CN111187238B - A kind of synthetic method of 2,5-furandicarboxylic acid - Google Patents
A kind of synthetic method of 2,5-furandicarboxylic acid Download PDFInfo
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- CN111187238B CN111187238B CN202010031253.0A CN202010031253A CN111187238B CN 111187238 B CN111187238 B CN 111187238B CN 202010031253 A CN202010031253 A CN 202010031253A CN 111187238 B CN111187238 B CN 111187238B
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- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000010189 synthetic method Methods 0.000 title claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 68
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 claims abstract description 62
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 56
- KEFJLCGVTHRGAH-UHFFFAOYSA-N 2-acetyl-5-methylfuran Chemical compound CC(=O)C1=CC=C(C)O1 KEFJLCGVTHRGAH-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 23
- NBXLPPVOZWYADY-UHFFFAOYSA-N 2-ethyl-5-methylfuran Chemical compound CCC1=CC=C(C)O1 NBXLPPVOZWYADY-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000011973 solid acid Substances 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 67
- 239000002904 solvent Substances 0.000 claims description 26
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 239000002808 molecular sieve Substances 0.000 claims description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 7
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 5
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052707 ruthenium Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical group CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims description 2
- 229960003750 ethyl chloride Drugs 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 239000003929 acidic solution Substances 0.000 claims 1
- 239000002134 carbon nanofiber Substances 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- KGMXPXPXPAAUMD-UHFFFAOYSA-N propane;dihydrochloride Chemical compound Cl.Cl.CCC KGMXPXPXPAAUMD-UHFFFAOYSA-N 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 claims 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 21
- 230000003647 oxidation Effects 0.000 abstract description 13
- 238000007254 oxidation reaction Methods 0.000 abstract description 13
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 abstract description 10
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 abstract description 10
- 230000021736 acetylation Effects 0.000 abstract description 7
- 238000006640 acetylation reaction Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 230000006315 carbonylation Effects 0.000 abstract description 4
- 238000005810 carbonylation reaction Methods 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 150000004696 coordination complex Chemical class 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000007791 liquid phase Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 235000000346 sugar Nutrition 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 12
- 238000004587 chromatography analysis Methods 0.000 description 12
- 238000001914 filtration Methods 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 229910052681 coesite Inorganic materials 0.000 description 11
- 229910052906 cristobalite Inorganic materials 0.000 description 11
- 229910052682 stishovite Inorganic materials 0.000 description 11
- 229910052905 tridymite Inorganic materials 0.000 description 11
- 239000007789 gas Substances 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 229920000728 polyester Polymers 0.000 description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- -1 corncobs Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 230000037361 pathway Effects 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000004128 high performance liquid chromatography Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 239000010902 straw Substances 0.000 description 3
- 150000008163 sugars Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- DNXDYHALMANNEJ-UHFFFAOYSA-N furan-2,3-dicarboxylic acid Chemical compound OC(=O)C=1C=COC=1C(O)=O DNXDYHALMANNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 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
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The application discloses a synthetic method of 2, 5-furandicarboxylic acid, which comprises the following steps: the first step is hydrogenation of furfural into methylfuran, and the second step is acetylation of methylfuran; the third step is the hydrogenation of 5-methyl-2-acetylfuran; the fourth step is the oxidation of 2-methyl-5-ethylfuran. Compared with a process for preparing 2, 5-furandicarboxylic acid by using 5-hydroxymethylfurfural as a raw material, the method has the advantages that the green and renewable bio-based platform compound furfural is used as the raw material, the source of the used raw material is wider, the raw material is easy to produce, the yield is higher, the cost of the raw material is lower, and the cost of the used oxidation catalyst is low, so that the method is favorable for large-scale production. Compared with a noble metal complex catalyst used in a process of taking CO carbonylation as carbon chain growth, the catalyst used in the carbon chain growth strategy is solid acid, so that the cost is greatly reduced.
Description
Technical Field
The application relates to the technical field of catalytic synthesis, in particular to a synthetic method of 2, 5-furandicarboxylic acid.
