/C-O-Mg as catalyst 2 The reaction was carried out at 110℃for 12 hours, with an FDCA yield of 97% (Green Chemistry,2016,18 (6): 1597-1604). Guan et al in Au 1 Pd 1 /pBNC-30％ HNO 3 As a catalyst at 2MPa O 2 The reaction was carried out at 100℃for 20h with an FDCA yield of 93.9% (ChemSuschem, 2022,15 (16): e 202201041). Although the FDCA yields were all 90% or more, the following problems were faced: incomplete oxidation of HMF produces a large number of partially oxidized intermediates, such as 5-formyl-2-furancarboxylic acid (FFCA) and 5-hydroxymethyl-2-furancarboxylic acid (HMFCA), reducing target product selectivity and atomic economy; oxygen is taken as an oxidant, so that potential safety hazards such as inflammability, explosiveness and the like exist; FDCA has low solubility in conventional solvents, and the use of solid catalysts results in difficulties in product isolation, etc.
In summary, the invention provides a sustainable and safe process route for directly catalyzing and synthesizing FDCA by a one-step reaction under the condition of no oxygen and no participation of a metal catalyst by using a downstream bio-based raw material 2, 5-furan Dicarboxaldehyde (DFF) of HMF for the first time, so as to eliminate potential safety hazards in the reaction.
Disclosure of Invention
Aiming at the defects of potential safety hazards such as inflammability and explosiveness, product separation difficulty caused by using a solid catalyst and the like in the prior art caused by using oxygen as an oxidant, the invention provides a reaction path for synthesizing 2, 5-furandicarboxylic acid by one step from 2, 5-furandicarboxaldehyde without participation of oxygen. The method is a green novel process for synthesizing FDCA in one step under the anaerobic condition by using ionic liquid as a catalyst to replace a traditional metal catalyst to catalyze a sustainable raw material DFF. The invention does not use oxygen as an oxidant, and has intrinsic safety; noble metal catalysts are not used, so that the cost is reduced; the target product has high selectivity and simple separation; the ionic liquid is easy to recycle and recycle.
The technical scheme of the invention is as follows:
a method for synthesizing 2, 5-furandicarboxylic acid by one step from 2, 5-furandicarboxaldehyde without oxygen participation, which comprises the following steps:
adding 2, 5-furan dicarboxaldehyde, ionic liquid, hydroxylamine salt and solvent into a closed reactor under nitrogen atmosphere, reacting for 2-9 h at 60-150 ℃ under mechanical stirring, and directly obtaining the product 2, 5-furan dicarboxylic acid through one-step reaction;
wherein, the molar ratio of the materials is as follows: adding 0.6-6 g of ionic liquid, 1-8 mmol of hydroxylamine salt and 1-10 mL of solvent into each 1mmol of 2, 5-furan dicarboxaldehyde;
the ionic liquid is one or more of 1-sulfobutyl-3-methylimidazole bisulfate, 1-sulfobutyl-3-methylimidazole trifluoromethanesulfonate, 1-sulfobutyl-3-methylimidazole p-toluenesulfonate, 1-butyl-3-methylimidazole bisulfate, 1-sulfobutyl-3-methylimidazole iodized salt, N, N, N-trimethyl-N-sulfobutyl hydrogen ammonium sulfate salt, N, N, N-trimethyl-N-sulfobutyl trifluoromethanesulfonate, N, N, N-trimethyl-N-sulfobutyl p-toluenesulfonate, 1-sulfobutylpyridine bisulfate, 1-sulfobutylpyridine trifluoromethanesulfonate and 1-sulfobutylpyridine p-toluenesulfonate;
the hydroxylamine salt is hydroxylamine hydrochloride, hydroxylamine sulfate, 1-sulfobutyl-3-methylimidazole bisulfate ionic liquid hydroxylamine salt, 1-sulfobutyl pyridine bisulfate ionic liquid hydroxylamine salt or N, N, N-trimethyl-N-sulfobutyl hydrogen sulfate ammonium salt ionic liquid hydroxylamine salt.
The solvent is one or two of water, tetrahydrofuran, ethanol and paraxylene.
The reactor is a high-pressure reactor.
The proportioning amount of the materials is preferably that 0.6-3.6 g of ionic liquid, 2-6 mmol of hydroxylamine salt and 3-6 mL of solvent are added per 1mmol of 2, 5-furandicarboxaldehyde.
The preferable reaction temperature is 80-140 ℃.
The preferable reaction time is 4-8 h.
The invention has the substantial characteristics that:
all documents in the prior art for the synthesis of FDCA are via the oxidation route.
