CN109985664B - Acidic solid catalyst for one-step method catalysis of fructose conversion into 2, 5-dimethylfuran - Google Patents
Acidic solid catalyst for one-step method catalysis of fructose conversion into 2, 5-dimethylfuran Download PDFInfo
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- CN109985664B CN109985664B CN201910396692.9A CN201910396692A CN109985664B CN 109985664 B CN109985664 B CN 109985664B CN 201910396692 A CN201910396692 A CN 201910396692A CN 109985664 B CN109985664 B CN 109985664B
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- acid
- fructose
- dimethylfuran
- solid catalyst
- acidic
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- GSNUFIFRDBKVIE-UHFFFAOYSA-N 2,5-dimethylfuran Chemical compound CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 title claims abstract description 187
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 105
- 229930091371 Fructose Natural products 0.000 title claims abstract description 89
- 239000005715 Fructose Substances 0.000 title claims abstract description 89
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 title claims abstract description 89
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000011949 solid catalyst Substances 0.000 title claims abstract description 45
- 238000006555 catalytic reaction Methods 0.000 title claims description 5
- 229920000642 polymer Polymers 0.000 claims abstract description 44
- 229910052751 metal Inorganic materials 0.000 claims abstract description 43
- 239000002184 metal Substances 0.000 claims abstract description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 239000000126 substance Substances 0.000 claims abstract description 26
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000003197 catalytic effect Effects 0.000 claims abstract description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 8
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 63
- 239000002253 acid Substances 0.000 claims description 56
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 51
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 239000003960 organic solvent Substances 0.000 claims description 29
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- 238000006297 dehydration reaction Methods 0.000 claims description 20
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims description 19
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 19
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 18
- 238000007327 hydrogenolysis reaction Methods 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 18
- 238000006722 reduction reaction Methods 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 238000002425 crystallisation Methods 0.000 claims description 14
- 230000008025 crystallization Effects 0.000 claims description 14
- 229910052700 potassium Inorganic materials 0.000 claims description 14
- 239000011591 potassium Substances 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000376 reactant Substances 0.000 claims description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 10
- -1 hydrogen siloxane Chemical class 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 10
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 239000003929 acidic solution Substances 0.000 claims description 8
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 claims description 7
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 claims description 7
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 claims description 7
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 6
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- QYZLKGVUSQXAMU-UHFFFAOYSA-N penta-1,4-diene Chemical compound C=CCC=C QYZLKGVUSQXAMU-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 239000013067 intermediate product Substances 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 3
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 3
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052759 nickel Inorganic materials 0.000 abstract description 7
- 229910017052 cobalt Inorganic materials 0.000 abstract description 5
- 239000010941 cobalt Substances 0.000 abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052703 rhodium Inorganic materials 0.000 abstract description 5
- 239000010948 rhodium Substances 0.000 abstract description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000463 material Substances 0.000 description 43
- 238000012360 testing method Methods 0.000 description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- 230000008569 process Effects 0.000 description 11
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 10
- 238000000926 separation method Methods 0.000 description 10
- 230000035484 reaction time Effects 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000002028 Biomass Substances 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000004873 anchoring Methods 0.000 description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 6
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 6
- 239000002685 polymerization catalyst Substances 0.000 description 6
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 5
- 235000019253 formic acid Nutrition 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910002093 potassium tetrachloropalladate(II) Inorganic materials 0.000 description 5
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 description 4
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 4
- 238000005265 energy consumption Methods 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
- 239000011148 porous material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- OXMIDRBAFOEOQT-UHFFFAOYSA-N 2,5-dimethyloxolane Chemical compound CC1CCC(C)O1 OXMIDRBAFOEOQT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000002551 biofuel Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- FJSKXQVRKZTKSI-UHFFFAOYSA-N 2,3-dimethylfuran Chemical compound CC=1C=COC=1C FJSKXQVRKZTKSI-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- 229910003336 CuNi Inorganic materials 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910020427 K2PtCl4 Inorganic materials 0.000 description 1
- 229910002837 PtCo Inorganic materials 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
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- 239000000843 powder Substances 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Substances C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- 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
-
- 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
- C07D307/36—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 only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
-
- 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
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention relates to an acidic solid catalyst for catalyzing fructose to be converted into 2, 5-dimethylfuran by a one-step method, and a preparation method and application thereof. The catalyst is composed of an acidic porous polymer loaded with metal nanoparticles, wherein the porous polymer is a multifunctional polymer, has different wettability and acidity, and can anchor metal ruthenium, platinum, rhodium, palladium, nickel and cobalt under mild conditions. The catalyst is used for one-step catalytic conversion of fructose into 2, 5-dimethylfuran, has excellent catalytic activity, high selectivity and strong stability, and provides a new idea and method for conversion of bio-based into high value-added chemicals.
Description
Technical Field
The invention belongs to the field of bio-based chemicals, and relates to an acidic solid catalyst for catalyzing fructose to be converted into 2, 5-dimethylfuran by a one-step method, and a preparation method and application thereof.
Background
2, 5-Dimethylfuran, the english name being Dimethylfuran. The united states energy center plans to produce 360 billion gallons of secondary biofuels annually in 2022, where 160 billion gallons would be obtained from cellulose, and ethanol obtained from lignin is undoubtedly one of the more reliable options for meeting this requirement. Compared with 2, 5-dimethylfuran, ethanol has higher O/C ratio and lower energy density, and is completely dissolved in water; in addition, the ethanol obtained from the biomass can be separated and distilled with high energy consumption to obtain the ethanol with higher purity, so that the cost of using the ethanol as a gasoline additive is greatly increased, and the ethanol as a second-generation biofuel for replacing petrochemical fuel is seriously limited; compared with ethanol, the 2, 5-dimethylfuran has higher energy density, octane number of 119, lower oxygen/carbon content and lower boiling point; meanwhile, 2, 5-dimethylfuran is insoluble in water, and has high stability, high energy density and water-insoluble property; this has led to an increasing search for fuels that are directed towards 2, 5-dimethylfuran. In addition, 2, 5-dimethylfuran can also generate addition reaction with ethylene to generate p-xylene, which can be further used for producing polyester sheets, polyester hollow containers and the first synthetic fiber polyester fiber in China. It can also be used for producing paint, dye, pesticide, etc. Therefore, the 2, 5-dimethylfuran is worthy of more intensive research and application no matter the 2, 5-dimethylfuran is used as a fuel additive or a precursor of p-xylene.
Production of 2, 5-dimethylfuran on biomass is mainly prepared from 5-Hydroxymethylfurfural (HMF) by hydrogenolysis. Today, either in noble metal catalysts, for example: PtCo/C, Pd-GVL/C, also on non-noble metal catalysts, such as:
/NGr/α-Al2O3and 2, 5-dimethylfuran on CuNi/C can be selected to be more than 95 percent, in addition, the source of 5-hydroxymethylfurfural can also be obtained by sugar dehydration, and the enterprise AVA of Switzerland has realized the scale of producing 20 tons every year in 2014. Therefore, theoretically, the production of 2, 5-dimethylfuran from biomass is an emerging process route which is green, environment-friendly, low in energy consumption and low in pollution.
