CN109675638A - A kind of composite catalyzing material, preparation method and dehydrogenation hydrogenation reaction mediates the application prepared in 2,5- dimethyl furan in situ - Google Patents
A kind of composite catalyzing material, preparation method and dehydrogenation hydrogenation reaction mediates the application prepared in 2,5- dimethyl furan in situ Download PDFInfo
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- GSNUFIFRDBKVIE-UHFFFAOYSA-N 2,5-dimethylfuran Chemical compound CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000000463 material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 23
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 22
- 239000002131 composite material Substances 0.000 title claims abstract description 17
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 13
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229920000642 polymer Polymers 0.000 claims abstract description 53
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 49
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000005859 coupling reaction Methods 0.000 claims abstract description 9
- 230000000694 effects Effects 0.000 claims abstract description 5
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 88
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 65
- 238000006243 chemical reaction Methods 0.000 claims description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 57
- 239000003054 catalyst Substances 0.000 claims description 44
- 229910052751 metal Inorganic materials 0.000 claims description 42
- 239000002184 metal Substances 0.000 claims description 42
- 238000005406 washing Methods 0.000 claims description 39
- 238000002156 mixing Methods 0.000 claims description 36
- 239000008367 deionised water Substances 0.000 claims description 29
- 229910021641 deionized water Inorganic materials 0.000 claims description 29
- 238000010792 warming Methods 0.000 claims description 27
- 229910001868 water Inorganic materials 0.000 claims description 26
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 25
- 239000013049 sediment Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 18
- 239000012279 sodium borohydride Substances 0.000 claims description 18
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 13
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 13
- 150000007524 organic acids Chemical class 0.000 claims description 13
- 230000001376 precipitating effect Effects 0.000 claims description 13
- 229910052603 melanterite Inorganic materials 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 11
- 229910001510 metal chloride Inorganic materials 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 7
- 239000011149 active material Substances 0.000 claims description 6
- 239000000696 magnetic material Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 5
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 5
- 239000000969 carrier Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims description 3
- JYCZLJUGLVWLMP-UHFFFAOYSA-N OC1=NC(=NC(=N1)O)O.[Hf] Chemical class OC1=NC(=NC(=N1)O)O.[Hf] JYCZLJUGLVWLMP-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 3
- LVPMIMZXDYBCDF-UHFFFAOYSA-N isocinchomeronic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)N=C1 LVPMIMZXDYBCDF-UHFFFAOYSA-N 0.000 claims description 3
- 150000002736 metal compounds Chemical class 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- 229960003512 nicotinic acid Drugs 0.000 claims description 3
- 235000001968 nicotinic acid Nutrition 0.000 claims description 3
- 239000011664 nicotinic acid Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- GJAWHXHKYYXBSV-UHFFFAOYSA-N pyridinedicarboxylic acid Natural products OC(=O)C1=CC=CN=C1C(O)=O GJAWHXHKYYXBSV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- XNSXUCJFKZNRHV-UHFFFAOYSA-N N1=C(C=CC(=C1)C(=O)O)C(=O)O.[Zr] Chemical compound N1=C(C=CC(=C1)C(=O)O)C(=O)O.[Zr] XNSXUCJFKZNRHV-UHFFFAOYSA-N 0.000 claims description 2
- KYRNFTRJARVVEU-UHFFFAOYSA-N 5-hydroxy-3-methylfuran-2-carbaldehyde Chemical compound CC=1C=C(O)OC=1C=O KYRNFTRJARVVEU-UHFFFAOYSA-N 0.000 claims 1
- YNFYCBDMMKUYKX-UHFFFAOYSA-N THTA Chemical compound OC(=O)CC1CCCS1 YNFYCBDMMKUYKX-UHFFFAOYSA-N 0.000 claims 1
- MPKRSTOWAGHZON-UHFFFAOYSA-N hafnium phenol Chemical compound [Hf].C1(=CC=CC=C1)O MPKRSTOWAGHZON-UHFFFAOYSA-N 0.000 claims 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims 1
- 230000005389 magnetism Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 17
- 239000000047 product Substances 0.000 abstract description 11
- 230000002378 acidificating effect Effects 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 55
- 235000019441 ethanol Nutrition 0.000 description 23
- 238000003756 stirring Methods 0.000 description 23
- 239000002244 precipitate Substances 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000001914 filtration Methods 0.000 description 14
- 239000007789 gas Substances 0.000 description 14
- 239000011541 reaction mixture Substances 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000002604 ultrasonography Methods 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 6
- 239000006104 solid solution Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 5
- 229910003865 HfCl4 Inorganic materials 0.000 description 5
- -1 aldehyde radical Chemical class 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 239000000852 hydrogen donor Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000002240 furans Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- FJSKXQVRKZTKSI-UHFFFAOYSA-N 2,3-dimethylfuran Chemical compound CC=1C=COC=1C FJSKXQVRKZTKSI-UHFFFAOYSA-N 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910006069 SO3H Inorganic materials 0.000 description 3
- 229910007932 ZrCl4 Inorganic materials 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 239000012675 alcoholic extract Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- VQKFNUFAXTZWDK-UHFFFAOYSA-N 2-Methylfuran Chemical compound CC1=CC=CO1 VQKFNUFAXTZWDK-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 229910019891 RuCl3 Inorganic materials 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000002551 biofuel Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000002215 pyrolysis infrared spectroscopy Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000009901 transfer hydrogenation reaction Methods 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/36—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of composite catalyzing material, preparation method and dehydrogenation hydrogenation coupled reaction mediates the application prepared in 2,5- dimethyl furan in situ.Magnetic inorganic organic hybrid polymer support of the catalysis material by activated bimetallic and with Lewis acid-base property site and Br nsted acidic site forms, and is provided simultaneously with stronger 1,4-butanediol ability of dehydrogenation and 5 hydroxymethyl furfural hydrogenation capability；The sectional temperature-controlled method used, the catalytic performance and synergistic effect of the property of can choose regulation activity bimetallic and magnetic inorganic organic hybrid polymer support effectively avoid the formation of by-product, improve the yield of target product, have good industrial applications potentiality.
Description
Technical field
The invention belongs to biomass energy chemical fields, and in particular to a kind of composite catalyzing material, preparation method and in original
Position dehydrogenation hydrogenation reaction mediates the application prepared in 2,5- dimethyl furan.
Background technique
With becoming increasingly conspicuous for fossil resource imbalance between supply and demand and being on the rise for environmental pollution phenomenon, lignocellulosic conduct
It is more and more wider that a kind of from a wealth of sources, rich reserves and cheap biomass resource have received lot of domestic and foreign researcher
General concern.It in recent years, is considered a kind of extremely important by the oriented obtained 5 hydroxymethyl furfural that converts of lignocellulosic
Platform chemicals, U.S. Department of Energy is classified as one of ten large platform compounds based on biomass resource, this is because with
It can prepare the chemicals, fuel and material of various high added values as starting material.Wherein, it is selected by 5 hydroxymethyl furfural
Property add hydrogen to obtain 2,5- dimethyl furan be considered as a kind of very promising new liquid bio-fuel, have it is many excellent
Point: 1) energy density is high (31.5 MJ/L), close with gasoline；2) boiling point is high (92 ~ 94 °C), not volatile；3) octane number is high
(119), explosion-proof performance is good；4) not soluble in water, it is easily stored and transport, these advantages make 2,5- dimethyl furan just gradually at
For one of most important source of the following liquid biofuel (Industrial & Engineering Chemistry
Research, 2014,53:3056-3064).
