CN111298798A - Preparation method of tin-based magnetic catalyst and application method thereof in preparation of furfural - Google Patents
Preparation method of tin-based magnetic catalyst and application method thereof in preparation of furfural Download PDFInfo
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- CN111298798A CN111298798A CN202010160208.5A CN202010160208A CN111298798A CN 111298798 A CN111298798 A CN 111298798A CN 202010160208 A CN202010160208 A CN 202010160208A CN 111298798 A CN111298798 A CN 111298798A
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- China
- Prior art keywords
- tin
- based magnetic
- magnetic catalyst
- ferroferric oxide
- furfural
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- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 172
- 239000003054 catalyst Substances 0.000 title claims abstract description 130
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 80
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 72
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000002105 nanoparticle Substances 0.000 claims abstract description 61
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 39
- 229960003638 dopamine Drugs 0.000 claims abstract description 36
- 239000002028 Biomass Substances 0.000 claims abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 31
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims abstract description 18
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 15
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000007983 Tris buffer Substances 0.000 claims abstract description 15
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims abstract description 15
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 15
- 239000001509 sodium citrate Substances 0.000 claims abstract description 15
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims abstract description 15
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims abstract description 15
- 229940038773 trisodium citrate Drugs 0.000 claims abstract description 15
- KHMOASUYFVRATF-UHFFFAOYSA-J tin(4+);tetrachloride;pentahydrate Chemical compound O.O.O.O.O.Cl[Sn](Cl)(Cl)Cl KHMOASUYFVRATF-UHFFFAOYSA-J 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 10
- VVTXSHLLIKXMPY-UHFFFAOYSA-L disodium;2-sulfobenzene-1,3-dicarboxylate Chemical compound [Na+].[Na+].OS(=O)(=O)C1=C(C([O-])=O)C=CC=C1C([O-])=O VVTXSHLLIKXMPY-UHFFFAOYSA-L 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 37
- 238000001035 drying Methods 0.000 claims description 31
- 238000005406 washing Methods 0.000 claims description 31
- 239000007787 solid Substances 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 22
- 239000012071 phase Substances 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 21
- 239000012074 organic phase Substances 0.000 claims description 20
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 18
- 239000012498 ultrapure water Substances 0.000 claims description 18
- 238000006555 catalytic reaction Methods 0.000 claims description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims description 12
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 241000609240 Ambelania acida Species 0.000 claims description 9
- 229920002488 Hemicellulose Polymers 0.000 claims description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 9
- 239000010905 bagasse Substances 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 6
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 5
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 5
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 4
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 4
- 244000166124 Eucalyptus globulus Species 0.000 claims description 4
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 4
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 4
- 241000209140 Triticum Species 0.000 claims description 4
- 235000021307 Triticum Nutrition 0.000 claims description 4
- 239000011425 bamboo Substances 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 239000010902 straw Substances 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 3
- 244000082204 Phyllostachys viridis Species 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 18
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000011084 recovery Methods 0.000 abstract 1
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 239000005457 ice water Substances 0.000 description 15
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 14
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 14
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 6
- 239000011973 solid acid Substances 0.000 description 6
- 239000011949 solid catalyst Substances 0.000 description 6
- 239000007848 Bronsted acid Substances 0.000 description 5
- 239000002841 Lewis acid Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000002638 heterogeneous catalyst Substances 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 150000007517 lewis acids Chemical class 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 241001330002 Bambuseae Species 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 description 1
- 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 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- XBWRJSSJWDOUSJ-UHFFFAOYSA-L chromium(ii) chloride Chemical compound Cl[Cr]Cl XBWRJSSJWDOUSJ-UHFFFAOYSA-L 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- TZRIUKNLJJXQMJ-UHFFFAOYSA-L disodium;2-phenylpropanedioate Chemical compound [Na+].[Na+].[O-]C(=O)C(C([O-])=O)C1=CC=CC=C1 TZRIUKNLJJXQMJ-UHFFFAOYSA-L 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 1
- 229940040102 levulinic acid Drugs 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000002029 lignocellulosic biomass Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- KERBAAIBDHEFDD-UHFFFAOYSA-N n-ethylformamide Chemical compound CCNC=O KERBAAIBDHEFDD-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002119 pyrolysis Fourier transform infrared spectroscopy Methods 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229940087562 sodium acetate trihydrate Drugs 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- JNVLJWBOAWSXKO-UHFFFAOYSA-K trichloronickel Chemical compound Cl[Ni](Cl)Cl JNVLJWBOAWSXKO-UHFFFAOYSA-K 0.000 description 1
- 239000010457 zeolite 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention particularly relates to a preparation method of a tin-based magnetic catalyst and an application method thereof in preparing furfural. The preparation method of the tin-based magnetic catalyst adopts a hydrothermal solvent method, dissolves ferric trichloride hexahydrate, trisodium citrate and anhydrous sodium acetate in ethylene glycol, and transfers the solution to a hydrothermal reaction kettle for full reaction to obtain ferroferric oxide nanoparticles; then adding the ferroferric oxide nanoparticles and dopamine hydrochloride into a Tris buffer solution to obtain dopamine-coated ferroferric oxide nanoparticles; and finally, fully reacting the tin tetrachloride pentahydrate, sodium sulfoisophthalate, dimethylformamide and dopamine-coated ferroferric oxide nano particles in a hydrothermal reaction kettle to obtain the tin-based magnetic catalyst. The preparation method of the tin-based magnetic catalyst and the application method of the tin-based magnetic catalyst in preparation of furfural have the advantages of high catalytic efficiency, good selectivity and easiness in recovery and circulation, so that the industrial cost of furfural is reduced, and the step-by-step high-valued utilization of biomass raw materials is realized.