However, HMF is obtained by dehydration of a saccharide compound and then separation and purification, and its extremely high boiling point causes high separation cost, which is an important factor limiting the process route. Therefore, how to rationally design a new process, realize the series connection of the multi-step catalytic reaction process, avoid the high separation cost of HMF, and improve the yield of the product 2, 5-dimethylfuran is the main problem faced at present.
Disclosure of Invention
The invention aims to solve the technical problem of the prior art and provides an acidic solid catalyst for catalyzing fructose to be converted into 2, 5-dimethylfuran by a one-step method and a preparation method and application thereof. The catalyst is composed of an acidic porous polymer loaded with metal nanoparticles, wherein the porous polymer is a multifunctional polymer, has different wettability and acidity, and can anchor metal ruthenium, platinum, rhodium, palladium, nickel and cobalt under mild conditions. The catalyst is used for one-step catalytic conversion of fructose into 2, 5-dimethylfuran, has excellent catalytic activity, high selectivity and strong stability, and provides a new idea and method for conversion of bio-based into high value-added chemicals.
The invention provides an acidic solid catalyst for catalyzing fructose to be converted into 2, 5-dimethylfuran by a one-step method, which is composed of an acidic porous polymer loaded with metal nano-particles.
In some embodiments of the invention, the wettability of the solid catalyst is between 0 ° and 160 °, preferably between 140 ° and 155 °.
In some embodiments of the invention, the solid catalyst has a B acid content of 0 to 1.0mmol/g, preferably 0.15 to 0.7 mmol/g.
In the present invention, the catalyst has a mesoporous structure.
In the present invention, the metal includes one or more of ruthenium, platinum, rhodium, palladium, nickel and cobalt; preferably one or more of ruthenium, palladium, platinum and nickel.
In a second aspect of the present invention, there is provided a method for preparing a solid catalyst according to the first aspect of the present invention, which comprises:
k, mixing a carbon source, a functional monomer and an organic solvent I and then reacting to prepare a precursor mixed solution of the porous polymer;
step L, performing crystallization treatment on the precursor mixed solution of the porous polymer, and then performing centrifugation, washing and drying to obtain the porous polymer;
step M, carrying out acid exchange treatment on the porous polymer and an acidic solution to obtain an acidic porous polymer;
and step N, mixing the acidic porous polymer and the aqueous solution of the metal salt in a II organic solvent, and then carrying out reduction reaction to prepare the acidic solid catalyst.
In the present invention, the carbon source comprises one or more of 1, 3-butadiene, 1, 4-pentadiene, 1, 5-hexadiene, vinylbenzene and divinylbenzene, and preferably one or more of 1, 4-pentadiene, 1, 5-hexadiene and divinylbenzene.
In the invention, the functional monomer molecules comprise one or more of sodium styrene sulfonate, 1-vinyl pyrrolidone, ethylene glycol dimethacrylate, N' -methylene bisacrylamide, 1-vinyl imidazole and azobisisobutyronitrile.
In the present invention, the first organic solvent comprises one or more of ethyl acetate, methyl acetate, tetrahydrofuran, dimethyl sulfoxide and dioxane, preferably one or more of ethyl acetate, tetrahydrofuran and dimethyl sulfoxide.
According to the method of the present invention, in the precursor mixed solution of the porous polymer, the mass fraction of the carbon source in the precursor mixed solution is 10% to 30%, preferably 15% to 25%.
In some embodiments of the present invention, the functional monomer is present in an amount of 0 to 10% by mass of the precursor mixed solution.
According to the invention, in step K, the reaction is carried out at room temperature for a period of 2 to 4 hours.
In some embodiments of the present invention, in step L, the temperature of the crystallization process is 298K to 423K, preferably 353K to 413K.
In some embodiments of the present invention, in step L, the crystallization time is 6 to 100 hours, preferably 12 to 48 hours.
According to the method of the invention, in step M, the acidic solution is prepared by mixing an acid with a III organic solvent.
In the invention, in the step M, the acid comprises one or more of hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid; further preferably, the acid is hydrochloric acid and/or sulfuric acid.
In the invention, the III organic solvent comprises one or more of methanol, ethanol, propanol, butanol and tetrahydrofuran.
In some embodiments of the invention, the concentration of the acidic solution is from 0.1mol/L to 4mol/L, preferably from 0.5mol/L to 2.5 mol/L.
In some embodiments of the invention, in step M, the acid exchange treatment is performed at room temperature for a period of 24 to 36 hours.
According to the invention, in the step N, the aqueous solution of the metal salt contains the metal simple substance in an amount of 0.005-0.01 g/mL.
In some embodiments of the present invention, in step N, the mass ratio of the elemental metal to the porous polymer in the aqueous solution of the metal salt is (0.04-0.01): 1.
in some embodiments of the invention, in step N, the volume ratio of the aqueous solution of the metal salt to the second organic solvent is (0.01-0.1): 1.
in the invention, the metal salt comprises one or more of ammonium chloroplatinate, potassium chloroplatinate, platinum nitrate, ammonium chloropalladate, palladium nitrate, potassium chlororuthenate, ruthenium nitrate, rhodium chloride, potassium chlororhodate, cobalt nitrate and nickel nitrate, and preferably one or more of ammonium chloroplatinate, potassium chloroplatinate, ammonium chloropalladate, potassium chlororuthenate and nickel nitrate.
In the invention, the II organic solvent comprises one or more of methanol, ethanol, propanol, glycol, isopropanol and glycerol, and preferably methanol and glycerol, ethanol and glycerol or glycol and glycerol.
In some embodiments of the invention, in step N, the temperature of the reduction reaction is 373K to 448K, preferably 373K to 423K.
In some embodiments of the present invention, in step N, the time for the reduction reaction is 2 to 6 hours, preferably 2 to 4 hours.
In a third aspect, the present invention provides an application of the acidic solid catalyst according to the first aspect of the present invention or the acidic solid catalyst prepared by the method according to the first aspect of the present invention in the one-step catalytic conversion of fructose into 2, 5-dimethylfuran, which comprises introducing a hydrogen source into a reactant feed liquid containing the acidic solid catalyst, fructose and an optional iv organic solvent, wherein the fructose undergoes a dehydration reaction under the action of an acidic catalytic site of the acidic solid catalyst to obtain an intermediate product, i.e., 5-hydroxymethylfurfural, and then undergoes a hydrogenolysis reaction to obtain biobased 2, 5-dimethylfuran.
In some embodiments of the invention, the fructose is present in a mass concentration of 0.5% to 10%, preferably 1% to 5%, based on the total mass of the reactant feed solution.
