CN109293608A - A kind of preparation method of 5- formoxyl furancarboxylic acid - Google Patents
A kind of preparation method of 5- formoxyl furancarboxylic acid Download PDFInfo
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- CN109293608A CN109293608A CN201811113027.6A CN201811113027A CN109293608A CN 109293608 A CN109293608 A CN 109293608A CN 201811113027 A CN201811113027 A CN 201811113027A CN 109293608 A CN109293608 A CN 109293608A
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- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical compound OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 16
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 104
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 104
- 239000003054 catalyst Substances 0.000 claims abstract description 65
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000001301 oxygen Substances 0.000 claims abstract description 50
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 29
- 239000003426 co-catalyst Substances 0.000 claims abstract description 14
- 230000000694 effects Effects 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 103
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 64
- 238000006243 chemical reaction Methods 0.000 claims description 40
- 238000001354 calcination Methods 0.000 claims description 37
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 32
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- -1 alkali metal salt Chemical class 0.000 claims description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical group O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 229910001882 dioxygen Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000011736 potassium bicarbonate Substances 0.000 claims description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 14
- 239000006227 byproduct Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 description 73
- 238000004128 high performance liquid chromatography Methods 0.000 description 37
- 238000003760 magnetic stirring Methods 0.000 description 35
- 239000012467 final product Substances 0.000 description 34
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 19
- 230000003647 oxidation Effects 0.000 description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 239000002028 Biomass Substances 0.000 description 6
- PCSKKIUURRTAEM-UHFFFAOYSA-N 5-hydroxymethyl-2-furoic acid Chemical compound OCC1=CC=C(C(O)=O)O1 PCSKKIUURRTAEM-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910020639 Co-Al Inorganic materials 0.000 description 2
- 229910020675 Co—Al Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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Abstract
The invention discloses a kind of preparation methods of 5- formoxyl furancarboxylic acid (FFCA).The described method includes: 5 hydroxymethyl furfural obtains product 5- formoxyl furancarboxylic acid under the collective effect of load type metal catalyst, co-catalyst, oxygen and organic solvent, through a step oxidation reaction.Selectivity of product of the present invention is high, by-product is few, and high income, purity is good, product convenient separation, simple process.
Description
Technical field
The present invention relates to a kind of methods of 5- formoxyl furancarboxylic acid preparation.In particular it relates to biomass plateform molecules
5 hydroxymethyl furfural (5-HMF) is the preparation method that raw material prepares 5- formoxyl furancarboxylic acid (FFCA).
Technical background
Ever-increasing energy demand causes fossil carbon source (coal, petroleum, natural gas) exhausted rapidly, while fossil resource
Consumption increase anthropogenic carbon dioxide emissions amount, it is therefore desirable to explore the substitutable resources (such as renewable carbon) of fossil resource.
Biomass resource is considered as that nature is generally the least expensive and carbon source abundant.It therefore is considered as the most promising substitution of fossil resource
Product.Since natural available terrestrial life matter contains at least 75% carbohydrate, so developing will much derive from
The carbohydrate (C6 and C5) of biomass is converted into the effective ways of value added chemicals.In manyization from renewable resource
It learns in structural unit, 5 hydroxymethyl furfural (5-HMF) is of greatest concern.5-HMF can be passed through by glucose and Fructose Isomerization
And it is dehydrated acquisition, or directly obtain from cellulose.It is the plateform molecules of various high value chemicals, such as 2,5- diformyl
Furans (DFF), 5- methylol-furancarboxylic acid (HMFCA), 5- formoxyl furancarboxylic acid, 2,5-furandicarboxylic acid (FDCA), levulic acid (LA)
With formic acid (FA) etc..Currently, many seminars are optimizing the synthetic route of 5-HMF and are studying its reaction being related to.5-HMF tool
There are two functional group, the i.e. part of alcohol radical and aldehyde radical, allow through oxidation, hydrogenation, the various chemistry of the production such as condensation and reduction
Product.
Since these products can be used as polymer monomer, pharmaceutical intermediate, the multifunctionality of ligand and other application, selection
Property oxidation 5-HMF to obtain DFF or FDCA extensive concern has been obtained.Although FFCA has very big potentiality, due to
The difficulty of conjunction process is isolated and purified, the selective oxidation of FFCA does not cause enough attention.Since there are two different anti-
The oxidation of answering property functional group, 5-HMF can produce several derivatives not.One common-denominator target of research is that 5-HMF was aoxidized
Cheng Keneng industrial application is found inexpensively, selectivity is good, will not generate the catalyst system of waste.In recent years, using oxygen or sky
Gas has been widely studied as oxidant.It has been reported that being oxidized to DFF for 5-HMF using metal oxide, and has acquirement
Good DFF yield.According to the literature, use ruthenium covering carbon nanotube and n,N-Dimethylformamide (DMF) as solvent,
The yield of DFF is more than 90%.According to the literature, it is 80% that DFF yield of the Au/MnO2 as solvent when is used in DMF.Root
It is boiled to according to document, in alkaline medium, uses Ce1-xBixO264% may be up to the selectivity of HMFCA.According to the literature, when
When using copper catalyst, nitrilo compound plays a significant role, because the coordination ability of this metal and nitrogen ligand enhances it
Reactivity.Gold is most common metal, because it has very high activity and selectivity to DFF or FDCA.When using Pd/C and
When the mixture of Bi, FFCA/FDCA's selects sex ratio for 70: 28.With the yield of Pd/C acquisition 98% in alkaline medium
FDCA.It is some studies have shown that catalyst may cause selectivity to have differences by forming different acidic site.Therefore it passes through
It is often used alkaline medium.But alkali may promote other adverse effects to reduce the availability for originating polyalcohol.In nearest report
In road, it was recently reported that under atmospheric oxygen tension in the water of 368K using hydrotalcite load gold nano grain obtained from 5-HMF it is excellent
The FDCA (99%) of different yield.Although this method is environmentally friendly, in the case where no alkaline medium, only only a few makes
Use water as the report of solvent.But it is the absence of the relevant report by 5-HMF selective oxidation at FFCA.