Description
Technical Field
The invention relates to the technical field of furfural preparation, and particularly relates to a preparation method of a tin-based magnetic catalyst and an application method of the tin-based magnetic catalyst in preparation of furfural.
Background
The furfural is an important platform chemical, can be derived into various products, such as furfuryl alcohol, levulinic acid, methyltetrahydrofuran, gamma-valerolactone and other high-value-added chemicals, and is a key bridge for replacing petrochemical products with future lignocellulose biomass derivatives. Furfural is mainly derived from xylan-like hemicellulose in lignocellulosic biomass, which is formed by dehydration of xylose or arabinose in the hemicellulose. At present, furfural is mainly prepared by hydrolyzing hemicellulose-rich biomass by sulfuric acid in China industry, and the defects of low target yield, low raw material utilization rate, environmental pollution caused by generated waste water and waste residues and the like exist. Based on the above, the development of novel catalysts with high efficiency and green color is urgent.
Catalysts for catalyzing the dehydration of xylose to furfural are generally classified into homogeneous catalysts and heterogeneous catalysts.
Homogeneous catalysts include organic acids (formic acid, acetic acid, etc.), inorganic acids (sulfuric acid, hydrochloric acid, etc.), metal salts (chloride salts, sulfate salts, etc.), ionic liquids, and the like. Inorganic acid, particularly sulfuric acid and hydrochloric acid, is a common catalyst for industrially preparing furfural at present, and although the use of the catalyst has the advantages of simple and convenient operation and easy popularization. However, the catalyst has strong corrosivity and high requirements on reaction equipment, and the generated acidic wastewater has great damage to the environment. Compared with the method, the metal salt has the advantages of small corrosion to equipment and high furfural yield. However, they are difficult to separate from the solvent system and such catalysts are generally toxic or corrosive. The effect of preparing furfural by catalyzing xylose with organic acid is relatively poor, and the ionic liquid is expensive and is not suitable for long-term large-scale use. Thus, heterogeneous catalysts are produced.
Common heterogeneous catalysts include: metal oxides, zeolite molecular sieves, carbon-based solid acids, natural clay minerals, ion exchange resins, and the like. Although the heterogeneous catalysts have the advantages of good catalytic performance and no pollution, the heterogeneous catalysts have the problem of difficult separation and recycling in the process of catalyzing solid biomass raw materials to prepare furfural.
In addition, the catalytic system is an important component in the catalytic reaction process and is divided into a single-phase system and a two-phase system, and the two-phase system generally comprises an organic solvent and water. In the preparation of furfural, the organic solvent can extract furfural produced by the reaction, thereby avoiding the degradation of furfural and improving the yield and selectivity of furfural. Currently, commonly used organic solvents include dimethyl sulfoxide, tetrahydrofuran, dichloromethane, N-dimethylformamide, gamma-valerolactone, and the like. The selection of the organic solvent should take into account the problems of environmental protection, subsequent product extraction and the like.
Based on the problems, in order to obtain a solid catalyst with good catalytic performance and solve the problem that the solid catalyst is difficult to separate after reacting with a solid biomass raw material, the invention provides a preparation method of a tin-based magnetic catalyst and an application method thereof for preparing furfural.
Disclosure of Invention
In order to make up for the defects of the prior art, the invention provides a preparation method of a tin-based magnetic catalyst which is convenient, flexible and efficient to use and an application method of the tin-based magnetic catalyst in preparation of furfural.
The invention is realized by the following technical scheme:
a preparation method of a tin-based magnetic catalyst and an application method thereof in preparing furfural are characterized in that a hydrothermal solvent method is adopted, and the method comprises the following steps:
dissolving ferric trichloride hexahydrate, trisodium citrate and anhydrous sodium acetate in ethylene glycol, fully stirring, transferring to a hydrothermal reaction kettle, fully reacting, cooling, filtering, washing and drying to obtain ferroferric oxide nanoparticles;
secondly, adding the obtained ferroferric oxide nanoparticles and dopamine hydrochloride into a Tris buffer solution with the pH value of 8.5, and filtering, washing and drying after full reaction at room temperature to obtain dopamine-coated ferroferric oxide nanoparticles;
and step three, uniformly mixing tin tetrachloride pentahydrate, sodium sulfoisophthalate, dimethylformamide and the obtained dopamine-coated ferroferric oxide nanoparticles, fully reacting in a hydrothermal reaction kettle, cooling, filtering and drying to obtain the tin-based magnetic catalyst.
In the first step, the mass ratio of ferric trichloride hexahydrate, anhydrous sodium acetate and trisodium citrate is 1-5: 1-3: 4-10, wherein the solid-to-liquid ratio of a solid mixed substance composed of ferric trichloride hexahydrate, anhydrous sodium acetate and trisodium citrate to ethylene glycol is 1: 10-30 g/mL; the temperature of hydrothermal reaction in the hydrothermal reaction kettle is 160-200 ℃, and the reaction time is 8-12 h.
In the second step, the mass ratio of the ferroferric oxide nanoparticles to the dopamine hydrochloride is 1: 1-3, the solid-to-liquid ratio of a solid mixed substance composed of ferroferric oxide nanoparticles and dopamine hydrochloride to a Tris buffer solution is 1: 200-500 g/mL, the concentration range of the Tris buffer solution with the pH value of 8.5 is 0.01-0.03M, and the reaction time is 8-12 hours.
In the third step, the mass ratio of the dopamine-coated ferroferric oxide nanoparticles to the tin tetrachloride pentahydrate to the isophthalic acid is 1-10: 1-180: 1-90; and the solid-liquid ratio of a solid mixed substance consisting of ferroferric oxide nanoparticles, stannic chloride pentahydrate and isophthalic acid to dimethylformamide is 1: 1-20 g/mL; the hydrothermal reaction temperature in the hydrothermal reaction kettle is 80-100 ℃, and the reaction time is 10-20 h.
