CN104277021B - Catalyzed conversion 5 hydroxymethyl furfural is prepared the method for 2,5-furans diamides - Google Patents
Catalyzed conversion 5 hydroxymethyl furfural is prepared the method for 2,5-furans diamides Download PDFInfo
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- CN104277021B CN104277021B CN201310275629.2A CN201310275629A CN104277021B CN 104277021 B CN104277021 B CN 104277021B CN 201310275629 A CN201310275629 A CN 201310275629A CN 104277021 B CN104277021 B CN 104277021B
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- furans
- diamides
- hydroxymethyl furfural
- ammonium
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- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 title claims abstract description 27
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001301 oxygen Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000002825 nitriles Chemical class 0.000 claims abstract description 11
- 238000005576 amination reaction Methods 0.000 claims abstract description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 9
- 238000009835 boiling Methods 0.000 claims abstract description 9
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 8
- 238000006703 hydration reaction Methods 0.000 claims abstract description 8
- 150000001412 amines Chemical class 0.000 claims abstract description 7
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 7
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 6
- 238000000746 purification Methods 0.000 claims abstract description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 14
- 238000000967 suction filtration Methods 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 9
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001953 recrystallisation Methods 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001408 amides Chemical class 0.000 claims description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- 239000012429 reaction media Substances 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims 2
- 241000772991 Aira Species 0.000 claims 1
- 238000004523 catalytic cracking Methods 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 22
- 238000002390 rotary evaporation Methods 0.000 description 12
- 229910001220 stainless steel Inorganic materials 0.000 description 12
- 239000010935 stainless steel Substances 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 238000004451 qualitative analysis Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- 239000002028 Biomass Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 150000002466 imines Chemical class 0.000 description 4
- -1 organic Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 150000002240 furans Chemical class 0.000 description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N 2,5-dimethylfuran Chemical compound CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- WBKFWQBXFREOFH-UHFFFAOYSA-N dichloromethane;ethyl acetate Chemical compound ClCCl.CCOC(C)=O WBKFWQBXFREOFH-UHFFFAOYSA-N 0.000 description 2
- 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 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 229960004592 isopropanol Drugs 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PXJJKVNIMAZHCB-UHFFFAOYSA-N 2,5-diformylfuran Chemical class O=CC1=CC=C(C=O)O1 PXJJKVNIMAZHCB-UHFFFAOYSA-N 0.000 description 1
- DSLRVRBSNLHVBH-UHFFFAOYSA-N 2,5-furandimethanol Chemical class OCC1=CC=C(CO)O1 DSLRVRBSNLHVBH-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- 239000005715 Fructose Substances 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
- HYBBIBNJHNGZAN-UHFFFAOYSA-N Furaldehyde Natural products O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 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
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 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
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 150000001470 diamides Chemical class 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- SRCZQMGIVIYBBJ-UHFFFAOYSA-N ethoxyethane;ethyl acetate Chemical compound CCOCC.CCOC(C)=O SRCZQMGIVIYBBJ-UHFFFAOYSA-N 0.000 description 1
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 125000000879 imine group Chemical group 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000035479 physiological effects, processes and functions Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 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
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A kind of catalyzed conversion 5 hydroxymethyl furfural prepares 2, the method of 5-furans diamides, it is characterized in that: taking oxygen or air as oxygen source, taking ammoniacal liquor, liquefied ammonia or ammonium salt as amine source, taking lower boiling alcohol, ether, nitrile or hydrocarbon as solvent, under catalyst action, 5 hydroxymethyl furfural is through peroxidating, amination, hydration reaction, obtain 2,5-furans diamides. The method raw material availability is high, and between each reaction, original position coupling efficiency is high, and catalyst easily reclaims, recycles, and target product is easily separated, purification.
Description
Technical field
The present invention relates to biomass conversion and prepare Field of Fine Chemicals, relate to particularly have oxidation,Under the multifunction catalyst catalytic action of amination and hydrolysis, biomass-based hardware and software platform compound 5-methylolFurfural catalyzed conversion is prepared the method for 2,5-furans diamides.