Summary of the invention
In order to solve the above-mentioned technical problem, that is, improve 5-HMF selective oxidation into the choosing during 5- formoxyl furancarboxylic acid
Selecting property and yield, the present invention provides a kind of by the highly selective method for preparing 5- formoxyl furancarboxylic acid of 5 hydroxymethyl furfural.
To realize above-mentioned target, the present invention adopts the following technical scheme:
<1>a kind of method that 5- formoxyl furancarboxylic acid is prepared by 5 hydroxymethyl furfural of, which comprises 5- methylol chaff
Aldehyde is obtained under the collective effect of load type metal catalyst, co-catalyst, oxygen and organic solvent by a step oxidation reaction
Product 5- formoxyl furancarboxylic acid,
Wherein the load type metal catalyst includes active metal and carrier, and the active metal is selected from Fe, Co, Ni
At least one of with Cu, and the carrier is selected from CeO2、ZrO2、Al2O3And TiO2At least one of, and
The co-catalyst is alkali metal salt or alkali metal hydroxide, for maintaining the pH value of oxidation reaction process
Alkalinity.
<2>is according to method as described above, wherein the co-catalyst is selected from Na2CO3、NaHCO3、K2CO3、KHCO3、
NaOH、CH3COONa and CH3At least one of COOK.
<3>is according to method as described above, wherein the reaction temperature of the oxidation reaction is 60-270 DEG C.
<4>is according to method as described above, wherein the organic solvent is selected from methanol, ethyl alcohol, water, acetonitrile, Isosorbide-5-Nitrae-
At least one of dioxane, methylene chloride and ethyl acetate.
<5>is according to method as described above, wherein the reaction time of the oxidation reaction is 1-36 hours.
<6>is according to method as described above, wherein the oxygen pressure of the oxidation reaction is 0.5-5MPa.
<7>is according to method as described above, wherein the 5 hydroxymethyl furfural and the load type metal catalyst
Molar ratio is 10: 1-0.1: 1
<8>is according to method as described above, wherein the molar ratio of the 5 hydroxymethyl furfural and the co-catalyst is
50∶1-0.01∶1。
<9>is according to method as described above, wherein the oxygen is molecular oxygen or air.
<10>is according to method as described above, wherein the active metal and load for including in the load type metal catalyst
Temperature calcination of the body experience at 400-600 DEG C.
5-HMF, as oxidation catalyst, is oxidized to FFCA using mixed oxide by the present invention with high selectivity, also,
The present invention in organic solvent, compared under temperate condition, using molecular oxygen or air to pass through cheap base metal as oxidant
The catalyst of load, highly selective oxidation 5-HMF to FFCA.
Detailed description of the invention
Fig. 1 is the hydrogen spectrogram of 5- formoxyl furancarboxylic acid prepared in embodiment 1, the instrument for testing hydrogen spectrum be by
The mass spectrograph of the 400 ' 54Ascend of model Magnet System of BRUKER manufacture.
Specific embodiment
In order to solve the above-mentioned technical problem, that is, improve 5-HMF selective oxidation into the choosing during 5- formoxyl furancarboxylic acid
Selecting property and yield, the present invention provides a kind of methods for preparing 5- formoxyl furancarboxylic acid by 5 hydroxymethyl furfural, which comprises
5 hydroxymethyl furfural passes through a step oxygen under the collective effect of load type metal catalyst, co-catalyst, oxygen and organic solvent
Change reaction and obtain product 5- formoxyl furancarboxylic acid,
Wherein the load type metal catalyst includes active metal and carrier, and the active metal is selected from Fe, Co, Ni
At least one of with Cu, and the carrier is CeO2、ZrO2、Al2O3And TiO2At least one of, and
The co-catalyst is alkali metal salt or alkali metal hydride, for the pH value of oxidation reaction process to be maintained alkali
Property.
Since 5 hydroxymethyl furfural as used in the present invention can be commercially available product, biomass platform point can be
Son, that is, by the regenerated 5 hydroxymethyl furfural of biomass, so the present invention, which is one, prepares 5- formoxyl furancarboxylic acid by renewable resource
Sustainable approach to development.
Term " biomass plateform molecules ", which refers to, is put down by lignocellulosic by the small molecule that chemistry or biological method obtain
Platform compound.
Being suitable for the load type metal catalyst being used in the present invention includes selected from active metal and carrier.The activity
Metal is selected from least one of Fe, Co, Ni and Cu.Relative to the overall weight of the load type metal catalyst, the work
Property content of the metal in load type metal catalyst be 5-20 weight %, preferably 8-15 weight %, most preferably 10-12 weight
Measure %.Used carrier is selected from CeO2、ZrO2、Al2O3And TiO2At least one of.
The example for being suitable for the load type metal catalyst being used in the present invention includes 10%Fe-CeO2-500℃、
10%Fe-CeO2- 550 DEG C, 20%Fe-CeO2- 500 DEG C, 20%Fe-CeO2- 550 DEG C, 50%Fe-CeO2- 500 DEG C, 10%
Co-Al2O3- 500 DEG C and 10%Ni-CeO2- 500 DEG C, wherein in 500 DEG C or 550 DEG C expression catalyst preparation process of suffix temperature
Calcination temperature.