Washing the ferroferric oxide nanoparticles and the dopamine-coated ferroferric oxide nanoparticles respectively three times by using ultrapure water and absolute ethyl alcohol, and washing the tin-based magnetic catalyst respectively three times by using ultrapure water and dimethylformamide; and drying the ferroferric oxide nanoparticles, the dopamine-coated ferroferric oxide nanoparticles and the tin-based magnetic catalyst in an oven at the temperature of 60 ℃.
The application method for preparing furfural by using the tin-based magnetic catalyst is characterized by comprising the following steps:
first, catalytic reaction
Adding biomass and a tin-based magnetic catalyst into a hydrothermal reaction kettle, adding an organic phase and a water phase, and reacting at 160-200 ℃ for 60-180 min;
second, post-treatment
And cooling by using a water bath after the catalytic reaction is finished, filtering and separating solid and liquid, distilling the organic phase in the liquid to obtain furfural, and separating residues in the solid and the used tin-based magnetic catalyst by using an additional magnet.
In the first step, the biomass is biomass waste containing hemicellulose, and can be any one or a combination of several of bagasse, corncob, wheat straw, eucalyptus powder and bamboo powder.
In the first step, the mass ratio of the tin-based magnetic catalyst to the biomass is 1: 2-10; the solid-liquid ratio of the biomass to the mixed liquid comprising the organic phase and the water phase in the reaction system is 1: 1-100 g/mL; in the mixed liquid, the volume ratio of the organic phase to the aqueous phase is 1: 1 to 2.
The water phase is any one of water, a sodium chloride solution or a potassium chloride solution; the organic phase is any one of dichloromethane, dimethyl tetrahydrofuran, gamma valerolactone, dimethyl sulfoxide, methyl isobutyl ketone or tetrahydrofuran.
In the second step, the used tin-based magnetic catalyst is separated from the residues through an additional magnet, washed by ethanol and hot water, and dried to be repeatedly used for catalyzing biomass to prepare furfural.
The invention has the beneficial effects that: the tin-based magnetic catalyst prepared by the preparation method and the application method for preparing furfural have high catalytic efficiency and good selectivity, can directly convert hemicellulose in biomass into furfural, can be directly recovered by an external magnetic field, and has good recycling availability; and the reaction condition for preparing furfural is mild, the operation and the control are easy, the industrialization is easy to realize, the reaction process is free from pollution and corrosion, the environment is friendly, the purposes of energy conservation and emission reduction can be achieved, the industrial cost of furfural is reduced, and the HIA realizes the step-by-step high-value utilization of biomass raw materials.
Drawings
The invention will be further described with reference to the accompanying drawings.
FIG. 1 is a magnetic force diagram (VSM) of a ferroferric oxide and dopamine coated ferroferric oxide and tin-based magnetic catalyst.
FIG. 2 shows pyridine infrared spectrograms (Py-FTIR) of the ferroferric oxide and dopamine coated ferroferric oxide and tin-based magnetic catalyst.
In the attached drawing, A is nano ferroferric oxide, B is dopamine-coated ferroferric oxide, and C is a tin-based magnetic catalyst.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is described in detail below with reference to the accompanying drawings and embodiments. It should be noted that the specific embodiments described herein are only for explaining the present invention and are not used to limit the present invention.
The preparation method of the tin-based magnetic catalyst adopts a hydrothermal solvent method and comprises the following steps:
dissolving ferric trichloride hexahydrate, trisodium citrate and anhydrous sodium acetate in ethylene glycol, fully stirring, transferring to a hydrothermal reaction kettle, fully reacting, cooling, filtering, washing and drying to obtain ferroferric oxide nanoparticles;
secondly, adding the obtained ferroferric oxide nanoparticles and dopamine hydrochloride into a Tris buffer solution with the pH value of 8.5, and filtering, washing and drying after full reaction at room temperature to obtain dopamine-coated ferroferric oxide nanoparticles;
and step three, uniformly mixing tin tetrachloride pentahydrate, sodium sulfoisophthalate, dimethylformamide and the obtained dopamine-coated ferroferric oxide nanoparticles, fully reacting in a hydrothermal reaction kettle, cooling, filtering and drying to obtain the tin-based magnetic catalyst.
In the first step, the mass ratio of ferric trichloride hexahydrate, anhydrous sodium acetate and trisodium citrate is 1-5: 1-3: 4-10, wherein the solid-to-liquid ratio of a solid mixed substance composed of ferric trichloride hexahydrate, anhydrous sodium acetate and trisodium citrate to ethylene glycol is 1: 10-30 g/mL; the temperature of hydrothermal reaction in the hydrothermal reaction kettle is 160-200 ℃, and the reaction time is 8-12 h.
In the second step, the mass ratio of the ferroferric oxide nanoparticles to the dopamine hydrochloride is 1: 1-3, the solid-to-liquid ratio of a solid mixed substance composed of ferroferric oxide nanoparticles and dopamine hydrochloride to a Tris buffer solution is 1: 200-500 g/mL, the concentration range of the Tris buffer solution with the pH value of 8.5 is 0.01-0.03M, and the reaction time is 8-12 hours.
In the third step, the mass ratio of the dopamine-coated ferroferric oxide nanoparticles to the tin tetrachloride pentahydrate to the isophthalic acid is 1-10: 1-180: 1-90; and the solid-liquid ratio of a solid mixed substance consisting of ferroferric oxide nanoparticles, stannic chloride pentahydrate and isophthalic acid to dimethylformamide is 1: 1-20 g/mL; the hydrothermal reaction temperature in the hydrothermal reaction kettle is 80-100 ℃, and the reaction time is 10-20 h.