Background technology
Obtain energy chemicals taking reproducible biomass resource as raw material, reduce chemicals to oil etc.The dependence of fossil resource, has important scientific meaning and application prospect. Carbohydrate is living beingsThe chief component of resource, can efficiently obtain biomass-based hardware and software platform compound through hydrolysis, dehydration5 hydroxymethyl furfural (HMF). In recent years, the preparation of HMF and catalyzed conversion have caused both at home and abroadResearcher's broad interest, and make great progress (Chin.J.Catal.2013,34,492; Chem.Rev.2013,113,1499.). HMF, through selective oxidation, hydrogenation, etherificate, can obtain 2,5-Diformyl furans (CN200910012844.7; CN200810012159.X), FDCA(CN201210302990.5; CN201210390203.7), maleic anhydride(CN201010258495.X), 2,5-dimethyl furan, 2,5-dihydroxymethyl furans, 2,5-dihydroxy fourHydrogen furans (CN201210436809.X) and 5-alkoxyl furfural (CN201110223487.6; ) etc.,These oxidations, hydrogenation or etherification product are important polymer monomer (CN201110163338.5;CN201110163339.X), liquid fuel or liquid fuel additive.
Organonitrogen compound has physiology and pharmaceutically active as various amine and amide structure are extensively present inIn compound and natural products, be also used to the macromolecular materials such as synthesizing polyamides, organic, medicine,During natural products and industry are synthetic, there is extremely important application. HMF can through selective ammonia oxidationObtain the nitrogenous furan derivatives such as imines, acid amides, nitrile. HMF and primary amine make through condensation reactionImines, further uses NaBH4Reduction obtains 5-methylol-N-alkyl furan methylamine (GreenChem.2010,12,1201）。Au/TiO2Catalytic molecular oxygen oxidation HMF and primary amine reaction, can obtain 5-Methylol-N-alkyl furan acid amides (Chem.Commun.2012,48,2427). Target of the present inventionThat catalytic ammoxidation HMF prepares 2,5-furans diamides. Set out and can prepare from 2,5-furans diamidesThe important polymer monomers such as 2,5-furans dimethoxy nitrile, adiponitrile, hexamethylene diamine. Therefore, developing green sideMethod, efficiently produces 2,5-furans diamides, has great importance.
Thinking of the present invention is, develops a kind of multifunction catalyst, taking oxygen or air as oxygen source, withAmmoniacal liquor, liquefied ammonia or ammonium salt are amine source, and catalyzed conversion HMF prepares 2,5-furans diamides, expand HMFPotential using value, be to supplement or part substitutes non-renewable fossil resource, provide a kind of newMethod and technology.
Summary of the invention
The object of the invention is, a kind of efficient, multi-functional catalyst of exploitation, for providing with living beingsSource is waste energy chemicals, the shortage of alleviating, substituting, supplement the fossil resources such as oil, forSynthesizing of energy chemicals, provide the new technology and method of sustainable development.
According to method provided by the invention, reaction substrate is living beings based platform compound H MF, its spyLevying is in molecular structure, to contain furan nucleus and lay respectively at 2 of furan nucleus and aldehyde radical and the methylol of 5,Can obtain from carbohydrate such as cellulose, glucose, fructose, there is very large potential using value.
According to method provided by the invention, the oxidation of substrate, amination and hydration reaction are to realize this processMust be through step. Oxidation need to adopt oxidation catalyst realize, amination and hydration need to adopt acidity orBase catalyst is realized, and the catalyst therefore using should have catalytic oxidation activity center and acid-base catalysisCenter.
According to method provided by the invention, described catalyst is NiO, Co3O4、CuO、Cu2O、Fe2O3、Fe3O4、MnO2、Mn3O4、VO2、V2O5、MoO3、CeO2In one or more. The total consumption of catalyst is the 1-30mol% of HMF material quantity. Reaction temperature is 30-180 ° of C, when reactionBetween be 0.1-48h. Better reaction temperature is 50-160 ° of C, and the better reaction time is 1-20h.
According to method provided by the invention, amine source is: ammoniacal liquor, liquefied ammonia or ammonium salt, and described ammonium salt is:Ammonium chloride, ammonium sulfate, ammonium bromide, ammonium carbonate, carbonic hydroammonium, ammonium oxalate, ammonium acetate, urea,The mol ratio in HMF and amine source is 1:2-20.