Load type metal catalyst suitable for being used in the present invention can be prepared by following general process:
The salt of the nitrate of active metal or other forms is proportionally added into water, 60-80 DEG C of temperature is heated to about,
Be slowly added dropwise the saturated solution (for example, saturated sodium carbonate solution) of carrier, stirring to pH ≈ 10, after standing overnight, spend from
Sub- water washing, is then dried.Catalyst after drying is pulverized, be put into Muffle furnace heating rate be 2.5-4 DEG C/
Min calcines 4-10h at 400-600 DEG C of final temperature.It is taken out after cooling, in nitrogen (such as the H containing hydrogen2∶N2=10: 90)
Gas flow rate and 2-2.5 DEG C of heating rate/min, restore 5-7h under conditions of 380-450 DEG C of final temperature, it is cooling take out it is stand-by.
Being suitable for the co-catalyst being used in the present invention is alkali carbonate, alkali metal hydrogencarbonate, alkali metal hydrogen
Compound, alkali metal acetate, etc., specific example include being selected from Na2CO3、NaHCO3、K2CO3、KHCO3、NaOH、
CH3COONa and CH3At least one of COOK.
In the preparation process in accordance with the present invention, 5 hydroxymethyl furfural be load type metal catalyst, co-catalyst, oxygen and
Under the collective effect of organic solvent, a step aoxidizes to obtain product 5- formoxyl furancarboxylic acid (FFCA) and a small amount of non-complete oxidation product
2,5 furandicarboxylic acid (2,5-FDCA) of 2,5-furandaldehyde (2,5-DFF) and deep oxidation product.In a reality of the invention
It applies in scheme, the yield of 5- formoxyl furancarboxylic acid can be up to about 93% or more, and 2,5-DFF yield is down to about 1,7%, 2,5-
The yield of FDCA is down to about 2.1%.
In the preparation process in accordance with the present invention, reaction temperature needed for the oxidation reaction is 60~270 DEG C, preferably 100-
200 DEG C, most preferably about 150 DEG C.
In the preparation process in accordance with the present invention, organic solvent used in the oxidation reaction is methanol, ethyl alcohol, water, acetonitrile, Isosorbide-5-Nitrae-
At least one of dioxane, methylene chloride and ethyl acetate.Consider from the yield of product, it is organic used in the oxidation reaction
Solvent is particularly preferably at least one of methanol, ethyl alcohol, acetonitrile and Isosorbide-5-Nitrae-dioxane.
In the preparation process in accordance with the present invention, it is suitable for oxygen used in the present invention as molecular oxygen or air, and oxygen
Pressure be 0.5-5MPa, preferably 1-3MPa, most preferably about 2MPa.
In the preparation process in accordance with the present invention, the reaction time needed for the oxidation reaction is 1-36 hours, preferably 5-
20h, most preferably about 10h.
In the preparation process in accordance with the present invention, the raw materials used 5-HMF of the oxidation reaction and catalyst ratio are 10: 1~0.1
: 1, preferably 5: 1~1: 1, most preferably 2: 1.
In the preparation process in accordance with the present invention, the raw materials used 5-HMF of the oxidation reaction and co-catalyst ratio be 50: 1~
0.01: 1, preferably 6: 1~0.1: 1, most preferably 3: 1.
Embodiment
The invention will be further described combined with specific embodiments below.Following methods are that changing effect of the present invention is preferable
Embodiment, but protection scope of the present invention is not limited to these embodiments.
The preparation embodiment of catalyst
Catalyst 10%Fe-CeO2- 550 DEG C, 10%Co-CeO2- 550 DEG C and 10%Ni-CeO2- 550 DEG C of preparation:
First by the Fe (NO of 724.1mg3)3.9H2O, the Co (NO of 494.0mg3)3.6H2Ni (the NO of O, 519.77mg3)3.6H2Ce (the NO of O and three part of 2522.5mg3)3.6H2O is respectively put into three clean 250mL round-bottomed flasks, then is separately added into
100mL H2O is placed in 60 DEG C of oil bath pan, and ready saturated sodium carbonate solution is slowly added dropwise, and is stirred continuously to pH ≈ 10,
Continue after stirring a period of time, is stood overnight at 60 DEG C.Obtained sediment is washed with deionized three times, is put into 100
It is dry in DEG C baking oven.Catalyst after drying is pulverized, being put into Muffle furnace in heating rate is 3 DEG C/min, and final temperature is about
6h is calcined at 550 DEG C.It is taken out after cooling, in H2∶N2=10: 90 2 DEG C/min of gas flow rate and heating rate, 400 DEG C of final temperature
Under the conditions of restore 6h, it is cooling take out it is stand-by.
Other catalyst are prepared by similar approach.
Embodiment 1:
Raw material uses 5-HMF (Hefei Li Fu Biotechnology Co., Ltd).
126mg raw material 5-HMF is added in autoclave, the methanol of 10ml, the 10%Fe-CeO of 50mg is added2-500℃
The K of (note: the load capacity of Fe is 10%, and the calcination temperature of catalyst is about 500 DEG C) and 40mg2CO3, apply the oxygen of 10atm,
150 DEG C are heated in magnetic stirring apparatus, reaction is kept for 10 hours, revolving speed 500r/min.Then cooled down.It is final to produce
The yield of object is measured by high performance liquid chromatography (HPLC).
Embodiment 2:
Raw material uses 5-HMF (Hefei Li Fu Biotechnology Co., Ltd).126mg raw material 5-HMF is added in autoclave,
The methanol of 10ml, the 10%Fe-CeO of 50mg is added2- 500 DEG C (note: the load capacity of Fe is 10%, and the calcination temperature of catalyst is
500 DEG C) and 40mg KHCO3, apply the oxygen of 10atm, 150 DEG C be heated in magnetic stirring apparatus, reaction holding 10 is small
When, revolving speed 500r/min.Then cooled down.The yield of final product is measured by high performance liquid chromatography (HPLC).
