CN107199028B - Solid acid catalyst, preparation method and application thereof, and method for preparing furfural compound - Google Patents
Solid acid catalyst, preparation method and application thereof, and method for preparing furfural compound Download PDFInfo
- Publication number
- CN107199028B CN107199028B CN201610157744.3A CN201610157744A CN107199028B CN 107199028 B CN107199028 B CN 107199028B CN 201610157744 A CN201610157744 A CN 201610157744A CN 107199028 B CN107199028 B CN 107199028B
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- China
- Prior art keywords
- acid catalyst
- solid acid
- range
- aluminum
- source
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- 239000011973 solid acid Substances 0.000 title claims abstract description 75
- HYBBIBNJHNGZAN-UHFFFAOYSA-N Furaldehyde Natural products O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 55
- -1 furfural compound Chemical class 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 36
- 239000010703 silicon Substances 0.000 claims abstract description 36
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000002028 Biomass Substances 0.000 claims abstract description 34
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 18
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 17
- 239000012429 reaction media Substances 0.000 claims abstract description 15
- 239000003292 glue Substances 0.000 claims abstract description 13
- 230000032683 aging Effects 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims description 41
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims description 20
- 229920006395 saturated elastomer Polymers 0.000 claims description 16
- 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 claims description 15
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 239000008103 glucose Substances 0.000 claims description 15
- 238000010521 absorption reaction Methods 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 14
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 10
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- 229930091371 Fructose Natural products 0.000 claims description 9
- 239000005715 Fructose Substances 0.000 claims description 9
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 9
- 238000003795 desorption Methods 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 9
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 8
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 8
- 229930006000 Sucrose Natural products 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 8
- 238000001179 sorption measurement Methods 0.000 claims description 8
- 239000005720 sucrose Substances 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- 238000004458 analytical method Methods 0.000 claims description 7
- 229920001202 Inulin Polymers 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-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
- 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 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 6
- JYJIGFIDKWBXDU-MNNPPOADSA-N inulin Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)OC[C@]1(OC[C@]2(OC[C@]3(OC[C@]4(OC[C@]5(OC[C@]6(OC[C@]7(OC[C@]8(OC[C@]9(OC[C@]%10(OC[C@]%11(OC[C@]%12(OC[C@]%13(OC[C@]%14(OC[C@]%15(OC[C@]%16(OC[C@]%17(OC[C@]%18(OC[C@]%19(OC[C@]%20(OC[C@]%21(OC[C@]%22(OC[C@]%23(OC[C@]%24(OC[C@]%25(OC[C@]%26(OC[C@]%27(OC[C@]%28(OC[C@]%29(OC[C@]%30(OC[C@]%31(OC[C@]%32(OC[C@]%33(OC[C@]%34(OC[C@]%35(OC[C@]%36(O[C@@H]%37[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O%37)O)[C@H]([C@H](O)[C@@H](CO)O%36)O)[C@H]([C@H](O)[C@@H](CO)O%35)O)[C@H]([C@H](O)[C@@H](CO)O%34)O)[C@H]([C@H](O)[C@@H](CO)O%33)O)[C@H]([C@H](O)[C@@H](CO)O%32)O)[C@H]([C@H](O)[C@@H](CO)O%31)O)[C@H]([C@H](O)[C@@H](CO)O%30)O)[C@H]([C@H](O)[C@@H](CO)O%29)O)[C@H]([C@H](O)[C@@H](CO)O%28)O)[C@H]([C@H](O)[C@@H](CO)O%27)O)[C@H]([C@H](O)[C@@H](CO)O%26)O)[C@H]([C@H](O)[C@@H](CO)O%25)O)[C@H]([C@H](O)[C@@H](CO)O%24)O)[C@H]([C@H](O)[C@@H](CO)O%23)O)[C@H]([C@H](O)[C@@H](CO)O%22)O)[C@H]([C@H](O)[C@@H](CO)O%21)O)[C@H]([C@H](O)[C@@H](CO)O%20)O)[C@H]([C@H](O)[C@@H](CO)O%19)O)[C@H]([C@H](O)[C@@H](CO)O%18)O)[C@H]([C@H](O)[C@@H](CO)O%17)O)[C@H]([C@H](O)[C@@H](CO)O%16)O)[C@H]([C@H](O)[C@@H](CO)O%15)O)[C@H]([C@H](O)[C@@H](CO)O%14)O)[C@H]([C@H](O)[C@@H](CO)O%13)O)[C@H]([C@H](O)[C@@H](CO)O%12)O)[C@H]([C@H](O)[C@@H](CO)O%11)O)[C@H]([C@H](O)[C@@H](CO)O%10)O)[C@H]([C@H](O)[C@@H](CO)O9)O)[C@H]([C@H](O)[C@@H](CO)O8)O)[C@H]([C@H](O)[C@@H](CO)O7)O)[C@H]([C@H](O)[C@@H](CO)O6)O)[C@H]([C@H](O)[C@@H](CO)O5)O)[C@H]([C@H](O)[C@@H](CO)O4)O)[C@H]([C@H](O)[C@@H](CO)O3)O)[C@H]([C@H](O)[C@@H](CO)O2)O)[C@@H](O)[C@H](O)[C@@H](CO)O1 JYJIGFIDKWBXDU-MNNPPOADSA-N 0.000 claims description 6
- 229940029339 inulin Drugs 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000008107 starch Substances 0.000 claims description 6
- 235000019698 starch Nutrition 0.000 claims description 6
- 241000609240 Ambelania acida Species 0.000 claims description 5
- 239000010905 bagasse Substances 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 235000000346 sugar Nutrition 0.000 claims description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000010902 straw Substances 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 229920002488 Hemicellulose Polymers 0.000 claims description 3
- 238000004566 IR spectroscopy Methods 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 235000019353 potassium silicate Nutrition 0.000 claims description 3
- 150000008163 sugars Chemical class 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 150000007529 inorganic bases Chemical class 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- 150000007522 mineralic acids Chemical group 0.000 claims description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 150000007530 organic bases Chemical class 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 1
- 235000019253 formic acid Nutrition 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000011949 solid catalyst Substances 0.000 abstract description 2
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 27
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 4