According to method provided by the invention, the oxygen source that reaction adopts is oxygen or air, and dividing potential drop is 0.1-2MPa。
According to route provided by the invention, the methylol of HMF is realized molecular oxygen oxygen under catalytic actionChange and generate aldehyde, aldehyde amination generates imines, and the further oxidative dehydrogenation of imine group generates nitrile, nitrile original position waterSymphysis becomes 2,5-furans diamides.
According to route provided by the invention, the oxidation of HMF, amination and hydration reaction are in same reactionIn device, carry out, the reaction intermediate of oxidation, amination, without separation, directly obtains target product 2,5-simultaneouslyFurans diamides.
According to method provided by the invention, reaction medium is lower boiling alcohol, ether, nitrile and hydrocarbon; WhereinLow-boiling point alcohol comprises methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol, n-butanol, isobutanol, amylalcohol, ownAlcohol; Low boiling ether comprises oxolane, dioxane, glycol dimethyl ether, diethylene glycol dimethylEther; Low boiling nitrile comprises acetonitrile, benzonitrile, acrylonitrile; Low boiling point hydrocarbon comprises benzene, toluene, neighbourDimethylbenzene, paraxylene, cyclohexane, n-hexane.
According to method provided by the invention, the separation of the thick product of gained, purification process are suction filtration, distillation, recrystallization; Recrystallization process solvent for use is methyl alcohol, ethanol, water, ethyl acetate, ether, justOne or more compounding ingredients in hexane, carrene etc. Obtain high-quality through recrystallization2,5-furans diamides.
Oxidation, amination and hydration reaction system can high selectivities, and high conversion catalysis HMF prepares high2 of quality, 5-furans diamides, product separation yield is high.
Specifically, the present invention finds that one has efficiently catalyzing and oxidizing activated centre and soda acid is urged exactlyChange the catalyst in activated centre, generated aldehyde, aldehyde amine thereby possess catalytic molecular oxygen oxidation alcohol simultaneouslyChange the multifunction catalyst that generates imines, imines oxidative dehydrogenation generation nitrile and nitrile hydration generation acid amides. Taking low-boiling point alcohol, ether, nitrile and hydro carbons as reaction medium, under catalytic action, HMF is through peroxidating, amination and hydration reaction, and the separation of product, purification process, prepare 2 of high-quality, 5-furansDiamides, and structure and purity to product tests, for application provides reference and foundation.
Brief description of the drawings
Fig. 1: embodiment 1 products of separated 2,5-furans diamides1HNMR（DMSO-d6) nuclear magnetic resonanceFigure.
Detailed description of the invention
By specific embodiments in detail the present invention is described in detail below, but the invention process is not limited to these embodiment:
Embodiment 1: by 1mmolHMF, 0.02mmolCo3O4, 0.2mL ammoniacal liquor, 2mL dioxane, join in 20mL band teflon-lined stainless steel cauldron, be filled with 0.1MPaO2, addHeat, to 100 ° of C, is reacted 4h at this temperature. Suction filtration, rotary evaporation is except desolventizing, with methyl alcohol-acetic acidEthyl ester recrystallization, obtain highly purified 2,5-furans diamides, the qualitative analysis of product by1HNMRDetermine separation yield 90%.
Embodiment 2: by 1mmolHMF, 0.1mmolNiO, 4mmol carbonic hydroammonium, 2mL isopropylAlcohol joins in 20mL band teflon-lined stainless steel cauldron, is filled with 0.3MPaO2, addHeat, to 40 ° of C, is reacted 48h at this temperature. Suction filtration, rotary evaporation, except desolventizing, is used alcohol-water weightCrystallization, obtain highly purified 2,5-furans diamides, the qualitative analysis of product by1HNMR is definite,Separation yield 80%.
Embodiment 3: by 1mmolHMF, 0.15mmolFe3O4, 2mmol ammonium carbonate, 2mL tetrahydrochysene furanMutter and join in 20mL band teflon-lined stainless steel cauldron, be filled with 0.5MPaO2, addHeat, to 110 ° of C, is reacted 14h at this temperature. Suction filtration, rotary evaporation, except desolventizing, is used ethyl acetate-carrene recrystallization, obtain highly purified 2,5-furans diamides, the qualitative analysis of product by1HNMR determines, separation yield 85%.