The invention does not use oxygen or metal catalyst, adopts ionic liquid as catalyst, and synthesizes 2, 5-furandicarboxylic acid in one step under the anaerobic condition.
The beneficial effects of the invention are as follows:
(1) The invention realizes the one-step synthesis of 2, 5-furandicarboxylic acid from 2, 5-furandicarboxaldehyde under the anaerobic condition for the first time, has short reaction flow, sustainable raw materials and product separation yield of 91.0 percent.
(2) Does not use oxygen and metal catalyst, and has intrinsic safety.
(3) The ionic liquid is used for replacing the metal catalyst, is more green, is dissolved in water, is convenient for recycling, and has good cycle performance.
(4) After the reaction is finished, FDCA is crystallized and separated out, and the product is simple to separate, so that the method has important industrial application value.
The specific embodiment is as follows:
the essential features and significant effects of the invention can be seen from the examples which follow, without however limiting the invention in any way, and those skilled in the art can make numerous insubstantial improvements and adaptations in accordance with the teachings of the invention. The invention is further illustrated by the following detailed description.
The ionic liquid related to the invention is a known material, and the composition of the ionic liquid comprises cations and anions. The following is 1-sulfobutyl-3-methylimidazole bisulfate ionic liquid ([ HSO) 3 -b-mim]·HSO 4 ) Is prepared by the following steps:
equimolar N-methylimidazole and 1,4-Butane sultone is added into a 250mL three-mouth bottle, reacted for 12 hours in a water bath at 40 ℃, the ionic liquid precursor is obtained after reduced pressure distillation and water removal, then the ionic liquid precursor is washed for a plurality of times by absolute ethyl alcohol, toluene and diethyl ether to remove unreacted raw materials and impurities, and then the washed precursor is placed into a vacuum drying oven at 80 ℃ for drying overnight. Then weighing equimolar precursor and concentrated sulfuric acid, adding into a 100mL three-necked flask, reacting for 6 hours in a water bath at 80 ℃ to obtain colorless transparent liquid, washing with absolute ethyl alcohol, toluene and diethyl ether for multiple times, and drying overnight in a vacuum drying oven at 80 ℃ to obtain [ HSO ] 3 -b-mim]·HSO 4 . Other ionic liquids were prepared as described above.
The preparation process of the ionic liquid hydroxylamine salt is as follows, taking 1-sulfobutyl-3-methylimidazole bisulfate ionic liquid hydroxylamine salt as an example: 0.25mol of hydroxylamine sulfate was weighed into 100mL of distilled water and stirred until completely dissolved. Placing the hydroxylamine sulfate aqueous solution into a low-temperature constant-temperature reactor at the temperature of-2 ℃, and dropwise adding 40g of 50 mass percent NaOH solution under stirring; after the addition, stirring and reacting for 5min are continued, and standing for 5min. Filtering to remove generated sodium sulfate, adding stabilizer ascorbic acid into the filtrate, and vacuum distilling at 52deg.C to obtain fraction which is free NH 2 Aqueous OH solution. Then under the condition of-2 ℃ and continuous stirring, the free NH is reacted with the catalyst 2 Slowly dripping the OH aqueous solution into the ionic liquid, strictly controlling the reaction temperature to be not more than 4 ℃, and continuously stirring for 2 hours after the dripping is finished. After the reaction is finished, removing water by rotary evaporation to obtain the 1-sulfobutyl-3-methylimidazole bisulfate ionic liquid hydroxylamine salt. Other ionic liquid hydroxylamine salts were prepared as described above.
Example 1
2, 5-Furandicarboxaldehyde (1 mmol), hydroxylamine hydrochloride (2 mmol), water (6 mL) and [ HSO ] 3 -b-mim]·HSO 4 (0.6 g) is added into a high-pressure reaction kettle, and N is introduced after the sealing 2 Air in the reaction kettle is replaced, the air in the reaction kettle is emptied, and the reaction is stopped after the mechanical stirring reaction is carried out for 8 hours at 140 ℃. Pouring the reaction solution into ice water, dissolving the ionic liquid in water phase, precipitating the product at the bottom, filtering, and rotary evaporating the water phase containing the ionic liquid to remove water to obtainRecovered ionic liquid; the filtered product was washed, dried and weighed to calculate the isolation yield, and the reaction result was 100% conversion of DFF and 77.4% yield of FDCA.
Example 2
Other steps are the same as in example 1, except that the added [ HSO ] 3 -b-mim]·HSO 4 1.8g. The DFF conversion was 100%, and the FDCA yield was 81.1%.
Example 3
Other steps are the same as in example 1, except that the added [ HSO ] 3 -b-mim]·HSO 4 3.6g. The DFF conversion was 100% and the FDCA yield was 87.8%.
