CN113956221A - Method for preparing furan acid compound by catalytic oxidation of furan aldehyde or furan alcohol under alkali-free condition - Google Patents
Method for preparing furan acid compound by catalytic oxidation of furan aldehyde or furan alcohol under alkali-free condition Download PDFInfo
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- CN113956221A CN113956221A CN202111123207.4A CN202111123207A CN113956221A CN 113956221 A CN113956221 A CN 113956221A CN 202111123207 A CN202111123207 A CN 202111123207A CN 113956221 A CN113956221 A CN 113956221A
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 239000002253 acid Substances 0.000 title claims abstract description 43
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 37
- -1 furan aldehyde Chemical class 0.000 title claims abstract description 33
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 30
- 230000003647 oxidation Effects 0.000 title claims abstract description 27
- 150000001875 compounds Chemical class 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 63
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 230000001590 oxidative effect Effects 0.000 claims abstract description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 59
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 45
- 229910052681 coesite Inorganic materials 0.000 claims description 40
- 229910052906 cristobalite Inorganic materials 0.000 claims description 40
- 229910052682 stishovite Inorganic materials 0.000 claims description 40
- 229910052905 tridymite Inorganic materials 0.000 claims description 40
- 239000000377 silicon dioxide Substances 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 31
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical group O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 18
- 238000001291 vacuum drying Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical group F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 14
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 13
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 13
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 12
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 12
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 7
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 6
- 239000012696 Pd precursors Substances 0.000 claims description 6
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- 229910052734 helium Inorganic materials 0.000 claims description 5
- 239000001307 helium Substances 0.000 claims description 5
- DSLRVRBSNLHVBH-UHFFFAOYSA-N 2,5-furandimethanol Chemical compound OCC1=CC=C(CO)O1 DSLRVRBSNLHVBH-UHFFFAOYSA-N 0.000 claims description 4
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- OUDFNZMQXZILJD-UHFFFAOYSA-N 5-methyl-2-furaldehyde Chemical compound CC1=CC=C(C=O)O1 OUDFNZMQXZILJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910003603 H2PdCl4 Inorganic materials 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 claims description 2
- UBTYFVJZTZYJHZ-UHFFFAOYSA-N n-[2-(prop-2-enoylamino)propyl]prop-2-enamide Chemical compound C=CC(=O)NC(C)CNC(=O)C=C UBTYFVJZTZYJHZ-UHFFFAOYSA-N 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical group Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(II) nitrate Inorganic materials [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 239000010931 gold Substances 0.000 abstract description 7
- 239000002028 Biomass Substances 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 6
- 229910052737 gold Inorganic materials 0.000 abstract description 5
- 229910052763 palladium Inorganic materials 0.000 abstract description 5
- 238000010494 dissociation reaction Methods 0.000 abstract description 3
- 230000005593 dissociations Effects 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 28
- 230000008929 regeneration Effects 0.000 description 16
- 238000011069 regeneration method Methods 0.000 description 16
- PCSKKIUURRTAEM-UHFFFAOYSA-N 5-hydroxymethyl-2-furoic acid Chemical compound OCC1=CC=C(C(O)=O)O1 PCSKKIUURRTAEM-UHFFFAOYSA-N 0.000 description 13
- 238000005119 centrifugation Methods 0.000 description 12
- 238000001514 detection method Methods 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- OVOCLWJUABOAPL-UHFFFAOYSA-N 5-methylfuran-2-carboxylic acid Chemical compound CC1=CC=C(C(O)=O)O1 OVOCLWJUABOAPL-UHFFFAOYSA-N 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 239000013078 crystal Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- SMNDYUVBFMFKNZ-UHFFFAOYSA-N 2-furoic acid Chemical class OC(=O)C1=CC=CO1 SMNDYUVBFMFKNZ-UHFFFAOYSA-N 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- VOZFDEJGHQWZHU-UHFFFAOYSA-N (5-methylfuran-2-yl)methanol Chemical compound CC1=CC=C(CO)O1 VOZFDEJGHQWZHU-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- BBKFSSMUWOMYPI-UHFFFAOYSA-N gold palladium Chemical compound [Pd].[Au] BBKFSSMUWOMYPI-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 2
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 238000001362 electron spin resonance spectrum Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000012673 precipitation polymerization Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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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 belongs to the field of preparing high-value oxygenated chemicals by biomass directional conversion, and provides a method for preparing a furan acid compound by catalytically oxidizing furan aldehyde or furan alcohol under an alkali-free condition. The catalyst is prepared by utilizing the hollow hemispherical nitrogen-doped carbon material loaded with gold and palladium bimetallic after oxidation treatment, and the furan acid compound is prepared by catalytically oxidizing furan aldehyde or furan alcohol in a green water solvent under the alkali-free condition by combining the synergistic catalytic action of the bimetallic and the generation of hydroxyl free radicals through water dissociation on the surface of the nitrogen-doped carbon carrier in the reaction process.
Description
Technical Field
The invention belongs to the field of development of novel green catalytic reaction systems, and particularly relates to a method for preparing a furan acid compound by catalytic oxidation of furan aldehyde or furan alcohol under an alkali-free condition.