Washing the ferroferric oxide nanoparticles and the dopamine-coated ferroferric oxide nanoparticles respectively three times by using ultrapure water and absolute ethyl alcohol, and washing the tin-based magnetic catalyst respectively three times by using ultrapure water and dimethylformamide; and drying the ferroferric oxide nanoparticles, the dopamine-coated ferroferric oxide nanoparticles and the tin-based magnetic catalyst in an oven at the temperature of 60 ℃.
According to the preparation method of the tin-based magnetic catalyst, the obtained tin-based magnetic catalyst has Bronsted acid and Lewis acid sites at the same time, and can be used for catalyzing hemicellulose in biomass to prepare furfural.
The application method for preparing furfural by using the tin-based magnetic catalyst comprises the following steps:
first, catalytic reaction
Adding biomass and a tin-based magnetic catalyst into a hydrothermal reaction kettle, adding an organic phase and a water phase, and reacting at 160-200 ℃ for 60-180 min;
second, post-treatment
And cooling by using a water bath after the catalytic reaction is finished, filtering and separating solid and liquid, distilling the organic phase in the liquid to obtain furfural, and separating residues in the solid and the used tin-based magnetic catalyst by using an additional magnet.
In the first step, the biomass is biomass waste containing hemicellulose, and can be any one or a combination of several of bagasse, corncob, wheat straw, eucalyptus powder and bamboo powder.
In the first step, the mass ratio of the tin-based magnetic catalyst to the biomass is 1: 2-10; the solid-liquid ratio of the biomass to the mixed liquid comprising the organic phase and the water phase in the reaction system is 1: 1-100 g/mL; in the mixed liquid, the volume ratio of the organic phase to the aqueous phase is 1: 1 to 2.
The water phase is any one of water, a sodium chloride solution or a potassium chloride solution; the organic phase is any one of dichloromethane, dimethyl tetrahydrofuran, gamma valerolactone, dimethyl sulfoxide, methyl isobutyl ketone or tetrahydrofuran.
In the second step, the used tin-based magnetic catalyst is separated from the residues through an additional magnet, washed by ethanol and hot water, and dried to be repeatedly used for catalyzing biomass to prepare furfural.
Example 1
The method for preparing the tin-based magnetic solid catalyst by adopting a solvent hydrothermal method comprises the following steps:
firstly, 0.65g of ferric chloride hexahydrate, 0.2g of trisodium citrate and 1.2g of anhydrous sodium acetate are dissolved in 20.5mL of glycol, fully stirred at 500rpm for 30min and then transferred to a hydrothermal reaction kettle at 200 ℃ for reaction for 10 h; after the reaction is finished, cooling by ice water, separating by an external magnet, washing for three times by using ultrapure water and absolute ethyl alcohol respectively, and drying for 12 hours in a 60 ℃ oven to obtain ferroferric oxide nanoparticles;
in order to prepare the ferroferric oxide nano-particles, ferric chloride hexahydrate and ferrous sulfate heptahydrate can be stirred in nitrogen for a certain time, and a small amount of citric acid can be added to obtain a precipitate, namely the ferroferric oxide; putting ferric trichloride hexahydrate and polyvinylpyrrolidone into ethylene glycol, stirring uniformly, carrying out hydrothermal reaction for a certain time, and obtaining black solid, namely ferroferric oxide particles; ferric trichloride hexahydrate and sodium acetate trihydrate are placed in a certain amount of glycol after being uniformly stirred, and ferroferric oxide can also be obtained after hydrothermal reaction for a certain time.
Then, 0.5g of the obtained ferroferric oxide nano-particles and 0.8g of dopamine hydrochloride are added into 400mL of Tris buffer solution with the pH value of 8.5 and the concentration range of 0.01M to react for 12 hours at the temperature of 30 ℃; filtering by an additional magnet after the reaction is finished, washing for three times by using ultrapure water and absolute ethyl alcohol respectively, and drying for 12 hours in a drying oven at the temperature of 60 ℃ to obtain dopamine-coated ferroferric oxide nanoparticles;
finally, 3.505g of tin tetrachloride pentahydrate, 2.816g of sodium sulfoisophthalate, 80mL of dimethylformamide and 0.5g of the prepared dopamine-coated ferroferric oxide nano-particles are uniformly mixed and then react for 20 hours in a hydrothermal reaction kettle at 100 ℃; after the reaction is finished, the mixture is cooled by ice water, filtered by an additional magnet, washed by ultrapure water and dimethylformamide for three times respectively, and dried in an oven at 60 ℃ for 12 hours to obtain the tin-based magnetic solid acid catalyst.
Wherein the stannic chloride pentahydrate is used for providing active site stannic ions and can be replaced by nickel trichloride, chromium dichloride, aluminum chloride, stannic chloride and germanium tetrachloride after indium trichloride; the sodium toluene dicarboxylate is used for providing a sulfonic acid group, plays a role in providing an acid site of the B acid, and can be replaced by sodium sulfonate, sodium dodecyl benzene sulfonate, sodium p-methyl sulfonate and other sodium salts containing the sulfonic acid group; dimethylformamide is mainly used as a solvent to provide a reaction environment, and can be replaced by an amide organic solvent such as formamide, ethylformamide, diethylformamide and the like.
The proper proportion of the three components is beneficial to the increase of active site tin, thereby improving the content of L acid acidic sites and increasing the catalytic capability of the catalyst.