Reaction mixture is using HPLC as detection means.
Detection method are as follows: mobile phase: A: methanol, B:0.5% trifluoroacetic acid aqueous solution；Flow phase composition: 20%A+80%
B；30 DEG C of column oven temperature；Flow velocity: 0.6mL/min；Pillar: C18 column；Detection wavelength is 264nm, passes through HPLC calibration curve method
Quantitatively measure each product yield.
Embodiment 3:
Raw material uses 5-HMF (Hefei Li Fu Biotechnology Co., Ltd).126mg raw material 5-HMF is added in autoclave,
The methanol of 10ml, the 10%Fe-CeO of 50mg is added2- 500 DEG C (note: the load capacity of Fe is 10%, and the calcination temperature of catalyst is
500 DEG C) and 40mg Na2CO3, apply the oxygen of 10atm, 150 DEG C be heated in magnetic stirring apparatus, reaction holding 10 is small
When, revolving speed 500r/min.Then cooled down.The yield of final product is measured by high performance liquid chromatography (HPLC).
Embodiment 4:
Raw material uses 5-HMF (Hefei Li Fu Biotechnology Co., Ltd).126mg raw material 5-HMF is added in autoclave,
The methanol of 10ml, the 10%Fe-CeO of 50mg is added2- 500 DEG C (note: the load capacity of Fe is 10%, and the calcination temperature of catalyst is
500 DEG C) and 40mg NaHCO3, apply the oxygen of 10atm, 150 DEG C be heated in magnetic stirring apparatus, reaction holding 10 is small
When, revolving speed 500r/min.Then cooled down.The yield of final product is measured by high performance liquid chromatography (HPLC).
Embodiment 5:
Raw material uses 5-HMF (Hefei Li Fu Biotechnology Co., Ltd).126mg raw material 5-HMF is added in autoclave,
The methanol of 10ml, the 10%Fe-CeO of 50mg is added2- 500 DEG C (note: the load capacity of Fe is 10%, and the calcination temperature of catalyst is
500 DEG C) and 40mg CH3COONa, applies the oxygen of 10atm, 150 DEG C is heated in magnetic stirring apparatus, reaction keeps 10
Hour, revolving speed 500r/min.Then cooled down.The yield of final product is surveyed by high performance liquid chromatography (HPLC)
It is fixed.
Embodiment 6:
Raw material uses 5-HMF (Hefei Li Fu Biotechnology Co., Ltd).126mg raw material 5-HMF is added in autoclave,
The methanol of 10ml, the 10%Fe-CeO of 50mg is added2- 500 DEG C (note: the load capacity of Fe is 10%, and the calcination temperature of catalyst is
500 DEG C) and 40mg CH3COOK, applies the oxygen of 10atm, 150 DEG C is heated in magnetic stirring apparatus, reaction keeps 10
Hour, revolving speed 500r/min.Then cooled down.The yield of final product is surveyed by high performance liquid chromatography (HPLC)
It is fixed.
Embodiment 7:
Raw material uses 5-HMF (Hefei Li Fu Biotechnology Co., Ltd).126mg raw material 5-HMF is added in autoclave,
The ethyl alcohol of 10ml, the 10%Fe-CeO of 50mg is added2- 500 DEG C (note: the load capacity of Fe is 10%, and the calcination temperature of catalyst is
500 DEG C) and 40mg K2CO3, apply the oxygen of 10atm, 150 DEG C be heated in magnetic stirring apparatus, reaction holding 10 is small
When, revolving speed 500r/min.Then cooled down.The yield of final product is measured by high performance liquid chromatography (HPLC).
Embodiment 8:
Raw material uses 5-HMF (Hefei Li Fu Biotechnology Co., Ltd).126mg raw material 5-HMF is added in autoclave,
The water of 10ml, the 10%Fe-CeO of 50mg is added2- 500 DEG C (note: the load capacity of Fe is 10%, and the calcination temperature of catalyst is
500 DEG C) and 40mg K2CO3, apply the oxygen of 10atm, 150 DEG C be heated in magnetic stirring apparatus, reaction holding 10 is small
When, revolving speed 500r/min.Then cooled down.The yield of final product is measured by high performance liquid chromatography (HPLC).
Embodiment 9:
Raw material uses 5-HMF (Hefei Li Fu Biotechnology Co., Ltd).126mg raw material 5-HMF is added in autoclave,
The acetonitrile of 10ml, the 10%Fe-CeO of 50mg is added2- 500 DEG C (note: the load capacity of Fe is 10%, and the calcination temperature of catalyst is
500 DEG C) and 40mg K2CO3, apply the oxygen of 10atm, 150 DEG C be heated in magnetic stirring apparatus, reaction holding 10 is small
When, revolving speed 500r/min.Then cooled down.The yield of final product is measured by high performance liquid chromatography (HPLC).
Embodiment 10:
Raw material uses 5-HMF (Hefei Li Fu Biotechnology Co., Ltd).126mg raw material 5-HMF is added in autoclave,
The methylene chloride of 10ml, the 10%Fe-CeO of 50mg is added2- 500 DEG C (note: the load capacity of Fe is 10%, the calcining temperature of catalyst
Degree be 500 DEG C) and 40mg K2CO3, apply the oxygen of 10atm, 150 DEG C be heated in magnetic stirring apparatus, reaction keeps 10
Hour, revolving speed 500r/min.Then cooled down.The yield of final product is surveyed by high performance liquid chromatography (HPLC)
It is fixed.