Background
Under the large background of 'carbon neutralization', the carbon neutrality and high oxygen content characteristics of biomass are utilized, the biomass directional conversion is developed with increased force, and biomass-based high-value oxygen-containing products are generated, so that the method has very important promotion effects on the goals of 'carbon peak reaching before 2030 years' and 'carbon neutralization before 2060 years'. Furanoic acid compounds (such as 2, 5-furandicarboxylic acid, furoic acid, 5-methyl-2-furoic acid and the like) derived from biomass are further applied to the fields of materials, energy, food, medicines and the like, and are important means for realizing high-value utilization of biomass resources. For example, 2, 5-furandicarboxylic acid (FDCA), which is one of the most valuable twelve bio-based platform compounds, has an aromatic ring system similar to petroleum-based bulk chemical terephthalic acid (PTA), contains a diacid structure, is similar to PTA in physicochemical properties, can be an ideal bio-based substitute for PTA, and is applied to the development of biodegradable plastics and series products thereof in the national encouragement industry (the "industry structure adjustment guide catalogue (2019)"). Furoic acid, also known as 2-furoic acid or 2-furoic acid, can be used for synthesizing methylfuran, furoamide, furoate ester and salt. Useful in the plastics industry as plasticizers, thermosetting resins, and the like; as a preservative in the food industry; also useful as an intermediate for paint additives, medicines, perfumes, etc. Therefore, the development of a method for efficiently preparing the furan acid compound is of great significance in the aspect of new energy development.
The furan acid compound is used as a weak acid, and a certain amount of alkali is added for neutralization in the preparation process so as to promote the forward direction of the reaction. However, the addition of alkaline substances is corrosive to the reaction apparatus, and increases the cost and difficulty of furan acid separation. Taking the synthesis preparation of FDCA as an example, the catalytic oxidation of HMF to prepare FDCA mainly involves the following reactions: (1) hydroxyl oxidation of HMF to DFF, or carbonyl oxidation to HMFCA; (2) carbonyl oxidation of DFF or hydroxyl oxidation of HMFCA to FFCA; (3) carbonyl oxidation of FFCA produces FDCA. The smooth proceeding of the HMF oxidation reaction requires the presence of a basic substance, and at the same time, requires a catalyst having high selectivity and excellent catalytic performance. In the reaction of synthesizing furoic acid, furfural or furfuryl alcohol is often used as a substrate to synthesize furoic acid under alkaline conditions. In order to solve the problem of adding alkaline substances, a metal catalyst loaded with alkaline substances such as hydrotalcite and the like as a carrier is often used for realizing multi-stage oxidation reaction. However, the carrier of the catalyst is easy to decompose in the reaction process, so that new impurities are introduced into the reaction system, the catalyst is poor in stability and cannot be reused, the difficulty of separation and extraction of furan acid is increased, and the reaction system is difficult to realize greenization.
Disclosure of Invention
The invention aims to provide a method for preparing a furan acid compound by catalytically oxidizing furan aldehyde or furan alcohol under alkali-free conditions. The method comprises the steps of coating a nitrogen-containing polymer on the surface of a silicon sphere in a precipitation polymerization mode, generating a nitrogen-doped carbon material after pyrolysis, removing a template, preparing a catalyst by using a hollow hemispherical nitrogen-doped carbon material loaded with gold and palladium bimetallic after oxidation treatment, combining the synergistic catalytic action of the bimetallic and the generation of hydroxyl radicals by water dissociation on the surface of the nitrogen-doped carbon carrier in a reaction process, and realizing the preparation of a furan acid compound by catalytic oxidation of furan aldehyde or furan alcohol in a green aqueous solvent under the alkali-free condition.
The technical scheme adopted by the invention is as follows:
a method for preparing furan acid compound by catalytically oxidizing furan aldehyde or furan alcohol under alkali-free condition comprises the following steps: dispersing reaction substrates furan aldehyde or furan alcohol and a catalyst AuPd/hollow hemispherical nitrogen-doped carbon material into distilled water, introducing oxygen into a reaction kettle to a specified pressure, setting a specified temperature, and catalytically oxidizing the furan aldehyde or furan alcohol to obtain furan acid.
The furan aldehyde is furfural, 5-hydroxymethylfurfural or 5-methylfurfural; the furan alcohol is furfuryl alcohol, 5-methyl-2-furancarbinol or 2, 5-furandimethanol.
The catalyst AuPd/hollow hemispherical nitrogen-doped carbon material, the reaction substrate and the distilled water are used in the following ratio: 10-100 mg: 10-80 mg: 20-80 mL; the specified pressure intensity is 1.0-2.0 MPa; the temperature of the reaction system is 80-180 ℃, and the reaction time is 4-54 h.