The VSM of the ferroferric oxide, dopamine-coated ferroferric oxide and tin-based magnetic catalyst obtained in example 1 is shown in attached figure 1. As can be seen from figure 1, the magnetism of the coated dopamine and the tin-loaded ferroferric oxide is slightly reduced, but the magnetism of the coated dopamine and the tin-loaded ferroferric oxide is obviously maintained, which indicates that the tin-based magnetic catalyst prepared by the method can be efficiently separated from a solid reaction substrate through an external magnetic field.
The pyridine infrared spectrum of the ferroferric oxide, dopamine-coated ferroferric oxide and tin-based magnetic catalyst obtained in example 1 at 200 ℃ is shown in the attached figure 2. As can be seen from FIG. 2, 1445cm-1 and 1596cm-1 belong to the characteristic absorption peaks of Bronsted acid, and 1489cm-1 belongs to the characteristic absorption peaks of both Bronsted acid and Lewis acid. The reaction temperature for catalyzing biomass is below 200 ℃, the tin-based magnetic catalyst prepared by the method simultaneously contains Bronsted acid and Lewis acid sites, and three samples of ferroferric oxide and dopamine-coated ferroferric oxide and tin-based magnetic catalyst respectively contain two acid sites. However, the acid strength of the tin-based magnetic catalyst of the sample is obviously higher than that of ferroferric oxide coated by ferroferric oxide and dopamine, which indicates that tin ions can provide stronger Lewis acid sites. The prepared tin-based magnetic catalyst simultaneously contains Bronsted acid and Lewis acid sites.
The application method for preparing furfural by using the tin-based magnetic catalyst comprises the following steps:
first, a catalytic reaction
Placing 120mg of bagasse and 30mg of the prepared tin-based magnetic catalyst into a reaction kettle, adding 5mL of saturated sodium chloride solution and 5mL of dichloromethane, uniformly mixing, and reacting at 170 ℃ for 90 min;
then, post-treating
After the catalytic reaction is finished, rapidly cooling in ice-water bath, separating two phases, distilling and concentrating furfural in a water phase, extracting and distilling at 30 ℃ by using ethyl acetate; and directly distilling the organic phase at 40-60 ℃ and collecting furfural.
Finally, the reuse of the catalyst
And separating the tin-based magnetic catalyst used in the post-treatment from the solid residue by an additional magnet, washing the obtained tin-based magnetic catalyst by using ultrapure water and ethanol, and drying the washed tin-based magnetic catalyst, so that the tin-based magnetic catalyst can be used for catalyzing the operation of preparing furfural from bagasse in the repeated post-treatment steps.
Calculating furfural yield, xylose conversion rate and furfural selectivity by using high performance liquid chromatography according to the following formulas:
through calculation, the furfural yield in example 1 is up to 83.5%, the xylose conversion rate is 95%, and the furfural selectivity is 88%. After the tin-based magnetic catalyst is repeatedly used once, the catalytic performance is reduced by 1.3 percent; after the catalyst is repeatedly used for 5 times, the catalytic performance is reduced by 2.4 percent, which shows that the catalyst has very stable performance.
The tin-based magnetic catalyst obtained by the preparation method of the tin-based magnetic catalyst has the advantages of high catalytic efficiency, good selectivity, easiness in recycling and the like, is directly used for catalyzing the reaction conditions of preparing furfural from hemicellulose in biomass, is mild, and is easy to industrialize.
Example 2
The method for preparing the tin-based magnetic solid catalyst by adopting a solvent hydrothermal method comprises the following steps:
firstly, 0.12g of ferric chloride hexahydrate, 0.36g of trisodium citrate and 0.48g of anhydrous sodium acetate are dissolved in 30mL of ethylene glycol, fully stirred for 30min at 500rpm and then transferred to a hydrothermal reaction kettle at 180 ℃ for reaction for 12 h; after the reaction is finished, cooling with ice water, separating and washing with an additional magnet, and drying in a 60 ℃ oven for 12 hours to obtain ferroferric oxide nanoparticles;
then, adding 0.8g of the obtained ferroferric oxide nanoparticles and 0.8g of dopamine hydrochloride into a Tris buffer solution with the pH value of 8.5-500mL-0.02M to react for 10 hours at 30 ℃, filtering by an additional magnet after the reaction is finished, washing for three times by using ultrapure water and absolute ethyl alcohol respectively, and drying for 12 hours in a 60 ℃ oven to obtain dopamine-coated ferroferric oxide nanoparticles;
and finally, uniformly mixing 3.505g of tin pentahydrate tetrachloride, 14.309g of sodium sulfoisophthalate, 100mL of dimethylformamide and 0.1g of the prepared dopamine-coated ferroferric oxide nano-particles, reacting in a hydrothermal reaction kettle at 90 ℃ for 18 hours, cooling with ice water, filtering with an additional magnet, washing with dimethylformamide and absolute ethyl alcohol for three times respectively, and drying in an oven at 60 ℃ for 12 hours to obtain the tin-based magnetic solid acid catalyst.
The VSM graph and the pyridine infrared graph of the tin-based magnetic catalyst obtained in example 2 are substantially the same as the results in example 1, and no description is made.
The application method for preparing furfural by using the tin-based magnetic catalyst comprises the following steps:
first, a catalytic reaction
Placing 150mg of corncob and 30mg of the prepared tin-based magnetic catalyst into a reaction kettle, adding 5mL of saturated potassium chloride solution and 8mL of tetrahydrofuran, uniformly mixing, and reacting at 180 ℃ for 120 min;
then, post-treating
After the catalytic reaction is finished, rapidly cooling in ice-water bath, separating two phases, distilling and concentrating furfural in a water phase, extracting and distilling at 30 ℃ by using ethyl acetate; and directly distilling the organic phase at 60-80 ℃ and collecting furfural.