Embodiment 11:
Raw material uses 5-HMF (Hefei Li Fu Biotechnology Co., Ltd).126mg raw material 5-HMF is added in autoclave,
The ethyl acetate of 10ml, the 10%Fe-CeO of 50mg is added2- 500 DEG C (note: the load capacity of Fe is 10%, the calcining temperature of catalyst
Degree be 500 DEG C) and 40mg K2CO3, apply the oxygen of 10atm, 150 DEG C be heated in magnetic stirring apparatus, reaction keeps 10
Hour, revolving speed 500r/min.Then cooled down.The yield of final product is surveyed by high performance liquid chromatography (HPLC)
It is fixed.
Embodiment 12:
Raw material uses 5-HMF (Hefei Li Fu Biotechnology Co., Ltd).126mg raw material 5-HMF is added in autoclave,
Isosorbide-5-Nitrae-dioxane of 10ml, the 10%Fe-CeO of 50mg is added2- 500 DEG C (note: the load capacity of Fe is 10%, and catalyst is forged
Burn temperature be 500 DEG C) and 40mg K2CO3, apply the oxygen of 10atm, 150 DEG C be heated in magnetic stirring apparatus, reaction is protected
It holds 10 hours, revolving speed 500r/min.Then cooled down.The yield of final product is carried out by high performance liquid chromatography (HPLC)
Measurement.
Embodiment 13:
Raw material uses 5-HMF (Hefei Li Fu Biotechnology Co., Ltd).126mg raw material 5-HMF is added in autoclave,
The methanol of 10ml, the 10%Fe-CeO of 50mg is added2- 500 DEG C (note: the load capacity of Fe is 10%, and the calcination temperature of catalyst is
500 DEG C) and 40mg K2CO3, apply the oxygen of 10atm, 120 DEG C be heated in magnetic stirring apparatus, reaction holding 10 is small
When, revolving speed 500r/min.Then cooled down.The yield of final product is measured by high performance liquid chromatography (HPLC).
Embodiment 14:
Raw material uses 5-HMF (Hefei Li Fu Biotechnology Co., Ltd).126mg raw material 5-HMF is added in autoclave,
The methanol of 10ml, the 10%Fe-CeO of 50mg is added2- 500 DEG C (note: the load capacity of Fe is 10%, and the calcination temperature of catalyst is
500 DEG C) and 40mg K2CO3, apply the oxygen of 10atm, 180 DEG C be heated in magnetic stirring apparatus, reaction holding 10 is small
When, revolving speed 500r/min.Then cooled down.The yield of final product is measured by high performance liquid chromatography (HPLC).
Embodiment 15:
Raw material uses 5-HMF (Hefei Li Fu Biotechnology Co., Ltd).126mg raw material 5-HMF is added in autoclave,
The methanol of 10ml, the 10%Fe-CeO of 50mg is added2- 500 DEG C (note: the load capacity of Fe is 10%, and the calcination temperature of catalyst is
500 DEG C) and 40mg K2CO3, apply the oxygen of 10atm, 200 DEG C be heated in magnetic stirring apparatus, reaction holding 10 is small
When, revolving speed 500r/min.Then cooled down.The yield of final product is measured by high performance liquid chromatography (HPLC).
Embodiment 16
Raw material uses 5-HMF (Hefei Li Fu Biotechnology Co., Ltd).126mg raw material 5-HMF is added in autoclave,
The methanol of 10ml, the 10%Fe-CeO of 50mg is added2- 500 DEG C (note: the load capacity of Fe is 10%, and the calcination temperature of catalyst is
500 DEG C) and 40mg K2CO3, applying the oxygen of 10atm, 150 DEG C are heated in magnetic stirring apparatus, reaction is kept for 1 hour,
Revolving speed is 500r/min.Then cooled down.The yield of final product is measured by high performance liquid chromatography (HPLC).
Embodiment 17
Raw material uses 5-HMF (Hefei Li Fu Biotechnology Co., Ltd).126mg raw material 5-HMF is added in autoclave,
The methanol of 10ml, the 10%Fe-CeO of 50mg is added2- 500 DEG C (note: the load capacity of Fe is 10%, and the calcination temperature of catalyst is
500 DEG C) and 40mg K2CO3, applying the oxygen of 10atm, 150 DEG C are heated in magnetic stirring apparatus, reaction is kept for 2 hours,
Revolving speed is 500r/min.Then cooled down.The yield of final product is measured by high performance liquid chromatography (HPLC).
Embodiment 18
Raw material uses 5-HMF (Hefei Li Fu Biotechnology Co., Ltd).126mg raw material 5-HMF is added in autoclave,
The methanol of 10ml, the 10%Fe-CeO of 50mg is added2- 500 DEG C (note: the load capacity of Fe is 10%, and the calcination temperature of catalyst is
500 DEG C) and 40mg K2CO3, applying the oxygen of 10atm, 150 DEG C are heated in magnetic stirring apparatus, reaction is kept for 4 hours,
Revolving speed is 500r/min.Then cooled down.The yield of final product is measured by high performance liquid chromatography (HPLC).
Embodiment 19
Raw material uses 5-HMF (Hefei Li Fu Biotechnology Co., Ltd).126mg raw material 5-HMF is added in autoclave,
The methanol of 10ml, the 10%Fe-CeO of 50mg is added2- 500 DEG C (note: the load capacity of Fe is 10%, and the calcination temperature of catalyst is
500 DEG C) and 40mg K2CO3, apply the oxygen of 10atm, 150 DEG C be heated in magnetic stirring apparatus, reaction holding 12 is small
When, revolving speed 500r/min.Then cooled down.The yield of final product is measured by high performance liquid chromatography (HPLC).