The preparation steps of the catalyst AuPd/hollow hemispherical nitrogen-doped carbon material are as follows:
a1, mixing SiO2Dispersing the spheres into a toluene solution, uniformly mixing, keeping for a period of time in an inert gas atmosphere, adding 3- (methacryloyloxy) propyl trimethoxy silane KH-570 into a mixed system under a stirring state, and modifying the surface functional groups of the silicon dioxide by using a reaction system at a certain temperature; surface-modified SiO2Ball i.e. v-SiO2Dispersing into acetonitrile solution, adding azo initiator, nitrogen-containing polymerizable monomer and crosslinking agentA linking agent; ultrasonically dispersing the mixed solution uniformly, keeping the mixed solution in an inert gas atmosphere, placing the mixed solution in a water bath oscillator, heating to a specified temperature, keeping the temperature, and continuing to heat to a target temperature after a certain time; after the reaction is finished, centrifugally collecting and vacuum drying the product to obtain polymer SiO2@ Poly; then SiO2@ Poly is put in a tube furnace, the temperature is programmed to the calcining temperature under the inert gas atmosphere, and the carbon material SiO is obtained after calcination2@NC；
A2, mixing SiO2Soaking @ NC in a mixed solution of a silicon removing agent and ethanol, centrifugally collecting a product after soaking, carrying out oxidation treatment on the product by using an oxidizing compound with a certain concentration after vacuum drying, centrifugally washing, collecting the product, and carrying out vacuum drying to obtain a hollow hemispherical nitrogen-doped carbon material, HhSNC (hollow helium nitro product bonded carbon);
a3 polyvinyl alcohol PVA, palladium precursor and HAuCl4·3H2Dropwise adding sodium borohydride NaBH into O mixed solution4And (3) uniformly stirring the solution, adjusting the pH value of the solution, adding the HhSNC obtained in the step (A2) into the solution, centrifugally collecting a product after the reaction is finished, and drying in vacuum to obtain the catalyst AuPd/hollow hemispherical nitrogen-doped carbon material, named AuPd/HhSNC for short.
In step A1, the SiO2The dosage ratio of the toluene to the KH-570 is 0.2-5 g: 50-500 mL: 1.0-20 mL; the reaction temperature is 50-120 ℃, and the reaction time is 6-48 h.
In step a1, the azo initiator is azobisisobutyronitrile or azobisisoheptonitrile; the nitrogen-containing polymerizable monomer is N, N-propylene bisacrylamide, imidazole, carbazole or acrylamide; the cross-linking agent is divinylbenzene, acrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate or methacrylic acid; the inert gas is: nitrogen, argon or helium;
in step A1, the v-SiO2The ratio of the azo initiator to the nitrogen-containing polymerizable monomer to the crosslinking agent to the acetonitrile is 1-100 mg: 10-200 mg: 1-800 mg: 1-800 mg: 10-100 mL; the reaction temperature is 50-80 ℃, and the reaction time is 2.0-48 h; the temperature for vacuum drying is 20-90 ℃.
In the step A1, the heating rate is 1.0-10 ℃/min, the calcination temperature is 400-1200 ℃, and the calcination time is 1-10 h; the inert gas is: nitrogen, argon or helium.
In the step A2, the silicon removing agent is hydrofluoric acid (HF), phosphoric acid or potassium hydroxide; the SiO2The ratio of @ NC to the silicon removing agent to the ethanol is 0.2-5 g: 5.0-20 mL: 1.0-20 mL; the soaking temperature is 20-50 deg.C, and the soaking time is 0.5-5.0 h.
In step A2, the oxidizing compound is nitric acid, hydrochloric acid, hydrogen peroxide or potassium hydroxide; the temperature of the oxidation treatment is 20-180 ℃, and the time of the oxidation treatment is 0.5-5.0 h; the temperature for vacuum drying is 40-120 ℃.
In step A3, the palladium precursor is PdCl2、Pd(NO3)2，Pd(NH3)4(NO3)2Or H2PdCl4(ii) a The PVA, the palladium precursor and the HAuCl4·3H2O、NaBH4The ratio of HhSNC is 0.01-3.0 g: 0.01-10 mL: 0.01-10 mL: 1.0-20 mL: 0.1-2.0 g; the reaction temperature is 20-50 ℃, and the reaction time is 0.5-5.0 h; the pH of the solution is in the range of 6-9.
The invention has the advantages that:
(1) catalyst properties: firstly, the catalyst AuPd/HhSNC prepared by loading gold-palladium bimetallic on a hollow hemispherical nitrogen-doped carbon material not only has the confinement effect of a nano reactor, but also has a synergistic effect with the loaded gold-palladium alloy, so that the catalytic activity of the catalyst is further improved; secondly, the surface of the prepared catalyst is modified by oxygen-containing functional groups, so that the catalyst has the capability of initiating the generation of hydroxyl radicals, and can effectively catalyze and oxidize furan aldehyde or furan alcohol to be converted into furan acid under the alkali-free condition.
(2) Aspect of catalytic reaction system: the catalytic reaction of the catalyst AuPd/HhSNC for catalytically oxidizing furan aldehyde or furan alcohol to obtain furan acid is carried out in an aqueous solution under the alkali-free condition, and after the reaction is finished, the catalyst can be separated under the action of centrifugal force, and simultaneously, the formation of a large amount of furan salts is avoided.
(3) The invention adopts the technology, has simple preparation process and easy operation, and has universality for oxidation reaction needing alkaline additive.
Drawings
FIG. 1 is a scanning electron microscope (a), a transmission electron microscope (b) and a high resolution image (c) of the catalyst prepared in example 1.
Fig. 2 is a nitrogen adsorption-desorption curve (a) and a pore size distribution diagram (b) of the catalyst prepared in example 1.
FIG. 3 is a wide-angle X-ray diffraction pattern (a) and a Raman spectrum (b) of the catalyst prepared in example 1.
FIG. 4 is an XPS energy spectrum of the catalyst prepared in example 1.