Example 4
Other steps are the same as in example 1, except that the added [ HSO ] 3 -b-mim]·HSO 4 6.0g. The DFF conversion was 100% and the FDCA yield was 68.9%.
Example 5
The other steps are the same as in example 1 except that hydroxylamine salt added is hydroxylamine sulfate. The DFF conversion was 100% and the FDCA yield was 61.2%.
Example 6
The other steps were the same as in example 1 except that the hydroxylamine salt added was 1-sulfobutyl-3-methylimidazole bisulfate ionic liquid type hydroxylamine salt. The DFF conversion was 100% and the FDCA yield was 45.8%.
Example 7
The other steps were the same as in example 1 except that the hydroxylamine salt added was 1-sulfobutylpyridine bisulfate ionic liquid type hydroxylamine salt. The DFF conversion was 100%, and the FDCA yield was 43.6%.
Example 8
The other steps were the same as in example 1 except that the hydroxylamine salt added was N, N, N-trimethyl-N-sulfobutyl hydrogen sulfate ammonium salt ionic liquid type hydroxylamine salt. The DFF conversion was 100% and the FDCA yield was 41.6%.
Example 9
The other procedure was as in example 1, except that 1mmol of hydroxylamine hydrochloride was added. The DFF conversion was 100% and the FDCA yield was 10.1%.
Example 10
The other procedure was as in example 1, except that 6mmol of hydroxylamine hydrochloride was added. The DFF conversion was 100% and the FDCA yield was 80.3%.
Example 11
The other procedure was as in example 1, except that 8mmol of hydroxylamine hydrochloride was added. The DFF conversion was 100% and the FDCA yield was 74.3%.
Example 12
The other procedure is as in example 1, except that the ionic liquid added is 1-sulfobutyl-3-methylimidazole triflate. The DFF conversion was 100% and the FDCA yield was 59.6%.
Example 13
The other procedure is as in example 1, except that the ionic liquid added is 1-sulfobutyl-3-methylimidazole p-toluenesulfonate. The DFF conversion was 100% and the FDCA yield was 39.7%.
Example 14
The other procedure is as in example 1, except that the ionic liquid added is 1-sulfobutyl-3-methylimidazolium iodide. The DFF conversion was 100% and the FDCA yield was 36.5%.
Example 15
The other procedure is as in example 1, except that the ionic liquid added is 1-butyl-3-methylimidazole bisulfate. The DFF conversion was 100% and the FDCA yield was 19.6%.
Example 16
The other steps were the same as in example 1 except that the added ionic liquid was N, N, N-trimethyl-N-sulfobutyl bisulfate. The DFF conversion was 100% and the FDCA yield was 62.2%.
Example 17
The other steps are the same as in example 1 except that the added ionic liquid is N, N, N-trimethyl-N-sulfobutyltriflate. The DFF conversion was 100% and the FDCA yield was 72.3%.
Example 18
The other steps were the same as in example 1 except that the ionic liquid added was N, N, N-trimethyl-N-sulfobutyl p-toluenesulfonate. The DFF conversion was 100%, and the FDCA yield was 53.6%.
Example 19
The other procedure is as in example 1, except that the ionic liquid added is 1-sulfobutylpyridine bisulfate. The DFF conversion was 100% and the FDCA yield was 35.9%.
Example 20
The other procedure is as in example 1, except that the ionic liquid added is 1-sulfobutylpyridine triflate. The DFF conversion was 100%, and the FDCA yield was 47.8%.
Example 21
The other procedure is as in example 1, except that the ionic liquid added is 1-sulfobutylpyridine p-toluenesulfonate. The DFF conversion was 100% and the FDCA yield was 69.6%.
Example 22
The other steps were the same as in example 1 except that the reaction time was 2h. The DFF conversion was 100% and the FDCA yield was 17.2%.
Example 23
The other steps were the same as in example 1, except that the reaction time was 4h. The DFF conversion was 100% and the FDCA yield was 58.3%.
Example 24
The other steps were the same as in example 1 except that the reaction time was 9h. The DFF conversion was 100% and the FDCA yield was 59.7%.
Example 25
The other steps were the same as in example 1 except that the reaction temperature was 60 ℃. The DFF conversion was 100% and the FDCA yield was 9.7%.
Example 26
The other steps were the same as in example 1 except that the reaction temperature was 80 ℃. The DFF conversion was 100% and the FDCA yield was 39.4%.
Example 27
The other steps were the same as in example 1 except that the reaction temperature was 150 ℃. The DFF conversion was 100% and the FDCA yield was 58.6%.