It is well known that contain an aldehyde radical, an alcoholic extract hydroxyl group and a furan nucleus in 5 hydroxymethyl furfural molecule simultaneously, this
So that its chemical property is very active, product when hydrogenation reaction occurs is more complicated, therefore, how to guarantee aldehyde radical and alcohol hydroxyl
The preferential plus hydrogen of base, while avoiding the excessive hydrogenation of furan nucleus as far as possible is 5 hydroxymethyl furfural selective hydrogenation preparation 2,5- diformazan
It needs to solve the problems, such as first during base furans, and develops suitable catalystic converter system for solving the problems, such as that this is then played
Vital effect.
Chinese patent CN103554066A, CN104557802A, CN105251491A, CN105032427A,
CN105597771A, CN106279075A and CN108863996A disclose a kind of 5 hydroxymethyl furfural hydrogenation deoxidation preparation 2,5-
The method of dimethyl furan, this method use hydrogen as hydrogen source, the dissolubility and atom utilization in different solvents compared with
Difference, and there are larger security risks for storage, transport and use process.
Chinese patent CN108047174A and Angewandte Chemie International Edition
(2010, 49: 6616-6618)、ChemSusChem (2012, 5: 1826-1833)、Fuel (2017, 187: 159-
166) a kind of method of 5 hydroxymethyl furfural transfer hydrogenation preparation 2,5- dimethyl furan is disclosed, this method is using formic acid as hydrogen
Source, since there are formic acid very strong acid and corrosivity, industrial applications to have received very big limitation.
Chinese patent CN108586392A and Green Chemistry (2012,14:2457-2461),
ChemSusChem (2013, 6: 1158-1162)、ChemSusChem (2013, 7: 268-275)、Catalysis
Science & Technology (2015, 5: 1463-1472) 、Applied Catalysis A: General
(2019,570:245-250) disclose a kind of method of 5 hydroxymethyl furfural transfer hydrogenation preparation 2,5- dimethyl furan,
Although this method uses free from corrosion methanol, ethyl alcohol or isopropanol as hydrogen donor, methanol needs very high critical-temperature
The selectivity of target product is lower in (up to 300 DEG C) and reaction process, and the product after ethyl alcohol and isopropanol hydrogen migration is easy
Occur to need to be filled with a large amount of inert gas maintenance high pressure in back reaction and reaction process.In addition, in patent CN108586392A
In the catalytic reaction process of use, it is necessary first to carry out catalytic hydrogenation after methanol dehydrogenation generation hydrogen, then by the hydrogen of generation
Reaction, however it remains higher security risk.
Summary of the invention
A kind of method that dehydrogenation hydrogenation coupled reaction in situ mediates preparation 2,5- dimethyl furan is provided, magnetic double function are passed through
The synergistic effect of energy nanocatalyst realizes 2,5- diformazan by reaction system in substance, energy and technologic matching advantage
The selectivity synthesis of base furans.
The first aspect of the invention provides:
A kind of composite catalyzing material, including carrier and the active material being carried on carrier, the active material includes
First active metal and the second active metal, first active metal are Ru, the second active metal be selected from Cu, Co, Ni,
One of Zn, Fe or Sn.
In one embodiment, second active metal is more preferably one of Cu, Co or Ni.
In one embodiment, the load capacity of first active metal and the second active metal on carrier is all
1-4wt%。
In one embodiment, the carrier is Fe3O4The third active metal of load and the hybrid polymer of organic acid
Object；The third active metal is selected from zirconium or hafnium.
In one embodiment, it is different to be selected from iminodiacetic acid, pyridinedicarboxylic acid, 2,6- dihydroxy for the organic acid
The mixing of one or more of niacin, phenol, 2,4,6- trihydroxy -1,3,5- triazine.
In one embodiment, the preferred zirconium-imino group of the hybridized polymer of the third active metal and organic acid
Oxalic acid hybridized polymer, hafnium-citrazinic acid hybridized polymer or hafnium -2,4,6- trihydroxy -1,3,5- triazine
Hybridized polymer.
The second aspect of the invention provides:
The preparation method of above-mentioned composite catalyzing material, includes the following steps:
Step 1, the preparation of magnetic carrier: by FeSO4·7H2O and FeCl3·6H2O is dissolved in anaerobic deionized water, is added dropwise
NH3×H2O, and temperature reaction is carried out, the sediment that reaction obtains is isolated, after washing, obtains magnetic carrier；
The Polymer-supported of surfaces of magnetic carriers: step 2 disperses having containing third active metal chloride for magnetic material
In solvent, mixed solution is obtained；Mixed solution is added dropwise to the n,N-Dimethylformamide solution of the ligand containing organic acid again, then
Triethylamine is added dropwise, after being reacted, then is aged, after sediment is washed and dried, it is organic miscellaneous to obtain magnetic inorganic
Fluidized polymer carrier；
Step 3, the load in activated centre: magnetic inorganic organic hybrid polymer support is scattered in the chlorine containing the first active metal
Compound, the second active metal chloride deionized water in, after mixing evenly, be added dropwise NaBH4Aqueous solution, carry out anti-
It answers, after carrying out washing drying to solid precipitating, obtains magnetic inorganic organic hybrid Polymer-supported activated bimetallic catalyst.
In one embodiment, in step 1, FeSO4·7H2O and FeCl3·6H2The molar ratio 1:1-3 of O；NH3×
H2The dripping quantity of O is to make the pH of solution to 9-11；Temperature reaction refers to 75-85 DEG C of reaction 0.5-1.5h.
In one embodiment, in one embodiment, in step 2, organic solvent refers to N, N- dimethyl methyl
Amide；Magnetic material, third active metal chloride, organic acid ligand, the amount ratio between triethylamine are: 1-2g:10-
20mmol:15-25mmol:100-150mmol；Reaction refers to reacts 2-4h at room temperature, and ageing refers to still aging 4- at 90 DEG C
8h。
In one embodiment, in one embodiment, in step 3, magnetic inorganic organic hybrid is polymer supported
Body and NaBH4Amount ratio be 1-2g:80-120mg, reaction is to react 1-3h at room temperature.
The third aspect of the invention provides:
Dehydrogenation hydrogenation coupled reaction mediates the purposes prepared in 2,5- dimethyl furan to above-mentioned composite catalyzing material in situ.
In one embodiment, the purposes includes the following steps:
Step 1, by 5 hydroxymethyl furfural, magnetic inorganic organic hybrid Polymer-supported activated bimetallic catalyst, Isosorbide-5-Nitrae-fourth two
Alcohol is placed in autoclave using gained mixture as material liquid after mixing；
Step 2 is first warming up to the first temperature, is reacted；
Step 3, then it is warming up to the first temperature, it is reacted, obtains 2,5- dimethyl furan.
In one embodiment, the 5 hydroxymethyl furfural dosage is the 2-4wt% of 1,4-butanediol dosage.
In one embodiment, the catalyst amount is the 60-100wt% of 5 hydroxymethyl furfural dosage.
In one embodiment, load capacity of the active metal on magnetic inorganic organic hybrid polymer support
For 1-4wt%.
In one embodiment, 130-160 DEG C of the first temperature in step 2, reaction time 1-6h.
In one embodiment, 180-220 DEG C of second temperature in step 3, reaction time 2-5h.
The present invention also provides the first active metals and/or the second active metal to be used in the activated centre as catalyst
It improves dehydrogenation hydrogenation coupled reaction in situ and mediates the purposes prepared in the selectivity and yield that 2,5- dimethyl furan reacts.