In some embodiments of the present invention, the molar weight ratio of the elemental metal to fructose in the solid catalyst is (0.001-1):1, preferably (0.005-0.2): 1.
In the invention, the hydrogen source comprises one or more of hydrogen, formic acid, acetic acid, polymethoxy hydrogen siloxane and polydimethylsiloxane, and formic acid and/or polymethoxy hydrogen siloxane are/is preferable.
In some embodiments of the invention, the molar weight ratio of the hydrogen source to fructose is (1-10):1, preferably (3-9): 1.
In the invention, the IV organic solvent comprises one or more of methanol, ethanol, propanol, n-butanol and isobutanol, and is preferably propanol and/or n-butanol.
In some embodiments of the invention, the dehydration reaction and hydrogenolysis reaction are at a temperature of 298K to 473K, preferably 353K to 423K.
In some embodiments of the invention, the time for the dehydration reaction and the hydrogenolysis reaction is between 1 and 24 hours, preferably between 2 and 10 hours.
The invention takes a multifunctional copolymer as a framework, regulates the wettability and acidity of the surface of the catalyst by introducing functional monomer molecules, and obtains the catalyst with a large specific surface area and a mesoporous structure after anchoring different metal nano particles, wherein the catalyst is used for directly catalyzing fructose to convert 2, 5-dimethylfuran. The catalyst has extremely high activity, and the direct yield of the 2, 5-dimethylfuran is 94.2 percent, which is far higher than the levels reported by other patents; and the conversion rate and the selectivity of the catalyst to raw materials are reduced within 5 cycles, which shows that the catalyst has excellent stability.
The invention avoids high energy consumption and low efficiency caused by the HMF separation process while efficiently converting the biomass molecular fructose into the 2, 5-dimethylfuran, thereby greatly reducing the cost for producing the bio-based 2, 5-dimethylfuran and providing a new idea and method for converting the bio-based into high value-added chemicals.
Drawings
The invention is described in further detail below with reference to the attached drawing figures:
FIG. 1 shows a reaction pathway scheme for the preparation of 2, 5-dimethylfuran from fructose.
Fig. 2 shows the function and effect of different chemical monomers of the multifunctional porous material of the present invention.
Fig. 3 shows a preparation process and method for anchoring nano-metal on multifunctional porous catalyst in the present invention.
Detailed Description
In order that the invention may be readily understood, a more particular description thereof will be rendered by reference to the appended drawings. However, before the invention is described in detail, it is to be understood that this invention is not limited to particular embodiments described. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to be limiting.
Unless otherwise defined, all terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although any methods and materials similar or equivalent to those described herein can also be used in the practice or testing of the present invention, the preferred methods and materials are now described.
Term (I)
Compared with a multi-step method, the term "one-step method" refers to a method that fructose is converted into 2, 5-dimethylfuran through traditional catalysis, the fructose is firstly converted into HMF through acid catalysis, then separation and purification are carried out, and then hydrogenation is carried out to obtain the 2, 5-dimethylfuran, wherein the term refers to a method that the fructose is directly used as a raw material without separation and purification, and the target product 2, 5-dimethylfuran is obtained through catalytic conversion.
The term "wettability" as used herein refers to the ability of a liquid to remain in contact with a solid surface, which is determined by intermolecular interactions. It is a result of comprehensive balance of intermolecular adhesion and affinity.
The term "hydrophobic" refers to that the material has a certain hydrophobic ability to repel water molecules and molecules with larger polarity, and the material can be easily adsorbed by lipophilic substances or substances with weaker polarity, and "hydrophilic" refers to that the material has a certain hydrophilic ability and a certain affinity to water molecules, and the material is difficult to adsorb by lipophilic substances or substances with weaker polarity.
The term "multifunctional porous polymeric material" as used herein refers to a polymeric material having different wettability and acidity by introducing different chemical monomers into the backbone of the polymeric material.
The term "mesoporous structure" as used herein, also referred to as mesoporous structure, refers to a porous structure having a pore size of 2 to 50 nm.
The term "acid site" as used herein refers to a catalytically active acid site, also referred to as an acid center or acid site, present on the solid surface of a solid acid catalyst.
The term "anchoring" means that metal ions and a functional monomer containing nitrogen on the multifunctional porous polymeric material are subjected to a complex reaction and are simultaneously reduced in situ in an alcohol solution so as to be loaded on the functional porous polymeric material; meanwhile, part of metal ions can directly fall into the multifunctional porous polymer material after in-situ reduction. The term "B acid" as used herein refers to Bronsted acid, and refers to B acid, wherever a proton is donated.
The term "water" as used herein means deionized water, distilled water or ultrapure water unless otherwise specified or limited.
The term "optional" as used herein means that optional ingredients may or may not be added.
Embodiments II
As previously mentioned, the current production of 2, 5-dimethylfuran on biomass is mainly prepared from 5-Hydroxymethylfurfural (HMF) by hydrogenolysis. However, HMF is obtained by dehydration of a saccharide compound and then separation and purification, and its extremely high boiling point causes high separation cost, which is an important factor limiting the process route. For this reason, the present inventors have conducted extensive studies on a process for producing 2, 5-dimethylfuran based on biomass.
The reaction process for converting fructose into 2, 5-dimethylfuran in one step is shown in FIG. 1. As can be seen from the figure I, fructose is subjected to dehydration reaction under acidic condition, HMF is firstly obtained, and then the HMF and a hydrogen source are subjected to hydrogenation reaction to obtain 2, 5-dimethylfuran under the action of a hydrogenation reaction center, so that the requirements on the catalyst are 1) acidity; 2) having a hydrogenation site.
As shown in fig. 1, there are three main types of side reactions that catalyze the conversion of fructose: 1) HMF can carry out hydrolysis, polymerization and esterification reaction at an acid site; 2)2, 5-dimethylfuran is hydrolyzed to generate 2, 5-hexanedione, and the 2, 5-hexanedione is subjected to hydrogenation reaction; 3) and (3) carrying out excessive hydrogenation reaction on the 2, 5-dimethylfuran to generate the 2, 5-dimethyltetrahydrofuran.
Based on the characteristics of the side reaction of the above system, the existing reported catalyst and catalytic system have the following problems: the yield of the 2, 5-dimethylfuran is more than 75 percent; severe hydrolysis side reactions, hydrogenation by-products and intermediates are present; the intermediate product HMF needs to be separated and hydrogenated after purification, so that the energy consumption is high and the cost is high.
In view of the above, the inventors hope to prepare a multifunctional catalyst, which can avoid the separation process of HMF while obtaining the target product 2, 5-dimethylfuran with high selectivity, and realize a one-step method for obtaining 2, 5-dimethylfuran from fructose by catalytic conversion.
The inventor researches and discovers that the process path of fructose catalytic conversion of 2, 5-dimethylfuran can be regulated and controlled by regulating and controlling the wettability of the surface of the catalyst, so that related side reactions are avoided, and the selectivity of a target product 2, 5-dimethylfuran is improved.