Background
With the steady development of Chinese economy and industry, the domestic demand for polymer materials is increasing, and the problem with the increasing demand is the degradation problem of the polymer materials. Polyolefin polymers are difficult to degrade in nature to form white garbage, so that environmental pollution is caused, and the living environment of human beings and the living environment of other organisms are influenced. There is a growing interest in degradable polyester-based polymer materials. Terephthalic acid is used as an important monomer of polyester, and the source of the terephthalic acid is mainly non-renewable petroleum resources, which are influenced by the increasing exhaustion of petrochemical resources. 2, 5-Furandicarboxylic acid is a derivative of bio-based sugars (5-carbon sugars and 6-carbon sugars) and has a rigid aromatic ring structure similar to that of terephthalic acid, and can be used as a monomer for producing polyester-based polymers in place of terephthalic acid. The polyester prepared from 2, 5-furandicarboxylic acid has higher strength, and the furan ring has lower aromaticity than the benzene ring, and the prepared polyester is more easily degraded. Therefore, the 2, 5-furandicarboxylic acid has good production and application prospects.
The major pathways currently used to produce 2, 5-furandicarboxylic acid from biobased sugars are the carbon 6 sugar pathway and the carbon 5 sugar pathway. The steps of the carbon 6 sugar pathway are mainly the hydrolysis of the carbon 6 sugar to prepare 5-hydroxymethylfurfural, followed by the oxidation of the 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid. This route has few steps and is simple and convenient, and thus has received attention from many researchers. Chinese patent CN107880002A discloses a method for preparing 2, 5-furandicarboxylic acid and furan polyester from straws. The method comprises the steps of hydrolyzing straws under an acidic condition to obtain a water solution containing sugar, continuously hydrolyzing the water solution containing sugar under the acidic condition to obtain 5-hydroxymethylfurfural, oxidizing the 5-hydroxymethylfurfural to obtain 2, 5-furandicarboxylic acid, and then carrying out esterification and polycondensation to obtain furan polyester. This process is simple but has a low yield of only 7% of the total yield. Mainly due to the low hydrolysis efficiency of the first two steps under acidic conditions. And the 5-hydroxymethylfurfural obtained by hydrolyzing the sugar water solution in the second step has the defects of difficult separation, instability and the like. Meanwhile, the oxidation of 5-hydroxymethylfurfural needs to use noble metal catalysts such as Au, Pd, Pt and the like. These reasons make the route from hydrolysis of the carbon 6 sugars to 5-hydroxymethylfurfural followed by oxidation of the 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid more costly.
The main steps of the carbon 5 sugar path are that the carbon 5 sugar is hydrolyzed to prepare furfural, and the furfural is subjected to carbon growth and oxidation steps to obtain 2,5 furandicarboxylic acid. Most of the carbon 5 sugar in the path is extracted from the agricultural and forestry wastes such as corncobs, straws and bagasse, so that the method does not compete for grains with people, is low in cost and has wide application prospect. Chinese patent CN 106977476B discloses a method for preparing furandicarboxylic acid from furoic acid. The method comprises the following specific steps: brominating furoic acid such that the hydrogen at position 5 of furoic acid is replaced by bromine; esterification, namely esterifying carboxyl; carbonylation, and reaction with carbon monoxide under the catalysis of a palladium complex catalyst; hydrolyzing to obtain the final reaction product furan dicarboxylic acid. The reaction condition of the process is mild, but the palladium complex catalyst used for carbonylation is high in price and is not suitable for large-scale production. Another similar method of carbon growth is carbonate catalyzed carbon dioxide insertion. Chinese patent CN 109678823A discloses a method for extracting furfural from furfural through CO2A process for the manufacture of 2, 5-furandicarboxylic acid by intercalation. Specifically, furfural is oxidized to be called furoic acid, and then carbonate, furoic acid and carbon dioxide which are supported by inorganic oxides are introduced into a high-pressure reaction kettle to react at the temperature of 190 ℃ and 260 ℃. The method is simple and does not require ligand combinationHowever, the cesium carbonate used is relatively expensive and is still difficult to scale up.