The present invention also provides above-mentioned carriers to mediate preparation 2,5- bis- for improving dehydrogenation hydrogenation coupled reaction in situ
Purposes in the selectivity and yield of methylfuran reaction.
Beneficial effect
Advantages of the present invention are as follows: 1) catalyst by activated bimetallic and has Lewis acid-base property site and Br nsted acidic site
The magnetic inorganic organic hybrid polymer support composition of point, catalyst not only have stronger Magneto separate characteristic, are conducive to be catalyzed
The separation and recovery of agent, and be provided simultaneously with stronger 1,4-butanediol ability of dehydrogenation and 5 hydroxymethyl furfural hydrogenation capability, can be with
The reactive hydrogen that 1,4-butanediol is taken off is used for the hydrogen that adds of 5 hydroxymethyl furfural, the efficient conjunction of realization 2,5- dimethyl furan in situ
At；2) 5 hydroxymethyl furfural hydrogenation reaction is an exothermic reaction, and 1,4-butanediol dehydrogenation reaction is an endothermic reaction, the former
The heat that hydrogenation reaction is released is used directly for the dehydrogenation reaction of the latter, and extraneous energy supply can be effectively reduced；3) work
Match in skill: the reaction of 1,4- butanediol dehydrogenation and 5 hydroxymethyl furfural hydrogenation reaction can be similar in the reaction temperatures and pressure
Carried out under liquid-phase condition, and the two reaction product gamma-butyrolacton and 2, the boiling point of 5- dimethyl furan differs greatly, separation compared with
It is easy；4) 1,4-butanediol is a kind of reproducible organic diol, not only can be simultaneously as efficient hydrogen donor in situ
And reaction medium, the use of external source hydrogen donor He other reaction dissolvents is avoided, and its dehydrogenation product g- butyrolactone is also one
The chemicals of class high added value further improves the economy of entire reaction process；5) sectional temperature-controlled method is used, can choose
The catalytic performance and synergistic effect of property regulation activity bimetallic and magnetic inorganic organic hybrid polymer support, effectively avoid by-product
The formation of object improves the yield of target product.
Detailed description of the invention
Fig. 1 is the XRD diagram of used catalyst in the embodiment of the present invention 1.
Fig. 2 is the Py-IR figure of used catalyst in the embodiment of the present invention 1.
Fig. 3 is the CO of used catalyst in the embodiment of the present invention 12- TPD figure.
Fig. 4 is the gas chromatogram for the 2,5- dimethyl furan being prepared in the embodiment of the present invention 6.
Specific embodiment
The invention discloses a kind of methods that dehydrogenation hydrogenation coupled reaction in situ mediates preparation 2,5- dimethyl furan, specifically
Step are as follows: 5 hydroxymethyl furfural and magnetic inorganic organic hybrid Polymer-supported activated bimetallic catalyst are added to 1,4- fourth
In glycol, after the sealed displaced air of autoclave, kept for a period of time after being first warming up to assigned temperature, it is further heated up to
Assigned temperature is kept for a period of time, can obtain 2,5- dimethyl furan.Original position dehydrogenation hydrogenation coupled reaction provided by the invention exists
There is substance matching advantage, energy complement advantage and process matching in 1,4- butanediol dehydrogenation and 5 hydroxymethyl furfural hydrogenation process
Efficiently synthesizing for 2,5- dimethyl furan may be implemented in advantage；Catalyst is by activated bimetallic and has Lewis acid-base property site
It is formed with the magnetic inorganic organic hybrid polymer support of Br nsted acidic site, not only there is stronger Magneto separate characteristic,
Be conducive to the separation and recovery of catalyst, and be provided simultaneously with stronger 1,4-butanediol ability of dehydrogenation and 5 hydroxymethyl furfural adds hydrogen
Ability；1,4-butanediol is a kind of reproducible organic diol, not only can be simultaneously as efficient hydrogen donor in situ and anti-
Medium is answered, the use of external source hydrogen donor He other reaction dissolvents is avoided, and is also overcomed methanol dehydrogenation in the prior art
Security risk of the hydrogen as hydrogen source is generated, and its dehydrogenation product g- butyrolactone is also the chemicals of a kind of high added value, into
One step improves the economy of entire reaction process；The sectional temperature-controlled method used, the property of can choose regulation activity bimetallic and magnetic
Property inorganic-organic hybrid polymer support catalytic performance and synergistic effect, effectively avoid the formation of by-product, improve target and produce
The yield of object has good industrial applications potentiality.
More specifically, detailed description are as follows for technical solution of the present invention:
A kind of composite catalyzing material, including carrier and the active material being carried on carrier, the active material includes
First active metal and the second active metal, first active metal are Ru, the second active metal be selected from Cu, Co, Ni,
One of Zn, Fe or Sn.
In one embodiment, second active metal is more preferably one of Cu, Co or Ni.
In one embodiment, the carrier is Fe3O4The third active metal of load and the hydridization of organic acid are poly-
Close object；The third active metal is selected from zirconium or hafnium.
In one embodiment, it is different to be selected from iminodiacetic acid, pyridinedicarboxylic acid, 2,6- dihydroxy for the organic acid
The mixing of one or more of niacin, phenol, 2,4,6- trihydroxy -1,3,5- triazine.
Wherein, the load capacity of first active metal and the second active metal on carrier is all 1-4wt%.
The magnetic inorganic organic hybrid polymer support is Fe3O4@Zr-INDAA(Zr-INDAA: zirconium-imino-diacetic
Acetic acid hybridized polymer), Fe3O4@Zr-PYDDC(Zr-PYDDC: zirconium -2,5- pyridinedicarboxylic acid hybridized polymer), Fe3O4@Hf-
DHINA(Hf-DHINA: hafnium-citrazinic acid hybridized polymer), Fe3O4@Hf-PHENOL(Hf-PHENOL: hafnium-benzene
Phenol hybridized polymer) or Fe3O4@Hf-THTA(Hf-THTA: hafnium -2,4,6- trihydroxy -1,3,5- triazine hybridized polymer) in
One kind, more preferably Fe3O4@Zr-INDAA、Fe3O4@Hf-DHINA or Fe3O4One of@Hf-THTA.
The preparation method of above-mentioned composite catalyzing material, includes the following steps:
Step 1, the preparation of magnetic carrier: by FeSO4·7H2O and FeCl3·6H2O is dissolved in deionized water, and NH is added dropwise3
×H2O, and temperature reaction is carried out, the sediment that reaction obtains is isolated, after washing, obtains magnetic carrier；
The Polymer-supported of surfaces of magnetic carriers: step 2 disperses having containing third active metal chloride for magnetic material
In solvent, mixed solution is obtained；Mixed solution is added dropwise to the n,N-Dimethylformamide solution of the ligand containing organic acid again, then
Triethylamine is added dropwise, after being reacted, then is aged, after sediment is washed and dried, it is organic miscellaneous to obtain magnetic inorganic
Fluidized polymer carrier；
Step 3, the load in activated centre: magnetic inorganic organic hybrid polymer support is scattered in the chlorine containing the first active metal
Compound, the second active metal chloride deionized water in, after mixing evenly, be added dropwise NaBH4Aqueous solution, carry out anti-
It answers, after carrying out washing drying to solid precipitating, obtains magnetic inorganic organic hybrid Polymer-supported activated bimetallic catalyst.