- 235000011613 Pinus brutia Nutrition 0.000 description 4
- 241000018646 Pinus brutia Species 0.000 description 4
- 240000008042 Zea mays Species 0.000 description 4
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 4
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 4
- YAIQCYZCSGLAAN-UHFFFAOYSA-N [Si+4].[O-2].[Al+3] Chemical compound [Si+4].[O-2].[Al+3] YAIQCYZCSGLAAN-UHFFFAOYSA-N 0.000 description 4
- 235000005822 corn Nutrition 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000002119 pyrolysis Fourier transform infrared spectroscopy Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 239000013043 chemical agent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000011534 incubation Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N 2,5-dimethylfuran Chemical compound CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 2
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UHDGCWIWMRVCDJ-CCXZUQQUSA-N Cytarabine Chemical compound O=C1N=C(N)C=CN1[C@H]1[C@@H](O)[C@H](O)[C@@H](CO)O1 UHDGCWIWMRVCDJ-CCXZUQQUSA-N 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 150000002016 disaccharides Chemical class 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 230000002431 foraging effect Effects 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
- 150000004676 glycans Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920001282 polysaccharide Polymers 0.000 description 2
- 239000005017 polysaccharide Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
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- 238000000926 separation method Methods 0.000 description 2
- 239000010907 stover Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- PXJJKVNIMAZHCB-UHFFFAOYSA-N 2,5-diformylfuran Chemical compound O=CC1=CC=C(C=O)O1 PXJJKVNIMAZHCB-UHFFFAOYSA-N 0.000 description 1
- PKAUICCNAWQPAU-UHFFFAOYSA-N 2-(4-chloro-2-methylphenoxy)acetic acid;n-methylmethanamine Chemical compound CNC.CC1=CC(Cl)=CC=C1OCC(O)=O PKAUICCNAWQPAU-UHFFFAOYSA-N 0.000 description 1
- ANJMXIRDWJMCLJ-UHFFFAOYSA-N 2-chloro-1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1C=CN(C)C1Cl ANJMXIRDWJMCLJ-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- COOGPNLGKIHLSK-UHFFFAOYSA-N aluminium sulfide Chemical compound [Al+3].[Al+3].[S-2].[S-2].[S-2] COOGPNLGKIHLSK-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011636 chromium(III) chloride Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000005216 hydrothermal crystallization Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- C07D307/38—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
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- 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
- C07D307/38—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
- C07D307/48—Furfural
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- 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
- C07D307/38—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
- C07D307/48—Furfural
- C07D307/50—Preparation from natural products
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Abstract
The invention relates to the field of catalytic chemistry, and discloses a solid acid catalyst, a preparation method and application thereof, and a method for preparing a furfural compound. The solid acid catalyst has an amorphous structure and has a chemical formula of AlxSiyO(3x+4y)/2Wherein x is 0.25-200: 1. The method for preparing the solid acid catalyst comprises the steps of preparing a silicon source and an aluminum source into dry glue in the presence of a hydrolytic agent, aging the dry glue, and sequentially washing and roasting the aged materials, wherein the molar ratio of the silicon source to the aluminum source is 0.25-200: 1. The method for preparing the furfural compounds comprises the step of subjecting a biomass raw material to intramolecular dehydration reaction in the presence of a solid acid catalyst, a reaction medium and a selectively used promoter. The invention also discloses the application of the solid acid catalyst in catalyzing intramolecular dehydration reaction. The solid catalyst can effectively catalyze the biomass raw material to be converted into the furfural compound, and is environment-friendly and mild in condition.
Description
Technical Field
The invention relates to the field of catalytic chemistry, in particular to a solid acid catalyst, a preparation method thereof and a method for preparing a furfural compound.
Background
Because biomass has the advantages of sustainability, wide sources and the like, research on synthesizing energy and fine chemicals by taking the biomass as a raw material becomes a hotspot in the field of biomass utilization at present. The furfural and 5-hydroxymethyl furfural are important furan compounds and can be used for preparing liquid fuels such as 2-methylfuran, 2, 5-dimethylfuran, long-chain alkane, drug intermediates such as 2, 5-diformylfuran, polyester monomer such as 2, 5-furandicarboxylic acid and the like, so that the furfural and 5-hydroxymethyl furfural are synthesized from biomass and derivatives thereof through dehydration reaction, and the method is an important way for efficiently utilizing biomass.
At present, inorganic liquid acid is generally used as a catalyst in reactions for synthesizing furfural and 5-hydroxymethylfurfural by dehydrating biomass or derivatives thereof, and the problems of difficult product separation, serious equipment corrosion, environmental pollution and the like exist. The research finds that the ionic liquid chloro-1-methyl-3-ethylimidazole is used as a reaction medium to convert glucose into 5-Hydroxymethylfurfural (HMF), and the HMF yield of 70 percent can be obtained (Science,2007,316,1597); when transforming corn stalks, rice straws and pine wood, the yield of 5-hydroxymethylfurfural and the yield of furfural are 45-52% and 23-31%, respectively (Tetrahedron Letters,2009,50, 5403). However, the cost of the ionic liquid is too high at present, and most of the catalysts used are CrCl3And chromium is a serious pollution to the environment, so that the industrial application thereof is greatly limited.