As shown in the second figure, the inventor researches and discovers that by selecting divinylbenzene as a framework, the porous polymer can have different wettability, acidity and metal anchoring capability by introducing different functional monomers (one or more of sodium styrene sulfonate, 1-vinyl pyrrolidone, ethylene glycol dimethacrylate, N' -methylene bisacrylamide, 1-vinyl imidazole and azodiisobutyronitrile). The N, N' -methylene bisacrylamide and ethylene glycol dimethacrylate can be used for changing the wettability of the surface of the catalyst, the sodium styrene sulfonate is responsible for providing an acid site, the 1-vinyl imidazole and the 1-vinyl pyrrolidone can complex metal, and the azobisisobutyronitrile is used as an initiator. The preparation path diagram is shown in figure three, and the acid crosslinking is sequentially carried out on the prepared multifunctional porous polymer carrier; and anchoring the hydrogenation metal in an alcohol solution; after reduction; a porous polymerization catalyst having multiple functions can be obtained.
The research of the invention finds that the multifunctional porous polymerization catalyst is used for catalyzing fructose to catalytically convert 2, 5-dimethylfuran, and after the surface wettability of the catalyst is regulated, the hydrophobic porous polymerization catalyst realizes 95% yield of the 2, 5-dimethylfuran, which is far higher than the levels reported in other documents, has good stability and can be recycled for multiple times.
Therefore, the hydrophobic nano metal-loaded multifunctional porous polymeric material designed by the inventor meets the requirement of high selectivity on 2, 5-dimethylfuran, avoids extra high cost caused by HMF separation and purification steps while avoiding relevant hydrolysis reaction to the maximum extent, and in addition, the liquid hydrogen source polymethylhydrosiloxane is selected to replace the traditional gaseous hydrogen source hydrogen as the main hydrogen source, so that the reaction safety is improved, and the hydrophobic nano metal-loaded multifunctional porous polymeric material has great application value.
The present invention has been made based on the above findings.
To this end, the invention relates in a first aspect to an acidic solid catalyst for the one-step catalytic conversion of fructose to 2, 5-dimethylfuran, consisting of an acidic porous polymer loaded with metal nanoparticles; the metal nanoparticles are loaded on the surface of the acidic porous polymer in an anchoring mode, and the acidic porous polymer is a multifunctional porous polymer material with different wettability and acidity.
The acidic solid catalyst has the following characteristics:
(1) the wettability of the solid catalyst is adjustable within 0-160 degrees, preferably 140-155 degrees; the content of B acid in the solid catalyst is 0-1.0mmol/g, preferably 0.15-0.7 mmol/g.
(2) The acidic solid catalyst may have different acidity and is mainly
Acid, wherein the content of the B acid in the solid catalyst is 0-1.0mmol/g, preferably 0.15-0.7 mmol/g.
(3) The acidic solid catalyst has a mesoporous structure.
(4) The multifunctional porous polymeric material may be anchored with a metal comprising one or more of ruthenium, platinum, rhodium, palladium, nickel and cobalt; preferably one or more of ruthenium, palladium, platinum and nickel.
It will be understood by those skilled in the art that the multifunctional porous polymeric material or multifunctional porous polymer mentioned above means that the porous material or porous polymer may have different wettability and acidity, and thus an acidic solid catalyst having different wettability and acidity is obtained, and that the catalyst has different catalytic functions or properties.
The second aspect of the present invention relates to a method for producing a solid catalyst according to the first aspect of the present invention, comprising:
k, mixing a carbon source, a functional monomer and an organic solvent I and then reacting to prepare a precursor mixed solution of the porous polymer;
step L, performing crystallization treatment on the precursor mixed solution of the porous polymer, and then performing centrifugation, washing and drying to obtain the porous polymer;
step M, carrying out acid exchange treatment on the porous polymer and an acidic solution to obtain an acidic porous polymer;
and step N, mixing the acidic porous polymer and the aqueous solution of the metal salt in a II organic solvent, and then carrying out reduction reaction to prepare the acidic solid catalyst.
In step K:
(1) the carbon source comprises one or more of 1, 3-butadiene, 1, 4-pentadiene, 1, 5-hexadiene, vinylbenzene and divinylbenzene, and preferably one or more of 1, 4-pentadiene, 1, 5-hexadiene and divinylbenzene.
(2) The functional monomer molecules comprise one or more of sodium styrene sulfonate, 1-vinyl pyrrolidone, ethylene glycol dimethacrylate, N' -methylene bisacrylamide, 1-vinyl imidazole and azobisisobutyronitrile.
(3) The first organic solvent comprises one or more of ethyl acetate, methyl acetate, tetrahydrofuran, dimethyl sulfoxide and dioxane, preferably one or more of ethyl acetate, tetrahydrofuran and dimethyl sulfoxide.
(4) In the precursor mixed solution of the porous polymer, the mass fraction of the carbon source in the precursor mixed solution is 10-30%, preferably 15-25%.
(5) The total mass fraction of the functional monomer in the precursor mixed solution is 0-10%.
In step K, the reaction is carried out at room temperature for a period of 2 to 4 hours, preferably 3.
In the step L, the temperature of the crystallization treatment is 298K-423K, preferably 353K-413K; the time for crystallization treatment is 6-100h, preferably 12-48h, and more preferably 24 h.
In step M:
(1) the acidic solution is prepared by mixing an acid and a III organic solvent.
The acid comprises one or more of hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid; further preferably, the acid is hydrochloric acid and/or sulfuric acid.
The III organic solvent comprises one or more of methanol, ethanol, propanol, butanol and tetrahydrofuran.
(2) In some embodiments of the invention, the concentration of the acidic solution is from 0.1mol/L to 4mol/L, preferably from 0.5mol/L to 2.5 mol/L.
(3) And performing acid exchange treatment at room temperature for 24-36 hours, preferably 24 hours.
In step N:
(1) the amount of the metal simple substance contained in the aqueous solution of the metal salt is 0.005-0.01 g/mL.
(2) The mass ratio of the metal simple substance contained in the aqueous solution of the metal salt to the porous polymer is (0.04-0.01): 1.
(3) the volume ratio of the aqueous solution of the metal salt to the II organic solvent is (0.01-0.1): 1.
(4) the metal salt comprises one or more of ammonium chloroplatinate, potassium chloroplatinate, platinum nitrate, ammonium chloropalladate, palladium nitrate, potassium chlororuthenate, ruthenium nitrate, rhodium chloride, potassium chlororhodate, cobalt nitrate and nickel nitrate, and preferably one or more of ammonium chloroplatinate, potassium chloroplatinate, ammonium chloropalladate, potassium chlororuthenate and nickel nitrate.
(5) The II organic solvent comprises one or more of methanol, ethanol, propanol, ethylene glycol, isopropanol and glycerol, preferably methanol and glycerol, ethanol and glycerol or ethylene glycol and glycerol.