Finally, the reuse of the catalyst
And separating the tin-based magnetic catalyst used in the post-treatment from the solid residue by an additional magnet, washing the obtained tin-based magnetic catalyst by using ultrapure water and ethanol, and drying the washed tin-based magnetic catalyst, so that the tin-based magnetic catalyst can be used for catalyzing the bagasse to prepare furfural in repeated post-treatment steps.
And calculating the furfural yield, xylose conversion rate and furfural selectivity by using high performance liquid chromatography according to the formulas (1) to (3). Through calculation, the furfural yield in example 2 is as high as 73.5%, the xylose conversion rate is 92.0%, and the furfural selectivity is 80%. After the tin-based magnetic catalyst is repeatedly used once, the catalytic performance is reduced by 2.3 percent; after the catalyst is repeatedly used for 5 times, the catalytic performance is reduced by 3.9 percent.
Example 3
The method for preparing the tin-based magnetic solid catalyst by adopting a solvent hydrothermal method comprises the following steps:
firstly, dissolving 1.5g of ferric trichloride hexahydrate, 0.3g of trisodium citrate and 3.0g of anhydrous sodium acetate in 60mL of ethylene glycol, fully stirring at 500rpm for 30min, transferring to a hydrothermal reaction kettle at 160 ℃ for reaction for 8h, cooling ice water after the reaction is finished, separating and washing by an additional magnet, and drying in an oven at 60 ℃ for 12h to obtain ferroferric oxide nanoparticles;
then, adding 0.3g of the obtained ferroferric oxide nanoparticles and 0.9g of dopamine hydrochloride into 300mL of Tris buffer solution with the pH value of 8.5 and the concentration range of 0.03M for reaction for 8 hours at 30 ℃, filtering the solution by an additional magnet after the reaction is finished, washing the solution three times by using ultrapure water and absolute ethyl alcohol respectively, and drying the solution for 10 hours in a 60 ℃ oven to obtain dopamine-coated ferroferric oxide nanoparticles;
and finally, uniformly mixing 18.0g of tin pentahydrate tetrachloride, 2.816g of sodium sulfoisophthalate, 100mL of dimethylformamide and 1.0g of the prepared dopamine-coated ferroferric oxide nano-particles, reacting in a hydrothermal reaction kettle at 80 ℃ for 10 hours, cooling with ice water, filtering with an additional magnet, washing with dimethylformamide and absolute ethyl alcohol for three times respectively, and drying in an oven at 60 ℃ for 11 hours to obtain the tin-based magnetic solid acid catalyst.
The VSM graph and the pyridine infrared graph of the tin-based magnetic catalyst obtained in example 3 are substantially the same as the results in example 1, and no description is made.
The application method for preparing furfural by using the tin-based magnetic catalyst comprises the following steps:
first, a catalytic reaction
Putting 90mg of eucalyptus powder and 30mg of the prepared tin-based magnetic catalyst into a reaction kettle, adding 5mL of potassium chloride solution and 4mL of dimethyl tetrahydrofuran, uniformly mixing, and reacting at 200 ℃ for 60 min;
then, post-treating
After the catalytic reaction is finished, rapidly cooling in ice-water bath, separating two phases, distilling and concentrating furfural in a water phase, extracting and distilling at 30 ℃ by using ethyl acetate; and directly distilling the organic phase at 80-100 ℃ and collecting furfural.
Finally, the reuse of the catalyst
And separating the tin-based magnetic catalyst used in the post-treatment from the solid residue by an additional magnet, washing the obtained tin-based magnetic catalyst by using ultrapure water and ethanol, and drying the washed tin-based magnetic catalyst, so that the tin-based magnetic catalyst can be used for catalyzing the bagasse to prepare furfural in repeated post-treatment steps.
And calculating the furfural yield, xylose conversion rate and furfural selectivity by using high performance liquid chromatography according to the formulas (1) to (3). Through calculation, the furfural yield in example 3 is as high as 86.4%, the xylose conversion rate is 93%, and the selectivity of furfural is 92.9%. After the tin-based magnetic catalyst is repeatedly used once, the catalytic performance is reduced by 0.7 percent; after the catalyst is repeatedly used for 5 times, the catalytic performance is reduced by 1.9 percent.
Example 4
The method for preparing the tin-based magnetic solid catalyst by adopting a solvent hydrothermal method comprises the following steps:
firstly, 0.8g of ferric trichloride hexahydrate, 1.2g of trisodium citrate and 1.6g of anhydrous sodium acetate are dissolved in 36mL of ethylene glycol, the mixture is fully stirred at 500rpm for 30min, then the mixture is transferred to a hydrothermal reaction kettle at 190 ℃ for reaction for 9h, after the reaction is finished, ice water is cooled, a magnet is added for separation and washing, and the mixture is dried in an oven at 60 ℃ for 12h to obtain ferroferric oxide nanoparticles;
then, adding 0.4g of the obtained ferroferric oxide nanoparticles and 0.8g of dopamine hydrochloride into 240mL of Tris buffer solution with the pH value of 8.5 and the concentration range of 0.02M, reacting for 10 hours at 30 ℃, filtering by an additional magnet after the reaction is finished, washing for three times by using ultrapure water and absolute ethyl alcohol respectively, and drying for 10 hours in a 60 ℃ oven to obtain dopamine-coated ferroferric oxide nanoparticles;
and finally, uniformly mixing 0.8g of tin pentahydrate tetrachloride, 0.8g of sodium m-phthalate sulfonate, 2.4mL of dimethylformamide and 0.8g of the prepared dopamine-coated ferroferric oxide nanoparticles, reacting in a hydrothermal reaction kettle at the temperature of 95 ℃ for 18h, cooling with ice water, filtering with an additional magnet, washing with dimethylformamide and absolute ethyl alcohol for three times respectively, and drying in an oven at the temperature of 60 ℃ for 9h to obtain the tin-based magnetic solid acid catalyst.