Disclosure of Invention
The application provides a method for producing 2, 5-furandicarboxylic acid by taking furfural as a raw material through four steps.
The following technical scheme is adopted in the application:
synthetic route developed by the scheme
A method for synthesizing 2, 5-furandicarboxylic acid, comprising the steps of:
(1) mixing furfural, a hydrogenation catalyst and a solvent, adding the mixture into a reactor, introducing inert gas to replace air in the reactor, then introducing hydrogen to replace the inert gas, keeping the pressure of the hydrogen at 0.1-4MPa, heating the temperature of the reactor to 180 ℃ and 280 ℃, continuously reacting for 0.1-24 hours, and separating to obtain methylfuran;
(2) mixing methylfuran with acetic anhydride, dissolving in a solvent, introducing into a normal-pressure fixed bed reactor filled with a solid acid catalyst, wherein the temperature of the reactor is 30-150 ℃, and separating to obtain 5-methyl-2-acetylfuran;
(3) adding 5-methyl-2-acetylfuran, a supported metal catalyst and a solvent into a reactor, introducing inert gas to replace air in the reactor, subsequently introducing hydrogen to replace the inert gas, keeping the pressure of the hydrogen at 1-4MPa, heating the reactor to 180 ℃ and 280 ℃, continuously reacting for 5 minutes-24 hours, and separating to obtain 2-methyl-5-ethylfuran;
(4) adding 2-methyl-5-ethyl furan into a reactor with a polytetrafluoroethylene lining, reacting for 0.1-16 hours under the catalytic action of an oxidant, and separating to obtain 2, 5-furandicarboxylic acid.
The hydrogenation catalyst in the step (1) is a supported catalyst containing one or more metals of Cu, Ni, Fe, Co and Ru, the total metal loading amount accounts for 0.05-50% of the mass ratio of the carrier, and the carrier is one or more of activated carbon, nano carbon fiber, silicon dioxide, titanium dioxide, alumina and pure silicon molecular sieves.
In the step (1), the mass ratio of the hydrogenation catalyst to the furfural is 5: 1 to 1: 20.
the solvent in the step (1) is one or more of methanol, ethanol, tetrahydrofuran, n-hexane and dodecane.
The solid acid catalyst in the step (2) is a solid molecular sieve, phosphotungstic acid, phosphomolybdic acid or a supported catalyst, and the supported catalyst takes phosphotungstic acid or phosphomolybdic acid as an active center. The solid molecular sieve is one or more of ZSM-5, HBEA, HY, HSUY and HMOR.
The solvent in the step (2) is chloralkane, and the chloralkane is ethyl chloride, dichloroethane, chloroform, chloropropane or dichloropropane.
The active center of the supported metal catalyst in the step (3) is one or more of Cu, Ni, Fe, Co and Ru, the total metal loading amount accounts for 0.05-50% of the mass ratio of the carrier, and the carrier is one or more of activated carbon, nano carbon fiber, silicon dioxide, titanium dioxide, aluminum oxide and pure silicon molecular sieve.
The solvent in the step (3) is one or more of methanol, ethanol, tetrahydrofuran, n-hexane and dodecane.
The oxidant in the step (4) is KMnO4Acid solution of (2) or H2O2And (3) solution.
The oxidant in the step (4) is oxygen of 0.1-4Mpa, the metallic salt of Co, the metallic salt of Mn, the metallic salt of Br or HBr solution is added into the reactor, wherein, the content of Co, Mn or Br accounts for 0.1-10% of the molar percentage of the raw material 2-methyl-5-ethyl furan, and the reactor is also added with solvent which is acetonitrile, 1, 2-dichloroethane, chloroform, acetic acid, propionic acid or n-butyric acid.