Fig. 5 is a contact angle before and after the oxidation treatment of the catalyst carrier prepared in example 1.
Fig. 6 is an in-situ infrared spectrum (a) and an ESR spectrum (b) of dissociated water molecules of the catalyst support prepared in example 1.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, but the scope of the invention is not limited thereto.
Example 1
(1) Preparation of the catalyst
2.0g of SiO2The spheres were dispersed in 200mL of toluene solution, mixed well and held under nitrogen for a period of time. Adding 12mL of 3- (methacryloyloxy) propyl trimethoxy silane KH-570 into the mixed system under the stirring state, and realizing the modification of the silica surface functional groups by the reaction system at the temperature of 90 ℃. 0.2g of surface-modified SiO2Ball i.e. v-SiO2Dispersed in 60mL acetonitrile and 80mg azobisisobutyronitrile, 0.4176g acrylamide and 0.3824g divinylbenzene were added. And ultrasonically dispersing the mixed solution uniformly, and keeping the mixed solution for 30min under the nitrogen atmosphere. Placing in a water bath oscillator, heating to 50 deg.C for 6.0h, and then heating to 60 deg.C for 24 h. After the reaction is finished, the product is centrifugally collected and dried in vacuum to obtain the polymer (SiO)2@Poly)。
1.0g of the SiO obtained in the preceding step2@ Poly is put in a tube furnace, and is calcined for 2.0h at the temperature of 800 ℃ by the programmed heating at the speed of 5 ℃/min under the nitrogen atmosphere to obtainCarbon material SiO2@NC。
0.5g of SiO2@ NC was placed in a mixed solution of 10.67mL of hydrofluoric acid and 9.33mL of ethanol, and after completion of soaking for 24 hours, the product was collected by centrifugation and dried in vacuum. 0.5g of sample was added to 20mL of 30% HNO3After soaking at 140 ℃ for 2.0h, the product is collected after centrifugal washing and vacuum drying to obtain a hollow hemispherical nitrogen-doped carbon material (HhSNC).
To 14mg of polyvinyl alcohol PVA, 5.75mL of PdCl2And 5.20mL HAuCl4·3H2Adding 13.2mL of NaBH into the O mixed solution dropwise4After the solution was stirred uniformly, the pH of the solution was adjusted to 7, and 1.0g of HhSNC obtained in the previous step was added to the solution. After reacting for 2.0h, the product is collected by centrifugation and dried in vacuum to obtain the catalyst AuPd/HhSNC.
From the scanning image of the AuPd/HhSNC catalyst prepared in FIG. 1, the catalyst is clearly seen to be hollow hemispheric overall, and the transmission image clearly shows that the metal particles are uniformly distributed on the surface of the hollow hemispheric carrier, and the average diameter of the metal is 4.88 nm. The metal lattice can be observed in a high resolution image, and the lattice stripes of 0.236nm and 0.229nm respectively correspond to the (111) crystal plane of Au and the (111) crystal plane of Pd.
In FIG. 2(a), the nitrogen adsorption/desorption diagram shows that the prepared catalyst has micropores and mesopores and has a specific surface area of 434.79m2 g-1The average pore diameter was 3.09 nm.
From the wide-angle X-ray diffraction pattern in fig. 3(a), it can be seen that the characteristic diffraction peaks of Au and Pd in the prepared catalyst coincide with each other and correspond to the corresponding crystal planes, i.e., (111) crystal plane at 38.84 °, (200) crystal plane at 45.01 °, and (220) crystal plane at 66.12 °, which is probably due to the fact that the supported Au and Pd appear in an alloy state and the characteristic peaks of both coincide with each other. In FIG. 3(b), the Raman spectrum is located at 1344.31cm-1The sum of characteristic peaks of D band at position is 1587.29cm-1The characteristic peak of G band is calculated to obtain ID/IG2.07, which indicates that the catalyst prepared has some carbon defects.
In fig. 4, the appearance of Au 4f and Pd 3p signal peaks in the XPS energy spectrum of the AuPd/HhSNC catalyst demonstrates the successful loading of Au and Pd nanoparticles on the hollow hemispherical nitrogen-doped carbon material HhSNC.
In fig. 5, the contact angle of the catalyst support after the oxidation treatment was changed from 118.2 ° to 32.1 °, indicating the transition of the support from a hydrophobic surface to a hydrophilic surface.
As can be seen from the in-situ infrared spectra of the catalyst carrier prepared in fig. 6(a) on dissociation of water molecules before and after nitration, the carrier has a stronger ability of dissociating water molecules to generate hydroxyl radicals after nitration. Compared with the free radical capture experiment in FIG. 6(b), the nitrified carrier has excellent free radical generating capacity.
(2) And (3) testing the catalytic activity, namely applying the catalyst to the reaction of preparing 2, 5-furandicarboxylic acid (FDCA) by catalytic oxidation of 5-Hydroxymethylfurfural (HMF):
firstly, 50mg of HMF and 50mg of catalyst are added into a 100mL polytetrafluoroethylene lining containing 40mL of distilled water, after uniform mixing, 2.0MPa of oxygen is introduced into a reaction kettle which is assembled, and reaction is carried out for 48h at the temperature of 100 ℃ and the rotating speed of 600 r/min. Detecting the reaction solution by using a High Performance Liquid Chromatography (HPLC) with an ultraviolet detector and a C18 column, and diluting the obtained product to 100 times in a volumetric flask. The detection conditions are as follows: 30 ℃; the mobile phase is 0.1 wt% acetic acid and acetonitrile, the proportion is 92: 8; the flow rate is 0.6 mL/min; the detection wavelength is 280 nm; the amount of sample was 5. mu.L.
