CN109675638B - Composite catalytic material, preparation method and application in-situ dehydrogenation hydrogenation reaction mediated preparation of 2, 5-dimethylfuran - Google Patents
Composite catalytic material, preparation method and application in-situ dehydrogenation hydrogenation reaction mediated preparation of 2, 5-dimethylfuran 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 76
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 25
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002131 composite material Substances 0.000 title claims abstract description 16
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 15
- 230000001404 mediated effect Effects 0.000 title claims abstract description 8
- 238000006356 dehydrogenation reaction Methods 0.000 title abstract description 19
- 229920000642 polymer Polymers 0.000 claims abstract description 75
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims abstract description 60
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 50
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000005859 coupling reaction Methods 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 85
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 81
- 238000003756 stirring Methods 0.000 claims description 62
- 239000002244 precipitate Substances 0.000 claims description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 56
- 239000000203 mixture Substances 0.000 claims description 51
- 229910052751 metal Inorganic materials 0.000 claims description 46
- 239000002184 metal Substances 0.000 claims description 46
- 239000008367 deionised water Substances 0.000 claims description 45
- 229910021641 deionized water Inorganic materials 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 44
- 239000003054 catalyst Substances 0.000 claims description 43
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 39
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 38
- 238000011068 loading method Methods 0.000 claims description 33
- 238000005406 washing Methods 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 22
- 239000011259 mixed solution Substances 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 19
- 150000007524 organic acids Chemical class 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 13
- 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
- 238000002156 mixing Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- 229910001868 water Inorganic materials 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 7
- 239000003446 ligand Substances 0.000 claims description 7
- 229910001510 metal chloride Inorganic materials 0.000 claims description 7
- 239000011149 active material Substances 0.000 claims description 6
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 claims description 6
- 239000000696 magnetic material Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- CSGQJHQYWJLPKY-UHFFFAOYSA-N CITRAZINIC ACID Chemical compound OC(=O)C=1C=C(O)NC(=O)C=1 CSGQJHQYWJLPKY-UHFFFAOYSA-N 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
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 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
- 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
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 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
- 239000000047 product Substances 0.000 abstract description 11
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 6
- 239000006227 byproduct Substances 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 45
- 238000001291 vacuum drying Methods 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000007789 gas Substances 0.000 description 14
- 239000011541 reaction mixture Substances 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052603 melanterite Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 229910019891 RuCl3 Inorganic materials 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000001132 ultrasonic dispersion Methods 0.000 description 6
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 5
- 229910003865 HfCl4 Inorganic materials 0.000 description 5
- 239000000852 hydrogen donor Substances 0.000 description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 230000001476 alcoholic effect Effects 0.000 description 4
- 125000003172 aldehyde group Chemical group 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000002028 Biomass Substances 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
- 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
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- JYCZLJUGLVWLMP-UHFFFAOYSA-N OC1=NC(=NC(=N1)O)O.[Hf] Chemical compound OC1=NC(=NC(=N1)O)O.[Hf] JYCZLJUGLVWLMP-UHFFFAOYSA-N 0.000 description 2
- 229910006069 SO3H Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 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
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- -1 hafnium-2, 6-dihydroxyisonicotinic acid Chemical compound 0.000 description 2
- 238000007885 magnetic separation Methods 0.000 description 2
- 238000002215 pyrolysis infrared spectroscopy Methods 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 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 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000009901 transfer hydrogenation reaction Methods 0.000 description 1
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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
- B01J31/26—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
-
- B01J35/33—
-
- 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
Abstract
A composite catalytic material, a preparation method and application thereof in-situ dehydrogenation hydrogenation coupling reaction mediated preparation of 2, 5-dimethylfuran. The catalytic material consists of active bimetal and a magnetic inorganic-organic hybrid polymer carrier with Lewis acid-base sites and Br ϕ nsted acid sites, and has stronger 1, 4-butanediol dehydrogenation capacity and 5-hydroxymethylfurfural hydrogenation capacity; the adopted segmented temperature control method can selectively regulate and control the catalytic performance and synergistic effect of the active bimetal and magnetic inorganic-organic hybrid polymer carrier, effectively avoid the formation of byproducts, improve the yield of target products and have good industrial application potential.
Description
Technical Field
The invention belongs to the field of biomass energy chemical industry, and particularly relates to a composite catalytic material, a preparation method and application thereof in-situ dehydrogenation and hydrogenation reaction mediated preparation of 2, 5-dimethylfuran.
Background
With the increasingly prominent contradiction between the supply and demand of fossil resources and the increasingly serious phenomenon of environmental pollution, lignocellulose as a biomass resource with wide source, abundant reserves and low price has been more and more widely concerned by numerous researchers at home and abroad. In recent years, 5-hydroxymethylfurfural obtained by oriented conversion of lignocellulose is considered as a very important platform compound, which is listed as one of ten major platform compounds based on biomass resources by the U.S. department of energy because various high-value-added chemicals, fuels and materials can be prepared by using the same as a starting material. Among them, 2, 5-dimethylfuran obtained by selective hydrogenation of 5-hydroxymethylfurfural is considered as a very promising novel liquid biofuel, having many advantages: 1) the energy density is high (31.5 MJ/L), and is close to that of gasoline; 2) the boiling point is high (92-94 ℃), and the volatile matter is not easy to volatilize; 3) high octane number (119), good explosion-proof performance; 4) insoluble in water and easy to store and transport, these advantages make 2, 5-dimethylfuran increasingly one of the most important sources of future liquid biofuels (Industrial & Engineering Research, 2014, 53: 3056-3064).