The above-mentioned at least one technical scheme that this application adopted can reach following beneficial effect:
the method takes a green renewable bio-based platform compound furfural as a raw material, generates methyl furan through hydrogenation, acetylates the methyl furan to increase a carbon chain, generates an ethyl group through hydrogenation of an acetyl group connected to a furan ring, and further oxidizes the ethyl group to generate the 2, 5-furandicarboxylic acid. Compared with the process for preparing 2, 5-furandicarboxylic acid by using 5-hydroxymethylfurfural as a raw material, the method has the advantages of wider raw material source, easy production of the raw material, higher yield, lower cost of the raw material, low cost of the used oxidation catalyst and contribution to large-scale production. Compared with a noble metal complex catalyst used in a process of taking CO carbonylation as carbon chain growth, the catalyst used in the carbon chain growth strategy is solid acid, so that the cost is greatly reduced.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the technical solutions of the present application will be described in detail and completely with reference to the specific embodiments of the present application. It should be apparent that the described embodiments are only some of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Example 1
(1) Preparation of methylfuran by furfural hydrodeoxygenation
The furfural hydrogenation catalyst is prepared by an impregnation method, and a proper amount of nickel nitrate is dissolved in water. Mixing SiO2Adding the powder into the solution, wherein the total metal amount is SiO215% of the mass of (a). The mixture was stirred to dryness, dried overnight at 80 ℃ and ground to a powder. Calcining the powder at 450 ℃ in air, and then reducing the calcined powder with hydrogen at the same temperature to obtain the furfural hydrogenation catalyst.
Adding 1g of hydrogenation catalyst into a reaction kettle, adding 10g of furfural, and adding 80ml of anhydrous methanol as a solvent. After the reaction kettle is sealed, N is firstly used2Replacing air in the reaction kettle, and recharging 4MPa of H2. The reaction kettle is heated to 200 ℃ and reacts for 10 hours.
After the reaction is finished, the kettle body is cooled to room temperature, and the catalyst and the liquid phase product are separated by filtration. The liquid phase product was quantitatively analyzed by gas chromatography-mass spectrometer. Instrument information: shimadzu QP-2010 Ultra; information on the chromatographic column: rtx-5 Sil MS (30 m.times.0.25 mm.times.0.25 μm). Setting a chromatographic program: after heating to 280 ℃ at 10 ℃ per minute from 100 ℃, the temperature was maintained for 20 minutes. The chromatographic analysis result shows that the conversion rate of the furfural reaches 100 percent and the yield of the methylfuran reaches 93 percent. The solvent was removed by distillation under reduced pressure to give methylfuran.
(2) Acetylation of methylfuran to prepare 5-methyl-2-acetylfuran
The acetylation of the methylfuran is carried out in a fixed bed at atmospheric pressure. 4g of HSUY catalyst was tableted and shaped, and then sieved to obtain catalyst particles having a particle size of 20-60 mesh. The catalyst is loaded in the reactor. Then 5g of methylfuran and 15.5g of acetic anhydride were weighed out and dissolved in 1, 2-dichloroethane. And heating the reactor to 80 ℃, introducing the reaction mixed liquor into the reactor through a constant flow pump, and reacting for 3 hours.
After the reaction is finished, the kettle body is cooled to room temperature, and the catalyst and the liquid phase product are separated by filtration. The liquid phase product was quantitatively analyzed by gas chromatography-mass spectrometer. Instrument information: shimadzu QP-2010 Ultra; information on the chromatographic column: rtx-5 Sil MS (30 m.times.0.25 mm.times.0.25 μm). Setting a chromatographic program: after heating to 280 ℃ at 10 ℃ per minute from 100 ℃, the temperature was maintained for 20 minutes. The chromatographic analysis result shows that the conversion rate of the methylfuran reaches 99 percent, and the yield of the 5-methyl-2-acetylfuran reaches 99 percent. The solvent was removed by distillation under reduced pressure to give 5-methyl-2-acetylfuran.