The standard curve of the HMF sample is 66.578x-14.026, the standard curve of the HMFCA sample is 5.0204x-0.3507, the standard curve of the FFCA sample is 60.458x-6.0935, and the standard curve of the FDCA sample is 21.068 x-5.1418. (x represents the concentrations corresponding to HMF, HMFCA, FFCA and FDCA, and is in mg/L, and y represents the peak area), and the concentrations of HMF, HMFCA, FFCA and FDCA can be calculated from the standard curve and converted into molar concentrations. The product yield is calculated as Y (molar yield) ═ n1/no × 100, n1 represents the molar yields of HMFCA, FFCA and FDCA obtained from the reaction, and no represents the molar amount of HMF contained in the reaction substrate. The calculation result shows that the product can achieve higher yield, and the yield of the FDCA is 93.9%.
(3) Test for regeneration Performance
In the present invention, the catalyst can be recovered by centrifugation, separation and drying. Putting the recovered catalyst into the catalytic test again to test the catalytic effect; five regeneration tests were carried out in this way. The detection method and test conditions of the catalytic product are the same as those of the catalytic test.
The results show that: the loss of catalyst activity during regeneration was low, and the yields of FDCA during one to five trials of regeneration were 93.7%, 93.1%, 92.6%, 90.1% and 80.2% in that order.
Example 2
(1) Preparation of the catalyst
1.0g of SiO2The spheres were dispersed in 100mL of toluene solution, mixed well and kept under nitrogen for a while. 6.0mL of 3- (methacryloyloxy) propyltrimethoxysilane KH-570 was added to the mixed system under stirring, and the reaction system achieved modification of the silica surface functional groups at 100 ℃. 0.1g of surface-modified SiO2Ball i.e. v-SiO2Dispersed in 60mL acetonitrile and 40mg azobisisobutyronitrile, 0.2138g acrylamide and 0.1912g divinylbenzene were added. And ultrasonically dispersing the mixed solution uniformly, and keeping the mixed solution for 30min under the nitrogen atmosphere. Placing in a water bath oscillator, heating to 50 deg.C for 6.0h, and then continuing heating to 60 deg.C for 12 h. After the reaction is finished, centrifugally collecting and vacuum drying the product to obtain polymer SiO2@Poly。
0.5g of the SiO obtained in the preceding step2@ Poly is put in a tube furnace, and is calcined for 2.0h at the temperature of 800 ℃ by the programmed heating at the speed of 5 ℃/min under the nitrogen atmosphere to obtain the carbon material SiO2@NC。
0.25g of SiO2@ NC was soaked in a mixture of 5.34mL hydrofluoric acid and 4.66mL ethanol for 12h, and the product was collected by centrifugation and dried under vacuum. 0.2g of sample was added to 10mL of 30% HNO3After soaking at 120 ℃ for 2.0h, the product is collected after centrifugal washing, and vacuum drying is carried out to obtain the hollow hemispherical nitrogen-doped carbon material (HhSNC).
To a solution of 7mg of PVA, 2.86mL of PdCl2And 2.65mL HAuCl4·3H26.6mL NaBH was added dropwise to the O mixed solution4After the solution was stirred uniformly, the pH of the solution was adjusted to 6.5, and 0.5g of HhSNC obtained in the previous step was added to the solution. After reacting for 2.0h, the product is collected by centrifugation and dried in vacuum to obtain the catalyst AuPd/HhSNC. (2) And (3) testing the catalytic activity, namely respectively applying the catalysts to the reaction of preparing furoic acid by catalyzing furfural:
firstly, 50mg of furfural and 50mg of catalyst are respectively added into a 100mL polytetrafluoroethylene lining containing 40mL of distilled water, after uniform mixing, 2.0MPa of oxygen is introduced into an assembled reaction kettle, and the reaction is carried out for 24 hours at the rotation speed of 600r/min at the temperature of 90 ℃. Detecting the product by using a High Performance Liquid Chromatography (HPLC) with an ultraviolet detector and a C18 column, and diluting the obtained product to 100 times in a volumetric flask. The detection conditions are as follows: room temperature; the mobile phase was water and methanol at pH 4, in a ratio of 80: 20; the flow rate is 1.0 mL/min; the detection wavelength is 220 nm; the amount of sample was 10. mu.L.
The standard curve of the furfural sample is 17.258x-0.862, the standard curve of the furfuryl alcohol sample is 56.565x-4.6834, and the standard curve of the furoic acid sample is 28.293x-6.333(x represents the corresponding concentration of furfural, furfuryl alcohol and furoic acid, the unit is mg/L, and y represents the peak area). The product yield calculation formula is that Y (molar yield) ═ n1/no × 100, n1 represents the molar yields of furfural, furfuryl alcohol and furoic acid obtained by the reaction, and no represents the molar amount of furfural contained in the reaction substrate. The calculation result shows that the product can achieve higher yield, and the yield of the furoic acid is 89.2%.