Embodiment 4: by 1mmolHMF, 0.25mmolMnO2, 8mmol ammonium sulfate, 2mL n-butanolJoin in 20mL band teflon-lined stainless steel cauldron, be filled with 1.6MPaO2, addHeat, to 130 ° of C, is reacted 1h at this temperature. Suction filtration, rotary evaporation is except desolventizing, heavily ties with etherCrystalline substance, obtain highly purified 2,5-furans diamides, the qualitative analysis of product by1HNMR determines, dividesFrom yield 95%.
Embodiment 5: by 1mmolHMF, 0.2mmolCuO, 6mmol ammonium acetate, 2mL benzonitrile addsEnter in 20mL band teflon-lined stainless steel cauldron, be filled with 1.4MPaO2, be heated to80 ° of C react 36h at this temperature. Suction filtration, rotary evaporation is except desolventizing, with ethyl acetate-dichloroMethane recrystallization, obtain highly purified 2,5-furans diamides, the qualitative analysis of product by1HNMRDetermine separation yield 75%.
Embodiment 6: by 1mmolHMF, 0.3mmolCu2O, 7mmol ammonium oxalate, 2mL ethylene glycol bisthioglycolateMethyl ether joins in 20mL band teflon-lined stainless steel cauldron, is filled with 0.6MPaO2，Be heated to 60 ° of C, at this temperature, react 7h. Suction filtration, rotary evaporation is except desolventizing, heavily ties with etherCrystalline substance, obtain highly purified 2,5-furans diamides, the qualitative analysis of product by1HNMR determines, dividesFrom yield 60%.
Embodiment 7: by 1mmolHMF, 0.2mmolFe2O3, 15mmol ammonium bromide, 2mL methyl alcohol addsEnter in 20mL band teflon-lined stainless steel cauldron, be filled with 1.8MPa air, heatingTo 180 ° of C, at this temperature, react 0.2h. Suction filtration, rotary evaporation, except desolventizing, is used Ethanol-Acetic AcidEthyl ester recrystallization, obtain highly purified 2,5-furans diamides, the qualitative analysis of product by1HNMRDetermine separation yield 76%.
Embodiment 8: by 1mmolHMF, 0.01mmolMn3O4, 20mmol ammonium chloride, 2mL tolueneJoin in 20mL band teflon-lined stainless steel cauldron, be filled with 2MPa air, heatingTo 120 ° of C, at this temperature, react 5h. Suction filtration, rotary evaporation is except desolventizing, with ethyl acetate-bis-Chloromethanes recrystallization, obtain highly purified 2,5-furans diamides, the qualitative analysis of product by1HNMRDetermine separation yield 65%.
Embodiment 9: by 1mmolHMF, 0.25mmolVO2, 0.3mL ammoniacal liquor, 2mL n-hexane addsIn 20mL band teflon-lined stainless steel cauldron, be filled with 0.7MPaO2, be heated to 90° C reacts 16h at this temperature. Suction filtration, rotary evaporation is except desolventizing, with ethyl acetate-ether knotCrystalline substance, obtain highly purified 2,5-furans diamides, the qualitative analysis of product by1HNMR determines, dividesFrom yield 74%.
Embodiment 10: by 1mmolHMF, 0.3mmolV2O5, 2mmol liquefied ammonia, 2mL cyclohexane addsEnter in 20mL band teflon-lined stainless steel cauldron, be filled with 0.3MPaO2, be heated to90 ° of C react 6h at this temperature. Suction filtration, rotary evaporation is except desolventizing, with ethyl acetate-n-hexaneRecrystallization, obtain highly purified 2,5-furans diamides, the qualitative analysis of product by1HNMR determines, separation yield 88%.
Embodiment 11: by 1mmolHMF, 0.15mmolMoO3，0.02mmolMnO2, 0.3mL ammoniaWater, 2mL acrylonitrile joins in 20mL band teflon-lined stainless steel cauldron, is filled with 1.1MPaO2, be heated to 70 ° of C, at this temperature, react 10h. Suction filtration, rotary evaporation removes desolventizing,With ethyl acetate-n-hexane recrystallization, obtain highly purified 2,5-furans diamides, product qualitativeAnalyze by1HNMR determines, separation yield 92%.