Example 28
The other steps were the same as in example 1 except that tetrahydrofuran was used as the solvent to be added. The DFF conversion was 100% and the FDCA yield was 32.7%.
Example 29
The other steps are the same as in example 1 except that the solvent added is ethanol. The DFF conversion was 100% and the FDCA yield was 25.9%.
Example 30
The other steps were the same as in example 1 except that the solvent added was p-xylene. The DFF conversion was 100% and the FDCA yield was 57.3%.
Example 31
The other procedure is as in example 1, except that the solvent added is water: paraxylene=1:2 (V: V). The DFF conversion was 100% and the FDCA yield was 91.0%.
Example 32
The other steps are the same as in example 1, except that the ionic liquid is reused 5 times. The DFF conversion was 100% and the FDCA yield was 75.4%.
As can be seen from the above examples, DFF can react with hydroxylamine in one step under oxygen-free conditions to produce FDCA, in which no oxygen is required, which solves the risk of flammability and explosiveness of the conventional oxidation process, and is intrinsically safe; the catalyst system is simple to operate, and the yield of FDCA is high; the ionic liquid used has simple preparation process and good circularity, and has important industrial application value.
The foregoing is only a few specific examples of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily make changes or substitutions within the technical scope of the present invention as reported in the present invention, and the present invention is also intended to be covered by the scope of the present invention. Therefore, the protection scope of the present invention should be limited by the claims.
The invention is not a matter of the known technology.
Claims (6)
1. The method for synthesizing 2, 5-furandicarboxylic acid by one step from 2, 5-furandicarboxaldehyde without oxygen participation is characterized by comprising the following steps:
adding 2, 5-furan dicarboxaldehyde, ionic liquid, hydroxylamine salt and solvent into a closed reactor under nitrogen atmosphere, reacting for 2-9 h at 60-150 ℃ under mechanical stirring, and directly obtaining the product 2, 5-furan dicarboxylic acid through one-step reaction;
wherein, the molar ratio of the materials is as follows: adding 0.6-6 g of ionic liquid, 1-8 mmol of hydroxylamine salt and 1-10 mL of solvent into each 1mmol of 2, 5-furan dicarboxaldehyde;
the ionic liquid is one or more of 1-sulfobutyl-3-methylimidazole bisulfate, 1-sulfobutyl-3-methylimidazole trifluoromethanesulfonate, 1-sulfobutyl-3-methylimidazole p-toluenesulfonate, 1-butyl-3-methylimidazole bisulfate, 1-sulfobutyl-3-methylimidazole iodized salt, N, N, N-trimethyl-N-sulfobutyl hydrogen ammonium sulfate salt, N, N, N-trimethyl-N-sulfobutyl trifluoromethanesulfonate, N, N, N-trimethyl-N-sulfobutyl p-toluenesulfonate, 1-sulfobutylpyridine bisulfate, 1-sulfobutylpyridine trifluoromethanesulfonate and 1-sulfobutylpyridine p-toluenesulfonate;
the hydroxylamine salt is hydroxylamine hydrochloride, hydroxylamine sulfate, 1-sulfobutyl-3-methylimidazole bisulfate ionic liquid hydroxylamine salt, 1-sulfobutyl pyridine bisulfate ionic liquid hydroxylamine salt or N, N, N-trimethyl-N-sulfobutyl hydrogen sulfate ammonium salt ionic liquid hydroxylamine salt.
2. The method for synthesizing 2, 5-furandicarboxylic acid in one step from 2, 5-furandicarboxaldehyde without participation of oxygen according to claim 1, wherein the solvent is one or two of water, tetrahydrofuran, ethanol and paraxylene.
3. The method for synthesizing 2, 5-furandicarboxylic acid in one step by using 2, 5-furandicarboxaldehyde without participation of oxygen according to claim 1, wherein the reactor is a high-pressure reactor.
4. The method for synthesizing 2, 5-furandicarboxylic acid by one step of 2, 5-furandicarboxaldehyde without participation of oxygen according to claim 1, wherein the material proportion is that 0.6-3.6 g of ionic liquid, 2-6 mmol of hydroxylamine salt and 3-6 mL of solvent are added to 1mmol of 2, 5-furandicarboxaldehyde.
5. The method for synthesizing 2, 5-furandicarboxylic acid in one step from 2, 5-furandicarboxaldehyde without participation of oxygen according to claim 1, wherein the reaction temperature is 80-140 ℃.