(3) Test for regeneration Performance
In the present invention, the catalyst can be recovered by centrifugation, separation and drying. Putting the recovered catalyst into the catalytic test again to test the catalytic effect; five regeneration tests were carried out in this way. The detection method and test conditions of the catalytic product are the same as those of the catalytic test.
The results show that: the loss of catalyst activity during regeneration was low, and the yield of furoic acid was 89.0%, 88.4%, 87.6%, 87.1% and 82.5% in sequence during one to five trials of regeneration.
Example 3
(1) Preparation of the catalyst
0.5g of SiO2The spheres were dispersed in 100mL of toluene solution, mixed well and kept under nitrogen for a while. 3.0mL of 3- (methacryloyloxy) propyltrimethoxysilane KH-570 was added to the mixed system under stirring, and the reaction system achieved modification of silica surface functional groups at 95 ℃. 0.2g of surface-modified SiO2Ball i.e. v-SiO2Dispersed in 60mL acetonitrile and 80mg azobisisobutyronitrile, 0.5487g acrylamide and 0.2513g divinylbenzene were added. And ultrasonically dispersing the mixed solution uniformly, and keeping the mixed solution for 30min under the nitrogen atmosphere. Placing in a water bath oscillator, heating to 50 deg.C for 6.0h, and then continuing heating to 60 deg.C for 18 h. After the reaction is finished, centrifugally collecting and vacuum drying the product to obtain polymer SiO2@Poly。
1.5g of the SiO obtained in the preceding step2@ Poly is put in a tube furnace, and is calcined for 2.0h at the temperature of 800 ℃ by the programmed heating at the speed of 5 ℃/min under the nitrogen atmosphere to obtain the carbon material SiO2@NC。
0.1g of SiO2@ NC was soaked in a mixed solution of 2.33mL of hydrofluoric acid and 1.68mL of ethanol for 18h, and the product was collected by centrifugation and dried under vacuum. 0.1g of sample was added to 5mL of 30% HNO3After soaking at 130 ℃ for 2.0h, the product is collected after centrifugal washing, and vacuum drying is carried out to obtain a hollow hemispherical nitrogen-doped carbon material (HhSNC).
To 21mg of polyvinyl alcohol PVA, 7.92mL of PdCl2And 7.85mL HAuCl4·3H218.6mL NaBH was added dropwise to the O mixed solution4After the solution was stirred uniformly, the pH of the solution was adjusted to 7.5, and 1.5g of HhSNC obtained in the previous step was added to the solution. After reacting for 2.0h, the product is collected by centrifugation and dried in vacuum to obtain the catalyst AuPd/HhSNC. (2) And (3) testing the catalytic activity, namely respectively applying the catalysts to the reaction of preparing furoic acid by catalyzing furfuryl alcohol:
firstly, 50mg of furfuryl alcohol and 40mg of catalyst are respectively added into a 100mL polytetrafluoroethylene lining containing 40mL of distilled water, after uniform mixing, 2.0MPa of oxygen is introduced into an assembled reaction kettle, and the reaction is carried out for 12 hours at the temperature of 90 ℃ and the rotating speed of 600 r/min. Detecting the product by using a High Performance Liquid Chromatography (HPLC) with an ultraviolet detector and a C18 column, and diluting the obtained product to 100 times in a volumetric flask. The detection conditions are as follows: room temperature; the mobile phase was water and methanol at pH 4, in a ratio of 80: 20; the flow rate is 1.0 mL/min; the detection wavelength is 220 nm; the amount of sample was 10. mu.L.
The furfuryl alcohol sample standard curve is 56.565x-4.6834, the furoic acid sample standard curve is 28.293x-6.333(x represents the concentration of furfuryl alcohol and furoic acid, and the unit is mg/L, and y represents the peak area), and the concentrations of furfuryl alcohol and furoic acid can be calculated according to the standard curve and converted into molar concentration. The product yield is calculated by the formula of Y (molar yield) ═ n1/no × 100, n1 represents the molar yields of furfuryl alcohol and furoic acid obtained by the reaction, and no represents the molar amount of furfuryl alcohol contained in the reaction substrate. The calculation result shows that the product can achieve higher yield, and the yield of the furoic acid is 81.6%.
(3) Test for regeneration Performance
In the present invention, the catalyst can be recovered by centrifugation, separation and drying. Putting the recovered catalyst into the catalytic test again to test the catalytic effect; five regeneration tests were carried out in this way. The detection method and test conditions of the catalytic product are the same as those of the catalytic test.
The results show that: the loss of catalyst activity during regeneration was low, and the yield of furoic acid was 81.2%, 80.8%, 80.6%, 80.1% and 72.5% in sequence during one to five times of the regeneration.