Embodiment 20
Raw material uses 5-HMF (Hefei Li Fu Biotechnology Co., Ltd).126mg raw material 5-HMF is added in autoclave,
The methanol of 10ml, the 10%Fe-CeO of 50mg is added2- 500 DEG C (note: the load capacity of Fe is 10%, and the calcination temperature of catalyst is
500 DEG C) and 40mg K2CO3, apply the oxygen of 10atm, 150 DEG C be heated in magnetic stirring apparatus, reaction holding 16 is small
When, revolving speed 500r/min.Then cooled down.The yield of final product is measured by high performance liquid chromatography (HPLC).
Embodiment 21
Raw material uses 5-HMF (Hefei Li Fu Biotechnology Co., Ltd).126mg raw material 5-HMF is added in autoclave,
The methanol of 10ml, the 10%Fe-CeO of 50mg is added2- 500 DEG C (note: the load capacity of Fe is 10%, and the calcination temperature of catalyst is
500 DEG C) and 40mg K2CO3, applying the oxygen of 5atm, 150 DEG C are heated in magnetic stirring apparatus, reaction is kept for 10 hours,
Revolving speed is 500r/min.Then cooled down.The yield of final product is measured by high performance liquid chromatography (HPLC).
Embodiment 22
Raw material uses 5-HMF (Hefei Li Fu Biotechnology Co., Ltd).126mg raw material 5-HMF is added in autoclave,
The methanol of 10ml, the 10%Fe-CeO of 50mg is added2- 500 DEG C (note: the load capacity of Fe is 10%, and the calcination temperature of catalyst is
500 DEG C) and 40mg K2CO3, apply the oxygen of 20atm, 150 DEG C be heated in magnetic stirring apparatus, reaction holding 10 is small
When, revolving speed 500r/min.Then cooled down.The yield of final product is measured by high performance liquid chromatography (HPLC).
Embodiment 23
Raw material uses 5-HMF (Hefei Li Fu Biotechnology Co., Ltd).126mg raw material 5-HMF is added in autoclave,
The methanol of 10ml, the 10%Fe-CeO of 50mg is added2- 500 DEG C (note: the load capacity of Fe is 10%, and the calcination temperature of catalyst is
500 DEG C) and 40mg K2CO3, apply the oxygen of 30atm, 150 DEG C be heated in magnetic stirring apparatus, reaction holding 10 is small
When, revolving speed 500r/min.Then cooled down.The yield of final product is measured by high performance liquid chromatography (HPLC).
Embodiment 24
Raw material uses 5-HMF (Hefei Li Fu Biotechnology Co., Ltd).126mg raw material 5-HMF is added in autoclave,
The methanol of 10ml, the 10%Fe-CeO of 10mg is added2- 500 DEG C (note: the load capacity of Fe is 10%, and the calcination temperature of catalyst is
500 DEG C) and 40mg K2CO3, apply the oxygen of 10atm, 150 DEG C be heated in magnetic stirring apparatus, reaction holding 10 is small
When, revolving speed 500r/min.Then cooled down.The yield of final product is measured by high performance liquid chromatography (HPLC).
Embodiment 25
Raw material uses 5-HMF (Hefei Li Fu Biotechnology Co., Ltd).126mg raw material 5-HMF is added in autoclave,
The methanol of 10ml, the 10%Fe-CeO of 25mg is added2- 500 DEG C (note: the load capacity of Fe is 10%, and the calcination temperature of catalyst is
500 DEG C) and 40mg K2CO3, apply the oxygen of 10atm, 150 DEG C be heated in magnetic stirring apparatus, reaction holding 10 is small
When, revolving speed 500r/min.Then cooled down.The yield of final product is measured by high performance liquid chromatography (HPLC).
Embodiment 26
Raw material uses 5-HMF (Hefei Li Fu Biotechnology Co., Ltd).126mg raw material 5-HMF is added in autoclave,
The methanol of 10ml, the 10%Fe-CeO of 100mg is added2- 500 DEG C (note: the load capacity of Fe is 10%, the calcination temperature of catalyst
Be 500 DEG C) and 40mg K2CO3, apply the oxygen of 10atm, 150 DEG C be heated in magnetic stirring apparatus, reaction holding 10 is small
When, revolving speed 500r/min.Then cooled down.The yield of final product is measured by high performance liquid chromatography (HPLC).
Embodiment 27
Raw material uses 5-HMF (Hefei Li Fu Biotechnology Co., Ltd).126mg raw material 5-HMF is added in autoclave,
The methanol of 10ml, the 20%Fe-CeO of 50mg is added2- 500 DEG C (note: the load capacity of Fe is 10%, and the calcination temperature of catalyst is
500 DEG C) and 40mg K2CO3, apply the oxygen of 10atm, 150 DEG C be heated in magnetic stirring apparatus, reaction holding 10 is small
When, revolving speed 500r/min.Then cooled down.The yield of final product is measured by high performance liquid chromatography (HPLC).
Embodiment 28
Raw material uses 5-HMF (Hefei Li Fu Biotechnology Co., Ltd).126mg raw material 5-HMF is added in autoclave,
The methanol of 10ml, the 50%Fe-CeO of 50mg is added2- 500 DEG C (note: the load capacity of Fe is 10%, and the calcination temperature of catalyst is
500 DEG C) and 40mg K2CO3, apply the oxygen of 10atm, 150 DEG C be heated in magnetic stirring apparatus, reaction holding 10 is small
When, revolving speed 500r/min.Then cooled down.The yield of final product is measured by high performance liquid chromatography (HPLC).