In one embodiment, in step 1, FeSO4·7H2O and FeCl3·6H2The molar ratio 1:1-3 of O；NH3×
H2The dripping quantity of O is to make the pH of solution to 9-11；Temperature reaction refers to 75-85 DEG C of reaction 0.5-1.5h.
In one embodiment, in step 2, organic solvent refers to n,N-Dimethylformamide；Magnetic material, third
Active metal chloride, organic acid ligand, the amount ratio between triethylamine are: 1-2g:10-20mmol:15-25mmol:100-
150mmol；Reaction refers to reacts 2-4h at room temperature, and ageing refers to still aging 4-8h at 90 DEG C.
In one embodiment, in one embodiment, in step 3, magnetic inorganic organic hybrid is polymer supported
Body and NaBH4Amount ratio be 1-2g:80-120mg, reaction is to react 1-3h at room temperature.
Magnetic inorganic organic hybrid Polymer-supported activated bimetallic catalyst is prepared by following method:
(1) by 5mmol FeSO4·7H2O and 10mmol FeCl3·6H2O is added in 200mL ultrasound deionized deoxygenated water, in nitrogen
Lower stirring to the solid of protection is completely dissolved；(2) it is slowly added to NH dropwise in Xiang Shangshu mixed liquor3×H2O is until pH value is 10 left
The right side, and reaction temperature is increased to 80 DEG C and continues to stir 1h；(3) reaction mixture is cooled to room temperature, in the side of strong magnets
Lower collection black precipitate is helped, and uses ultrasonic deionized deoxygenated water to carry out washing to it until pH value is 7；(4) 1-2g is washed
Black precipitate after washing is resuspended in 400mL and contains 15mmol ZrCl4Or HfCl4N,N-Dimethylformamide in, stirring
Continue ultrasonic disperse 10min after 30min；(5) 400mL is slowly added into Xiang Shangshu mixed liquor, and to contain 20mmol accordingly organic
The n,N-Dimethylformamide solution of sour ligand, and 120 mmol triethylamines are added dropwise in 1h；(6) reaction mixture is in room
Continue to stir 3h, and the still aging 6h at 90 DEG C under temperature；(7) sediment uses N,N-dimethylformamide and ethyl alcohol after filtering
It is sufficiently washed, until it can't detect chloride ion；(8) sediment after filtration washing is placed in a vacuum drying oven,
It can be obtained magnetic inorganic organic hybrid polymer support after 80 °C of dry 12h；(9) 1g magnetic inorganic organic hybrid polymer is taken
Support dispersion after 45min is stirred by ultrasonic continues that 3h is stirred at room temperature in the deionized water that 200mL contains active metal chloride；
(10) 200mL is slowly added dropwise into above-mentioned mixed liquor under condition of ice bath and contains 100mg NaBH4Aqueous solution, continue room
Temperature stirring 2h；(11) solid precipitating deionized water and ethanol washing 6 times, 12 h are finally dried in vacuo at 80 DEG C, can be obtained
Magnetic inorganic organic hybrid Polymer-supported activated bimetallic catalyst.
Above-mentioned catalysis material is applied to dehydrogenation hydrogenation coupled reaction in situ and mediates in preparation 2,5- dimethyl furan.Step
It is:
5 hydroxymethyl furfural and magnetic inorganic organic hybrid Polymer-supported activated bimetallic catalyst are added according to a certain percentage
Enter into 1,4-butanediol, is placed in autoclave using gained mixture as material liquid after mixing, autoclave
After sealed displaced air, assigned temperature 1 is first warming up under the mixing speed of 500rpm, after being kept for one section of reaction time 1, then
It is continuously heating to assigned temperature 2, after being kept for one section of reaction time 2,2,5- dimethyl furan can be obtained.
Wherein, the 5 hydroxymethyl furfural dosage is the 2-4wt% of 1,4-butanediol dosage.
Wherein, the catalyst amount is the 60-100wt% of 5 hydroxymethyl furfural dosage.
The reason of present invention uses double activated metal in the middle is addition Cu, Co, Ni, Zn, Fe or Sn on the basis of Ru
Equal base metals can not only increase the dispersion degree of Ru, improve the atom utilization of Ru as auxiliary agent, but also can increase pair
The adsorption capacity of aldehyde radical and alcoholic extract hydroxyl group improves the selectivity of target product.
Catalyst Lewis acid-base property site and Br nsted acidic site are mainly had by magnetic inorganic in the present invention
What Zr-O-C or Hf-O-C structure and the-COOH not being coordinated that formation is coordinated on machine hybridized polymer carrier or-OH were introduced, Zr-
O-C or Hf-O-C structure Zr4+/Hf4+Show that Lewis is acid, O2-Show Lewis alkalinity ,-COOH or-OH show Br nsted
It is acid.
Wherein, the assigned temperature 1 is 130-160 DEG C, and the reaction time 1 is 1-6h, and assigned temperature 2 is 180-220 DEG C,
Reaction time is 2-5h.
Embodiment 1
The preparation of magnetic inorganic organic hybrid Polymer-supported activated bimetallic catalyst: (1) by 5mmol FeSO4·7H2O and
10mmol FeCl3·6H2O is added in 200mL ultrasound deionized deoxygenated water, is stirred under nitrogen protection completely molten to solid
Solution；(2) it is slowly added to NH dropwise in Xiang Shangshu mixed liquor3×H2O is until pH value is 10 or so, and reaction temperature is increased to 80
DEG C continue to stir 1h；(3) reaction mixture is cooled to room temperature, black precipitate is collected with the help of strong magnets, and adopt
Washing is carried out to it with ultrasonic deionized deoxygenated water until pH value is 7；(4) black precipitate after washing 1g is resuspended in
400mL contains 15mmol ZrCl4N,N-Dimethylformamide in, stir 30min after continue ultrasonic disperse 10min；(5) to
It is slowly added into the n,N-Dimethylformamide solution that 400mL contains 20mmol iminodiacetic acid in above-mentioned mixed liquor, and
120 mmol triethylamines are added dropwise in 1h；(6) reaction mixture continues to stir 3h at room temperature, and still aging at 90 DEG C
6h；(7) sediment is sufficiently washed with n,N-Dimethylformamide and ethyl alcohol after filtering, is up to can't detect chloride ion
Only；(8) sediment after filtration washing is placed in a vacuum drying oven, it is organic to can be obtained magnetic inorganic after 80 °C of dry 12h
Hybridized polymer carrier；(9) 1g magnetic inorganic organic hybrid polymer support is taken to be scattered in 200mL containing with good grounds load capacity meter
RuCl3And CuCl2Deionized water in, be stirred by ultrasonic 45min after continue that 3h is stirred at room temperature；(10) to above-mentioned under condition of ice bath
It is slowly added dropwise 200mL in mixed liquor and contains 100mg NaBH4Aqueous solution, continue that 2h is stirred at room temperature；(11) solid precipitates
With deionized water and ethanol washing 6 times, it is finally dried in vacuo 12 h at 80 DEG C, the polymerization of magnetic inorganic organic hybrid can be obtained
Object supported active bimetallic catalyst (RuCu/Fe3O4@Zr-INDAA).
By 0.5g 5 hydroxymethyl furfural and 0.3g RuCu/Fe3O4@Zr-INDAA(Ru load capacity is 1wt%, Cu load capacity
It is added in 24.5g 1,4-butanediol for 4wt%), is placed in reaction under high pressure using gained mixture as material liquid after mixing
In kettle, after the sealed displaced air of autoclave, it is first warming up to 150 DEG C under the mixing speed of 400rpm, keeps 3h, then
220 DEG C are continuously heating to, 2h is kept, 2,5- dimethyl furan can be obtained, is detected through gas chromatograph it is found that its final yield is
The conversion ratio of 90.6%, HMF are 100%.