Example 4
(1) Preparation of the catalyst
2.5g of SiO2The spheres were dispersed in 250mL of toluene solution, mixed well and held for a period of time under nitrogen. Adding 15.0mL of 3- (methacryloyloxy) propyl trimethoxy silane KH-570 into the mixed system under the stirring state, and realizing the modification of the surface functional groups of the silicon dioxide by the reaction system at the temperature of 90 ℃. 0.4g of surface-modified SiO2Ball i.e. v-SiO2Dispersing into 100mL acetonitrile solution, adding 160mg azobisisobutyronitrile, 125g of acrylamide and 1.06g of divinylbenzene. And ultrasonically dispersing the mixed solution uniformly, and keeping the mixed solution for 30min under the nitrogen atmosphere. Placing in a water bath oscillator, heating to 50 deg.C for 6.0h, and then continuing heating to 60 deg.C for 12 h. After the reaction is finished, centrifugally collecting and vacuum drying the product to obtain polymer SiO2@Poly。
2g of the SiO obtained in the preceding step2@ Poly is put in a tube furnace, and is calcined for 2.0h at the temperature of 800 ℃ by the programmed heating at the speed of 5 ℃/min under the nitrogen atmosphere to obtain the carbon material SiO2@NC。
1.0g of SiO2@ NC was soaked in a mixture of 15.68mL hydrofluoric acid and 14.40mL ethanol for 6.0h, and the product was collected by centrifugation and dried under vacuum. 1.0g of sample was added to 30mL of 30% HNO3After soaking at 140 ℃ for 2.0h, the product is collected after centrifugal washing and vacuum drying to obtain a hollow hemispherical nitrogen-doped carbon material (HhSNC).
To 10mg of polyvinyl alcohol PVA, 3.86mL of PdCl2And 3.94mL HAuCl4·3H2Adding 9.8mL of NaBH into the O mixed solution dropwise4After the solution was stirred uniformly, the pH of the solution was adjusted to 7.0, and 0.5g of HhSNC obtained in the previous step was added to the solution. After reacting for 2.0h, the product is collected by centrifugation and dried in vacuum to obtain the catalyst AuPd/HhSNC. (2) And (3) testing the catalytic activity, namely respectively applying the catalysts to the reaction of catalyzing 5-methyl-2-furanmethanol to prepare 5-methyl-2-furoic acid:
firstly, 50mg of 5-methyl-2-furancarbinol and 60mg of catalyst are respectively added into a 100mL polytetrafluoroethylene lining containing 40mL of distilled water, after uniform mixing, 2.0MPa of oxygen is introduced into a reaction kettle which is assembled, and the reaction is carried out for 24 hours at the rotating speed of 600r/min at the temperature of 100 ℃. Detecting the product by using a High Performance Liquid Chromatography (HPLC) with an ultraviolet detector and a C18 column, and diluting the obtained product to 100 times in a volumetric flask. The detection conditions are as follows: room temperature; the mobile phase was water and methanol at pH 4, in a ratio of 80: 20; the flow rate is 1.0 mL/min; the detection wavelength is 220 nm; the amount of sample was 10. mu.L.
The standard curve of the 5-methyl-2-furancarbinol sample is 46.075x-32.578, the standard curve of the 5-methyl-2-furoic acid sample is y 11.335x +12.247(x represents the corresponding concentration of the 5-methyl-2-furancarbinol and the 5-methyl-2-furoic acid, the unit is mg/L, and y represents the peak area), and the concentrations of the 5-methyl-2-furancarbinol and the 5-methyl-2-furoic acid can be calculated according to the standard curve and converted into molar concentrations. The product yield was calculated as Y (molar yield) ═ n1/no × 100, n1 represents the molar yields of 5-methyl-2-furanmethanol and 5-methyl-2-furoic acid obtained by the reaction, and no represents the molar amount of 5-methyl-2-furanmethanol contained in the reaction substrate. The calculation result shows that the product can achieve higher yield, and the yield of the 5-methyl-2-furoic acid is 89.4%.
(3) Test for regeneration Performance
In the present invention, the catalyst can be recovered by centrifugation, separation and drying. Putting the recovered catalyst into the catalytic test again to test the catalytic effect; five regeneration tests were carried out in this way. The detection method and test conditions of the catalytic product are the same as those of the catalytic test.
The results show that: the loss of catalyst activity during regeneration is low, and the yields of 5-methyl-2-furoic acid during one to five times of regeneration are 89.2%, 88.8%, 88.6%, 88.1% and 86.5% in sequence.
The present invention is not limited to the above-described embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.
Claims (10)
1. A method for preparing furan acid compound by catalytic oxidation of furan aldehyde or furan alcohol under alkali-free condition is characterized by comprising the following steps: dispersing reaction substrates furan aldehyde or furan alcohol and a catalyst AuPd/hollow hemispherical nitrogen-doped carbon material into distilled water, introducing oxygen into a reaction kettle to a specified pressure, setting a specified temperature, and catalytically oxidizing the furan aldehyde or furan alcohol to obtain furan acid.
2. The method for producing a furan acid compound by the catalytic oxidation of furan aldehyde or furan alcohol under alkali-free conditions according to claim 1, wherein the furan aldehyde is furfural, 5-hydroxymethylfurfural or 5-methylfurfural; the furan alcohol is furfuryl alcohol, 5-methyl-2-furancarbinol or 2, 5-furandimethanol.
3. The method for preparing furan acid compound by catalytic oxidation of furan aldehyde or furan alcohol under alkali-free condition as claimed in claim 1, wherein the catalyst AuPd/hollow hemispherical nitrogen-doped carbon material, reaction substrate and distilled water are used in the following dosage ratio: 10-100 mg: 10-80 mg: 20-80 mL; the specified pressure intensity is 1.0-2.0 MPa; the temperature of the reaction system is 80-180 ℃, and the reaction time is 4-54 h.