Embodiment 29
Raw material uses 5-HMF (Hefei Li Fu Biotechnology Co., Ltd).126mg raw material 5-HMF is added in autoclave,
The methanol of 10ml, the 10%Fe-CeO of 50mg is added2- 400 DEG C (note: the load capacity of Fe is 10%, and the calcination temperature of catalyst is
400 DEG C) and 40mg K2CO3, apply the oxygen of 10atm, 150 DEG C be heated in magnetic stirring apparatus, reaction holding 10 is small
When, revolving speed 500r/min.Then cooled down.The yield of final product is measured by high performance liquid chromatography (HPLC).
Embodiment 30
Raw material uses 5-HMF (Hefei Li Fu Biotechnology Co., Ltd).126mg raw material 5-HMF is added in autoclave,
The methanol of 10ml, the 10%Fe-CeO of 50mg is added2- 600 DEG C (note: the load capacity of Fe is 10%, and the calcination temperature of catalyst is
600 DEG C) and 40mg K2CO3, apply the oxygen of 10atm, 150 DEG C be heated in magnetic stirring apparatus, reaction holding 10 is small
When, revolving speed 500r/min.Then cooled down.The yield of final product is measured by high performance liquid chromatography (HPLC).
Embodiment 31
Raw material uses 5-HMF (Hefei Li Fu Biotechnology Co., Ltd).126mg raw material 5-HMF is added in autoclave,
The methanol of 10ml, the 10%Co-Al of 50mg is added2O3- 500 DEG C (note: the load capacity of Fe is 10%, and the calcination temperature of catalyst is
500 DEG C) and 40mg K2CO3, apply the oxygen of 10atm, 150 DEG C be heated in magnetic stirring apparatus, reaction holding 10 is small
When, revolving speed 500r/min.Then cooled down.The yield of final product is measured by high performance liquid chromatography (HPLC).
Embodiment 32
Raw material uses 5-HMF (Hefei Li Fu Biotechnology Co., Ltd).126mg raw material 5-HMF is added in autoclave,
The methanol of 10ml, the 10%Co-Al of 50mg is added2O3- 500 DEG C (note: the load capacity of Fe is 10%, and the calcination temperature of catalyst is
500 DEG C) and 40mg K2CO3, apply the oxygen of 10atm, 150 DEG C be heated in magnetic stirring apparatus, reaction holding 10 is small
When, revolving speed 500r/min.Then cooled down.The yield of final product is measured by high performance liquid chromatography (HPLC).
Embodiment 33
Raw material uses 5-HMF (Hefei Li Fu Biotechnology Co., Ltd).126mg raw material 5-HMF is added in autoclave,
The methanol of 10ml, the 10%Ni-CeO of 50mg is added2- 500 DEG C (note: the load capacity of Fe is 10%, and the calcination temperature of catalyst is
500 DEG C) and 40mg K2CO3, apply the oxygen of 10atm, 150 DEG C be heated in magnetic stirring apparatus, reaction holding 10 is small
When, revolving speed 500r/min.Then cooled down.The yield of final product is measured by high performance liquid chromatography (HPLC).
Embodiment 34
Raw material uses 5-HMF (Hefei Li Fu Biotechnology Co., Ltd).126mg raw material 5-HMF is added in autoclave,
Methanol, the 10%Fe-CeO of 10ml is added2- 500 DEG C (note: the load capacity of Fe is 10%, and the calcination temperature of catalyst is about 500
DEG C) and 20mg K2CO3, apply the oxygen of 10atm, 150 DEG C be heated in magnetic stirring apparatus, reaction is kept for 10 hours, is turned
Speed is 500r/min.Then cooled down.The yield of final product is measured by high performance liquid chromatography (HPLC).
Embodiment 35
Raw material uses 5-HMF (Hefei Li Fu Biotechnology Co., Ltd).126mg raw material 5-HMF is added in autoclave,
Methanol, the 10%Fe-CeO of 10ml is added2- 500 DEG C (note: the load capacity of Fe is 10%, and the calcination temperature of catalyst is about 500
DEG C) and 100mg K2CO3, applying the oxygen of 10atm, 150 DEG C are heated in magnetic stirring apparatus, reaction is kept for 10 hours,
Revolving speed is 500r/min.Then cooled down.The yield of final product is measured by high performance liquid chromatography (HPLC).
Table 1 below illustrates the testing results of embodiment 1-35.
Table 1
It can be seen from the above embodiments that, the present invention realizes a kind of by 5 hydroxymethyl furfural preparation 5- formoxyl furancarboxylic acid
Method, and the invention has the following advantages that product yield high, catalyst is high-efficient and easily separated, simple process, instead
Mild condition is answered, it is environmental-friendly, there is very strong industrial application meaning.
Claims (10)
1. a kind of method for preparing 5- formoxyl furancarboxylic acid by 5 hydroxymethyl furfural, which comprises 5 hydroxymethyl furfural is negative
Supported type metal catalyst, co-catalyst, oxygen and organic solvent collective effect under, product 5- is obtained by a step oxidation reaction
Formoxyl furancarboxylic acid,
Wherein the load type metal catalyst includes active metal and carrier, and the active metal is selected from Fe, Co, Ni and Cu
At least one of, and the carrier is selected from CeO2、ZrO2、Al2O3And TiO2At least one of, and
The co-catalyst is alkali metal salt or alkali metal hydroxide, for the pH value of oxidation reaction process to be maintained alkali
Property.
2. according to the method described in claim 1, wherein, the co-catalyst is selected from Na2CO3、NaHCO3、K2CO3、KHCO3、
NaOH、CH3COONa and CH3At least one of COOK.
3. according to the method described in claim 1, wherein, the reaction temperature of the oxidation reaction is 60-270 DEG C.