As is known, 5-hydroxymethylfurfural molecules simultaneously contain an aldehyde group, an alcoholic hydroxyl group and a furan ring, so that the chemical properties of the 5-hydroxymethylfurfural are very active, and the product generated in the hydrogenation reaction is relatively complex, so that how to ensure the preferential hydrogenation of the aldehyde group and the alcoholic hydroxyl group and avoid the over-hydrogenation of the furan ring as much as possible is the problem which needs to be solved firstly in the process of preparing 2, 5-dimethylfuran by selective hydrogenation of 5-hydroxymethylfurfural, and the development of a proper catalytic reaction system plays a crucial role in solving the problem.
Chinese patents CN103554066A, CN104557802A, CN105251491A, CN105032427A, CN105597771A, CN106279075A and CN108863996A disclose a method for preparing 2, 5-dimethylfuran by hydrodeoxygenation of 5-hydroxymethylfurfural, which uses hydrogen as a hydrogen source, and has poor solubility and atom utilization in different solvents, and has great potential safety hazard in the processes of storage, transportation and use.
Chinese patent CN108047174A and Angewandte Chemie International Edition (2010, 49: 6616-.
Chinese patents CN108586392A and Green Chemistry (2012, 14: 2457-2461), ChemUSchem (2013, 6: 1158-1162), ChemUSchem (2013, 7: 268-275), Catalysis Science & Technology (2015, 5: 1463-1472), Applied Catalysis A: General (2019, 570: 245-250) disclose a method for preparing 2, 5-dimethylfuran by transfer hydrogenation of 5-hydroxymethylfurfural, which uses non-corrosive methanol, ethanol or isopropanol as a hydrogen donor, but methanol requires a high critical temperature (up to 300 ℃) and the selectivity of the target product during the reaction is low, while ethanol and isopropanol after hydrogen transfer are easy to undergo a reverse reaction and a large amount of inert gas is required to maintain high pressure during the reaction. In addition, in the catalytic reaction process adopted in patent CN108586392A, methanol needs to be dehydrogenated to generate hydrogen first, and then the generated hydrogen is subjected to catalytic hydrogenation reaction, which still has higher safety risk.
Disclosure of Invention
The method for preparing the 2, 5-dimethylfuran through the in-situ dehydrogenation hydrogenation coupling reaction mediation is provided, and the selective synthesis of the 2, 5-dimethylfuran is realized through the synergistic effect of the magnetic bifunctional nano-catalyst and by virtue of the matching advantages of a reaction system in material, energy and process.
In a first aspect of the present invention, there is provided:
a composite catalytic material comprises a carrier and an active material loaded on the carrier, wherein the active material comprises a first active metal and a second active metal, the first active metal is Ru, and the second active metal is one selected from Cu, Co, Ni, Zn, Fe or Sn.
In one embodiment, the second active metal is more preferably one of Cu, Co or Ni.
In one embodiment, the first active metal and the second active metal are each present at a support loading of 1 to 4 wt%.
In one embodiment, the support is Fe3O4A hybrid polymer of a supported third active metal and an organic acid; the third active metal is selected from zirconium or hafnium.
In one embodiment, the organic acid is selected from one or more of iminodiacetic acid, dipicolinic acid, 2, 6-dihydroxyisonicotinic acid, phenol, and 2,4, 6-trihydroxy-1, 3, 5-triazine.
In one embodiment, the hybrid polymer of the third active metal and the organic acid is preferably a zirconium-iminodiacetic acid hybrid polymer, a hafnium-2, 6-dihydroxyisonicotinic acid hybrid polymer, or a hafnium-2, 4, 6-trihydroxy-1, 3, 5-triazine hybrid polymer.
In a second aspect of the present invention, there is provided:
the preparation method of the composite catalytic material comprises the following steps:
step 2, polymer loading of the surface of the magnetic carrier: dispersing the magnetic material in an organic solvent containing a third active metal chloride to obtain a mixed solution; dropwise adding the mixed solution into an N, N-dimethylformamide solution containing an organic acid ligand, dropwise adding triethylamine, reacting, aging, washing and drying the precipitate to obtain a magnetic inorganic organic hybrid polymer carrier;
step 3, loading of active center: dispersing the magnetic inorganic organic hybrid polymer carrier in deionized water containing the chloride of the first active metal and the chloride of the second active metal, stirring uniformly,NaBH is dripped4The solid precipitate is washed and dried to obtain the magnetic inorganic organic hybrid polymer loaded active bimetallic catalyst.
In one embodiment, in step 1, FeSO4·7H2O and FeCl3·6H2The molar ratio of O is 1: 1-3; NH (NH)3×H2The dropwise adding amount of O is to ensure that the pH value of the solution is 9-11; the heating reaction is carried out at 75-85 ℃ for 0.5-1.5 h.
In one embodiment, in step 2, the organic solvent is N, N-dimethylformamide; the dosage ratio of the magnetic material, the third active metal chloride, the organic acid ligand and the triethylamine is as follows: 1-2g, 10-20mmol:15-25mmol, 100-150 mmol; the reaction is carried out for 2-4h at room temperature, and the aging is carried out for 4-8h at 90 ℃.