Fig. 1 is RuCu/Fe3O4The XRD diagram of@Zr-INDAA, as the result is shown: RuCu/Fe3O4@Zr-INDAA is only 2qFor
There are two wider diffraction maximums in 20-40 ° and 40-70 °, in addition to this without other apparent diffraction maximums, this illustrate Ru with
Cu is in Fe3O4It distributes very evenly on@Zr-INDAA carrier；Fig. 2 is RuCu/Fe3O4The Py-IR of@Zr-INDAA schemes, wherein
1452 and 1594cm-1Belong to the Lewis acidic site of catalyst, 1540cm-1Belong to the Brfnsted acidic site of catalyst
Point, 1490cm-1Belong to the Lewis acidic site and Brfnsted acidic site of catalyst；Fig. 3 is RuCu/Fe3O4@Zr-
The CO of INDAA2- TPD schemes, and shows an apparent CO in figure2Desorption peaks, this illustrates RuCu/Fe3O4@Zr-INDAA have compared with
Strong Lewis basic site.
Embodiment 2
The preparation of magnetic inorganic organic hybrid Polymer-supported activated bimetallic catalyst: (1) by 5mmol FeSO4·7H2O and
10mmol FeCl3·6H2O is added in 200mL ultrasound deionized deoxygenated water, is stirred under nitrogen protection completely molten to solid
Solution；(2) it is slowly added to NH dropwise in Xiang Shangshu mixed liquor3×H2O is until pH value is 10 or so, and reaction temperature is increased to 80
DEG C continue to stir 1h；(3) reaction mixture is cooled to room temperature, black precipitate is collected with the help of strong magnets, and adopt
Washing is carried out to it with ultrasonic deionized deoxygenated water until pH value is 7；(4) black precipitate after washing 1g is resuspended in
400mL contains 15mmol HfCl4N,N-Dimethylformamide in, stir 30min after continue ultrasonic disperse 10min；(5) to
It is slowly added into 400mL in above-mentioned mixed liquor and contains 20mmol 2, the n,N-Dimethylformamide solution of 6- citrazinic acid,
And 120 mmol triethylamines are added dropwise in 1h；(6) reaction mixture continues to stir 3h at room temperature, and stands at 90 DEG C
It is aged 6h；(7) sediment is sufficiently washed with n,N-Dimethylformamide and ethyl alcohol after filtering, until can't detect chlorine from
Until son；(8) sediment after filtration washing is placed in a vacuum drying oven, can be obtained magnetic inorganic after 80 °C of dry 12h
Organic hybrid polymer support；(9) 1g magnetic inorganic organic hybrid polymer support is taken to be scattered in 200mL containing with good grounds load capacity
The RuCl of meter3And NiCl2Deionized water in, be stirred by ultrasonic 45min after continue that 3h is stirred at room temperature；(10) under condition of ice bath to
It is slowly added dropwise 200mL in above-mentioned mixed liquor and contains 100mg NaBH4Aqueous solution, continue that 2h is stirred at room temperature；(11) solid
Precipitating deionized water and ethanol washing 6 times, 12 h are finally dried in vacuo at 80 DEG C, can obtain magnetic inorganic organic hybrid
Polymer-supported activated bimetallic catalyst (RuNi/Fe3O4@Hf-DHINA).
By 1g 5 hydroxymethyl furfural and 0.8g RuNi/Fe3O4@Hf-DHINA(Ru load capacity is 2wt%, and Ni load capacity is
It 2wt%) is added in 24g 1,4-butanediol, is placed in autoclave using gained mixture as material liquid after mixing,
After the sealed displaced air of autoclave, it is first warming up to 130 DEG C under the mixing speed of 400rpm, keeps 6h, then proceedes to
200 DEG C are warming up to, 3h is kept, 2,5- dimethyl furan can be obtained, through gas chromatograph detection it is found that its final yield is 93.3%,
The conversion ratio of HMF is 100%.
Embodiment 3
The preparation of magnetic inorganic organic hybrid Polymer-supported activated bimetallic catalyst: (1) by 5mmol FeSO4·7H2O and
10mmol FeCl3·6H2O is added in 200mL ultrasound deionized deoxygenated water, is stirred under nitrogen protection completely molten to solid
Solution；(2) it is slowly added to NH dropwise in Xiang Shangshu mixed liquor3×H2O is until pH value is 10 or so, and reaction temperature is increased to 80
DEG C continue to stir 1h；(3) reaction mixture is cooled to room temperature, black precipitate is collected with the help of strong magnets, and adopt
Washing is carried out to it with ultrasonic deionized deoxygenated water until pH value is 7；(4) black precipitate after washing 1g is resuspended in
400mL contains 15mmol HfCl4N,N-Dimethylformamide in, stir 30min after continue ultrasonic disperse 10min；(5) to
The N that 400mL contains 20mmol 2,4,6- trihydroxy -1,3,5- triazine, N- dimethyl formyl are slowly added into above-mentioned mixed liquor
Amine aqueous solution, and 120 mmol triethylamines are added dropwise in 1h；(6) reaction mixture continues to stir 3h at room temperature, and 90
Still aging 6h at DEG C；(7) sediment is sufficiently washed with n,N-Dimethylformamide and ethyl alcohol after filtering, until detection
Until chloride ion；(8) sediment after filtration washing is placed in a vacuum drying oven, is can be obtained after 80 °C of dry 12h
Magnetic inorganic organic hybrid polymer support；(9) it takes 1g magnetic inorganic organic hybrid polymer support to be scattered in 200mL and contains root
According to the RuCl of load meter3And CoCl2Deionized water in, be stirred by ultrasonic 45min after continue that 3h is stirred at room temperature；(10) in ice bath
Under the conditions of be slowly added dropwise 200mL into above-mentioned mixed liquor and contain 100mg NaBH4Aqueous solution, continue that 2h is stirred at room temperature；
(11) solid precipitating deionized water and ethanol washing 6 times, 12 h are finally dried in vacuo at 80 DEG C, can obtain magnetic inorganic
Organic hybrid Polymer-supported activated bimetallic catalyst (RuCo/Fe3O4@Hf-THTA).
By 0.6g 5 hydroxymethyl furfural and 0.6g RuCo/Fe3O4@Hf-THTA(Ru load capacity is 3wt%, and Co load capacity is
It 1wt%) is added in 19.4g 1,4-butanediol, is placed in autoclave using gained mixture as material liquid after mixing
In, after the sealed displaced air of autoclave, be first warming up to 160 DEG C under the mixing speed of 400rpm, keep 1h, then after
It is continuous to be warming up to 180 DEG C, 5h is kept, 2,5- dimethyl furan can be obtained, is detected through gas chromatograph it is found that its final yield is
The conversion ratio of 91.2%, HMF are 100%.