(6) The temperature of the reduction reaction is 373K to 448K, preferably 373K to 423K; the time of the reduction reaction is 2 to 6 hours, preferably 2 to 4 hours.
It should be understood by those skilled in the art that the amount of the elemental metal contained in the aqueous solution of the metal salt refers to the amount of the elemental metal that can be displaced in the aqueous solution of the metal salt.
The third aspect of the present invention relates to the use of an acidic solid catalyst according to the first aspect of the present invention or an acidic solid catalyst obtained by the process according to the first aspect of the present invention for the one-step catalytic conversion of fructose to 2, 5-dimethylfuran, it is understood that the acidic solid catalyst according to the first aspect of the present invention or the acidic solid catalyst obtained by the process according to the first aspect of the present invention is used in a one-step process for the conversion of fructose to 2, 5-dimethylfuran, introducing a hydrogen source into reactant feed liquid containing the acidic solid catalyst, fructose and an optional IV organic solvent, performing dehydration reaction on the fructose under the action of an acidic catalytic site of the acidic solid catalyst to obtain an intermediate product 5-hydroxymethylfurfural, and performing hydrogenolysis reaction to obtain the bio-based 2, 5-dimethylfuran.
The method comprises the following steps:
(1) the mass concentration of the fructose in terms of the total mass of the reactant feed liquid is 0.5-10%, preferably 1-5%.
(2) The molar weight ratio of the metal simple substance to the fructose in the solid catalyst is (0.001-1):1, preferably (0.005-0.2): 1.
(3) The hydrogen source comprises one or more of hydrogen, formic acid, acetic acid, polymethoxy hydrogen siloxane and polydimethylsiloxane, and preferably formic acid and/or polymethoxy hydrogen siloxane.
(4) The molar weight ratio of the hydrogen source to the fructose is (1-10):1, preferably (3-9): 1.
(5) The IV organic solvent comprises one or more of methanol, ethanol, propanol, n-butanol and isobutanol, and is preferably propanol and/or n-butanol.
(6) The temperature of the dehydration reaction and the hydrogenolysis reaction is 298K-473K, preferably 353K-423K; the time for the dehydration reaction and the hydrogenolysis reaction is 1-24h, preferably 2-10 h.
It will be appreciated by those skilled in the art that the dehydration reaction and hydrogenolysis reaction described above are in series, and may also be understood as two reactions carried out in series, macroscopically as a one-step reaction. Accordingly, the temperature of the dehydration reaction and the hydrogenolysis reaction means that the dehydration reaction and the hydrogenolysis reaction are performed at the same temperature, and the time of the dehydration reaction and the hydrogenolysis reaction means the total reaction time of the dehydration reaction and the hydrogenolysis reaction.
The nanometer metal particles for catalyzing the conversion of fructose into 2, 5-dimethylfuran by one-step method provided by the invention are anchored in a multifunctional porous polymerization catalyst to form a mesoporous structure, the wettability and acidity of the catalyst can be accurately regulated by introducing different functional monomers, and the multifunctional porous material can be anchored with different metals including ruthenium, platinum, rhodium, palladium, nickel and cobalt. The catalyst is used for catalyzing fructose to be converted into 2, 5-dimethylfuran by a one-step method, has excellent activity, high selectivity and strong stability, and provides a new idea and a new way for producing 2, 5-dimethylfuran on a biological basis.
III example
The present invention will be specifically described below with reference to specific examples. The experimental methods described below are, unless otherwise specified, all routine laboratory procedures. The experimental materials described below, unless otherwise specified, are commercially available.
In the present invention, the wettability of the material was measured by measuring the contact angle with water on a contact angle measuring instrument (DSA10MK2G140, Kruss, Germany), and the acidity of the material was characterized by acid-base titration.
In the invention, the components of the reaction liquid are quantified by gas chromatography, and the conversion rate of fructose is calculated by (I); the yield of 2, 5-dimethylfuran was calculated by (II). In the present invention, the total weight ratio of the internal standard substance to the reactant solution is (0.01-0.3):1, preferably the total weight ratio of the internal standard substance to the reactant solution is (0.01-0.1):1, and more preferably the total weight ratio of the internal standard substance to the reactant solution is 0.02, based on the total mass of the reaction solution. The internal standard substance in the present invention is not particularly limited, and toluene is preferably used as the internal standard substance.
In formula (I):
n0is the amount of starting material of fructose added in mol;
n1the amount of substance remaining after completion of the reaction was determined in mol using an internal standard.
In formula (II):
n0is the amount of fructose starting material added in mol;
n2, 5-dimethylfuranThe amount of the substance of 2, 5-dimethylfuran produced after completion of the reaction was measured by using an internal standard substance in mol.
Example 1:
(1) divinylbenzene (2.0g) and azobisisobutyronitrile (0.05g) were added to a mixed solution of THF (20mL) and water (2mL), followed by adding sodium p-styrenesulfonate (0.16g) and 1-vinyl-2-pyrrolidine (0.23g), respectively, and stirring at room temperature for 3 hours to obtain a precursor mixed solution of a porous polymer support.
(2) And transferring the precursor mixed solution of the prepared porous polymer carrier into an autoclave, carrying out crystallization treatment for 24 hours at 373K, and evaporating the solvent at room temperature to obtain the precursor of the multifunctional porous polymer.
(3) 1g of porous polymer carrier is taken and dispersed in a mixed solution (1mol/L) of sulfuric acid and ethanol, and acid exchange treatment is carried out for 24 hours; drying at room temperature to obtain the acidic porous polymeric material.
(4) 1g of the above-synthesized acidic porous polymeric material was immersed in degassed ethylene glycol/glycerol (40 ml; volume ratio 1; 1). At room temperature adding K2PdCl4(69.8mg, 0.02g of elemental palladium) was dissolved in degassed water (4mL) and the solution was added.
(5) The mixture was stirred vigorously in a 398K pre-heated oil bath for 3 hours. After cooling to room temperature, the brown suspension was diluted with water and filtered. Fully washing the brown powder with water, then washing with Tetrahydrofuran (THF) for a plurality of times, and drying at ambient temperature to obtain the multifunctional polymerization catalyst loaded with the metal nanoparticles; by measuring the contact angle of the material with water to be 150 DEG, the amount of acid is 0.23 mmol/g.
(6) 60mL of butanol, 1.2g of fructose and 0.35g of multifunctional polymerization catalyst containing supported palladium nanoparticles (the molar weight ratio of the metal simple substance content to the fructose in the catalyst is 0.01:1), 1g of toluene and 6g of polymethylhydrosiloxane (the molar weight ratio of the introduced amount to the fructose is 6:1) are added into a 100mL reaction kettle, and then the mixture is heated to 393K for reaction for 6 hours to obtain 2, 5-dimethylfuran. Tests and calculations carried out according to formulae (I) and (II) show that the conversion of fructose is > 99% and the yield of 2, 5-dimethylfuran is 94%.