(3) Preparation of 2-methyl-5-ethyl furan by hydrodeoxygenation of 5-methyl-2-acetylfuran
The 5-methyl-2-acetylfuran hydrogenation catalyst is prepared by a hydrothermal method. Dissolving Co precursor cobalt nitrate into a certain amount of water, adding a certain amount of ammonium chloride and ammonia water, and fully dissolving. A certain amount of SiO2Adding into the mixed solution, the metal is SiO2100% by mass. After the mixed solution is stirred for 2 hours, the mixed solution is transferred into a self-pressure hydrothermal kettle, and the hydrothermal kettle is placed in a 120 ℃ oven for reaction for 6 hours. The resulting catalyst was washed with water and oven dried at 60 ℃ overnight. The obtained solid was ground and calcined at 450 ℃ for 4 hours in an air atmosphere, followed by reduction at the same temperature for 4 hours in a hydrogen atmosphereObtaining the hydrogenation catalyst.
0.5g of hydrogenation catalyst was added to the reaction vessel, and 5g of 5-methyl-2-acetylfuran and 50ml of 1, 4-dioxane were added. After the reaction kettle is sealed, N is firstly used2Replacing air in the reaction kettle, and recharging 3MPa of H2. The reaction kettle is heated to 220 ℃ and reacted for 5 hours. After the reaction is finished, the kettle body is cooled to room temperature, and the catalyst and the liquid phase product are separated by filtration. The liquid phase product was quantitatively analyzed by gas chromatography-mass spectrometer. Instrument information: shimadzu QP-2010 Ultra; information on the chromatographic column: rtx-5 Sil MS (30 m.times.0.25 mm.times.0.25 μm). Setting a chromatographic program: after heating to 280 ℃ at 10 ℃ per minute from 100 ℃, the temperature was maintained for 20 minutes. The chromatographic analysis result shows that the conversion rate of the 5-methyl-2-acetylfuran reaches 99 percent, and the yield of the 2-methyl-5-ethylfuran reaches 97 percent. The solvent was removed by rotary evaporation to give 2-methyl-5-ethylfuran.
(4) Preparation of 2, 5-furandicarboxylic acid by oxidation of 2-methyl-5-ethylfuran
0.5g of 2-methyl-5-ethyl furan and a proper amount of KMnO are sequentially added into a reaction kettle with a polytetrafluoroethylene lining4And 10ml of a 1mol/L aqueous sulfuric acid solution, and the reaction vessel was sealed. The reaction kettle is heated to 70 ℃ to react for 1 hour.
After the reaction is finished, cooling the kettle to room temperature, filtering to separate out solids, washing with ice water for three times, and drying in an oven at 60 ℃ for 12 hours. The white solid was subjected to composition analysis by high performance liquid chromatography. Instrument information: the Shimadzu high performance liquid chromatograph has a UV-VIS detector with the model of SPD-16, a liquid delivery pump with the model of LC-16 and a column incubator with the model of CTO-16; information on the chromatographic column: wondasil C18-WR5um (5 μm × 4.6mm I.D. × 150 mm); in the test conditions, the mobile phase: methanol/1% acetic acid solution 10:90 at a flow rate of 1mL/min, a column temperature of 30 ℃, a detection wavelength of 264nm, and a sample injection volume of 10 μ L. The chromatographic analysis showed a 2, 5-furandicarboxylic acid content of 98.5% giving a yield of 92% in the oxidation step by calculation.
Example 2
(1) Preparation of methylfuran by furfural hydrodeoxygenation
The furfural hydrogenation catalyst is prepared by an impregnation method by mixing copper nitrate withNickel nitrate was dissolved in water at a molar ratio of Cu to Ni of 2 to 8. Mixing SiO2Adding the powder into the solution, wherein the total metal amount is SiO220% of the mass of (a). The mixture was stirred to dryness, dried overnight at 80 ℃ and ground to a powder. Calcining the powder at 450 ℃ in air, and then reducing the calcined powder with hydrogen at the same temperature to obtain the furfural hydrogenation catalyst.
Adding 0.5g of hydrogenation catalyst into a reaction kettle, adding 8g of furfural, and adding 80ml of absolute ethyl alcohol as a solvent. After the reaction kettle is sealed, N is firstly used2Replacing air in the reaction kettle, and recharging 3MPa of H2. The reaction kettle is heated to 240 ℃ and reacted for 6 hours.