Embodiment 4
The preparation of magnetic inorganic organic hybrid Polymer-supported activated bimetallic catalyst: (1) by 5mmol FeSO4·7H2O and
10mmol FeCl3·6H2O is added in 200mL ultrasound deionized deoxygenated water, is stirred under nitrogen protection completely molten to solid
Solution；(2) it is slowly added to NH dropwise in Xiang Shangshu mixed liquor3×H2O is until pH value is 10 or so, and reaction temperature is increased to 80
DEG C continue to stir 1h；(3) reaction mixture is cooled to room temperature, black precipitate is collected with the help of strong magnets, and adopt
Washing is carried out to it with ultrasonic deionized deoxygenated water until pH value is 7；(4) black precipitate after washing 1g is resuspended in
400mL contains 15mmol ZrCl4N,N-Dimethylformamide in, stir 30min after continue ultrasonic disperse 10min；(5) to
It is slowly added into the n,N-Dimethylformamide solution that 400mL contains 20mmol iminodiacetic acid in above-mentioned mixed liquor, and
120 mmol triethylamines are added dropwise in 1h；(6) reaction mixture continues to stir 3h at room temperature, and still aging at 90 DEG C
6h；(7) sediment is sufficiently washed with n,N-Dimethylformamide and ethyl alcohol after filtering, is up to can't detect chloride ion
Only；(8) sediment after filtration washing is placed in a vacuum drying oven, it is organic to can be obtained magnetic inorganic after 80 °C of dry 12h
Hybridized polymer carrier；(9) 1g magnetic inorganic organic hybrid polymer support is taken to be scattered in 200mL containing with good grounds load capacity meter
RuCl3And NiCl2Deionized water in, be stirred by ultrasonic 45min after continue that 3h is stirred at room temperature；(10) to above-mentioned under condition of ice bath
It is slowly added dropwise 200mL in mixed liquor and contains 100mg NaBH4Aqueous solution, continue that 2h is stirred at room temperature；(11) solid precipitates
With deionized water and ethanol washing 6 times, it is finally dried in vacuo 12 h at 80 DEG C, the polymerization of magnetic inorganic organic hybrid can be obtained
Object supported active bimetallic catalyst (RuNi/Fe3O4@Zr-INDAA).
By 0.5g 5 hydroxymethyl furfural and 0.35g RuNi/Fe3O4@Zr-INDAA(Ru load capacity is 4wt%, Ni load capacity
It is added in 24.5g 1,4-butanediol for 1wt%), is placed in reaction under high pressure using gained mixture as material liquid after mixing
In kettle, after the sealed displaced air of autoclave, it is first warming up to 140 DEG C under the mixing speed of 400rpm, keeps 5h, then
190 DEG C are continuously heating to, 4h is kept, 2,5- dimethyl furan can be obtained, is detected through gas chromatograph it is found that its final yield is
The conversion ratio of 94.7%, HMF are 100%.
Embodiment 5
The preparation of magnetic inorganic organic hybrid Polymer-supported activated bimetallic catalyst: (1) by 5mmol FeSO4·7H2O and
10mmol FeCl3·6H2O is added in 200mL ultrasound deionized deoxygenated water, is stirred under nitrogen protection completely molten to solid
Solution；(2) it is slowly added to NH dropwise in Xiang Shangshu mixed liquor3×H2O is until pH value is 10 or so, and reaction temperature is increased to 80
DEG C continue to stir 1h；(3) reaction mixture is cooled to room temperature, black precipitate is collected with the help of strong magnets, and adopt
Washing is carried out to it with ultrasonic deionized deoxygenated water until pH value is 7；(4) black precipitate after washing 1g is resuspended in
400mL contains 15mmol HfCl4N,N-Dimethylformamide in, stir 30min after continue ultrasonic disperse 10min；(5) to
It is slowly added into 400mL in above-mentioned mixed liquor and contains 20mmol 2, the n,N-Dimethylformamide solution of 6- citrazinic acid,
And 120 mmol triethylamines are added dropwise in 1h；(6) reaction mixture continues to stir 3h at room temperature, and stands at 90 DEG C
It is aged 6h；(7) sediment is sufficiently washed with n,N-Dimethylformamide and ethyl alcohol after filtering, until can't detect chlorine from
Until son；(8) sediment after filtration washing is placed in a vacuum drying oven, can be obtained magnetic inorganic after 80 °C of dry 12h
Organic hybrid polymer support；(9) 1g magnetic inorganic organic hybrid polymer support is taken to be scattered in 200mL containing with good grounds load capacity
The RuCl of meter3And CoCl2Deionized water in, be stirred by ultrasonic 45min after continue that 3h is stirred at room temperature；(10) under condition of ice bath to
It is slowly added dropwise 200mL in above-mentioned mixed liquor and contains 100mg NaBH4Aqueous solution, continue that 2h is stirred at room temperature；(11) solid
Precipitating deionized water and ethanol washing 6 times, 12 h are finally dried in vacuo at 80 DEG C, can obtain magnetic inorganic organic hybrid
Polymer-supported activated bimetallic catalyst (RuCo/Fe3O4@Hf-DHINA).
By 1g 5 hydroxymethyl furfural and 0.7g RuCo/Fe3O4@Hf-DHINA(Ru load capacity is 1.5wt%, Co load capacity
It is added in 24g 1,4-butanediol for 3.5wt%), is placed in reaction under high pressure using gained mixture as material liquid after mixing
In kettle, after the sealed displaced air of autoclave, it is first warming up to 150 DEG C under the mixing speed of 400rpm, keeps 3h, then
210 DEG C are continuously heating to, 2h is kept, 2,5- dimethyl furan can be obtained, is detected through gas chromatograph it is found that its final yield is
The conversion ratio of 92.9%, HMF are 100%.
Embodiment 6
The preparation of magnetic inorganic organic hybrid Polymer-supported activated bimetallic catalyst: (1) by 5mmol FeSO4·7H2O and
10mmol FeCl3·6H2O is added in 200mL ultrasound deionized deoxygenated water, is stirred under nitrogen protection completely molten to solid
Solution；(2) it is slowly added to NH dropwise in Xiang Shangshu mixed liquor3×H2O is until pH value is 10 or so, and reaction temperature is increased to 80
DEG C continue to stir 1h；(3) reaction mixture is cooled to room temperature, black precipitate is collected with the help of strong magnets, and adopt
Washing is carried out to it with ultrasonic deionized deoxygenated water until pH value is 7；(4) black precipitate after washing 1g is resuspended in
400mL contains 15mmol HfCl4N,N-Dimethylformamide in, stir 30min after continue ultrasonic disperse 10min；(5) to
The N that 400mL contains 20mmol 2,4,6- trihydroxy -1,3,5- triazine, N- dimethyl formyl are slowly added into above-mentioned mixed liquor
Amine aqueous solution, and 120 mmol triethylamines are added dropwise in 1h；(6) reaction mixture continues to stir 3h at room temperature, and 90
Still aging 6h at DEG C；(7) sediment is sufficiently washed with n,N-Dimethylformamide and ethyl alcohol after filtering, until detection
Until chloride ion；(8) sediment after filtration washing is placed in a vacuum drying oven, is can be obtained after 80 °C of dry 12h
Magnetic inorganic organic hybrid polymer support；(9) it takes 1g magnetic inorganic organic hybrid polymer support to be scattered in 200mL and contains root
According to the RuCl of load meter3And CuCl2Deionized water in, be stirred by ultrasonic 45min after continue that 3h is stirred at room temperature；(10) in ice bath
Under the conditions of be slowly added dropwise 200mL into above-mentioned mixed liquor and contain 100mg NaBH4Aqueous solution, continue that 2h is stirred at room temperature；
(11) solid precipitating deionized water and ethanol washing 6 times, 12 h are finally dried in vacuo at 80 DEG C, can obtain magnetic inorganic
Organic hybrid Polymer-supported activated bimetallic catalyst (RuCu/Fe3O4@Hf-THTA).