Example 2:
this example differs from example 1 in that:
in step (1), 0.16g N, N' -methylenebisacrylamide was added.
The contact angle of the material with water was measured to be 131 ℃ and the amount of acid was measured to be 0.21 mmol/g.
The remaining reaction conditions were the same as in example 1.
Tests and calculations carried out according to formulae (I) and (II) show that the fructose conversion is > 99% and the yield of 2, 5-dimethylfuran is 83%.
Example 3:
this example differs from example 1 in that:
0.32g of ethylene glycol dimethacrylate was added in step (1).
The contact angle of the material with water was measured to be 81 ℃ and the amount of acid was measured to be 0.24 mmol/g.
The remaining reaction conditions were the same as in example 1.
Tests and calculations carried out according to formulae (I) and (II) show that the fructose conversion is > 99% and the yield of 2, 5-dimethylfuran is 41%.
Example 4:
this example differs from example 1 in that:
in step (1), 0.36g N, N' -methylenebisacrylamide was added.
The measurement was made by measuring the contact angle of the material with water to be 0 ℃ and the amount of acid to be 0.19 mmol/g.
The remaining reaction conditions were the same as in example 1.
Tests and calculations carried out according to formulae (I) and (II) show that the fructose conversion is > 99% and the yield of 2, 5-dimethylfuran is 12%.
Example 5:
in step (1), 0.5g of 1, 5-hexadiene and 0.5g of divinylbenzene were added.
The contact angle of the material with water was measured to be 142 ° and the amount of acid was 0.5 mmol/g.
The reaction time in the step (6) is 3 h.
The remaining reaction conditions were the same as in example 1.
Tests and calculations carried out according to formulae (I) and (II) show that the fructose conversion is > 99% and the yield of 2, 5-dimethylfuran is 90%.
Example 6:
this example differs from example 1 in that:
in the step (1), sodium styrene sulfonate is not added.
The contact angle of the material with water was measured to be 157 ℃ and the amount of acid was 0 mmol/g.
The remaining reaction conditions were the same as in example 1.
According to the test and calculation of the formulas (I) and (II), the conversion rate of the fructose is 80 percent, and the yield of the 2, 5-dimethylfuran reaches 34 percent.
Example 7:
this example differs from example 1 in that:
0.48g of sodium styrene sulfonate is added in the step (1).
The contact angle of the material with water was measured to be 142 ° and the amount of acid was measured to be 0.6 mmol/g.
The reaction time in the step (6) is 3 hours
The remaining reaction conditions were the same as in example 1.
Tests and calculations carried out according to formulae (I) and (II) showed that the fructose conversion was 89% and the yield of 2, 5-dimethylfuran was 34%.
Example 8:
this example differs from example 1 in that:
in the step (1), 1-vinyl pyrrolidone is not added.
The contact angle of the material with water was measured to be 151 ℃ and the amount of acid was measured to be 0.22 mmol/g.
The remaining reaction conditions were the same as in example 1.
Tests and calculations carried out according to formulae (I) and (II) show that the fructose conversion is > 99% and the yield of 2, 5-dimethylfuran is 78%.
Example 9:
this example differs from example 1 in that:
adding 1-vinyl imidazole into the mixture in the step (1).
The contact angle of the material with water was measured to be 148 ℃ and the amount of acid was measured to be 0.23 mmol/g.
The remaining reaction conditions were the same as in example 1.
Tests and calculations carried out according to formulae (I) and (II) show that the fructose conversion is > 99% and the yield of 2, 5-dimethylfuran is 90%.
Example 10:
this example differs from example 1 in that:
step (1) tetrahydrofuran was replaced with ethyl acetate.
The contact angle of the material with water was measured to be 143 ℃ and the amount of acid was measured to be 0.18 mmol/g.
The remaining reaction conditions were the same as in example 1.
Tests and calculations carried out according to formulae (I) and (II) show that the fructose conversion is > 99% and the yield of 2, 5-dimethylfuran is 85%.
Example 11:
this example differs from example 1 in that:
and (2) changing the crystallization time to 36 h.
It was determined by measuring the contact angle of the material with water at 155 ℃ and the amount of acid at 0.21 mmol/g.
The remaining reaction conditions were the same as in example 1.
Tests and calculations carried out according to formulae (I) and (II) show that the fructose conversion is > 99% and the yield of 2, 5-dimethylfuran is 91%.
Example 12:
this example differs from example 1 in that:
in the step (2), the crystallization temperature is changed to 393K.
The measurement was made by measuring the contact angle of the material with water at 153 ℃ and the amount of acid at 0.19 mmol/g.
The remaining reaction conditions were the same as in example 1.
Tests and calculations carried out according to formulae (I) and (II) show that the fructose conversion is > 99% and the yield of 2, 5-dimethylfuran is 88%.
Example 13:
this example differs from example 1 in that:
and (3) replacing the sulfuric acid with hydrochloric acid.
The contact angle of the material with water was measured to be 155 ℃ and the amount of acid was measured to be 0.1 mmol/g.
The remaining reaction conditions were the same as in example 1.
Tests and calculations carried out according to formulae (I) and (II) show that the fructose conversion is > 99% and the yield of 2, 5-dimethylfuran is 74%.
Example 14:
this example differs from example 1 in that:
the operations of step (4) and step (5) are not performed.
It was determined by measuring the contact angle of the material with water at 155 ℃ and the amount of acid at 0.23 mmol/g.
The remaining reaction conditions were the same as in example 1.
Tests and calculations performed according to formulae (I) and (II) showed that fructose conversion was > 99% and 2, 5-dimethylfuran yield was 0%.
Example 15:
this example differs from example 1 in that:
step (4) adding K2PdCl4Instead of (NH4)2PdCl4(53.6mg)。
The contact angle of the material with water was measured to be 151 ℃ and the amount of acid was measured to be 0.25 mmol/g.
The remaining reaction conditions were the same as in example 1.
Tests and calculations carried out according to formulae (I) and (II) show that the fructose conversion is > 99% and the yield of 2, 5-dimethylfuran is 92%.
Example 16:
this example differs from example 1 in that:
step (4) adding K2PdCl4Substitution by K2RuCl4(53.6mg)。
The contact angle of the material with water was measured to be 150 ℃ and the amount of acid was measured to be 0.22 mmol/g.
The remaining reaction conditions were the same as in example 1.
Tests and calculations carried out according to formulae (I) and (II) show that the fructose conversion is > 99% and the yield of 2, 5-dimethylfuran is 82%.
Example 17:
this example differs from example 1 in that:
step (4) adding K2PdCl4Substitution by K2PtCl4(52mg)。
The contact angle of the material with water was measured to be 150 ℃ and the amount of acid was measured to be 0.19 mol/L.
The remaining reaction conditions were the same as in example 1.
Tests and calculations carried out according to formulae (I) and (II) show that the fructose conversion is > 99% and the yield of 2, 5-dimethylfuran is 85%.