After the reaction is finished, the kettle body is cooled to room temperature, and the catalyst and the liquid phase product are separated by filtration. The liquid phase product was quantitatively analyzed by gas chromatography-mass spectrometer. Instrument information: shimadzu QP-2010 Ultra; information on the chromatographic column: rtx-5 Sil MS (30 m.times.0.25 mm.times.0.25 μm). Setting a chromatographic program: after heating to 280 ℃ at 10 ℃ per minute from 100 ℃, the temperature was maintained for 20 minutes. The chromatographic analysis result shows that the conversion rate of the furfural reaches 96 percent, and the yield of the methylfuran reaches 94 percent. The solvent was removed by distillation under reduced pressure to give methylfuran.
(2) Acetylation of methylfuran to prepare 5-methyl-2-acetylfuran
The acetylation of the methylfuran is carried out in a fixed bed at atmospheric pressure. 4g of HBEA catalyst was tableted and formed, and then sieved to obtain catalyst particles having a particle size of 20-60 mesh. The catalyst is loaded in the reactor. Then 6g of methylfuran and 11.2g of acetic anhydride were weighed out and dissolved in 1, 2-dichloroethane. Heating the reactor to 50 ℃, introducing the reaction mixed liquor into the reactor through a constant flow pump, and reacting for 2 hours.
After the reaction is finished, the kettle body is cooled to room temperature, and the catalyst and the liquid phase product are separated by filtration. The liquid phase product was quantitatively analyzed by gas chromatography-mass spectrometer. Instrument information: shimadzu QP-2010 Ultra; information on the chromatographic column: rtx-5 Sil MS (30 m.times.0.25 mm.times.0.25 μm). Setting a chromatographic program: after heating to 280 ℃ at 10 ℃ per minute from 100 ℃, the temperature was maintained for 20 minutes. The chromatographic analysis result shows that the conversion rate of the methylfuran reaches 96 percent, and the yield of the 5-methyl-2-acetylfuran reaches 91 percent. The solvent was removed by distillation under reduced pressure to give 5-methyl-2-acetylfuran.
(3) Preparation of 2-methyl-5-ethyl furan by hydrodeoxygenation of 5-methyl-2-acetylfuran
The 5-methyl-2-acetylfuran hydrogenation catalyst is prepared by a hydrothermal method. Dissolving nickel nitrate into a certain amount of water, adding a certain amount of ammonium chloride and ammonia water, and fully dissolving. A certain amount of SiO2Adding into the mixed solution, the metal is SiO230% of the mass. After the mixed solution is stirred for 2 hours, the mixed solution is transferred into a self-pressure hydrothermal kettle, and the hydrothermal kettle is placed in a 120 ℃ oven for reaction for 6 hours. The resulting catalyst was washed with water and oven dried at 60 ℃ overnight. The obtained solid was ground and calcined at 450 ℃ for 4 hours in an air atmosphere, followed by reduction at the same temperature for 4 hours in a hydrogen atmosphere, to obtain a hydrogenation catalyst.
0.5g of a hydrogenation catalyst was charged into a reaction vessel, and 8g of 5-methyl-2-acetylfuran and 50ml of tetrahydrofuran were added. After the reaction kettle is sealed, N is firstly used2Replacing air in the reaction kettle, and recharging 2MPa of H2. The reaction kettle is heated to 260 ℃ and reacted for 4 hours. After the reaction is finished, the kettle body is cooled to room temperature, and the catalyst and the liquid phase product are separated by filtration. The liquid phase product was quantitatively analyzed by gas chromatography-mass spectrometer. Instrument information: shimadzu QP-2010 Ultra; information on the chromatographic column: rtx-5 Sil MS (30 m.times.0.25 mm.times.0.25 μm). Setting a chromatographic program: after heating to 280 ℃ at 10 ℃ per minute from 100 ℃, the temperature was maintained for 20 minutes. The chromatographic analysis result shows that the conversion rate of the 5-methyl-2-acetylfuran reaches 99 percent, and the yield of the methylfuran reaches 93 percent. The solvent was removed by rotary evaporation to give 2-methyl-5-ethylfuran.