By 0.6g 5 hydroxymethyl furfural and 0.5g RuCu/Fe3O4@Hf-THTA(Ru load capacity is 2wt%, and Cu load capacity is
It 3wt%) is added in 19.4g 1,4-butanediol, is placed in autoclave using gained mixture as material liquid after mixing
In, after the sealed displaced air of autoclave, be first warming up to 150 DEG C under the mixing speed of 400rpm, keep 2h, then after
It is continuous to be warming up to 200 DEG C, 3h is kept, 2,5- dimethyl furan can be obtained, is detected through gas chromatograph it is found that its final yield is
The conversion ratio of 95.5%, HMF are 100%(Fig. 4).
Comparative example 1
Difference with embodiment 6 is, using the composite catalyst of single active center, activated centre load the step of be:
1g magnetic inorganic organic hybrid polymer support is taken to be scattered in RuCl of the 200mL containing with good grounds load capacity meter3Deionized water in,
After ultrasonic agitation 45min continue that 3h is stirred at room temperature；200mL is slowly added dropwise into above-mentioned mixed liquor under condition of ice bath to contain
100mg NaBH4Aqueous solution, continue that 2h is stirred at room temperature；Solid precipitating deionized water and ethanol washing 6 times, finally 80
It is dried in vacuo 12 h at DEG C, magnetic inorganic organic hybrid Polymer-supported active metal catalyst (Ru/Fe can be obtained3O4@Hf-
THTA).
By 0.6g 5 hydroxymethyl furfural and 0.5g Ru/Fe3O4@Hf-THTA(Ru load capacity is 5wt%) it is added to 19.4g
In 1,4-butanediol, it is placed in autoclave using gained mixture as material liquid after mixing, autoclave is through close
After sealing displaced air, it is first warming up to 150 DEG C under the mixing speed of 400rpm, keeps 2h, then proceedes to be warming up to 200 DEG C, protect
3h is held, 2,5- dimethyl furan can be obtained, through gas chromatograph detection it is found that the conversion ratio that its final yield is 88.1%, HMF is
100%。
Comparative example 2
Difference with embodiment 6 is, using the composite catalyst of single active center, activated centre load the step of be:
1g magnetic inorganic organic hybrid polymer support is taken to be scattered in CuCl of the 200mL containing with good grounds load capacity meter2Deionized water in,
After ultrasonic agitation 45min continue that 3h is stirred at room temperature；200mL is slowly added dropwise into above-mentioned mixed liquor under condition of ice bath to contain
100mg NaBH4Aqueous solution, continue that 2h is stirred at room temperature；Solid precipitating deionized water and ethanol washing 6 times, finally 80
It is dried in vacuo 12 h at DEG C, magnetic inorganic organic hybrid Polymer-supported active metal catalyst (Cu/Fe can be obtained3O4@Hf-
THTA).
By 0.6g 5 hydroxymethyl furfural and 0.5g Cu/Fe3O4@Hf-THTA(Cu load capacity is 5wt%) it is added to 19.4g
In 1,4-butanediol, it is placed in autoclave using gained mixture as material liquid after mixing, autoclave is through close
After sealing displaced air, it is first warming up to 150 DEG C under the mixing speed of 400rpm, keeps 2h, then proceedes to be warming up to 200 DEG C, protect
3h is held, 2,5- dimethyl furan can be obtained, through gas chromatograph detection it is found that the conversion ratio that its final yield is 69.7%, HMF is
100%。
It can be seen that the catalysis in the double activated site used in the present invention by the comparison of embodiment 6 and comparative example 1,2
Agent, while the metals such as Cu are utilized to the dispersion degree for increasing Ru, the atom utilization of Ru is improved, but also can increase to aldehyde radical
With the adsorption capacity of alcoholic extract hydroxyl group, the selectivity of target product is improved.
Comparative example 3
It is from the difference of embodiment 6: changes different temperature reaction programs.
By 0.6g 5 hydroxymethyl furfural and 0.5g RuCu/Fe3O4@Hf-THTA(Ru load capacity is 2wt%, and Cu load capacity is
It 3wt%) is added in 19.4g 1,4-butanediol, is placed in autoclave using gained mixture as material liquid after mixing
In, after the sealed displaced air of autoclave, it is warming up to 150 DEG C under the mixing speed of 400rpm, keeps 5h, 2,5- can be obtained
Dimethyl furan is detected through gas chromatograph it is found that the conversion ratio that its final yield is 58.3%, HMF is 100%.
Comparative example 4
It is from the difference of embodiment 6: changes different temperature reaction programs.
By 0.6g 5 hydroxymethyl furfural and 0.5g RuCu/Fe3O4@Hf-THTA(Ru load capacity is 2wt%, and Cu load capacity is
It 3wt%) is added in 19.4g 1,4-butanediol, is placed in autoclave using gained mixture as material liquid after mixing
In, after the sealed displaced air of autoclave, it is warming up to 200 DEG C under the mixing speed of 400rpm, keeps 5h, 2,5- can be obtained
Dimethyl furan is detected through gas chromatograph it is found that the conversion ratio that its final yield is 89.2%, HMF is 100%.
It can be seen that by the comparison of embodiment 6 and comparative example 3,4 through sectional temperature-controlled method, the property of can choose regulation is lived
The catalytic performance and synergistic effect of property bimetallic and magnetic inorganic organic hybrid polymer support, effectively avoid the shape of by-product
At improving the selectivity of target product.
Comparative example 5
Difference with embodiment 6 is: changing the carrier of double activated metal.
Take 1g Fe3O4@Al2O3Support dispersion is in RuCl of the 200mL containing with good grounds load capacity meter3And CuCl2Deionized water
In, after 45min is stirred by ultrasonic continue that 3h is stirred at room temperature；200mL is slowly added dropwise into above-mentioned mixed liquor under condition of ice bath
Contain 100mg NaBH4Aqueous solution, continue that 2h is stirred at room temperature；Solid precipitating deionized water and ethanol washing 6 times, finally exist
It is dried in vacuo 12 h at 80 DEG C, magnetic inorganic organic hybrid Polymer-supported active metal catalyst (RuCu/Fe can be obtained3O4@
Al2O3).
By 0.6g 5 hydroxymethyl furfural and 0.5g RuCu/Fe3O4@Al2O3(Ru load capacity is 2wt%, and Cu load capacity is
It 3wt%) is added in 19.4g 1,4-butanediol, is placed in autoclave using gained mixture as material liquid after mixing
In, after the sealed displaced air of autoclave, be first warming up to 150 DEG C under the mixing speed of 400rpm, keep 2h, then after
It is continuous to be warming up to 200 DEG C, 3h is kept, 2,5- dimethyl furan can be obtained, is detected through gas chromatograph it is found that its final yield is
The conversion ratio of 72.2%, HMF are 100%.
Comparative example 6
Difference with embodiment 6 is: changing the carrier of double activated metal.
Take 1g Fe3O4@ZrO2Support dispersion is in RuCl of the 200mL containing with good grounds load capacity meter3And CuCl2Deionized water
In, after 45min is stirred by ultrasonic continue that 3h is stirred at room temperature；200mL is slowly added dropwise into above-mentioned mixed liquor under condition of ice bath
Contain 100mg NaBH4Aqueous solution, continue that 2h is stirred at room temperature；Solid precipitating deionized water and ethanol washing 6 times, finally exist
It is dried in vacuo 12 h at 80 DEG C, magnetic inorganic organic hybrid Polymer-supported active metal catalyst (RuCu/Fe can be obtained3O4@
ZrO2).