6. The method for synthesizing 2, 5-furandicarboxylic acid by one step without participation of oxygen in 2, 5-furandicarboxaldehyde according to claim 1, wherein the reaction time is 4-8 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310631803.6A CN116655566B (en) | 2023-05-31 | 2023-05-31 | Method for synthesizing 2, 5-furandicarboxylic acid by one step through 2, 5-furandicarboxaldehyde without participation of oxygen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310631803.6A CN116655566B (en) | 2023-05-31 | 2023-05-31 | Method for synthesizing 2, 5-furandicarboxylic acid by one step through 2, 5-furandicarboxaldehyde without participation of oxygen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116655566A true CN116655566A (en) | 2023-08-29 |
| CN116655566B CN116655566B (en) | 2024-09-27 |
Family
ID=87710375
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310631803.6A Active CN116655566B (en) | 2023-05-31 | 2023-05-31 | Method for synthesizing 2, 5-furandicarboxylic acid by one step through 2, 5-furandicarboxaldehyde without participation of oxygen |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116655566B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104529957A (en) * | 2014-12-26 | 2015-04-22 | 中国科学技术大学先进技术研究院 | Preparation method of 2,5-furandicarboxylate |
| CN109593073A (en) * | 2019-01-22 | 2019-04-09 | 河北工业大学 | A kind of method that 2,5- furans dicarbaldehyde catalyzes and synthesizes 2,5- dicyano furans |
-
2023
- 2023-05-31 CN CN202310631803.6A patent/CN116655566B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104529957A (en) * | 2014-12-26 | 2015-04-22 | 中国科学技术大学先进技术研究院 | Preparation method of 2,5-furandicarboxylate |
| CN109593073A (en) * | 2019-01-22 | 2019-04-09 | 河北工业大学 | A kind of method that 2,5- furans dicarbaldehyde catalyzes and synthesizes 2,5- dicyano furans |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116655566B (en) | 2024-09-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yu et al. | Synthesis of γ-valerolactone from different biomass-derived feedstocks: Recent advances on reaction mechanisms and catalytic systems | |
| CN108484545B (en) | Method and system for continuously synthesizing furan dicarboxylic acid | |
| RU2732326C2 (en) | Method of producing furan-2,5-dicarboxylic acid | |
| Van de Vyver et al. | Emerging catalytic processes for the production of adipic acid | |
| EP3015448B1 (en) | Method for producing acrylic acid from glycerol | |
| BR112012029996B1 (en) | PREPARATION OF CAPROLACTON, CAPROLACTON, 2,5-TETRAHYDROFURAN-DIMETHANOL, 1,6-HEXANODIOL OR 1,2,6-HEXANOTRIOL FROM 5-HYDROXYMETHYL-2-FURFURALDEHYDE | |
| KR101715169B1 (en) | Method for preparing 2,5-furandicarboxylic acid | |
| CN113788793B (en) | Sulfonic acid functionalized imidazole ionic liquid catalyst and preparation method and application thereof | |
| CN113563289B (en) | Method for preparing 2, 5-furandicarboxylic acid from furfural | |
| CN116655566B (en) | Method for synthesizing 2, 5-furandicarboxylic acid by one step through 2, 5-furandicarboxaldehyde without participation of oxygen | |
| CN104817524A (en) | Method for preparing 5-hydroxymethyl furoic acid through catalytic conversion on fructose | |
| CN111138392B (en) | Method for preparing furandicarboxylic acid by using furfural | |
| CN114456203B (en) | Method for preparing beta-boron-based ketone by catalysis of chitosan Schiff base copper functional material | |
| CN112851490B (en) | Method for producing levulinic acid by efficiently catalyzing saccharides | |
| CN102329222B (en) | Method for oxidizing cyclohexane to prepare hexane diacid through one-step method and catalyst used by same | |
| CN113318730A (en) | Delta-MnO 2 catalyst and preparation method and application thereof | |
| CN116262692B (en) | Preparation method of cyclopentanone | |
| CN116606267B (en) | Method for preparing 2, 5-furan dicarboxaldehyde from 5-hydroxymethyl furfural | |
| JP7278315B2 (en) | Method for producing 5-alkoxymethylfurfural | |
| CN111253231B (en) | Preparation method of 4-cyclopentene-1, 3-dione | |
| CN116640051B (en) | Preparation method of glutaric acid | |
| CN114907296B (en) | Method for efficiently catalyzing succinic acid to dehydrate to generate succinic anhydride | |
| EP4424678A1 (en) | Method and system for continuously producing 5-hydroxymethylfurfural and 2,5-furandicarboxylic acid | |
| CN102452923A (en) | Method for catalytic oxidation of lactone | |
| CN115960058A (en) | Method for preparing tetrahydrofuran by catalyzing 1,4-butanediol cyclodehydration with inorganic iron salt |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |