CN106732803B - A kind of composite catalyst, preparation method and application - Google Patents
A kind of composite catalyst, preparation method and application Download PDFInfo
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- CN106732803B CN106732803B CN201610902396.8A CN201610902396A CN106732803B CN 106732803 B CN106732803 B CN 106732803B CN 201610902396 A CN201610902396 A CN 201610902396A CN 106732803 B CN106732803 B CN 106732803B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 239000007788 liquid Substances 0.000 claims abstract description 29
- 229920000831 ionic polymer Polymers 0.000 claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 24
- 229930091371 Fructose Natural products 0.000 claims abstract description 18
- 239000005715 Fructose Substances 0.000 claims abstract description 18
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims abstract description 18
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 25
- 239000010949 copper Substances 0.000 claims description 24
- 235000019441 ethanol Nutrition 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 15
- 229910016383 CuV2O6 Inorganic materials 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000002608 ionic liquid Substances 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 9
- MONMFXREYOKQTI-UHFFFAOYSA-N 2-bromopropanoic acid Chemical class CC(Br)C(O)=O MONMFXREYOKQTI-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims description 7
- -1 Alcohol ester Chemical class 0.000 claims description 7
- 229910003206 NH4VO3 Inorganic materials 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 230000000977 initiatory effect Effects 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 238000000643 oven drying Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 5
- 239000002127 nanobelt Substances 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract description 3
- 238000010189 synthetic method Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000000320 mechanical mixture Substances 0.000 abstract description 2
- 238000012805 post-processing Methods 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 description 15
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 14
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000009835 boiling Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 235000021050 feed intake Nutrition 0.000 description 3
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- 230000010148 water-pollination Effects 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NPDACUSDTOMAMK-UHFFFAOYSA-N 4-Chlorotoluene Chemical compound CC1=CC=C(Cl)C=C1 NPDACUSDTOMAMK-UHFFFAOYSA-N 0.000 description 1
- KYRNFTRJARVVEU-UHFFFAOYSA-N 5-hydroxy-3-methylfuran-2-carbaldehyde Chemical compound CC=1C=C(O)OC=1C=O KYRNFTRJARVVEU-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- WXQDFOGZIYLEGP-UHFFFAOYSA-N C(C(C)C)#N.C(C(C)C)#N.[N] Chemical compound C(C(C)C)#N.C(C(C)C)#N.[N] WXQDFOGZIYLEGP-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 210000000695 crystalline len Anatomy 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N iso-butyl alcohol Natural products CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- 229940035429 isobutyl alcohol Drugs 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- CCEKAJIANROZEO-UHFFFAOYSA-N sulfluramid Chemical group CCNS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F CCEKAJIANROZEO-UHFFFAOYSA-N 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000004885 tandem mass spectrometry Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/36—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of vanadium, niobium or tantalum
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of catalyst more particularly to a kind of composite catalysts, preparation method and application, belong to technical field of chemistry.The present invention utilizes the CuV of hydro-thermal method synthesis2O6The synthetic method of the novel composite catalyst of nanobelt material and acid mesoporous poly ion liquid composition.The two is prepared into composite catalyst by mechanical mixture and is applied to the reaction that one step of fructose is converted into 2,5- furans dicarbaldehyde.Catalyst used in the present invention is cheap and easy to get；Reaction time is short, energy-efficient；Target product yield is high, and lower by-product generates；Using air or oxygen as oxygen source, economy and Environmental costs are low；Product and catalyst are easily separated, and post-processing is simple；Catalyst is easy to reuse, and waste discharge is few, environmentally protective；Very low to equipment requirement, equipment investment is small, is conducive to Progress in industrialization, has highly important application prospect.
Description
Technical field
The present invention relates to a kind of catalyst more particularly to a kind of composite catalyst, preparation method and application, belonging to
Learn technical field.
Background technique
2,5- furans dicarbaldehyde (DFF) is that 5 hydroxymethyl furfural (5-HMF) aoxidizes resulting important products, it is by widely
It is used as polymerized monomer, medicine intermediate, antibacterial agent, the renewable furans-urea resin of synthesis etc. of furans quasi polymer.Institute
To be had received widespread attention by the reaction that 5-HMF prepares DFF.It simultaneously can be to avoid by the reaction that fructose one-step method generates DFF
The separation and purification of intermediate product HMF, are the hot issues of current research.And the reaction of DFF is generated by fructose one-step method
The technological difficulties faced are that easy contact with oxidation catalyst of fructose leads to have a large amount of by-product in reaction in reaction system
It generates, how to design the difficult point that the catalyst with suitable acidic site and oxidation activity position is research.
Summary of the invention
The purpose of the present invention is in view of the defects existing in the prior art, propose a kind of composite catalyst, preparation method
And application, heterogeneous bimetallic Cu, V catalysis material is introduced into the oxidation reaction of 5 hydroxymethyl furfural, it is real in a mild condition
The oxidation reaction of existing efficient catalytic 5 hydroxymethyl furfural, the present invention have probed into different Cu/V feed ratios to reactivity and microcosmic
The influence of pattern, and synthesized the novel mesoporous poly ion liquid of acidity.It will focus on the catalytic performance for improving composite catalyst,
And have the characteristics that quick, efficient, recyclable.
The present invention solves technical problem by the following technical programs: a kind of composite catalyst, by 0.05g nano strip
CuV2O6It is formed with the acid mesoporous poly ion liquid of 0.09g.
CuV2O6In copper divalent is presented, and vanadium shows the valence state of pentavalent, in the oxidation reaction Cu2+To Cu+And V5+
To V4+The process of appraising at the current rate be catalytic cycle key point.Traditional synthetic method be synthesized by high temperature method it is blocky or other
The CuV of pattern2O6, and emphasis of the invention is the CuV that nano strip is prepared using hydro-thermal method2O6.It is equally CuV2O6, due to
The CuV of nano strip2O6Good dispersibility and more active sites contact area are shown in reaction solution, so in this way
Material be more suitable for catalysis reaction.
Ionic liquid (Ionic Liquid, IL) is big since its difficult volatility and adjustable structure receive researcher
The concern of amount.It, can be using the special functionalized ion liquid of design performance as catalyst or solvent for many organic reactions.
The heterogeneouss strategy that acid poly ion liquid utilizes can allow homogeneous ionic liquid to separate from reaction system, recycling
Realize the utilization and recycle of catalyst, while acid poly ion liquid also shows more homogeneous ionic liquid to the dehydration of carbohydrate
The high catalytic activity of body.The present invention is using the CuV prepared2O6As oxidation catalyst, using acid poly ion liquid as carbohydrate
The acid catalyst of dehydration is made of the multi-functional composite catalyst system of mixing the two, it is therefore an objective to realize that one kettle way is direct by fructose
Prepare DFF.
The present invention further provides the preparation methods of composite catalyst, comprising the following steps:
The first step, by copper nitrate and ammonium metavanadate, in certain proportion, hydro-thermal reaction is carried out at 210 DEG C, obtains nanometer
Band-like CuV2O6；
Second step by solvent-thermal method by vinyl imidazole synthesizes ionic liquid monomer with three bromo-propionic acids first, then by this
Monomer is copolymerized with ethylene glycol dimethacrylate under the initiation of azodiisobutyronitrile and generates acid mesoporous poly ion liquid；
Third step, the CuV by nano strip2O6It mixes, is answered by specified wt proportion with acid mesoporous poly ion liquid
Mould assembly catalyst.
Present invention discover that difference Cu (NO3)2With NH4VO3The catalyst of feed ratio synthesis have different microscopic appearance and
Therefore catalytic effect filters out specific synthesis ratio, that is, the molar ratio of only Cu/V is that 1:2 Shi Caineng is had
The catalyst of the special appearance of nanobelt.Specific method is in the first step, to weigh the NH of 2.3g according to a certain ratio4VO3It is dissolved in
NH is obtained in the deionized water of 20mL4VO3Solution, heating stirring 30min is to stirring to being completely dissolved at 75 DEG C, by the Cu of 1.9g
(NO3)2It is dissolved in the deionized water of 10mL, the Cu (NO that will be obtained3)2Solution is added drop-wise to NH4VO3In solution, until it is outstanding yellow occur
Turbid little particle, keeps 75 DEG C of stirring 30min, and yellow suspension gradually becomes orange-yellow suspension, orange-yellow suspension is moved on to
In the water heating kettle of 50mL, kept for 20 hours as 210 DEG C of baking ovens, cooled to room temperature, respectively three times with water and ethanol washing,
Flaxen powder is obtained, 60 DEG C of oven drying 12h is placed in, finally obtains flaxen solid powder.
In the second step, ionic liquid monomer is synthesized with three bromo-propionic acids by vinyl imidazole by solvent-thermal method first,
Preparation process is as follows: 1.808g vinyl imidazole and 3.02g bromo-propionic acid being added in 50mL round-bottomed flask, 20mL ethyl alcohol is added
As solvent, nitrogen protection is cooled to room temperature and rotates removing alcohol solvent on magnetic stirring apparatus after 80 DEG C of stirrings for 24 hours,
Five times are washed with acetonitrile and finally obtains white solid, are placed in 60 DEG C of baking oven 12h, are obtained the ionic liquid monomer of carboxylic acid functional
VIM-COOH；Synthesis hydrophilic poly ion liquid P (ED-VIM-COOH) again, by 1.236g VIM-COOH, 0.716g dimethyl
Acrylic acid glycol ester be added 10mL ethyl alcohol, 10mL water, 20mL mixed solvent solution in, be added initiator azodiisobutyronitrile
(AIBN) 0.09g, nitrogen protection, for 24 hours, room temperature is cooling, the white solid being obtained by filtration for 80 DEG C of stirrings on magnetic stirring apparatus, uses
Ethanol washing removes not reacted monomer, is put into 100 DEG C of baking ovens, and dry 12h obtains acid mesoporous poly ion liquid P
(ED-VIM-COOH)。
The present invention further provides a kind of application of composite catalyst, by the CuV of nano strip2O6It is mesoporous with acidity
The composite catalyst of poly ion liquid composition is converted into the reaction of 2,5- furans dicarbaldehyde for one step of fructose.Mainly adopt
With the method for solid-phase grinding by the CuV of nano strip2O6It is put into reaction system with acid mesoporous poly ion liquid one kettle way,
Using fructose as reaction substrate, it is continuously passed through oxygen during the reaction.
Catalyst used in the present invention is cheap and easy to get；Reaction time is short, energy-efficient；Target product yield is high, lower
By-product generates；Using air or oxygen as oxygen source, economy and Environmental costs are low；Product and catalyst are easily separated, post-processing letter
It is single；Catalyst is easy to reuse, and waste discharge is few, environmentally protective；Very low to equipment requirement, equipment investment is small, is conducive to work
Industryization progress, has highly important application prospect.
Detailed description of the invention
Fig. 1 is CuV2O6SEM microscopic appearance.
Fig. 2 is the SEM microscopic appearance of P (ED-VIM-COOH).
Fig. 3 is CuV2O6It is catalyzed the utilization and recycle performance map of reaction.
Specific embodiment
Embodiment
In order to detect CuV of the present invention2O6For nanobelt catalyst to 5 hydroxymethyl furfural oxidation reaction ability, the present invention will
CuV2O6Nanobelt catalyst and acid mesoporous poly ion liquid P (ED-VIM-COOH) form composite catalyst and are applied to 5- hydroxyl first
In base furfural synthesis under normal pressure, fructose is efficiently converted in the short time under atmospheric oxygen atmosphere and generates DFF.To product in embodiment
The yield of 2,5-furandaldehyde is analyzed with gas chromatograph (Shimadzu GC-2014), and chromatographic column is SE30 capillary column, and specification is
50m × 0.25mm × 0.6 μm, detector are flame ionization ditector.Using temperature programming, 100 DEG C of initial temperature, keep
2min, 10 DEG C/min are warming up to 240 DEG C, 250 DEG C of detector temperature, 250 DEG C of injector temperature.Carrier gas is N2, split sampling, column
Volume flow rate is 0.75mL min-1, split ratio 150:1.LC- is used to the conversion ratio detection of HMF and fructose in embodiment
The detection method of MS/MS.Detection system includes Agilent 1260LC as liquid phase separation part, using equipped with ESI ion source
Agilent G6420A mass spectrum is as detector, using the aqueous solution of 10% methanol as mobile phase.When detection, the sample of 2 μ L is infused
Liquid chromatogram is injected, using the method for MRM using external standard method detection HMF and the conversion ratio of fructose under ESI (+) mode.
The present embodiment carries out in the steps below:
5 hydroxymethyl furfural oxidation reaction has the stone of magnetic rotor, 25mL with cock and a blow vent at one
It is carried out in English reaction tube.5 hydroxymethyl furfural is oxidized to model reaction, investigates the catalytic reaction activity of catalyst.1mmol 5- hydroxyl
Methyl furfural, 0-0.1g catalyst, 4mL solvent are added in 25mL reaction tube, connect oxygen ball in blow vent, and 100-130 DEG C
React a few hours.After reaction, cooling to reaction system, it is that internal standard and reaction system mix that methyl isobutyl alcohol, which is added, is taken
Supernatant liquid is analyzed.Reaction dissolvent is investigated first, has chosen CuV2O6As catalysts, due to reactant
System is normal pressure, so under the premise of selection same temperature as far as possible, a small amount of low boiling point solvent is anti-according to the difference of the boiling point of solvent
System is answered to select to react at a temperature of slightly lower, fixed catalyst dosage is anti-under conditions of the pressure of oxygen is 0.1MPa
Answer 6h.In case study on implementation, the descending sequence of the solvent polarity of selection is water > DMSO > acetonitrile > DMF > p-chlorotoluene > methyl- tert
Butyl ether.The result shows that having good catalytic activity when higher boiling, highly polar DMSO are as solvent, it is possible to obtain same
When with higher boiling and have highly polar solvent be optimal selection.The yield of DFF is 60.3% under this condition.
Influence of the different solvent of table 1 to 5 hydroxymethyl furfural oxidation reaction.
In order to prove the concerted catalysis effect of Cu and V, in the process change type of raw material of synthetic catalyst, selection
Ce3+、Fe3+、Al3+、Ti4+As the source of cation, a series of comparative catalyst has been synthesized applied to the reaction.It is synthesizing
During, tend to be hardly formed mentioned-above suspension in the synthesis process when using the cation of lower valency, and make
With lower valency it is cupric when may be implemented this process, trivalent and more than valence state metal cation as cation
Substantially all synthesis of solid catalyst, especially Ti when source4+And Al3+The catalyst synthesized when as cation
The hard crystalline lens of red with good metallic luster.The reaction effect of comparative catalyst is listed in following table 2.
The performance of the catalyst of the different cationic Material synthesis of table 2.
The result shows that selecting different cation: Ce3+、Fe3+、Al3+、Ti4+、Cu2+When, gained catalyst all has centainly
Catalytic activity, wherein Cu2+Available 2,5-furandaldehyde illustrates Cu close to 100% yield when as cation2+
There is high catalytic activity to the reaction.The Cu in catalyst and V that high activity may be come special bimetallic acts synergistically.
Change Cu (NO) in the synthesis process2With NH4VO3Feed ratio can prepare the catalyst with different Cu/V ratios.
The difference Cu (NO) during synthesis2With NH4VO3Feed ratio has the pattern and crystal topological structure of resulting materials very big
It influences.It chooses feed ratio of the molar ratio of Cu/V from 2 to 1/4 and has synthesized catalyst series, be applied to 5 hydroxymethyl furfural and select
Property oxidation reaction, experimental results are listed in Table 3 below.
Influence of the catalyst of 3 difference Cu/V feed ratio of table synthesis to reactivity.
The result shows that with the reduction of Cu in catalyst synthesis processes to feed intake, ammonium metavanadate feed intake increase, 5- hydroxyl
The conversion ratio of methyl furfural gradually increases, and selectivity is in the volcano shape distribution for first rising and declining afterwards, when the Cu/V to feed intake is arrived 1
There is relatively good conversion ratio when 1/2 section, obtains maximum 2,5-furandaldehyde most when Cu/V is equal to 1/2
Big yield, close to 100%.
Poly ion liquid and other two kinds of solid acid catalyst acid catalytic properties are investigated, the hydrophily of preparation with
And the N content of Hydrophobic Catalyst is suitable, the acid amount for being also maintained for two kinds of catalyst is essentially identical.Pass through acid base titration
Method identifies practical acid content, controls the amount of catalyst during the reaction, keeps the acid amount being added suitable.It the results are shown in Table 4.
The acid catalysis ability of 4 different catalysts of table.
The result shows that different catalysts all have certain catalytic performance to reaction, but from the perspective of hydrophily really
Hydrophobic catalyst is more advantageous to the reaction that fructose dehydration prepares 5-HMF, super-hydrophobic catalyst such as SBA-15-SO3H and
Activity of the acid catalytic property of P (VB-VIM-COOH) than hydrophilic catalyst P (ED-VIM-COOH) and Amberlyst-15
It is higher.
By above-mentioned experiment, the present embodiment is selected: being only the condition of 1:2 in the molar ratio of specifically synthesis ratio Cu/V
Under be synthesized be as shown in Figure 1 with nano strip special appearance CuV2O6With by solvent-thermal method by vinyl miaow
Azoles synthesizes ionic liquid monomer with three bromo-propionic acids, then by the monomer under the initiation of azodiisobutyronitrile (AIBN) and dimethyl propylene
Olefin(e) acid glycol ester (EGDMA) copolymerization, which generates, has good hydrophilic poly ion liquid, will by the method for mechanical mixture
The two is put into reaction system by one kettle way, using fructose as reaction substrate, is continuously passed through oxygen during the reaction.Specifically
Method is as follows:
The first step is denoted as CuV according to the ratio of measured Cu/V/O2O6.Preparation process is as follows: weighing according to a certain ratio
The NH of 2.3g4VO3It is dissolved in the deionized water of 20mL, heating stirring 30min is to stirring to being completely dissolved at 75 DEG C, by 1.9g's
Cu(NO3)2It is dissolved in the deionized water of 10mL, slowly by Cu (NO3)2Solution is added drop-wise to NH4VO3In solution, there are a large amount of yellow
Suspended little particle.75 DEG C of stirring 30min are kept, yellow suspension gradually becomes orange-yellow suspension, suspension is moved on to 50mL
Water heating kettle in, kept for 20 hours as 210 DEG C of baking ovens.Cooled to room temperature obtains respectively three times with water and ethanol washing
The powder for showing slightly yellow is placed in 60 DEG C of oven drying 12h, finally obtain flaxen solid catalyst, i.e. nano strip
CuV2O6；
Second step by solvent-thermal method by vinyl imidazole synthesizes ionic liquid monomer with three bromo-propionic acids first, prepares
Journey is as follows: 1.808g vinyl imidazole and 3.02g bromo-propionic acid are added in 50mL round-bottomed flask, and 20mL ethyl alcohol is added as molten
Agent, nitrogen protection are cooled to room temperature and rotate removing alcohol solvent on magnetic stirring apparatus after 80 DEG C of stirrings for 24 hours, use acetonitrile
It washs five times and finally obtains white solid, be placed in 60 DEG C of baking oven 12h, obtain the ionic liquid monomer of carboxylic acid functional: VIM-
COOH.The synthetic method of hydrophily poly ion liquid P (ED-VIM-COOH) is as follows: 1.236g VIM-COOH, 0.716g diformazan
Base acrylic acid glycol ester (EGDMA) be added 10mL ethyl alcohol, 10mL water, 20mL mixed solvent solution in, it is even that initiator is added
Nitrogen bis-isobutyronitrile (AIBN) 0.09g, nitrogen protection, 80 DEG C of stirrings are for 24 hours on magnetic stirring apparatus.Room temperature is cooling, is obtained by filtration
White solid removes not reacted monomer with a large amount of ethanol washing.It is put into 100 DEG C of baking ovens, dry 12h obtains ion
The copolymer of liquid functional: P (ED-VIM-COOH), i.e., acid mesoporous poly ion liquid；
Third step, the CuV by nano strip2O6It is mixed in proportion with acid mesoporous poly ion liquid, obtains compound catalysis
Agent.
The catalytic activity of DFF is prepared by fructose in order to further investigate the combination catalyst in one-step method.Table 5 list by
Acidic catalyst and CuV2O6The reaction result that reaction system reacts one section of 3.5h is added simultaneously.
5 one-step method of table prepares DFF by fructose.
The result shows that in P (EVPI-Br) and α-CuV2O6Available 63.1% one-step method under the action of composite catalyst
The yield of DFF is prepared by fructose.
Utilization and recycle for heterogeneous catalytic reaction catalyst is also an important parameter for evaluating catalytic effect.To anti-
Catalyst after answering has carried out multiple utilization and recycle, as shown in Figure 2.By repeatedly recycling, there is no apparent drops for catalytic activity
It is low, illustrate that catalyst has good utilization and recycle performance.
The above result shows that the patent provides a kind of being simple and efficient applied to the fructose converting generation DFF reaction of biomass
Multiphase composite catalyst.Synthesized catalyst has quick, efficient, easy and environmental products and catalyst easily separated, after
Processing is simple；Catalyst is easy to reuse, and does not reduce by multiple utilization and recycle catalytic activity, meets wanting for heterogeneous catalysis
It asks, no waste discharge is environmentally protective；It is very low to equipment requirement.Equipment investment is small, is conducive to Progress in industrialization, has very heavy
The application prospect wanted.
In addition to above-mentioned implementation, the present invention can also have other embodiments.It is all to be formed using equivalent substitution or equivalent transformation
Technical solution, fall within the scope of protection required by the present invention.
Claims (6)
1. a kind of preparation method of composite catalyst, by the CuV of 0.05g nano strip2O6With the acid mesoporous polyion of 0.09g
Liquid composition, specifically includes the following steps:
The first step, by copper nitrate and ammonium metavanadate, be the ratio of 1:2 with molar ratio, hydro-thermal reaction carried out at 210 DEG C, is obtained
The CuV of nano strip2O6；
Second step by solvent-thermal method by vinyl imidazole synthesizes ionic liquid monomer with three bromo-propionic acids first, then by the monomer
It is copolymerized under the initiation of azodiisobutyronitrile with ethylene glycol dimethacrylate and generates acid mesoporous poly ion liquid；
Third step, the CuV by nano strip2O6Pass through solid-phase grinding by specified wt proportion with acid mesoporous poly ion liquid, stir
It mixes uniformly mixed, obtains composite catalyst.
2. the preparation method of composite catalyst according to claim 1, it is characterised in that: in the first step, Cu/V's
Molar ratio is 1:2.
3. the preparation method of composite catalyst according to claim 1, it is characterised in that: in the first step, according to tool
The proportion of body weighs the NH of 2.3g4VO3It is dissolved in the deionized water of 20mL and obtains NH4VO3Solution, heating stirring 30 at 75 DEG C
Min is to stirring to being completely dissolved, by Cu (NO3)2It is dissolved in the 10mL deionized water of 1.9g, the Cu (NO that will be obtained3)2Solution drop
It is added to NH4VO3In solution, until there is the suspended little particle of yellow, 75 DEG C of 30 min of stirring are kept, yellow suspension gradually becomes orange
Yellow suspension moves on to orange-yellow suspension in the water heating kettle of 50 mL, is placed in 210 DEG C of baking ovens and is kept for 20 hours, natural cooling
Flaxen powder is obtained, 60 DEG C of 12 h of oven drying is placed in, finally obtains respectively three times with water and ethanol washing to room temperature
Flaxen solid powder.
4. the preparation method of composite catalyst according to claim 1, it is characterised in that: in the second step, by 1.808
G vinyl imidazole and 3.02 g bromo-propionic acids are added in 50 mL round-bottomed flasks, 20 mL ethyl alcohol are added as solvent, nitrogen is protected
It protects, on magnetic stirring apparatus after 80 DEG C of 24 h of stirring, is cooled to room temperature and rotates removing alcohol solvent, wash five with acetonitrile
It is secondary to finally obtain white solid, 60 DEG C of 12 h of baking oven are placed in, the ionic liquid monomer VIM-COOH of carboxylic acid functional is obtained；Again
Synthesis hydrophilic poly ion liquid P (ED-VIM-COOH), by 1.236 g VIM-COOH, 0.716 g dimethacrylate second two
Alcohol ester be added 10 mL ethyl alcohol, 10 mL water, 20mL mixed solvent solution in, be added initiator azodiisobutyronitrile (AIBN)
0.09 g, nitrogen protection, 80 DEG C of 24 h of stirring on magnetic stirring apparatus, room temperature is cooling, and the white solid being obtained by filtration uses ethyl alcohol
Washing, removes not reacted monomer, is put into 100 DEG C of baking ovens, and dry 12 h obtain acid mesoporous poly ion liquid P (ED-
VIM-COOH)。
5. the application of composite catalyst made from the preparation method according to claim 1, it is characterised in that: by nano strip
CuV2O62,5- furans dicarbaldehyde is converted into for one step of fructose with the composite catalyst of acid mesoporous poly ion liquid composition
Reaction.
6. the application of composite catalyst according to claim 5, it is characterised in that: make two using the method for solid-phase grinding
Kind catalyst is uniformly mixed, by the CuV of nano strip2O6It is put into acid mesoporous poly ion liquid composite catalyst one kettle way
In reaction system, using fructose as reaction substrate, it is continuously passed through oxygen during the reaction.
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