By 0.6g 5 hydroxymethyl furfural and 0.5g RuCu/Fe3O4@ZrO2(Ru load capacity is 2wt%, and Cu load capacity is
It 3wt%) is added in 19.4g 1,4-butanediol, is placed in autoclave using gained mixture as material liquid after mixing
In, after the sealed displaced air of autoclave, be first warming up to 150 DEG C under the mixing speed of 400rpm, keep 2h, then after
It is continuous to be warming up to 200 DEG C, 3h is kept, 2,5- dimethyl furan can be obtained, is detected through gas chromatograph it is found that its final yield is
The conversion ratio of 81.9%, HMF are 100%.
Comparative example 7
Difference with embodiment 6 is: changing the carrier of double activated metal.
Take 1g Fe3O4@C-SO3H support dispersion is in RuCl of the 200mL containing with good grounds load capacity meter3And CuCl2Deionization
In water, after 45min is stirred by ultrasonic continue that 3h is stirred at room temperature；It is slowly added dropwise under condition of ice bath into above-mentioned mixed liquor
200mL contains 100mg NaBH4Aqueous solution, continue that 2h is stirred at room temperature；Solid precipitating deionized water and ethanol washing 6 times,
It is finally dried in vacuo 12 h at 80 DEG C, magnetic inorganic organic hybrid Polymer-supported active metal catalyst can be obtained
(RuCu/Fe3O4@C-SO3H).
By 0.6g 5 hydroxymethyl furfural and 0.5g RuCu/Fe3O4@C-SO3H(Ru load capacity is 2wt%, and Cu load capacity is
It 3wt%) is added in 19.4g 1,4-butanediol, is placed in autoclave using gained mixture as material liquid after mixing
In, after the sealed displaced air of autoclave, be first warming up to 150 DEG C under the mixing speed of 400rpm, keep 2h, then after
It is continuous to be warming up to 200 DEG C, 3h is kept, 2,5- dimethyl furan can be obtained, is detected through gas chromatograph it is found that its final yield is
The conversion ratio of 64.7%, HMF are 100%.
By the comparison of embodiment 6 and comparative example 5,6 and 7 as can be seen that the carrier soda acid for passing through adjusting activated bimetallic
Property, the catalytic activity of magnetic inorganic organic hybrid Polymer-supported activated bimetallic catalyst can be enhanced, effectively avoid by-product
The formation of object improves the selectivity of target product.
Claims (9)
1. a kind of composite catalyzing material, including carrier and the active material being carried on carrier, which is characterized in that described
Active material includes the first active metal and the second active metal, and first active metal is Ru, the choosing of the second active metal
From one of Cu, Co, Ni, Zn, Fe or Sn.
2. composite catalyzing material according to claim 1, which is characterized in that second active metal is more preferably
One of Cu, Co or Ni；The carrier is Fe3O4The third active metal of load and the hybridized polymer of organic acid；It is described
Third active metal be selected from zirconium or hafnium；It is different that the organic acid is selected from iminodiacetic acid, pyridinedicarboxylic acid, 2,6- dihydroxy
The mixing of one or more of niacin, phenol, 2,4,6- trihydroxy -1,3,5- triazine；First active metal and
Load capacity of two active metals on carrier is all 1-4wt%.
3. composite catalyzing material according to claim 1, which is characterized in that the magnetic inorganic organic hybrid polymer
Carrier is Fe3O4@Zr-INDAA(Zr-INDAA: zirconium-iminodiacetic acid hybridized polymer), Fe3O4@Zr-PYDDC(Zr-
PYDDC: zirconium -2,5- pyridinedicarboxylic acid hybridized polymer), Fe3O4@Hf-DHINA(Hf-DHINA: hafnium-citrazinic acid
Hybridized polymer), Fe3O4@Hf-PHENOL(Hf-PHENOL: hafnium-phenol hybridized polymer) or Fe3O4@Hf-THTA(Hf-
One of THTA: hafnium -2,4,6- trihydroxy -1,3,5-triazines hybridized polymer), more preferably Fe3O4@Zr-INDAA、
Fe3O4@Hf-DHINA or Fe3O4One of@Hf-THTA.
4. the preparation method of composite catalyzing material described in claim 1, which comprises the steps of:
Step 1, the preparation of magnetic carrier: by FeSO4·7H2O and FeCl3·6H2O is dissolved in anaerobic deionized water, is added dropwise
NH3×H2O, and temperature reaction is carried out, the sediment that reaction obtains is isolated, after washing, obtains magnetic carrier；
The Polymer-supported of surfaces of magnetic carriers: step 2 disperses having containing third active metal chloride for magnetic material
In solvent, mixed solution is obtained；The n,N-Dimethylformamide solution of the ligand containing organic acid is added dropwise to mixed solution again, then drips
Add triethylamine, after being reacted, then be aged, after sediment is washed and dried, obtains magnetic inorganic organic hybrid
Polymer support；
Step 3, the load in activated centre: magnetic inorganic organic hybrid polymer support is scattered in the chlorine containing the first active metal
Compound, the second active metal chloride deionized water in, after mixing evenly, be added dropwise NaBH4Aqueous solution, carry out anti-
It answers, after carrying out washing drying to solid precipitating, obtains magnetic inorganic organic hybrid Polymer-supported activated bimetallic catalyst.
5. the preparation method of composite catalyzing material according to claim 7, which is characterized in that in step 1, FeSO4·
7H2O and FeCl3·6H2The molar ratio 1:1-3 of O；NH3×H2The dripping quantity of O is to make the pH of solution to 9-11；Temperature reaction refers to
75-85 DEG C of reaction 0.5-1.5h；In step 2, organic solvent refers to n,N-Dimethylformamide；Magnetic material, third activity
Metal chloride, organic acid ligand, the amount ratio between triethylamine are: 1-2g:10-20mmol:15-25mmol:100-
150mmol；Reaction refers to reacts 2-4h at room temperature, and ageing refers to still aging 4-8h at 90 DEG C；In step 3, magnetic inorganic
Organic hybrid polymer support and NaBH4Amount ratio be 1-2g:80-120mg, reaction is to react 1-3h at room temperature.
6. dehydrogenation hydrogenation coupled reaction mediates preparation 2,5- dimethyl furan to composite catalyzing material described in claim 1 in situ
In application.
7. purposes according to claim 6, which is characterized in that the purposes includes the following steps: step 1, by 5- hydroxyl
Methyl furfural, magnetic inorganic organic hybrid Polymer-supported activated bimetallic catalyst and 1,4-butanediol after mixing will
Gained mixture is placed in autoclave as material liquid；Step 2 is first warming up to the first temperature, is reacted；Step 3, then
It is warming up to the first temperature, is reacted, 2,5- dimethyl furan is obtained.
8. purposes according to claim 7, which is characterized in that the 5 hydroxymethyl furfural dosage is 1,4-butanediol use
The 2-4wt% of amount；The catalyst amount is the 60-100wt% of 5 hydroxymethyl furfural dosage；The active metal is in magnetism
Load capacity on inorganic-organic hybrid polymer support is 1-4wt%.
9. purposes according to claim 12, which is characterized in that 130-160 DEG C of the first temperature in step 2, reaction time 1-
6h；180-220 DEG C of second temperature in step 3, reaction time 2-5h.
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