(4) Preparation of 2, 5-furandicarboxylic acid by oxidation of 2-methyl-5-ethylfuran
2g of 2-methyl-5-ethyl furan, 10ml of water and a proper amount of H are sequentially added into a reaction kettle with a polytetrafluoroethylene lining2O2And sealing the reaction kettle. The reaction kettle is heated to 60 ℃ to react for 3 hours.
After the reaction is finished, cooling the kettle to room temperature, filtering to separate out solids, washing with ice water for three times, and drying in an oven at 60 ℃ for 12 hours. The white solid was subjected to composition analysis by high performance liquid chromatography. Instrument information: the Shimadzu high performance liquid chromatograph has a UV-VIS detector with the model of SPD-16, a liquid delivery pump with the model of LC-16 and a column incubator with the model of CTO-16; information on the chromatographic column: wondasil C18-WR5um (5 μm × 4.6mm I.D. × 150 mm); in the test conditions, the mobile phase: methanol/1% acetic acid solution 10:90 at a flow rate of 1mL/min, a column temperature of 30 ℃, a detection wavelength of 264nm, and a sample injection volume of 10 μ L. The chromatographic analysis showed a 2, 5-furandicarboxylic acid content of 97% giving a yield of 95.3% by calculation of the oxidation step.
Example 3
(1) Preparation of methylfuran by furfural hydrodeoxygenation
The furfural hydrogenation catalyst was prepared by an impregnation method, in which appropriate amounts of copper nitrate and nickel nitrate were dissolved in water in a molar ratio of Fe to Ni of 1 to 9. Adding aluminum oxide powder into the solution, wherein the total metal accounts for SiO218% of the mass of (a). The mixture was stirred to dryness, dried overnight at 80 ℃ and ground to a powder. Calcining the powder at 450 ℃ in air, and then reducing the calcined powder with hydrogen at the same temperature to obtain the furfural hydrogenation catalyst.
Adding 1g of hydrogenation catalyst into a reaction kettle, adding 15g of furfural, and adding 80ml of absolute ethyl alcohol as a solvent. After the reaction kettle is sealed, N is firstly used2Replacing air in the reaction kettle, and recharging 4MPa of H2. The reaction kettle is heated to 240 ℃ and reacted for 10 hours.
After the reaction is finished, the kettle body is cooled to room temperature, and the catalyst and the liquid phase product are separated by filtration. The liquid phase product was quantitatively analyzed by gas chromatography-mass spectrometer. Instrument information: shimadzu QP-2010 Ultra; information on the chromatographic column: rtx-5 Sil MS (30 m.times.0.25 mm.times.0.25 μm). Setting a chromatographic program: after heating to 280 ℃ at 10 ℃ per minute from 100 ℃, the temperature was maintained for 20 minutes. The chromatographic analysis result shows that the conversion rate of the furfural reaches 98 percent and the yield of the methylfuran reaches 95 percent. The solvent was removed by distillation under reduced pressure to give methylfuran.
(2) Acetylation of methylfuran to prepare 5-methyl-2-acetylfuran
The acetylation of the methylfuran is carried out in a fixed bed at atmospheric pressure. 6g of HBEA catalyst was tableted and formed, and then sieved to obtain catalyst particles having a particle size of 20-60 mesh. The catalyst is loaded in the reactor. Then 8g of methylfuran and 22.4g of acetic anhydride were weighed out and dissolved in 1, 2-dichloroethane. And heating the reactor to 100 ℃, introducing the reaction mixed liquor into the reactor through a constant flow pump, and reacting for 8 hours.