Embodiment 12: by 1mmolHMF, 0.3mmolCeO2, 0.2mL ammoniacal liquor, 2mL amylalcohol joinsIn 20mL band teflon-lined stainless steel cauldron, be filled with 0.5MPaO2, be heated to 110 ° of C, at this temperature, react 1h. Suction filtration, rotary evaporation is except desolventizing, heavily ties with ethyl acetate-n-hexaneCrystalline substance, obtain highly purified 2,5-furans diamides, the qualitative analysis of product by1HNMR determines, dividesFrom yield 81%.
The present invention has developed a kind of bifunctional catalyst of efficiently realizing ammoxidation, with biomass-based hardware and software platformCompound HMF is raw material, taking low-boiling point alcohol, ether, nitrile and hydro carbons as reaction medium, with oxygen or airFor oxygen source, taking ammoniacal liquor, liquefied ammonia and ammonium salt as ammonia source, under catalytic action, produce 2,5-furans diamides. This catalyst, dicyandiamide solution are cheap and easy to get, and easily and separation of products, solvent can be realized circulation profitWith. Excellent product performance, purity is very high. This technology path, for the shortage of alleviating petroleum resources, subtractsFew chemical products and the dependence of energy chemicals to fossil resources such as oil, have great importance.
Claims (7)
1. catalyzed conversion 5 hydroxymethyl furfural is prepared the method for 2,5-furans diamides, it is characterized in that, in oxygen or airA kind of or two kinds be oxygen source, taking the one in ammoniacal liquor, liquefied ammonia or ammonium salt or two kinds as amine source, with one in organic solventKind or two kinds be reaction medium, under catalyst action, 5 hydroxymethyl furfural is through peroxidating, amination, hydration reaction, warpSeparation and purification, obtains 2,5-furans diamides;
Described oxygen source pressure is 0.5 – 2MPa;
In described 5 hydroxymethyl furfural and amine source, the mol ratio of " nitrogen " is 1:2-20;
Described catalyst is: NiO, Co3O4、CuO、Cu2O、Fe2O3、Fe3O4、Mn3O4、VO2、V2O5、MoO3、CeO2In one or more.
2. method according to claim 1, is characterized in that: ammonium salt is: ammonium chloride, ammonium sulfate, ammonium bromide,One or two or more kinds in ammonium carbonate, carbonic hydroammonium, ammonium oxalate, ammonium acetate, ammoniacal liquor mass concentration 26-28%.
3. method according to claim 1, is characterized in that: the medium of 5 hydroxymethyl furfural catalytic conversion reaction isLower boiling alcohol, ether, nitrile or hydrocarbon; Be selected from methyl alcohol, isopropyl alcohol, n-butanol, amylalcohol, oxolane, dioxane,One or two or more kinds in glycol dimethyl ether, benzonitrile, acrylonitrile, toluene, cyclohexane, n-hexane.
4. method according to claim 1, is characterized in that: 5 hydroxymethyl furfural catalytic cracking 2,5-furans twoThe reaction temperature of acid amides is 30-180 DEG C, and the reaction time is 0.1-48h.
5. method according to claim 1, is characterized in that:
The total consumption of catalyst is the 1-30mol% of 5 hydroxymethyl furfural consumption.
6. method according to claim 1, is characterized in that: the separation of product, purification process are suction filtration, distillation, recrystallization.
7. method according to claim 1, is characterized in that: better reaction temperature is 50-160 DEG C; Better anti-Between seasonable, be 1-20h.
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| CN107814782B (en) * | 2016-09-14 | 2021-04-13 | 中国科学院大连化学物理研究所 | Method for preparing 5-hydroxymethyl-2-furancarbonitrile by catalytic ammoxidation |
| CN106565647B (en) * | 2016-10-29 | 2020-01-10 | 华东理工大学 | Method for preparing 2, 5-furandicarboxylic acid by catalytic oxidation of 5-hydroxymethylfurfural |
| CN109956918A (en) * | 2017-12-14 | 2019-07-02 | 中国科学院大连化学物理研究所 | A method of catalysis 5 hydroxymethyl furfural ammoxidation prepares 2,5- furans diformamide |
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