4. according to the method described in claim 1, wherein, the organic solvent is selected from methanol, ethyl alcohol, water, acetonitrile, Isosorbide-5-Nitrae-two
At least one of six ring of oxygen, methylene chloride and ethyl acetate.
5. according to the method described in claim 1, wherein, the reaction time of the oxidation reaction is 1-36 hours.
6. according to the method described in claim 1, wherein, the oxygen pressure of the oxidation reaction is 0.5-5MPa.
7. according to the method described in claim 1, wherein, the 5 hydroxymethyl furfural rubs with the load type metal catalyst
You are than being 10: 1-0.1: 1.
8. according to the method described in claim 1, wherein, the molar ratio of the 5 hydroxymethyl furfural and the co-catalyst is 50
∶1-0.01∶1。
9. according to the method described in claim 1, wherein, the oxygen is molecular oxygen or air.
10. according to the method described in claim 1, wherein, the active metal and load for including in the load type metal catalyst
Temperature calcination of the body experience at 400-600 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110452195A (en) * | 2019-09-03 | 2019-11-15 | 河北工业大学 | A kind of method that 5 hydroxymethyl furfural dehydrogenation prepares 2,5- furans dicarbaldehyde |
| CN114315768A (en) * | 2021-12-08 | 2022-04-12 | 南京工业大学 | Method for one-step synthesis of 5-hydroxymethylfurfural and derivatives thereof by catalyzing fructose through microwave-microreactor |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009023916A (en) * | 2007-07-17 | 2009-02-05 | Canon Inc | Method for producing 2,5-furan dicarboxylic acid |
| JP2009242312A (en) * | 2008-03-31 | 2009-10-22 | Air Water Inc | Process for producing 2,5-furandicarboxylic acid |
| JP2013203666A (en) * | 2012-03-27 | 2013-10-07 | Kao Corp | Method of producing 5-hydroxymethylfurfural oxide |
| CN104846027A (en) * | 2015-04-30 | 2015-08-19 | 华南理工大学 | Method for synthesizing derivative with high added value through enzymatic catalysis of 5-hydroxymethylfurfural |
| CN107365286A (en) * | 2016-05-11 | 2017-11-21 | 中国石油化工股份有限公司 | A kind of method of synthesis 2,5- furandicarboxylic acids |
| CN107848998A (en) * | 2015-06-05 | 2018-03-27 | 辛维纳有限合伙公司 | For the method for the acid composition for preparing purifying |
| US20180187224A1 (en) * | 2015-06-15 | 2018-07-05 | Biome Bioplastics Limited | Processes for the formation of furandicarboxylic acid (fdca) via a multistep biocatalytic oxidation reaction of 5-hydroxymethylfurfural (hmf) |
| CN108484545A (en) * | 2018-04-24 | 2018-09-04 | 浙江大学 | A kind of method and system of continuous synthesis furandicarboxylic acid |
-
2018
- 2018-09-21 CN CN201811113027.6A patent/CN109293608B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009023916A (en) * | 2007-07-17 | 2009-02-05 | Canon Inc | Method for producing 2,5-furan dicarboxylic acid |
| JP2009242312A (en) * | 2008-03-31 | 2009-10-22 | Air Water Inc | Process for producing 2,5-furandicarboxylic acid |
| JP2013203666A (en) * | 2012-03-27 | 2013-10-07 | Kao Corp | Method of producing 5-hydroxymethylfurfural oxide |
| CN104846027A (en) * | 2015-04-30 | 2015-08-19 | 华南理工大学 | Method for synthesizing derivative with high added value through enzymatic catalysis of 5-hydroxymethylfurfural |
| CN107848998A (en) * | 2015-06-05 | 2018-03-27 | 辛维纳有限合伙公司 | For the method for the acid composition for preparing purifying |
| US20180187224A1 (en) * | 2015-06-15 | 2018-07-05 | Biome Bioplastics Limited | Processes for the formation of furandicarboxylic acid (fdca) via a multistep biocatalytic oxidation reaction of 5-hydroxymethylfurfural (hmf) |
| CN107365286A (en) * | 2016-05-11 | 2017-11-21 | 中国石油化工股份有限公司 | A kind of method of synthesis 2,5- furandicarboxylic acids |
| CN108484545A (en) * | 2018-04-24 | 2018-09-04 | 浙江大学 | A kind of method and system of continuous synthesis furandicarboxylic acid |
Non-Patent Citations (3)
| Title |
|---|
| FLORENTINA NEATU ET AL.: ""Selective oxidation of 5-hydroxymethyl furfural over non-precious metal heterogeneous catalysts"", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
| MARIA VENTURA ET AL.: ""Selective Aerobic Oxidation of 5-(Hydroxymethyl)furfural to 5-Formyl-2-furancarboxylic Acid in Water"", 《CHEMSUSCHEM》 * |
| RAMAKANTA SAHU ET AL.: ""Synthesis of 2,5-furandicarboxylic acid by the aerobic oxidation of 5-hydroxymethyl furfural over supported "metal catalysts", 《REAC KINET MECH CAT》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110452195A (en) * | 2019-09-03 | 2019-11-15 | 河北工业大学 | A kind of method that 5 hydroxymethyl furfural dehydrogenation prepares 2,5- furans dicarbaldehyde |
| CN114315768A (en) * | 2021-12-08 | 2022-04-12 | 南京工业大学 | Method for one-step synthesis of 5-hydroxymethylfurfural and derivatives thereof by catalyzing fructose through microwave-microreactor |
| CN114315768B (en) * | 2021-12-08 | 2023-06-16 | 南京工业大学 | Method for one-step synthesis of 5-hydroxymethylfurfural and derivatives thereof by using microwave-microreactor to catalyze fructose |
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