4. The method for preparing a furan acid compound by catalytically oxidizing furan aldehyde or furan alcohol under the alkali-free condition as claimed in claim 1, wherein the catalyst AuPd/hollow hemispherical nitrogen-doped carbon material is prepared by the step of
A1, mixing SiO2Dispersing the spheres into a toluene solution, uniformly mixing, keeping for a period of time in an inert gas atmosphere, adding 3- (methacryloyloxy) propyl trimethoxy silane KH-570 into a mixed system under a stirring state, and modifying the surface functional groups of the silicon dioxide by using a reaction system at a certain temperature; surface-modified SiO2Ball i.e. v-SiO2Dispersing into acetonitrile solution, and continuously adding azo initiator, nitrogen-containing polymerizable monomer and cross-linking agent; ultrasonically dispersing the mixed solution uniformly, and keeping the mixed solution in an inert gas atmosphere; placing the mixture in a water bath oscillator, heating to a specified temperature, keeping the temperature, and continuing to heat to a target temperature after a certain time; after the reaction is finished, centrifugally collecting and vacuum drying the product to obtain polymer SiO2@ Poly; then SiO2@ Poly is put in a tube furnace, the temperature is programmed to the calcining temperature under the inert gas atmosphere, and the carbon material SiO is obtained after calcination2@NC；
A2, mixing SiO2Soaking in mixed solution of silicon removing agent and ethanol, centrifuging to collect product, vacuum drying, oxidizing with certain concentration of oxidizing compound, centrifuging to collect product, and vacuum dryingObtaining a hollow hemispherical nitrogen-doped carbon material HhSNC for short;
a3 polyvinyl alcohol PVA, palladium precursor and HAuCl4·3H2Dropwise adding sodium borohydride NaBH into O mixed solution4And (3) uniformly stirring the solution, adjusting the pH value of the solution, adding the HhSNC obtained in the step (A2) into the solution, centrifugally collecting a product after the reaction is finished, and drying in vacuum to obtain the catalyst AuPd/hollow hemispherical nitrogen-doped carbon material, named AuPd/HhSNC for short.
5. The method for preparing furan acid compound by catalytic oxidation of furan aldehyde or furan alcohol under alkali-free conditions as claimed in claim 4, wherein, in the step A1, the SiO is2The dosage ratio of the toluene to the KH-570 is 0.2-5 g: 50-500 mL: 1.0-20 mL; the reaction temperature is 50-120 ℃, and the reaction time is 6-48 h.
6. The method for producing a furan acid compound by catalytic oxidation of furan aldehyde or furan alcohol under alkali-free conditions as claimed in claim 4, wherein, in the step A1, the azo initiator is azobisisobutyronitrile or azobisisoheptonitrile; the nitrogen-containing polymerizable monomer is N, N-propylene bisacrylamide, imidazole, carbazole or acrylamide; the cross-linking agent is divinylbenzene, acrylic acid, hydroxyethyl acrylate, hydroxypropyl acrylate or methacrylic acid; the inert gas is: nitrogen, argon or helium;
in step A1, the v-SiO2The ratio of the azo initiator to the nitrogen-containing polymerizable monomer to the crosslinking agent to the acetonitrile is 1-100 mg: 10-200 mg: 1-800 mg: 1-800 mg: 10-100 mL; the reaction temperature is 50-80 ℃, and the reaction time is 2.0-48 h; the temperature for vacuum drying is 20-90 ℃.
7. The method for preparing a furan acid compound by the catalytic oxidation of furan aldehyde or furan alcohol under the alkali-free condition as claimed in claim 4, wherein, in the step A1, the temperature rise rate is 1.0-10 ℃/min, the calcination temperature is 400-1200 ℃, and the calcination time is 1-10 h; the inert gas is: nitrogen, argon or helium.
8. The method for preparing furan acid compound by catalytic oxidation of furan aldehyde or furan alcohol under alkali-free condition as claimed in claim 4, wherein, in step A2, said silicon removing agent is hydrofluoric acid (HF), phosphoric acid or potassium hydroxide; the SiO2The ratio of @ NC to the silicon removing agent to the ethanol is 0.2-5 g: 5.0-20 mL: 1.0-20 mL; the soaking temperature is 20-50 deg.C, and the soaking time is 0.5-5.0 h.
9. The method for preparing a furan acid compound by catalytically oxidizing furan aldehyde or furan alcohol under alkali-free conditions of claim 4, wherein in step A2, the oxidizing compound is nitric acid, hydrochloric acid, hydrogen peroxide or potassium hydroxide; the temperature of the oxidation treatment is 20-180 ℃, and the time of the oxidation treatment is 0.5-5.0 h; the temperature for vacuum drying is 40-120 ℃.
10. The method of claim 4, wherein in step A3, the palladium precursor is PdCl2、Pd(NO3)2，Pd(NH3)4(NO3)2Or H2PdCl4(ii) a The PVA, the palladium precursor and the HAuCl4·3H2O、NaBH4The ratio of HhSNC is 0.01-3.0 g: 0.01-10 mL: 0.01-10 mL: 1.0-20 mL: 0.1-2.0 g; the reaction temperature is 20-50 ℃, and the reaction time is 0.5-5.0 h; the pH of the solution is in the range of 6-9.
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