Example 18:
this example differs from example 1 in that:
step (4) adding K2PdCl4Substitution with Ni (NO)3)2(63mg)。
The contact angle of the material with water was measured to be 150 ℃ and the amount of acid was measured to be 0.20 mol/L.
The remaining reaction conditions were the same as in example 1.
Tests and calculations carried out according to formulae (I) and (II) show that the fructose conversion is > 99% and the yield of 2, 5-dimethylfuran is 65%.
Example 19:
this example differs from example 1 in that:
and (4) replacing glycol/glycerol (40 ml; volume ratio of 1:1) with glycerol/methanol (45 ml; volume ratio of 1: 1).
The contact angle of the material with water was measured to be 150 ℃ and the amount of acid was measured to be 0.21 mmol/g.
The remaining reaction conditions were the same as in example 1.
Tests and calculations carried out according to formulae (I) and (II) show that the fructose conversion is > 99% and the yield of 2, 5-dimethylfuran is 81%.
Example 20:
this example differs from example 1 in that:
and (4) replacing glycol/glycerol (40 ml; volume ratio of 1:1) with glycerol/ethanol (45 ml; volume ratio of 1: 1).
The contact angle of the material with water was measured to be 150 ℃ and the amount of acid was measured to be 0.23 mmol/g.
The remaining reaction conditions were the same as in example 1.
Tests and calculations carried out according to formulae (I) and (II) show that the fructose conversion is > 99% and the yield of 2, 5-dimethylfuran is 85%.
Example 21:
this example differs from example 1 in that:
in step (5), the mixture was vigorously stirred in a preheated oil bath in which 398K was changed to 423K for 3 hours.
The contact angle of the material with water was measured to be 152 ℃ and the amount of acid was measured to be 0.19 mmol/g.
The remaining reaction conditions were the same as in example 1.
Tests and calculations carried out according to formulae (I) and (II) show that the fructose conversion is > 99% and the yield of 2, 5-dimethylfuran is 91%.
Example 22:
this example differs from example 1 in that:
in step (5), the mixture was vigorously stirred in a preheated oil bath in which 398K was changed to 423K for 6 hours.
The measurement was made by measuring the contact angle of the material with water at 153 ℃ and the amount of acid at 0.21 mmol/g.
The remaining reaction conditions were the same as in example 1.
Tests and calculations carried out according to formulae (I) and (II) show that the fructose conversion is > 99% and the yield of 2, 5-dimethylfuran is 81%.
Example 23:
this example differs from example 1 in that:
the mass of the catalyst added in the step (6) is 0.7g, and the reaction time is 4.5 h.
The remaining reaction conditions were the same as in example 1.
Tests and calculations carried out according to formulae (I) and (II) show that the fructose conversion is > 99% and the yield of 2, 5-dimethylfuran is 89%.
Example 24:
this example differs from example 1 in that:
9g of polymethylhydrosiloxane is added in the step (6), and the reaction time is 4.5 h.
The remaining reaction conditions were the same as in example 1.
Tests and calculations carried out according to formulae (I) and (II) show that the fructose conversion is > 99% and the yield of 2, 5-dimethylfuran is 89%.
Example 25:
this example differs from example 1 in that:
in the step (6), 0.7g of catalyst and 9g of polymethylhydrosiloxane are added, and the reaction time is 2 hours.
The remaining reaction conditions were the same as in example 1.
Tests and calculations carried out according to formulae (I) and (II) show that the fructose conversion is > 99% and the yield of 2, 5-dimethylfuran is 90%.
Example 26:
this example differs from example 1 in that:
the amount of fructose added in step (6) was 2.4 g.
The remaining reaction conditions were the same as in example 1.
Tests and calculations carried out according to formulae (I) and (II) showed that the fructose conversion was 91% and the yield of 2, 5-dimethylfuran was 82%.
Example 27:
this example differs from example 1 in that:
and (4) prolonging the reaction time in the step (6) to 8 h.
The remaining reaction conditions were the same as in example 1.
Tests and calculations carried out according to formulae (I) and (II) show that the fructose conversion is > 99% and the yield of 2, 5-dimethylfuran is 87%.
Example 28:
this example differs from example 1 in that:
in the step (6), the reaction time is 8 h.
The remaining reaction conditions were the same as in example 1.
Tests and calculations carried out according to formulae (I) and (II) show that the fructose conversion is > 99% and the yield of 2, 5-dimethylfuran is 87%.
Example 29:
this example differs from example 1 in that:
in the step (6), polymethyl hydrogen siloxane is not added.
The remaining reaction conditions were the same as in example 1.
Tests and calculations carried out according to formulae (I) and (II) showed that the fructose conversion was 70% and the yield of 2, 5-dimethylfuran was 0%.
Example 30:
this example differs from example 1 in that:
in step (6), polymethylhydrosiloxane was substituted with formic acid (4.5 g).
The remaining reaction conditions were the same as in example 1.
Tests and calculations carried out according to formulae (I) and (II) show that the fructose conversion is > 99% and the yield of 2, 5-dimethylfuran is 28%.
Example 31:
this example differs from example 1 in that:
and (6) replacing the polymethylhydrosiloxane with hydrogen (2 MPa).
The remaining reaction conditions were the same as in example 1.
Tests and calculations carried out according to formulae (I) and (II) showed that the fructose conversion was 98% and the yield of 2, 5-dimethylfuran was 11%.
Example 32:
this example differs from example 1 in that:
and (6) replacing butanol with methanol.
The remaining reaction conditions were the same as in example 1.
Tests and calculations carried out according to formulae (I) and (II) showed that the fructose conversion was 85% and the yield of 2, 5-dimethylfuran was 37%.
Example 33:
this example differs from example 1 in that:
and (6) replacing butanol with ethanol.
The remaining reaction conditions were the same as in example 1.
Tests and calculations carried out according to formulae (I) and (II) show that the fructose conversion is 93% and the yield of 2, 5-dimethylfuran is 50%.
Example 34:
this example differs from example 1 in that:
and (6) replacing butanol with isobutanol.
The remaining reaction conditions were the same as in example 1.
Tests and calculations carried out according to formulae (I) and (II) showed that the fructose conversion was 89% and the 2, 5-dimethylfuran yield was 44%.
Example 35:
this example differs from example 1 in that:
step (6) the reaction temperature was changed to 373K.
The remaining reaction conditions were the same as in example 1.
Tests and calculations carried out according to formulae (I) and (II) showed that the fructose conversion was 94% and the yield of 2, 5-dimethylfuran was 78%.
Example 36:
this example differs from example 1 in that:
step (6) the reaction temperature was changed to 413K.
The remaining reaction conditions were the same as in example 1.
Tests and calculations carried out according to formulae (I) and (II) show that the fructose conversion is > 99% and the yield of 2, 5-dimethylfuran is 81%.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (22)
1. An acidic solid catalyst for one-step catalysis of fructose conversion into 2, 5-dimethylfuran, which is composed of an acidic porous polymer loaded with metal nanoparticles; the wettability of the solid catalyst is 140-155 degrees; the content of B acid in the solid catalyst is 0-1.0mmol/g, and the content of B acid in the solid catalyst is not 0; the catalyst has a mesoporous structure; the metal is one or more of ruthenium, palladium and platinum.
2. The catalyst according to claim 1, wherein the solid catalyst has a B acid content of 0.15 to 0.7 mmol/g.
3. A method for preparing the solid catalyst of claim 1 or 2, comprising:
k, mixing and reacting a carbon source, a functional monomer, azodiisobutyronitrile and an organic solvent I to prepare a precursor mixed solution of the porous polymer;
step L, performing crystallization treatment on the precursor mixed solution of the porous polymer, and then performing centrifugation, washing and drying to obtain the porous polymer;
step M, carrying out acid exchange treatment on the porous polymer and an acidic solution to obtain an acidic porous polymer;
and step N, mixing the acidic porous polymer and the aqueous solution of the metal salt in a II organic solvent, and then carrying out reduction reaction to prepare the acidic solid catalyst.
4. The method according to claim 3, wherein the carbon source comprises one or more of 1, 3-butadiene, 1, 4-pentadiene, 1, 5-hexadiene, vinylbenzene and divinylbenzene; and/or the functional monomer molecules comprise one or more of sodium styrene sulfonate, 1-vinylpyrrolidone, ethylene glycol dimethacrylate, N' -methylenebisacrylamide and 1-vinylimidazole; and/or, the I organic solvent comprises one or more of ethyl acetate, methyl acetate, tetrahydrofuran, dimethyl sulfoxide and dioxane.
5. The method according to claim 4, wherein the carbon source is one or more of 1, 4-pentadiene, 1, 5-hexadiene, and divinylbenzene; and/or the I organic solvent is one or more of ethyl acetate, tetrahydrofuran and dimethyl sulfoxide.
6. The method according to any one of claims 3 to 5, wherein the mass fraction of the carbon source in the precursor mixed solution of the porous polymer is 10% to 30%; and/or the total mass fraction of the functional monomer in the precursor mixed solution is 0-10%; and/or, in step K, the reaction is carried out at room temperature for a time of 2 to 4 hours.
7. The method according to claim 6, wherein the mass fraction of the carbon source in the precursor mixed solution of the porous polymer is 15 to 25%.
8. The production method according to any one of claims 3 to 5, wherein in step L, the temperature of the crystallization treatment is 298K to 423K; and/or the time of the crystallization treatment is 6-100 h.
9. The method according to claim 8, wherein in step L, the temperature of the crystallization treatment is 353K to 413K; and/or the time of the crystallization treatment is 12-48 h.
10. The method according to any one of claims 3 to 5, wherein in step M, the acidic solution is prepared by mixing an acid with a III organic solvent; the acid comprises one or more of hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid; and/or the III organic solvent comprises one or more of methanol, ethanol, propanol, butanol and tetrahydrofuran; and/or the concentration of the acid solution is 0.1-4 mol/L; and/or, in the step M, performing acid exchange treatment at room temperature, wherein the time of the acid exchange treatment is 24-36 hours.
11. The method according to claim 10, wherein in step M, the acid is hydrochloric acid and/or sulfuric acid; and/or the concentration of the acid solution is 0.5mol/L-2.5 mol/L.
12. The production method according to any one of claims 3 to 5, wherein in step N, the aqueous solution of the metal salt contains the elemental metal in an amount of 0.005 to 0.01 g/mL; and/or the mass ratio of the metal simple substance contained in the aqueous solution of the metal salt to the porous polymer is (0.04-0.01): 1; and/or the volume ratio of the aqueous solution of the metal salt to the organic solvent II is (0.01-0.1): 1; and/or the metal salt comprises one or more of ammonium chloroplatinate, potassium chloroplatinate, platinum nitrate, ammonium chloropalladate, palladium nitrate, potassium chlororuthenate and ruthenium nitrate; and/or the II organic solvent comprises one or more of methanol, ethanol, propanol, glycol, isopropanol and glycerol.
13. The preparation method according to claim 12, wherein in step N, the metal salt is one or more of ammonium chloroplatinate, potassium chloroplatinate, ammonium chloropalladate and potassium chlororuthenate; and/or, the second organic solvent is methanol and glycerol, ethanol and glycerol or glycol and glycerol.
14. The production method according to claim 12, wherein in step N, the temperature of the reduction reaction is 373K to 448K; and/or the time of the reduction reaction is 2-6 h.
15. The production method according to claim 14, wherein in step N, the temperature of the reduction reaction is 373K to 423K; and/or the time of the reduction reaction is 2-4 h.
16. The production method according to claim 13, wherein in step N, the temperature of the reduction reaction is 373K to 448K; and/or the time of the reduction reaction is 2-6 h.
17. The production method according to claim 16, wherein in step N, the temperature of the reduction reaction is 373K to 423K; and/or the time of the reduction reaction is 2-4 h.
18. The use of the acidic solid catalyst according to claim 1 or 2 or the acidic solid catalyst prepared by the method according to any one of claims 3 to 17 for the one-step catalytic conversion of fructose into 2, 5-dimethylfuran, comprising introducing a hydrogen source into a reactant feed liquid containing the acidic solid catalyst, fructose and a IV organic solvent, wherein the fructose is subjected to a dehydration reaction under the action of an acidic catalytic site of the acidic solid catalyst to obtain an intermediate product 5-hydroxymethylfurfural, and then subjected to a hydrogenolysis reaction to obtain a bio-based 2, 5-dimethylfuran; the hydrogen source is polymethoxy hydrogen siloxane, and the IV organic solvent is n-butyl alcohol.
19. The use according to claim 18, wherein the fructose is present in the reactant liquor at a mass concentration of 0.5-10% based on the total mass of the reactant liquor; and/or the molar weight ratio of the metal simple substance to the fructose in the solid catalyst is (0.001-1): 1; and/or the molar weight ratio of the hydrogen source to the fructose is (1-10): 1.
20. The use according to claim 19, wherein the fructose is present in the reactant liquor in a mass concentration of 1-5% based on the total mass of the reactant liquor; and/or the molar weight ratio of the metal simple substance to the fructose in the solid catalyst is (0.005-0.2): 1; and/or the molar weight ratio of the hydrogen source to the fructose is (3-9): 1.
21. Use according to any one of claims 18 to 20, wherein the dehydration and hydrogenolysis reactions are carried out at a temperature of 298K to 473K; and/or the time of the dehydration reaction and the hydrogenolysis reaction is 1-24 h.
22. The use according to claim 21, wherein the dehydration reaction and hydrogenolysis reaction are carried out at a temperature of from 353K to 423K; and/or the time of the dehydration reaction and the hydrogenolysis reaction is 2-10 h.
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