In one embodiment, in step 3, the magnetic inorganic-organic hybrid polymer support and NaBH are combined4The dosage ratio of the raw materials is 1-2g:80-120mg, and the reaction is carried out for 1-3h at room temperature.
In a third aspect of the present invention, there is provided:
the composite catalytic material is used for preparing 2, 5-dimethylfuran by in-situ dehydrogenation and hydrogenation coupling reaction mediation.
In one embodiment, the use comprises the steps of:
step 2, heating to a first temperature to perform reaction;
and step 3, heating to the first temperature again, and reacting to obtain the 2, 5-dimethylfuran.
In one embodiment, the 5-hydroxymethylfurfural is used in an amount of 2 to 4wt% based on the amount of 1, 4-butanediol.
In one embodiment, the amount of the catalyst is 60 to 100wt% of the amount of 5-hydroxymethylfurfural.
In one embodiment, the loading of the active metal on the magnetic inorganic organic hybrid polymer support is 1-4 wt%.
In one embodiment, the first temperature in step 2 is 130-.
In one embodiment, the second temperature in step 3 is 180-.
The invention also provides application of the first active metal and/or the second active metal as an active center of a catalyst to improve selectivity and yield of a reaction for preparing 2, 5-dimethylfuran mediated by in-situ dehydrogenation-hydrogenation coupling reaction.
The invention also provides application of the carrier in improving selectivity and yield of the reaction for preparing 2, 5-dimethylfuran mediated by in-situ dehydrogenation hydrogenation coupling reaction.
Advantageous effects
The invention has the advantages that: 1) the catalyst consists of active bimetal and a magnetic inorganic-organic hybrid polymer carrier with Lewis acid-base sites and Br ϕ nsted acid sites, has stronger magnetic separation characteristic, is beneficial to separation and recovery of the catalyst, has stronger 1, 4-butanediol dehydrogenation capacity and 5-hydroxymethylfurfural hydrogenation capacity, can use active hydrogen removed by 1, 4-butanediol in situ for hydrogenation of 5-hydroxymethylfurfural, and realizes efficient synthesis of 2, 5-dimethylfuran; 2) the hydrogenation reaction of the 5-hydroxymethylfurfural is an exothermic reaction, the dehydrogenation reaction of the 1, 4-butanediol is an endothermic reaction, the heat released by the hydrogenation reaction of the 5-hydroxymethylfurfural can be directly used for the dehydrogenation reaction of the 1, 4-butanediol, and the external energy supply can be effectively reduced; 3) the matching in the process: the dehydrogenation reaction of 1, 4-butanediol and the hydrogenation reaction of 5-hydroxymethylfurfural can be carried out under the liquid phase condition with similar reaction temperature and pressure, and the reaction products of gamma-butyrolactone and 2, 5-dimethylfuran have large difference in boiling point and are easy to separate; 4) 1, 4-butanediol is a renewable organic dihydric alcohol, not only can be used as a high-efficiency in-situ hydrogen donor and a reaction medium at the same time, but also avoids the use of an exogenous hydrogen donor and other reaction solvents, and a dehydrogenation product g-butyrolactone is a chemical with a high added value, so that the economy of the whole reaction process is further improved; 5) by adopting a segmented temperature control method, the catalytic performance and synergistic effect of the active bimetal and magnetic inorganic-organic hybrid polymer carrier can be selectively regulated, the formation of byproducts is effectively avoided, and the yield of target products is improved.
Drawings
FIG. 1 is an XRD pattern of the catalyst used in example 1 of the present invention.
FIG. 2 is a Py-IR diagram of the catalyst used in example 1 of the present invention.
FIG. 3 is CO of the catalyst used in example 1 of the present invention2-TPD map.
FIG. 4 is a gas chromatogram of 2, 5-dimethylfuran produced in example 6 of the present invention.
Detailed Description
The invention discloses a method for preparing 2, 5-dimethylfuran by in-situ dehydrogenation and hydrogenation coupling reaction mediation, which comprises the following specific steps: adding 5-hydroxymethylfurfural and a magnetic inorganic-organic hybrid polymer loaded active bimetallic catalyst into 1, 4-butanediol, sealing a high-pressure reaction kettle to replace air, heating to a specified temperature, keeping for a period of time, and then continuously heating to the specified temperature and keeping for a period of time to obtain the 2, 5-dimethylfuran. The in-situ dehydrogenation and hydrogenation coupling reaction provided by the invention has the advantages of substance matching, energy complementation and process matching in the processes of 1, 4-butanediol dehydrogenation and 5-hydroxymethylfurfural hydrogenation, and can realize the high-efficiency synthesis of 2, 5-dimethylfuran; the catalyst consists of active bimetal and a magnetic inorganic-organic hybrid polymer carrier with Lewis acid-base sites and Br ϕ nsted acid sites, has stronger magnetic separation characteristic, is beneficial to separation and recovery of the catalyst, and simultaneously has stronger 1, 4-butanediol dehydrogenation capacity and 5-hydroxymethylfurfural hydrogenation capacity; the 1, 4-butanediol is a renewable organic dihydric alcohol, can be used as a high-efficiency in-situ hydrogen donor and a reaction medium at the same time, avoids the use of an exogenous hydrogen donor and other reaction solvents, overcomes the safety risk of dehydrogenating methanol to generate hydrogen as a hydrogen source in the prior art, and further improves the economy of the whole reaction process because the dehydrogenation product g-butyrolactone is a chemical with high added value; the adopted segmented temperature control method can selectively regulate and control the catalytic performance and synergistic effect of the active bimetal and magnetic inorganic-organic hybrid polymer carrier, effectively avoid the formation of byproducts, improve the yield of target products and have good industrial application potential.