The VSM graph and the pyridine infrared graph of the tin-based magnetic catalyst obtained in example 4 are substantially the same as the results in example 1, and no description is made.
The application method for preparing furfural by using the tin-based magnetic catalyst comprises the following steps:
first, a catalytic reaction
Placing 100mg wheat straw and 50mg of the prepared tin-based magnetic catalyst into a reaction kettle, adding 0.04mL of sodium chloride solution and 0.06mL of gamma valerolactone, uniformly mixing, and reacting at 160 ℃ for 70 min;
then, post-treating
After the catalytic reaction is finished, rapidly cooling in ice-water bath, separating two phases, distilling and concentrating furfural in a water phase, extracting and distilling at 30 ℃ by using ethyl acetate; and directly distilling the organic phase at 80-100 ℃ and collecting furfural.
Finally, the reuse of the catalyst
And separating the tin-based magnetic catalyst used in the post-treatment from the solid residue by an additional magnet, washing the obtained tin-based magnetic catalyst by using ultrapure water and ethanol, and drying the washed tin-based magnetic catalyst, so that the tin-based magnetic catalyst can be used for catalyzing the bagasse to prepare furfural in repeated post-treatment steps.
And calculating the furfural yield, xylose conversion rate and furfural selectivity by using high performance liquid chromatography according to the formulas (1) to (3). Through calculation, the furfural yield in example 4 is up to 89.4%, the xylose conversion rate is 92%, and the selectivity of furfural is 92.6%. After the tin-based magnetic catalyst is repeatedly used once, the catalytic performance is reduced by 0.6 percent; after the catalyst is repeatedly used for 5 times, the catalytic performance is reduced by 2.3 percent.
Example 5
Firstly, dissolving 0.21g of ferric trichloride hexahydrate, 0.45g of trisodium citrate and 2.1g of anhydrous sodium acetate in 82.8mL of ethylene glycol, fully stirring at 500rpm for 30min, transferring the mixture into a hydrothermal reaction kettle at 175 ℃ for reaction for 11h, cooling ice water after the reaction is finished, separating and washing by an additional magnet, and drying in an oven at 60 ℃ for 8h to obtain ferroferric oxide nanoparticles;
then, adding 0.4g of the obtained ferroferric oxide nanoparticles and 1.2g of dopamine hydrochloride into 800mL of Tris buffer solution with the pH value of 8.5 and the concentration range of 0.02M to react for 11 hours at 30 ℃, filtering by an additional magnet after the reaction is finished, washing for three times by using ultrapure water and absolute ethyl alcohol respectively, and drying for 8 hours in a 60 ℃ oven to obtain dopamine-coated ferroferric oxide nanoparticles;
and finally, uniformly mixing 16.2g of tin pentahydrate tetrachloride, 8.1g of sodium sulfoisophthalate, 50.4mL of dimethylformamide and 0.9g of dopamine-coated ferroferric oxide nano-particles prepared above, reacting in a hydrothermal reaction kettle at 88 ℃ for 15 hours, cooling with ice water, filtering with an additional magnet, washing with dimethylformamide and absolute ethyl alcohol for three times respectively, and drying in an oven at 60 ℃ for 14 hours to obtain the tin-based magnetic solid acid catalyst.
The VSM graph and the pyridine infrared graph of the tin-based magnetic catalyst obtained in example 5 are substantially the same as the results in example 1, and no description is made.
The application method for preparing furfural by using the tin-based magnetic catalyst comprises the following steps:
first, a catalytic reaction
Putting 260mg of bamboo powder and 26mg of the prepared tin-based magnetic catalyst into a reaction kettle, adding 1mL of pure water solution and 0.2mL of methyl isobutyl ketone, uniformly mixing, and reacting at 190 ℃ for 180 min;
then, post-treating
After the catalytic reaction is finished, rapidly cooling in ice-water bath, separating two phases, distilling and concentrating furfural in a water phase, extracting and distilling at 30 ℃ by using ethyl acetate; and directly distilling the organic phase at 100-120 ℃ and collecting furfural.
Finally, the reuse of the catalyst
And separating the tin-based magnetic catalyst used in the post-treatment from the solid residue by an additional magnet, washing the obtained tin-based magnetic catalyst by using ultrapure water and ethanol, and drying the washed tin-based magnetic catalyst, so that the tin-based magnetic catalyst can be used for catalyzing the bagasse to prepare furfural in repeated post-treatment steps.
And calculating the furfural yield, xylose conversion rate and furfural selectivity by using high performance liquid chromatography according to the formulas (1) to (3). Through calculation, the furfural yield in example 5 is up to 90.4%, the xylose conversion rate is 95%, and the furfural selectivity is 94.1%. After the tin-based magnetic catalyst is repeatedly used once, the catalytic performance is reduced by 0.5 percent; after the catalyst is repeatedly used for 5 times, the catalytic performance is reduced by 1.2 percent.
Compared with the prior art, the preparation method of the tin-based magnetic catalyst and the application method thereof for preparing furfural have the following characteristics:
firstly, when the tin-based magnetic catalyst prepared by the method selectively catalyzes the half fiber in the biomass raw material to be the furfural, the tin-based magnetic catalyst has higher catalytic efficiency, better selectivity and good recycling availability,
secondly, in the process of preparing furfural by catalyzing biomass raw materials by using the tin-based magnetic catalyst prepared by the method, solid residues and the magnetic catalyst are easy to separate, the solid residues mainly contain cellulose and lignin, and the structure and the performance of the solid residues are not obviously changed, so that the high-efficiency utilization of downstream industries is facilitated, the industrial cost of furfural is reduced, and the step-by-step high-valued utilization of the biomass raw materials is realized;
thirdly, in the process of preparing furfural by catalyzing biomass raw materials, the tin-based magnetic catalyst prepared by the method is mild in reaction conditions, easy to control, easy to realize industrialization, free of pollution and corrosion in the reaction process, environment-friendly and capable of achieving the purposes of energy conservation and emission reduction.