Disclosure of Invention
The invention aims to overcome the defects of complex operation and strict requirements on conditions in the prior art, and provides a solid acid catalyst suitable for preparing a furfural compound more conveniently, a preparation method thereof and a method for preparing the furfural compound.
The present inventors have conducted extensive studies in order to achieve the above object and as a result, have found that the use of a solid acid catalyst of silicon aluminum oxide having specific physicochemical properties is effective for catalyzing dehydration of a biomass raw material, and therefore, in a first aspect, the present invention provides a solid acid catalyst having an amorphous structure and a chemical formula of AlxSiyO(3x+4y)/2Wherein y and x are each independently a positive integer and y: x is 0.25-200: 1.
In a second aspect, the present invention provides a method of preparing a solid acid catalyst, the method comprising: preparing a silicon source and an aluminum source into dry glue in the presence of a hydrolytic agent, aging the dry glue, and sequentially washing and roasting the aged materials, wherein the molar ratio of the silicon source to the aluminum source is 0.25-200:1, the silicon source is calculated by silicon element, and the aluminum source is calculated by aluminum element.
In a third aspect, the present invention provides a solid acid catalyst produced by the method of the second aspect.
In a fourth aspect, the present invention provides a method for preparing a furfural compound represented by formula I, which comprises: subjecting the biomass feedstock to an intramolecular dehydration reaction in the presence of a solid acid catalyst, a reaction medium and optionally a promoter, the solid acid catalyst being as described in the first and/or third aspect,
in the formula I, R is hydrogen or hydroxymethyl.
In a fifth aspect, the present invention provides the use of a solid acid catalyst according to the first and/or third aspect for catalysing an intramolecular dehydration reaction.
The solid catalyst provided by the invention can effectively catalyze the biomass raw material to be converted into the furfural compound, so that the method for preparing the furfural compound is environment-friendly, mild in condition and low in cost, and overcomes the defects of high requirement on reaction equipment, difficulty in product separation, difficulty in catalyst recycling, environmental pollution and the like in the prior art.
In addition, the silicon-aluminum oxide solid acid catalyst is prepared by a dry gel conversion method under the condition of not using a template agent, and compared with a common hydrothermal crystallization method, the dry gel conversion method has the advantages of high yield, less waste materials, simple flow, convenience, easiness in operation and the like, more importantly, the complicated step of separating a product from a mother solution can be omitted, the two-phase separation operation is effectively avoided, and the waste liquid discharge is reduced.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a temperature programmed desorption analysis (NH) of ammonia gas from a solid acid catalyst obtained according to an embodiment of the present invention3TPD) results.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In a first aspect, the present invention provides a solid acid catalyst having an amorphous structure and a chemical formula of AlxSiyO(3x+4y)/2Wherein y and x are each independently a positive integer and y: x is 0.25-200:1, preferably y: x is 40-60: 1.
Preferably, the acid amount of the solid acid catalyst is above 0.3mmol/g, more preferably 0.4-0.6mmol/g (e.g., 0.4mmol/g, 0.45mmol/g, 0.5mmol/g, 0.55mmol/g, 0.6mmol/g or any value therebetween).
Preferably, the specific surface area of the solid acid catalyst is 750m2More preferably 770-850m2G (e.g. 770 m)2/g、780m2/g、790m2/g、800m2/g、810m2/g、820m2/g、830m2/g、840m2/g、850m2/g or any value in between the foregoing values).
Preferably, the solid acid catalyst has an average pore diameter in the range of 2.3 to 3.5nm, more preferably 2.8 to 3nm (2.8nm, 2.85nm, 2.9nm, 2.95nm, 3nm or any value in between the foregoing values).
Wherein the acid amount is determined by NH3-TPD measurement; specific surface area by N2Measuring by an absorption and desorption method; the average pore diameter was determined by the BJH (Barrett-Joyner-Halenda) model method.
Preferably, pyridine adsorption infrared spectroscopy (Py-FTIR) shows that the ratio between the amount of L acid and the amount of B acid of the solid acid catalyst is 0.05 to 50:1 (e.g., 0.05:1, 0.1:1, 0.5:1, 1:1, 5:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, 50:1, or any value therebetween), preferably 0.1 to 5: 1. the amounts of L-acid and B-acid can be calculated according to the literature (Catal. Commun.,2008,9, 1959-. Py-FTIR results were measured using a Nicolet Model 710 Infrared spectrometer, USA, at 100 deg.C (or 200 deg.C or 400 deg.C). The specific operation steps can be as follows: drying 50mg of catalyst under an infrared lamp, grinding the catalyst into powder, transferring the powder into a tabletting machine, tabletting to obtain a round slice, and then putting the slice into a sample groove; pumping the sample tank to a high vacuum state, pretreating the sample slice for 2 hours, and removing water and other impurities adsorbed by the sample; then, cooling the sample to room temperature (25 ℃), recording the infrared spectrum of the sample after pretreatment at the moment as a background, and introducing pyridine vapor at the room temperature until the sample is saturated in adsorption (when the infrared spectrogram does not change any more, the sample is considered to be saturated in adsorption); the sample was gradually warmed to 100 ℃ (or 200 ℃ or 400 ℃) and held at that temperature for 1 hour, at which time the infrared spectrum of the sample was recorded.
Preferably, NH3The TPD analysis also shows that the absorption peak area of the solid acid catalyst in the range of 100-200 ℃ accounts for 15-50% of the total area of the broad peak in the range of 100-700 ℃, the absorption peak area in the range of 200-400 ℃ accounts for 30-70% of the total area of the broad peak in the range of 100-700 ℃, and the absorption peak area in the range of 400-700 ℃ accounts for 5-40% of the total area of the broad peak in the range of 100-700 ℃. More preferably, NH3TPD analysis shows that the absorption peak area of the solid acid catalyst in the range of 100-200 ℃ accounts for 20-40% (such as 20%, 25%, 28%, 30%, 32%, 35%, 40% or any value between the aforementioned values) of the total area of the broad peak in the range of 100-700 ℃, the absorption peak area in the range of 200-400 ℃ accounts for 40-60% (such as 40%, 45%, 50%, 55%, 60% or any value between the aforementioned values) of the total area of the broad peak in the range of 100-700 ℃, and the absorption peak area in the range of 400-700 ℃ accounts for 10-30% (such as 10%, 15%, 18%, 20%, 22%, 25%, 28%, 30% or any value between the aforementioned values) of the total area of the broad peak in the range of 100-700 ℃. Wherein, the percentage of the absorption peak area of the solid acid catalyst in the ranges of 100-200 ℃, 200-400 ℃ and 400-700 ℃ to the total broad peak area in the range of 100-700 ℃ respectively reflects the contents of the weak acid, the medium acid and the strong acid in the solid acid catalyst.
NH3The specific operating steps of the TPD may be: the catalyst sample was placed in a U-shaped quartz tube at 45mL/min N2At 10 ℃ min under atmosphere-1The temperature rising rate of (A) is increased from room temperature to 500 ℃, and the pretreatment is carried out for 1 hour at the temperature; after the pretreatment is finished, the temperature is reduced to 50 ℃ and kept constant, and N is introduced2/NH3Pre-adsorbing the gas (9: 1), keeping the gas adsorbed at the temperature for 45min, and after the adsorption is finished, raising the temperature to 90 ℃ to ensure that NH is physically adsorbed on the surface of the catalyst3The desorption is clean, the bridge opening current is used for walking the base line, and after the base line is stably walked, the temperature is 10 ℃ per minute-1The temperature rise rate of the temperature sensor is increased from 90 ℃ to 500 ℃, and NH is synchronously collected at 110 ℃ by a TCD detector3The signal of desorption.
The solid acid catalyst of the present invention converts glucose to 5-hydroxymethylfurfural in a yield of 15 to 60% (e.g., 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 52%, 55%, 56%, 57%, 58%, 59%, 60%, or any value therebetween), wherein the yield of 5-hydroxymethylfurfural is 5-hydroxymethylfurfural/glucose × 100%. The solid acid catalyst of the present invention converts xylose to furfural in a yield of 25-75% (e.g., 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 62%, 65%, 68%, 70%, 71%, 72%, 73%, 74%, 75%, or any value therebetween), wherein the yield of furfural is furfural/xylose molar amount × 100%. The test conditions for the above yields include: adding 0.5g of glucose or xylose into 10ml of mixed solution of methyl isobutyl ketone and potassium chloride saturated aqueous solution in a volume ratio of 7:3, adding 0.1g of solid acid catalyst, charging nitrogen, heating to 160 ℃, cooling a reaction system to 25 ℃ after reacting for 3 hours, separating out the solid acid catalyst, analyzing the obtained liquid phase by using a high performance liquid chromatography, and calculating the yield of 5-hydroxymethylfurfural or furfural.
Preferably, the solid acid catalyst has the chemical formula Al2Si100O203The acid amount is 0.4mmol/g, and the specific surface area is 770m2(ii)/g, average pore diameter of 2.8nm, weight ratio of weak acid, medium strong acid and strong acid of 3:4:3, ratio of L acid amount and B acid amount of 5:1, yield of conversion of xylose to furfural of 73.2%, and yield of conversion of glucose to 5-hydroxymethylfurfural of 58.6%.
In a second aspect, the present invention provides a method of preparing a solid acid catalyst comprising: preparing a silicon source and an aluminum source into dry glue in the presence of a hydrolytic agent, aging the dry glue, and sequentially washing and roasting the aged materials, wherein the molar ratio of the silicon source to the aluminum source is 0.25-200:1 (preferably 40-60:1), the silicon source is calculated by silicon element, and the aluminum source is calculated by aluminum element.
The method avoids the use of a template (or aging is carried out in a system without the template), the amorphous solid acid catalyst can be obtained by avoiding the use of the template, and the amorphous solid acid catalyst can obtain higher yield when used for preparing furfural compounds in a catalytic manner.
In the second aspect, the method of preparing the dry glue may be performed according to a conventional manner, for example, the method of preparing the dry glue may include: mixing a silicon source, an aluminum source, a hydrolytic agent and water, and sequentially incubating and drying the obtained mixture under the condition of stirring. After drying, grinding can be carried out to obtain dry glue powder with smaller particle size (such as 1-2 mm). Wherein, the silicon source, the aluminum source and the water are firstly mixed uniformly, and then the hydrolytic agent is added and mixed uniformly for incubation. The temperature of incubation may be 20-50 ℃. The incubation time may be 10-20 h.
In the second aspect, the amount and kind of the hydrolyzing agent are not particularly limited. Preferably, the weight ratio of the hydrolytic agent to the silicon source is 0.1-0.4: 1. the hydrolytic agent can be various acidic substances or alkaline substances which are easily dissolved in water (the solubility in water at 20 ℃ is more than or equal to 10g/100g of water). Preferably, the hydrolytic agent is an inorganic acid and/or an organic acid (C1-C10), or an inorganic base and/or an organic base (C1-C10), more preferably HCl, H2SO4、HNO3、CH3At least one of COOH and oxalic acid, or at least one of NaOH, KOH, triethylamine, ethylenediamine, and tetramethylethylenediamine.
In the second aspect, the silicon source may be various silicon-containing substances (or substances capable of providing silicon) conventionally used in the art for preparing silicon aluminum oxide, for example, at least one of silicon ester (C1-C10, such as ethyl orthosilicate), silicon oxide (which may be provided in the form of silica sol or silica white), silicate (such as sodium silicate). Preferably, the silicon source is at least one of tetraethoxysilane, silica sol, water glass and white carbon black, and more preferably tetraethoxysilane.
In the second aspect, the aluminum source may be various aluminum-containing materials (or materials capable of providing aluminum) conventionally used in the art for preparing a silicon aluminum oxide, for example, at least one of inorganic aluminum salts (such as aluminum sulfate, aluminum trichloride, aluminum sulfide), organic aluminum salts (C1-C10, such as aluminum isopropoxide), aluminum hydroxide and aluminum oxide. Preferably, the aluminum source is at least one of aluminum isopropoxide, pseudo-boehmite, aluminum trichloride and aluminum sulfate, more preferably aluminum isopropoxide.
In a second aspect, aging is a process of setting (standing at a temperature for a period of time) the dry gel. The conditions of the aging may be conventional in the art. Preferably, the aging temperature is 100-300 ℃, and the aging time is 50-100 h. Calcination is a process that converts (at high temperature) silicon and aluminum to the oxide form. The conditions for the calcination may be conventional in the art. Preferably, the roasting temperature is 300-800 ℃ (preferably 450-550 ℃), and the roasting time is 3-100 h.
In the second aspect, according to the most preferred embodiment, the hydrolysis agent is triethylamine, the molar ratio of the silicon source to the aluminum source is 40-60:1, the silicon source is tetraethoxysilane, the aluminum source is aluminum isopropoxide, and the calcination temperature is 450-550 ℃. The solid acid catalyst produced according to the preferred embodiment has higher catalytic efficiency.
In the second aspect, there is no particular requirement for the manner of washing or the like, as long as the hydrolyzing agent in the aged material can be removed to make it neutral. The washing agent may be water, and the washing method is well known to those skilled in the art and will not be described herein.
In a third aspect, the present invention provides a solid acid catalyst made by the method of the second aspect. The acid amount, specific surface area, average pore diameter, and the like of the solid acid catalyst prepared by the method of the second aspect are as described above and are not described in detail.
In a fourth aspect, the invention provides a method for preparing a furfural compound shown as the formula I, which comprises the following steps: subjecting the biomass feedstock to an intramolecular dehydration reaction in the presence of a solid acid catalyst, a reaction medium and optionally a promoter, the solid acid catalyst being as described in the first and/or third aspect,
in the formula I, R is hydrogen or hydroxymethyl.
In the fourth aspect, the amount of the solid acid catalyst used is not particularly limited, and is preferably 100-200g per kg of the biomass raw material.
In the fourth aspect, there is no particular requirement for the choice of the reaction medium, and various organic solvents (e.g., C2-C10) which do not participate in the intramolecular dehydration reaction may be used. The reaction medium is used in an amount of 10 to 25L per kg of biomass feedstock. Preferably, the reaction medium is an organic solvent more polar than heptane (e.g., C3-C7), such as hexane, toluene, acetone, 1, 4-dioxane, 1-butanol, 2-butanol, tetrahydrofuran, and methyl isobutyl ketone (CH)3COCH2CH(CH3)2) At least one of (1). More preferably, the reaction medium is an organic solvent with a polarity between that of chloropropane and acetone (e.g., C4-C6), such as at least one of 1, 4-dioxane, 2-butanol, tetrahydrofuran, and methyl isobutyl ketone, most preferably methyl isobutyl ketone.
In the fourth aspect, the promoter is a selectively used substance, and when the promoter is used, the intramolecular dehydration reaction is more complete, and the yield of the product is higher. The choice of the accelerator is not particularly limited, and may be various conventional substances capable of accelerating intramolecular dehydration reaction, such as a solution capable of binding water. Preferably, the amount of the accelerator is 1 to 20L per kg of biomass raw material. Preferably, the accelerator is a saturated aqueous solution of an inorganic salt, more preferably at least one of a saturated aqueous solution of potassium chloride, a saturated aqueous solution of sodium chloride, a saturated aqueous solution of lithium chloride, a saturated aqueous solution of potassium sulfate, and a saturated aqueous solution of sodium sulfate.
In the fourth aspect, the conditions for the intramolecular dehydration reaction generally include: the inert atmosphere is at the temperature of 100 ℃ and 300 ℃ for 1-100 h. The gas for providing the inert atmosphere may be a conventional inert gas such as nitrogen, helium, argon, and the like.
The solid acid catalyst of the present invention has activity of isomerizing and intramolecular dehydrating various sugars, and therefore, in the fourth aspect, in order to obtain the furfural-based compound represented by formula I, the biomass raw material may be various raw materials containing sugars (monosaccharides, disaccharides, or polysaccharides) which may be glucose, fructose, xylose, or the like; the disaccharide can be sucrose and the like; the polysaccharide can be inulin, starch, cellulose, hemicellulose, etc. The biomass raw material can also be various biomass wastes (such as straws, seed shells and the like). Preferably, the biomass feedstock is provided from at least one of glucose, fructose, sucrose, inulin, starch, xylose, cellulose, hemicellulose, bagasse, straw, seed hulls, and woody material, more preferably fructose and/or sucrose.
According to one embodiment of the invention, the method for preparing the furfural compound shown in the formula I comprises the following steps: (1) preparing a solid acid catalyst according to the method of the second aspect (as described above and not described herein); (2) subjecting the biomass feedstock to an intramolecular dehydration reaction in the presence of the solid acid catalyst, a reaction medium and optionally a promoter. According to the most preferred embodiment, the hydrolysis agent is triethylamine, the molar ratio of the silicon source to the aluminum source is 40-60:1, the silicon source is tetraethoxysilane, the aluminum source is aluminum isopropoxide, the roasting temperature is 450-550 ℃, the biomass raw material is fructose and/or sucrose, and the reaction medium is methyl isobutyl ketone.
In a fifth aspect, the present invention provides the use of a solid acid catalyst according to the first and/or third aspect in catalysing an intramolecular dehydration reaction. In a preferred embodiment of the invention, the solid acid catalyst is capable of achieving yields of up to 58.6% when catalyzing the conversion of glucose to 5-hydroxymethylfurfural; the yield of up to 75.3 percent can be obtained when the fructose is catalyzed and converted into the 5-hydroxymethylfurfural; yields as high as 73.2% can be obtained when catalyzing the conversion of xylose to furfural; when the sucrose is catalyzed, the yield of the 5-hydroxymethylfurfural can reach 42.9 percent.
In the following examples, the yield of 5-hydroxymethylfurfural (or furfural) in the product is the molar amount of 5-hydroxymethylfurfural (or furfural) in the product/the molar amount of the raw material X100% in the process in which sugar (such as glucose, fructose, sucrose, inulin, starch and cellulose) is directly used as the biomass raw material, the yield of 5-hydroxymethylfurfural (or furfural) in the product is the weight of 5-hydroxymethylfurfural (or furfural) in the product/the weight of the raw material X100% in the process in which biomass waste (such as bagasse, corn stover, pine) is used as the biomass raw material, silica sol, water glass, white carbon, pseudo-boehmite, inulin and starch are available from the pharmaceutical industry chemical agents limited, cellulose is available from the arabitin chemical agents limited, bagasse, corn stover and pine are all obtained from yunnan, X-ray diffraction (XRD) is used in siens 5-X diffraction (X-ray diffraction) 5 mA, the aluminum source is used as the aluminum source, the yield of 5-hydroxymethylfurfural (or furfural) in the product/the weight of the raw material X-ray diffraction (or furfural) is obtained from the arabitin chemical agents limited, the X-ray diffraction (XRD) is obtained from the siens X-ray diffraction (XRD) and the X-ray diffraction (X) is obtained by the XRD X-ray scanning test, the measurement is carried out on the test, the test is carried out on the Cu-ray diffraction instrument, the test is carried;
acid amount analysis by ammonia temperature programmed desorption (NH)3TPD), the specific operating steps are as follows: the catalyst sample was placed in a U-shaped quartz tube at 45mL/min N2At 10 ℃ min under atmosphere-1The temperature rising rate of (2) was increased from room temperature to 500 ℃ and the pretreatment was carried out at this temperature for 1 hour. After the pretreatment is finished, the temperature is reduced to 50 ℃ and kept constant, and N is introduced2/NH3Pre-adsorbing the gas (9: 1), keeping the gas adsorbed at the temperature for 45min, and after the adsorption is finished, raising the temperature to 90 ℃ to ensure that NH is physically adsorbed on the surface of the catalyst3The desorption is clean, the bridge opening current is used for walking the base line, and after the base line is stably walked, the temperature is 10 ℃ per minute-1The temperature rise rate of the temperature sensor is increased from 90 ℃ to 500 ℃, and NH is synchronously collected by a TCD detector (110℃)3A signal of desorption;
the specific surface area and the average pore diameter are measured on an ASAP2405 static nitrogen adsorption instrument of Micromeritics, firstly, a sample is pretreated under the vacuum condition of 180 ℃, after the pretreatment, the analysis is carried out at the liquid nitrogen temperature (77K), nitrogen is used as an adsorbate, the pore structure and the specific surface area of the catalyst are measured, and the average pore diameter of the catalyst is calculated by adopting a BJH method.
Examples 1 to 23
The solid acid catalyst was prepared according to the following method:
and weighing a silicon source and an aluminum source in a pp bottle, and magnetically stirring for 1 hour to obtain a solution A. Then adding a hydrolytic agent (the weight ratio of the hydrolytic agent to the silicon source is 0.2: 1) and deionized water into the solution A, and stirring for 40 minutes. Then the bottle cap is opened, the mixture is stirred for 12 hours in an oil bath pan with constant temperature (35 ℃), and finally the obtained material is put into an oven to be dried overnight; grinding to fine powder to obtain dry glue. Putting the dry glue into a PTFE container with a small hole, putting the container into a crystallization kettle, adding a small amount of water into the bottom of the crystallization kettle, screwing a kettle cover, and putting the crystallization kettle into a constant-temperature oven at 160 ℃ for aging for 72 hours. And then taking out, carrying out suction filtration and washing to neutrality, drying a filter cake (100 ℃, 12 hours), and then placing the filter cake in a muffle furnace for roasting for 5 hours to obtain the solid acid catalyst (the silicon source, the aluminum source, the silicon-aluminum ratio, the hydrolysis agent, the roasting temperature and the like are shown in table 1, and partial physicochemical parameter characterization results of each solid acid catalyst are shown in table 2). Example 1 the solid acid catalyst obtained was reacted with NH3The results of the TPD measurement are shown in FIG. 1, and it can be seen from FIG. 1 that the solid acid catalyst of the present invention has weak acid, medium strong acid and strong acid, in which the weak acid and the medium strong acid are dominant and a small amount of strong acid (the weight ratio of weak acid, medium strong acid and strong acid is 3:4: 3). The results of Py-FTIR measurement of the solid acid catalyst obtained in example 1 showed that the solid acid catalyst was mainly based on L acid with a small amount of B acid (ratio between the amount of L acid and the amount of B acid is 5: 1), and this acid distribution facilitated the isomerization of glucose to fructose and thus the entire intramolecular dehydration reaction.
Adding 10ml of mixed solution of methyl isobutyl ketone and saturated aqueous solution of potassium chloride in a volume ratio of 7:3 into a batch reactor, then adding 0.5g of glucose, respectively adding 0.1g of the solid acid catalyst prepared in the previous step, introducing nitrogen, heating to 160 ℃, stirring at constant temperature, reacting for 3 hours, cooling the reaction system to room temperature (25 ℃), and centrifuging to separate the catalyst. And analyzing the reaction liquid by using a high performance liquid chromatograph, and calculating the yield of the 5-hydroxymethylfurfural. The yield of furfural was calculated by replacing glucose with xylose. The results are shown in Table 2.
The conditions for HPLC analysis were as follows:
the reaction mixture was analyzed by HPLC using Agilent model 1200 on an XDB-C18 column (4.5 μm, 250mm, Eclipse USA) thermostatted at 35 ℃. The liquid chromatography was equipped with an Agilent model G1329A autosampler to increase sample reproducibility. Detecting HMF and furfural products generated by the reaction by using an Agilent G1314B type ultraviolet detector (VWD), wherein the ultraviolet wavelength is 254nm, the mobile phase is a mixed solution of methanol and pure water, the volume ratio is 20:80, and the flow rate is 0.6 mL/min-1. Preparing Agilent G1362A type differential refraction detector (RID) and Bio-Rad Aminex HPX-87H sugar column by Agilent 1200 type HPLC chromatography to detect residual xylose and glucose after reaction, wherein the chromatographic column is kept at 80 deg.C, the mobile phase is pure water, and the flow rate is 0.8mL min-1。
TABLE 1
TABLE 2
Comparative example 1
Solid acid catalyst D1 and furfural were prepared in the same manner as in example 1, except that the dry gel was aged in the presence of oxalic acid as a template (used in an amount of 0.2g per gram of dry gel), and the results of characterization of part of physicochemical parameters of the solid acid catalyst and the yields of furfural and 5-hydroxymethylfurfural were measured as shown in table 2 above. NH (NH)3The results of the TPD and Py-FTIR measurements show a weight ratio of weak, medium and strong acid of 2: 1: 7, the ratio of the amount of L acid to the amount of B acid is 1: 2.
examples 24 to 31
Furfural-based compounds were produced in the same manner as in example 1 except that "glucose" was replaced with the biomass materials shown in table 3, respectively, and the yields of furfural and 5-hydroxymethylfurfural were measured as shown in table 3 below.
TABLE 3
| Example numbering | Biomass feedstock | Yield of Furfural (%) | Yield of 5-hydroxymethylfurfural (%) |
| 24 | Fructose | 0 | 75.3 |
| 25 | Sucrose | 3.2 | 42.9 |
| 26 | Inulin | 0.9 | 55.2 |
| 27 | Starch | 0 | 40.8 |
| 28 | Bagasse | 12.7 | 17.2 |
| 29 | Corn stalk | 11.2 | 14.9 |
| 30 | Pine wood | 12.9 | 10.5 |
| 31 | Cellulose, process for producing the same, and process for producing the same | 0.8 | 38.8 |
Examples 32 to 40
Furfural compounds were produced in the same manner as in example 1 except that "methyl isobutyl ketone" was replaced with the reaction medium shown in table 4, respectively, and the yields of furfural and 5-hydroxymethylfurfural were measured as shown in table 4 below.
TABLE 4
Examples 41 and 42
Solid acid catalysts 41 to 42 and furfural-based compounds were prepared in the same manner as in example 1, except that the weight ratio of the hydrolysis agent to the silicon source, the temperature and time for aging, the calcination time, the amount of the solid acid catalyst used, and the temperature and time for dehydration were carried out as shown in table 5 below. The results of characterization of physicochemical parameters of the solid acid catalyst and the yields of furfural and 5-hydroxymethylfurfural were measured as shown in table 5 below.
TABLE 5
From the above examples and comparative examples, it can be seen that the solid acid catalyst of the present invention can effectively catalyze the conversion of biomass raw material into furfural compounds.
In particular, from the results of example 1 and examples 2-23, it can be seen that a solid acid catalyst with more excellent performance can be obtained by adopting the preferred embodiment mode of the invention, and the yield of the catalytic biomass raw material converted into the furfural compound is higher.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (22)
1. A solid acid catalyst, characterized in that the solid acid catalyst has an amorphous structure and has a chemical formula of AlxSiyO(3x+4y)/2Wherein y and x are each independently a positive integer and y: x =40-60:1, the acid amount of the solid acid catalyst is 0.3mmol/g or more, and the specific surface areaAt 750m2(ii)/g or more, the average pore diameter is in the range of 2.3 to 3.5nm, and pyridine adsorption infrared spectrometry shows that the ratio between the L acid amount and the B acid amount of the solid acid catalyst is 0.05 to 50:1, ammonia temperature programmed desorption analysis shows that the absorption peak area of the solid acid catalyst in the range of 100-200 ℃ accounts for 15-50% of the total area of the broad peak in the range of 100-700 ℃, the absorption peak area in the range of 200-400 ℃ accounts for 30-70% of the total area of the broad peak in the range of 100-700 ℃, and the absorption peak area in the range of 400-700 ℃ accounts for 5-40% of the total area of the broad peak in the range of 100-700 ℃.
2. The solid acid catalyst as claimed in claim 1, wherein the acid amount of the solid acid catalyst is 0.4 to 0.6mmol/g, and the specific surface area is 770-850m2(iv)/g, average pore diameter of 2.8-3nm, pyridine adsorption infrared spectroscopy shows that the ratio between the amount of L acid and the amount of B acid in the solid acid catalyst is 0.1-5: 1, ammonia temperature programmed desorption analysis shows that the absorption peak area of the solid acid catalyst in the range of 100-200 ℃ accounts for 20-40% of the total area of the broad peak in the range of 100-700 ℃, the absorption peak area in the range of 200-400 ℃ accounts for 40-60% of the total area of the broad peak in the range of 100-700 ℃, and the absorption peak area in the range of 400-700 ℃ accounts for 10-30% of the total area of the broad peak in the range of 100-700 ℃.
3. A method of preparing the solid acid catalyst of claim 1 or 2, comprising: preparing a silicon source and an aluminum source into dry glue in the presence of a hydrolytic agent, aging the dry glue, and sequentially washing and roasting the aged materials, wherein the molar ratio of the silicon source to the aluminum source is 40-60:1, the silicon source is calculated by silicon element, and the aluminum source is calculated by aluminum element.
4. The method of claim 3, wherein the weight ratio of the hydrolyzing agent to the silicon source is 0.1-0.4: 1; the hydrolytic agent is inorganic acid and/or organic acid, or inorganic base and/or organic base.
5. The method of claim 3, whereinThe hydrolytic agent is HCl and H2SO4、HNO3、HCOOH、CH3At least one of COOH and oxalic acid.
6. The method of claim 3, wherein the hydrolyzing agent is at least one of NaOH, KOH, triethylamine, ethylenediamine, and tetramethylethylenediamine.
7. The method according to claim 3, wherein the silicon source is at least one of tetraethoxysilane, silica sol, water glass and white carbon black; the aluminum source is at least one of aluminum isopropoxide, pseudo-boehmite, aluminum trichloride and aluminum sulfate.
8. The method of claim 3, wherein the silicon source is tetraethyl orthosilicate.
9. The method of claim 3 wherein the aluminum source is aluminum isopropoxide.
10. The method as claimed in any one of claims 3 to 9, wherein the aging temperature is 100 ℃ and 300 ℃, and the aging time is 50 to 100 hours; the roasting temperature is 300-800 ℃, and the roasting time is 3-100 h.
11. The method as claimed in any one of claims 3 to 9, wherein the hydrolysis agent is triethylamine, the molar ratio of the silicon source to the aluminium source is 40-60:1, the silicon source is tetraethoxysilane, the aluminium source is aluminium isopropoxide, and the calcination temperature is 450-550 ℃.
12. A solid acid catalyst obtainable by the process of any one of claims 3 to 11.
13. A method for preparing a furfural compound shown as a formula I is characterized by comprising the following steps: subjecting a biomass feedstock to an intramolecular dehydration reaction in the presence of a solid acid catalyst according to claim 1, 2 or 12, a reaction medium and optionally a promoter,
in the formula I, R is hydrogen or hydroxymethyl.
14. The method as claimed in claim 13, wherein the amount of the solid acid catalyst is 100-200g per kg of the biomass raw material.
15. The process according to claim 13, wherein the reaction medium is used in an amount of 10-25L per kg of biomass feedstock; the reaction medium is an organic solvent with polarity greater than heptane.
16. The process of claim 13, wherein the reaction medium is at least one of hexane, toluene, acetone, 1, 4-dioxane, 1-butanol, 2-butanol, tetrahydrofuran, and methyl isobutyl ketone.
17. The method of claim 13, wherein the promoter is used in an amount of 1-20L per kg of biomass feedstock; the accelerator is a saturated aqueous solution of an inorganic salt.
18. The method of claim 13, wherein the promoter is at least one of a saturated aqueous solution of potassium chloride, a saturated aqueous solution of sodium chloride, a saturated aqueous solution of lithium chloride, a saturated aqueous solution of potassium sulfate, and a saturated aqueous solution of sodium sulfate.
19. The method of any one of claims 13-18, wherein the conditions of the intramolecular dehydration reaction include: the inert atmosphere is at the temperature of 100 ℃ and 300 ℃ for 1-100 h.
20. The method of any of claims 13-18, wherein the biomass feedstock contains sugars.
21. The method of any of claims 13-18, wherein the biomass feedstock is provided from at least one of glucose, fructose, sucrose, inulin, starch, xylose, cellulose, hemicellulose, bagasse, straw, seed hulls, and woody material.
22. Use of the solid acid catalyst of claim 1, 2 or 12 for catalyzing an intramolecular dehydration reaction.
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