More specifically, the technical scheme of the invention is explained in detail as follows:
a composite catalytic material comprises a carrier and an active material loaded on the carrier, wherein the active material comprises a first active metal and a second active metal, the first active metal is Ru, and the second active metal is one selected from Cu, Co, Ni, Zn, Fe or Sn.
In one embodiment, the second active metal is more preferably one of Cu, Co or Ni.
In one embodiment, the support is Fe3O4A hybrid polymer of a supported third active metal and an organic acid; the third active metal is selected from zirconium or hafnium.
In one embodiment, the organic acid is selected from one or more of iminodiacetic acid, dipicolinic acid, 2, 6-dihydroxyisonicotinic acid, phenol, and 2,4, 6-trihydroxy-1, 3, 5-triazine.
Wherein the loading amount of the first active metal and the second active metal on the carrier is 1-4 wt%.
The magnetic inorganic organic hybrid polymer carrier is Fe3O4@ Zr-INDAA (Zr-INDAA: zirconium-iminodiacetic acid hybrid Polymer), Fe3O4@ Zr-PYDDC (Zr-PYDDC: zirconium-2, 5-pyridinedicarboxylic acid hybrid polymer), Fe3O4@ Hf-DHINA (Hf-DHINA: hafnium-2, 6-dihydroxyisonicotinic acid hybrid polymer), Fe3O4@ Hf-PHENOL (Hf-PHENOL hybrid polymer) or Fe3O4@ Hf-THTA (Hf-THTA: hafnium-2, 4, 6-trihydroxy-1, 3, 5-triazine hybrid polymer), more preferably Fe3O4@Zr-INDAA、Fe3O4@ Hf-DHINA or Fe3O4@ Hf-THTA.
The preparation method of the composite catalytic material comprises the following steps:
step 2, polymer loading of the surface of the magnetic carrier: dispersing the magnetic material in an organic solvent containing a third active metal chloride to obtain a mixed solution; dropwise adding the mixed solution into an N, N-dimethylformamide solution containing an organic acid ligand, dropwise adding triethylamine, reacting, aging, washing and drying the precipitate to obtain a magnetic inorganic organic hybrid polymer carrier;
step 3, loading of active center: dispersing the magnetic inorganic organic hybrid polymer carrier in deionized water containing the chloride of the first active metal and the chloride of the second active metal, stirring uniformly, and dripping NaBH4The solid precipitate is washed and dried to obtain the magnetic inorganic organic hybrid polymer loaded active bimetallic catalyst.
In one embodiment, in step 1, FeSO4·7H2O and FeCl3·6H2The molar ratio of O is 1: 1-3; NH (NH)3×H2The dropwise adding amount of O is to ensure that the pH value of the solution is 9-11; the heating reaction is carried out at 75-85 ℃ for 0.5-1.5 h.
In one embodiment, in step 2, the organic solvent is N, N-dimethylformamide; the dosage ratio of the magnetic material, the third active metal chloride, the organic acid ligand and the triethylamine is as follows: 1-2g of 10-20mmol, 15-25mmol, 100-150 mmol; the reaction is carried out for 2-4h at room temperature, and the aging is carried out for 4-8h at 90 ℃.
In one embodiment, in step 3, the magnetic inorganic organic hybrid polymerizationArticle carrier and NaBH4The dosage ratio of the raw materials is 1-2g:80-120mg, and the reaction is carried out for 1-3h at room temperature.
The magnetic inorganic organic hybrid polymer supported active bimetallic catalyst is prepared by the following method: (1) adding 5mmol of FeSO4·7H2O and 10mmol FeCl3·6H2Adding O into 200mL of ultrasonic deoxidized deionized water, and stirring under the protection of nitrogen until the solid is completely dissolved; (2) adding NH into the mixed solution dropwise and slowly3×H2O until the pH value is about 10, raising the reaction temperature to 80 ℃, and continuing stirring for 1 h; (3) cooling the reaction mixture to room temperature, collecting black precipitate with the help of a strong magnet, and washing the black precipitate by using ultrasonic deoxidized deionized water until the pH value is 7; (4) 1-2g of the washed black precipitate were resuspended in 400mL of a suspension containing 15mmol of ZrCl4Or HfCl4Stirring in N, N-dimethylformamide for 30min, and continuing ultrasonic dispersion for 10 min; (5) slowly adding 400mL of N, N-dimethylformamide solution containing 20mmol of corresponding organic acid ligand into the mixed solution, and dropwise adding 120 mmol of triethylamine within 1 h; (6) the reaction mixture is continuously stirred for 3 hours at room temperature and is kept stand and aged for 6 hours at the temperature of 90 ℃; (7) filtering the precipitate, and fully washing with N, N-dimethylformamide and ethanol until no chloride ion is detected; (8) putting the filtered and washed precipitate into a vacuum drying oven, and drying at 80 ℃ for 12h to obtain the magnetic inorganic organic hybrid polymer carrier; (9) dispersing 1g of magnetic inorganic-organic hybrid polymer carrier in 200mL of deionized water containing active metal chloride, ultrasonically stirring for 45min, and then continuing stirring at room temperature for 3 h; (10) 200mL of a solution containing 100mg of NaBH was added dropwise slowly to the above mixture under ice-bath conditions4The aqueous solution is continuously stirred for 2 hours at room temperature; (11) washing the solid precipitate with deionized water and ethanol for 6 times, and finally drying in vacuum at 80 ℃ for 12h to obtain the magnetic inorganic-organic hybrid polymer loaded active bimetallic catalyst.
The catalytic material is applied to the in-situ dehydrogenation hydrogenation coupling reaction mediated preparation of 2, 5-dimethylfuran. The method comprises the following steps:
adding 5-hydroxymethylfurfural and a magnetic inorganic-organic hybrid polymer loaded active bimetallic catalyst into 1, 4-butanediol according to a certain proportion, uniformly mixing, taking the obtained mixture as a raw material solution, placing the raw material solution into a high-pressure reaction kettle, hermetically replacing air in the high-pressure reaction kettle, heating to a specified temperature 1 at a stirring speed of 500rpm, keeping the reaction for 1 period of time, continuing to heat to a specified temperature 2, and keeping the reaction for 2 periods of time to obtain 2, 5-dimethylfuran.
Wherein the dosage of the 5-hydroxymethylfurfural is 2-4wt% of that of the 1, 4-butanediol.
Wherein the dosage of the catalyst is 60-100wt% of that of the 5-hydroxymethylfurfural.
The reason why the double-active metal is adopted in the invention is that non-noble metals such as Cu, Co, Ni, Zn, Fe or Sn are added on the basis of Ru as an auxiliary agent, so that the dispersion degree of Ru can be increased, the atom utilization rate of Ru is improved, the adsorption capacity to aldehyde groups and alcoholic hydroxyl groups can be increased, and the selectivity of a target product is improved.
In the invention, Lewis acid-base sites and Br ϕ nsted acid sites of the catalyst are mainly introduced by a Zr-O-C or Hf-O-C structure formed by coordination on a magnetic inorganic-organic hybrid polymer carrier and uncoordinated-COOH or-OH, and the Zr-O-C or Hf-O-C structure Zr4+/Hf4+Shows Lewis acidity, O2-Shows Lewis basicity, -COOH or-OH shows Br ϕ nsted acidity.
Wherein the specified temperature 1 is 130-160 ℃, the reaction time 1 is 1-6h, the specified temperature 2 is 180-220 ℃, and the reaction time is 2-5 h.
Example 1
Preparation of magnetic inorganic organic hybrid polymer loaded active bimetallic catalyst: (1) adding 5mmol of FeSO4·7H2O and 10mmol FeCl3·6H2Adding O into 200mL of ultrasonic deoxidized deionized water, and stirring under the protection of nitrogen until the solid is completely dissolved; (2) adding NH into the mixed solution dropwise and slowly3×H2O until the pH value is about 10, raising the reaction temperature to 80 ℃, and continuing stirring for 1 h; (3) the reaction mixture was cooled to room temperature under a strong magnetCollecting black precipitate with the help of the ultrasonic deoxidation deionized water, and washing the black precipitate by adopting the ultrasonic deoxidation deionized water until the pH value is 7; (4) 1g of the washed black precipitate was resuspended in 400mL of a suspension containing 15mmol of ZrCl4Stirring in N, N-dimethylformamide for 30min, and continuing ultrasonic dispersion for 10 min; (5) slowly adding 400mL of N, N-dimethylformamide solution containing 20mmol of iminodiacetic acid into the mixed solution, and dropwise adding 120 mmol of triethylamine within 1 h; (6) the reaction mixture is continuously stirred for 3 hours at room temperature and is kept stand and aged for 6 hours at the temperature of 90 ℃; (7) filtering the precipitate, and fully washing with N, N-dimethylformamide and ethanol until no chloride ion is detected; (8) putting the filtered and washed precipitate into a vacuum drying oven, and drying at 80 ℃ for 12h to obtain the magnetic inorganic organic hybrid polymer carrier; (9) 1g of magnetic inorganic-organic hybrid polymer carrier was dispersed in 200mL of a solution containing RuCl in terms of the amount of the supported RuCl3And CuCl2Stirring the mixture in deionized water for 45min by ultrasonic wave, and then continuing stirring the mixture for 3h at room temperature; (10) 200mL of a solution containing 100mg of NaBH was added dropwise slowly to the above mixture under ice-bath conditions4The aqueous solution is continuously stirred for 2 hours at room temperature; (11) washing the solid precipitate with deionized water and ethanol for 6 times, and vacuum drying at 80 deg.C for 12h to obtain magnetic inorganic-organic hybrid polymer loaded active bimetallic catalyst (RuCu/Fe)3O4@Zr-INDAA）。
0.5g of 5-hydroxymethylfurfural and 0.3g of RuCu/Fe3O4Adding @ Zr-INDAA (the loading capacity of Ru is 1wt percent and the loading capacity of Cu is 4wt percent) into 24.5g of 1, 4-butanediol, uniformly mixing, then placing the obtained mixture as a raw material liquid into a high-pressure reaction kettle, hermetically replacing air in the high-pressure reaction kettle, heating to 150 ℃ at a stirring speed of 400rpm, keeping the temperature for 3 hours, then continuously heating to 220 ℃ and keeping the temperature for 2 hours to obtain 2, 5-dimethylfuran, and detecting by a gas chromatograph, wherein the final yield is 90.6 percent and the conversion rate of HMF is 100 percent.
FIG. 1 shows RuCu/Fe3O4XRD pattern of @ Zr-INDAA, the results show: RuCu/Fe3O4@ Zr-INDAA at 2 onlyqTwo broad diffraction peaks in the range of 20-40 DEG and 40-70 DEG, except forNo other obvious diffraction peak, which shows that Ru and Cu are in Fe3O4The distribution on the @ Zr-INDAA carrier is very uniform; FIG. 2 shows RuCu/Fe3O4Py-IR diagram of @ Zr-INDAA, wherein 1452 and 1594cm-1Lewis acid site belonging to catalyst, 1540cm-1Brfnsted acid site, 1490cm, ascribed to catalyst-1Lewis acid sites and Brfnsted acid sites belonging to the catalyst; FIG. 3 shows RuCu/Fe3O4CO of @ Zr-INDAA2TPD plot showing a significant CO2Desorption peak, which indicates RuCu/Fe3O4@ Zr-INDAA has a strong Lewis basic site.
Example 2
Preparation of magnetic inorganic organic hybrid polymer loaded active bimetallic catalyst: (1) adding 5mmol of FeSO4·7H2O and 10mmol FeCl3·6H2Adding O into 200mL of ultrasonic deoxidized deionized water, and stirring under the protection of nitrogen until the solid is completely dissolved; (2) adding NH into the mixed solution dropwise and slowly3×H2O until the pH value is about 10, raising the reaction temperature to 80 ℃, and continuing stirring for 1 h; (3) cooling the reaction mixture to room temperature, collecting black precipitate with the help of a strong magnet, and washing the black precipitate by using ultrasonic deoxidized deionized water until the pH value is 7; (4) 1g of the washed black precipitate was resuspended in 400mL of a suspension containing 15mmol of HfCl4Stirring in N, N-dimethylformamide for 30min, and continuing ultrasonic dispersion for 10 min; (5) slowly adding 400mL of N, N-dimethylformamide solution containing 20mmol of 2, 6-dihydroxy isonicotinic acid into the mixed solution, and dropwise adding 120 mmol of triethylamine within 1 h; (6) the reaction mixture is continuously stirred for 3 hours at room temperature and is kept stand and aged for 6 hours at the temperature of 90 ℃; (7) filtering the precipitate, and fully washing with N, N-dimethylformamide and ethanol until no chloride ion is detected; (8) putting the filtered and washed precipitate into a vacuum drying oven, and drying at 80 ℃ for 12h to obtain the magnetic inorganic organic hybrid polymer carrier; (9) 1g of magnetic inorganic-organic hybrid polymer carrier was dispersed in 200mL of a solution containing RuCl in terms of the amount of the supported RuCl3And NiCl2Stirring the mixture in deionized water for 45min by ultrasonic wave, and then continuing stirring the mixture for 3h at room temperature; (10) 200mL of a solution containing 100mg of NaBH was added dropwise slowly to the above mixture under ice-bath conditions4The aqueous solution is continuously stirred for 2 hours at room temperature; (11) washing the solid precipitate with deionized water and ethanol for 6 times, and vacuum drying at 80 deg.C for 12h to obtain magnetic inorganic-organic hybrid polymer loaded active bimetallic catalyst (RuNi/Fe)3O4@Hf-DHINA）。
1g of 5-hydroxymethylfurfural and 0.8g of RuNi/Fe3O4Adding @ Hf-DHINA (the loading capacity of Ru is 2wt% and the loading capacity of Ni is 2 wt%) into 24g of 1, 4-butanediol, uniformly mixing, placing the obtained mixture as a raw material solution into a high-pressure reaction kettle, hermetically replacing air in the high-pressure reaction kettle, heating to 130 ℃ at a stirring speed of 400rpm, keeping the temperature for 6 hours, then continuously heating to 200 ℃ and keeping the temperature for 3 hours to obtain 2, 5-dimethylfuran, wherein the final yield is 93.3% and the conversion rate of HMF is 100% as detected by a gas chromatograph.
Example 3
Preparation of magnetic inorganic organic hybrid polymer loaded active bimetallic catalyst: (1) adding 5mmol of FeSO4·7H2O and 10mmol FeCl3·6H2Adding O into 200mL of ultrasonic deoxidized deionized water, and stirring under the protection of nitrogen until the solid is completely dissolved; (2) adding NH into the mixed solution dropwise and slowly3×H2O until the pH value is about 10, raising the reaction temperature to 80 ℃, and continuing stirring for 1 h; (3) cooling the reaction mixture to room temperature, collecting black precipitate with the help of a strong magnet, and washing the black precipitate by using ultrasonic deoxidized deionized water until the pH value is 7; (4) 1g of the washed black precipitate was resuspended in 400mL of a suspension containing 15mmol of HfCl4Stirring in N, N-dimethylformamide for 30min, and continuing ultrasonic dispersion for 10 min; (5) slowly adding the mixed solution into 400mL of N, N-dimethylformamide solution containing 20mmol of 2,4, 6-trihydroxy-1, 3, 5-triazine, and dropwise adding 120 mmol of triethylamine in 1 h; (6) the reaction mixture is continuously stirred for 3 hours at room temperature and is kept stand and aged for 6 hours at the temperature of 90 ℃; (7) the precipitate was filtered off and washed with N, N-dimethylformamide andfully washing with ethanol until no chloride ion is detected; (8) putting the filtered and washed precipitate into a vacuum drying oven, and drying at 80 ℃ for 12h to obtain the magnetic inorganic organic hybrid polymer carrier; (9) 1g of magnetic inorganic-organic hybrid polymer carrier was dispersed in 200mL of a solution containing RuCl in terms of the amount of the supported RuCl3And CoCl2Stirring the mixture in deionized water for 45min by ultrasonic wave, and then continuing stirring the mixture for 3h at room temperature; (10) 200mL of a solution containing 100mg of NaBH was added dropwise slowly to the above mixture under ice-bath conditions4The aqueous solution is continuously stirred for 2 hours at room temperature; (11) washing the solid precipitate with deionized water and ethanol for 6 times, and vacuum drying at 80 deg.C for 12 hr to obtain magnetic inorganic-organic hybrid polymer loaded active bimetallic catalyst (RuCo/Fe)3O4@Hf-THTA）。
0.6g of 5-hydroxymethylfurfural and 0.6g of RuCo/Fe3O4Adding @ Hf-THTA (the load of Ru is 3wt% and the load of Co is 1 wt%) into 19.4g of 1, 4-butanediol, uniformly mixing, placing the obtained mixture as a raw material solution into a high-pressure reaction kettle, hermetically replacing air in the high-pressure reaction kettle, heating to 160 ℃ at a stirring speed of 400rpm, keeping the temperature for 1h, then continuously heating to 180 ℃ and keeping the temperature for 5h to obtain 2, 5-dimethylfuran, wherein the final yield is 91.2% and the conversion rate of HMF is 100% as detected by a gas chromatograph.
Example 4
Preparation of magnetic inorganic organic hybrid polymer loaded active bimetallic catalyst: (1) adding 5mmol of FeSO4·7H2O and 10mmol FeCl3·6H2Adding O into 200mL of ultrasonic deoxidized deionized water, and stirring under the protection of nitrogen until the solid is completely dissolved; (2) adding NH into the mixed solution dropwise and slowly3×H2O until the pH value is about 10, raising the reaction temperature to 80 ℃, and continuing stirring for 1 h; (3) cooling the reaction mixture to room temperature, collecting black precipitate with the help of a strong magnet, and washing the black precipitate by using ultrasonic deoxidized deionized water until the pH value is 7; (4) 1g of the washed black precipitate was resuspended in 400mL of a suspension containing 15mmol of ZrCl4Stirring in N, N-dimethylformamide for 30min, and continuously performing ultrafiltrationDispersing sound for 10 min; (5) slowly adding 400mL of N, N-dimethylformamide solution containing 20mmol of iminodiacetic acid into the mixed solution, and dropwise adding 120 mmol of triethylamine within 1 h; (6) the reaction mixture is continuously stirred for 3 hours at room temperature and is kept stand and aged for 6 hours at the temperature of 90 ℃; (7) filtering the precipitate, and fully washing with N, N-dimethylformamide and ethanol until no chloride ion is detected; (8) putting the filtered and washed precipitate into a vacuum drying oven, and drying at 80 ℃ for 12h to obtain the magnetic inorganic organic hybrid polymer carrier; (9) 1g of magnetic inorganic-organic hybrid polymer carrier was dispersed in 200mL of a solution containing RuCl in terms of the amount of the supported RuCl3And NiCl2Stirring the mixture in deionized water for 45min by ultrasonic wave, and then continuing stirring the mixture for 3h at room temperature; (10) 200mL of a solution containing 100mg of NaBH was added dropwise slowly to the above mixture under ice-bath conditions4The aqueous solution is continuously stirred for 2 hours at room temperature; (11) washing the solid precipitate with deionized water and ethanol for 6 times, and vacuum drying at 80 deg.C for 12h to obtain magnetic inorganic-organic hybrid polymer loaded active bimetallic catalyst (RuNi/Fe)3O4@Zr-INDAA）。
0.5g of 5-hydroxymethylfurfural and 0.35g of RuNi/Fe3O4Adding @ Zr-INDAA (the loading capacity of Ru is 4wt percent and the loading capacity of Ni is 1wt percent) into 24.5g of 1, 4-butanediol, uniformly mixing, then placing the obtained mixture as a raw material liquid into a high-pressure reaction kettle, hermetically replacing air in the high-pressure reaction kettle, heating to 140 ℃ at a stirring speed of 400rpm, keeping the temperature for 5 hours, then continuously heating to 190 ℃ and keeping the temperature for 4 hours to obtain 2, 5-dimethylfuran, and detecting by a gas chromatograph, wherein the final yield is 94.7 percent and the conversion rate of HMF is 100 percent.