After the reaction is finished, the kettle body is cooled to room temperature, and the catalyst and the liquid phase product are separated by filtration. The liquid phase product was quantitatively analyzed by gas chromatography-mass spectrometer. Instrument information: shimadzu QP-2010 Ultra; information on the chromatographic column: rtx-5 Sil MS (30 m.times.0.25 mm.times.0.25 μm). Setting a chromatographic program: after heating to 280 ℃ at 10 ℃ per minute from 100 ℃, the temperature was maintained for 20 minutes. The chromatographic analysis result shows that the conversion rate of the methyl furan reaches 93 percent, and the yield of the 5-methyl-2-acetylfuran reaches 89 percent. The solvent was removed by distillation under reduced pressure to give 5-methyl-2-acetylfuran.
(3) Preparation of 2-methyl-5-ethyl furan by hydrodeoxygenation of 5-methyl-2-acetylfuran
The 5-methyl-2-acetylfuran hydrogenation catalyst is prepared by a hydrothermal method. Dissolving nickel nitrate into a certain amount of water, adding a certain amount of ammonium chloride and ammonia water, and fully dissolving. A certain amount of SiO2Adding into the mixed solution, the metal is SiO230% of the mass. After the mixed solution is stirred for 2 hours, the mixed solution is transferred into a self-pressure hydrothermal kettle, and the hydrothermal kettle is placed in a 120 ℃ oven for reaction for 6 hours. The resulting catalyst was washed with water and oven dried at 60 ℃ overnight. The obtained solid was ground and calcined at 450 ℃ for 4 hours in an air atmosphere, followed by reduction at the same temperature for 4 hours in a hydrogen atmosphere, to obtain a hydrogenation catalyst.
1g of a hydrogenation catalyst was charged into a reaction vessel, and 15g of 5-methyl-2-acetylfuran and 80ml of tetrahydrofuran were added. After the reaction kettle is sealed, N is firstly used2Replacing air in the reaction kettle, and recharging 4MPa of H2. The reaction kettle is heated to 250 ℃ and reacts for 4 hours. After the reaction is finished, the kettle body is cooled to room temperature, and the catalyst and the liquid phase product are separated by filtration. The liquid phase product was quantitatively analyzed by gas chromatography-mass spectrometer. Instrument information: shimadzu QP-2010 Ultra;information on the chromatographic column: rtx-5 Sil MS (30 m.times.0.25 mm.times.0.25 μm). Setting a chromatographic program: after heating to 280 ℃ at 10 ℃ per minute from 100 ℃, the temperature was maintained for 20 minutes. The chromatographic analysis result shows that the conversion rate of the 5-methyl-2-acetylfuran reaches 96 percent, and the yield of the methylfuran reaches 92 percent. The solvent was removed by rotary evaporation to give 2-methyl-5-ethylfuran.
(4) Preparation of 2, 5-furandicarboxylic acid by oxidation of 2-methyl-5-ethylfuran
2g of 2-methyl-5-ethyl furan, a proper amount of NaBr and MnCl are sequentially added into a reaction kettle with a polytetrafluoroethylene lining2And 10mL of acetic acid, sealing the reaction vessel, and adding N2Replacing air in the reaction kettle, and recharging 0.5MPa of O2. The reaction kettle is heated to 160 ℃ and reacted for 5 hours.
After the reaction is finished, cooling the kettle to room temperature, filtering to separate out solids, washing with ice water for three times, and drying in an oven at 60 ℃ for 12 hours. The white solid was subjected to composition analysis by high performance liquid chromatography. Instrument information: the Shimadzu high performance liquid chromatograph has a UV-VIS detector with the model of SPD-16, a liquid delivery pump with the model of LC-16 and a column incubator with the model of CTO-16; information on the chromatographic column: wondasil C18-WR5um (5 μm × 4.6mm I.D. × 150 mm); in the test conditions, the mobile phase: methanol/1% acetic acid solution 10:90 at a flow rate of 1mL/min, a column temperature of 30 ℃, a detection wavelength of 264nm, and a sample injection volume of 10 μ L. The chromatographic analysis showed a content of 93% of 2, 5-furandicarboxylic acid, which was calculated to give a yield of 86% in the oxidation step.
The above description is only an example of the present application and is not intended to limit the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the scope of the claims of the present application.
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