Claims (10)
1. A preparation method of a tin-based magnetic catalyst is characterized by adopting a hydrothermal solvent method and comprising the following steps:
dissolving ferric trichloride hexahydrate, trisodium citrate and anhydrous sodium acetate in ethylene glycol, fully stirring, transferring to a hydrothermal reaction kettle, fully reacting, cooling, filtering, washing and drying to obtain ferroferric oxide nanoparticles;
secondly, adding the obtained ferroferric oxide nanoparticles and dopamine hydrochloride into a Tris buffer solution with the pH value of 8.5, and filtering, washing and drying after full reaction at room temperature to obtain dopamine-coated ferroferric oxide nanoparticles;
and step three, uniformly mixing tin tetrachloride pentahydrate, sodium sulfoisophthalate, dimethylformamide and the obtained dopamine-coated ferroferric oxide nanoparticles, fully reacting in a hydrothermal reaction kettle, cooling, filtering and drying to obtain the tin-based magnetic catalyst.
2. The method for preparing a tin-based magnetic catalyst according to claim 1, characterized in that: in the first step, the mass ratio of ferric trichloride hexahydrate, anhydrous sodium acetate and trisodium citrate is 1-5: 1-3: 4-10, wherein the solid-to-liquid ratio of a solid mixed substance composed of ferric trichloride hexahydrate, anhydrous sodium acetate and trisodium citrate to ethylene glycol is 1: 10-30 g/mL; the temperature of hydrothermal reaction in the hydrothermal reaction kettle is 160-200 ℃, and the reaction time is 8-12 h.
3. The method for preparing a tin-based magnetic catalyst according to claim 1, characterized in that: in the second step, the mass ratio of the ferroferric oxide nanoparticles to the dopamine hydrochloride is 1: 1-3, wherein the solid-to-liquid ratio of a solid mixed substance composed of ferroferric oxide nanoparticles and dopamine hydrochloride to a Tris buffer solution is 1: 200-500 g/mL, the concentration range of the Tris buffer solution with the pH value of 8.5 is 0.01-0.03M, and the reaction time is 8-12 h.
4. The method for preparing a tin-based magnetic catalyst according to claim 1, characterized in that: in the third step, the mass ratio of the dopamine-coated ferroferric oxide nanoparticles to the tin tetrachloride pentahydrate to the isophthalic acid is 1-10: 1-180: 1-90; and the solid-liquid ratio of a solid mixed substance consisting of ferroferric oxide nanoparticles, stannic chloride pentahydrate and isophthalic acid to dimethylformamide is 1: 1-20 g/mL; the hydrothermal reaction temperature in the hydrothermal reaction kettle is 80-100 ℃, and the reaction time is 10-20 h.
5. A method of preparing a tin-based magnetic catalyst according to any one of claims 1 to 4, characterized in that: washing the ferroferric oxide nanoparticles and the dopamine-coated ferroferric oxide nanoparticles respectively three times by using ultrapure water and absolute ethyl alcohol, and washing the tin-based magnetic catalyst respectively three times by using ultrapure water and dimethylformamide; and drying the ferroferric oxide nanoparticles, the dopamine-coated ferroferric oxide nanoparticles and the tin-based magnetic catalyst in an oven at the temperature of 60 ℃.
6. An application method of preparing furfural by using the tin-based magnetic catalyst as set forth in claims 1 to 5 is characterized by comprising the following steps:
first, catalytic reaction
Adding biomass and a tin-based magnetic catalyst into a hydrothermal reaction kettle, adding an organic phase and a water phase, and reacting at 160-200 ℃ for 60-180 min;
second, post-treatment
And cooling by using a water bath after the catalytic reaction is finished, filtering and separating solid and liquid, distilling the organic phase in the liquid to obtain furfural, and separating residues in the solid and the used tin-based magnetic catalyst by using an additional magnet.
7. The use of a tin-based magnetic catalyst for the preparation of furfural according to claim 6, characterized in that: in the first step, the biomass is biomass waste containing hemicellulose, and can be any one or a combination of several of bagasse, corncob, wheat straw, eucalyptus powder and bamboo powder.
8. The use of a tin-based magnetic catalyst for the preparation of furfural according to claim 6 or 7 wherein: in the first step, the mass ratio of the tin-based magnetic catalyst to the biomass is 1: 2-10; the solid-liquid ratio of the biomass to the mixed liquid comprising the organic phase and the water phase in the reaction system is 1: 1-100 g/mL; in the mixed liquid, the volume ratio of the organic phase to the aqueous phase is 1: 1 to 2.
9. The use of a tin-based magnetic catalyst for the preparation of furfural according to claim 8, characterized in that: the water phase is any one of water, a sodium chloride solution or a potassium chloride solution; the organic phase is any one of dichloromethane, dimethyl tetrahydrofuran, gamma valerolactone, dimethyl sulfoxide, methyl isobutyl ketone or tetrahydrofuran.
10. The use of a tin-based magnetic catalyst for the preparation of furfural according to claim 6, characterized in that: in the second step, the used tin-based magnetic catalyst is separated from the residues through an additional magnet, washed by ethanol and hot water, and dried to be repeatedly used for catalyzing biomass to prepare furfural.
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