Example 5
Preparation of magnetic inorganic organic hybrid polymer loaded active bimetallic catalyst: (1) adding 5mmol of FeSO4·7H2O and 10mmol FeCl3·6H2Adding O into 200mL of ultrasonic deoxidized deionized water, and stirring under the protection of nitrogen until the solid is completely dissolved; (2) adding NH into the mixed solution dropwise and slowly3×H2O until the pH value is about 10, and raising the reaction temperature to 80 ℃ and thenContinuously stirring for 1 h; (3) cooling the reaction mixture to room temperature, collecting black precipitate with the help of a strong magnet, and washing the black precipitate by using ultrasonic deoxidized deionized water until the pH value is 7; (4) 1g of the washed black precipitate was resuspended in 400mL of a suspension containing 15mmol of HfCl4Stirring in N, N-dimethylformamide for 30min, and continuing ultrasonic dispersion for 10 min; (5) slowly adding 400mL of N, N-dimethylformamide solution containing 20mmol of 2, 6-dihydroxy isonicotinic acid into the mixed solution, and dropwise adding 120 mmol of triethylamine within 1 h; (6) the reaction mixture is continuously stirred for 3 hours at room temperature and is kept stand and aged for 6 hours at the temperature of 90 ℃; (7) filtering the precipitate, and fully washing with N, N-dimethylformamide and ethanol until no chloride ion is detected; (8) putting the filtered and washed precipitate into a vacuum drying oven, and drying at 80 ℃ for 12h to obtain the magnetic inorganic organic hybrid polymer carrier; (9) 1g of magnetic inorganic-organic hybrid polymer carrier was dispersed in 200mL of a solution containing RuCl in terms of the amount of the supported RuCl3And CoCl2Stirring the mixture in deionized water for 45min by ultrasonic wave, and then continuing stirring the mixture for 3h at room temperature; (10) 200mL of a solution containing 100mg of NaBH was added dropwise slowly to the above mixture under ice-bath conditions4The aqueous solution is continuously stirred for 2 hours at room temperature; (11) washing the solid precipitate with deionized water and ethanol for 6 times, and vacuum drying at 80 deg.C for 12 hr to obtain magnetic inorganic-organic hybrid polymer loaded active bimetallic catalyst (RuCo/Fe)3O4@Hf-DHINA）。
1g of 5-hydroxymethylfurfural and 0.7g of RuCo/Fe3O4Adding @ Hf-DHINA (the load of Ru is 1.5wt% and the load of Co is 3.5 wt%) into 24g of 1, 4-butanediol, uniformly mixing, placing the obtained mixture as a raw material solution into a high-pressure reaction kettle, hermetically replacing air in the high-pressure reaction kettle, heating to 150 ℃ at a stirring speed of 400rpm, keeping the temperature for 3 hours, then continuously heating to 210 ℃ and keeping the temperature for 2 hours to obtain 2, 5-dimethylfuran, wherein the final yield is 92.9% and the conversion rate of HMF is 100% according to detection of a gas chromatograph.
Example 6
Preparation of magnetic inorganic organic hybrid polymer loaded active bimetallic catalyst: (1) Adding 5mmol of FeSO4·7H2O and 10mmol FeCl3·6H2Adding O into 200mL of ultrasonic deoxidized deionized water, and stirring under the protection of nitrogen until the solid is completely dissolved; (2) adding NH into the mixed solution dropwise and slowly3×H2O until the pH value is about 10, raising the reaction temperature to 80 ℃, and continuing stirring for 1 h; (3) cooling the reaction mixture to room temperature, collecting black precipitate with the help of a strong magnet, and washing the black precipitate by using ultrasonic deoxidized deionized water until the pH value is 7; (4) 1g of the washed black precipitate was resuspended in 400mL of a suspension containing 15mmol of HfCl4Stirring in N, N-dimethylformamide for 30min, and continuing ultrasonic dispersion for 10 min; (5) slowly adding the mixed solution into 400mL of N, N-dimethylformamide solution containing 20mmol of 2,4, 6-trihydroxy-1, 3, 5-triazine, and dropwise adding 120 mmol of triethylamine in 1 h; (6) the reaction mixture is continuously stirred for 3 hours at room temperature and is kept stand and aged for 6 hours at the temperature of 90 ℃; (7) filtering the precipitate, and fully washing with N, N-dimethylformamide and ethanol until no chloride ion is detected; (8) putting the filtered and washed precipitate into a vacuum drying oven, and drying at 80 ℃ for 12h to obtain the magnetic inorganic organic hybrid polymer carrier; (9) 1g of magnetic inorganic-organic hybrid polymer carrier was dispersed in 200mL of a solution containing RuCl in terms of the amount of the supported RuCl3And CuCl2Stirring the mixture in deionized water for 45min by ultrasonic wave, and then continuing stirring the mixture for 3h at room temperature; (10) 200mL of a solution containing 100mg of NaBH was added dropwise slowly to the above mixture under ice-bath conditions4The aqueous solution is continuously stirred for 2 hours at room temperature; (11) washing the solid precipitate with deionized water and ethanol for 6 times, and vacuum drying at 80 deg.C for 12h to obtain magnetic inorganic-organic hybrid polymer loaded active bimetallic catalyst (RuCu/Fe)3O4@Hf-THTA）。
0.6g of 5-hydroxymethylfurfural and 0.5g of RuCu/Fe3O4Adding @ Hf-THTA (Ru loading is 2wt% and Cu loading is 3 wt%) into 19.4g of 1, 4-butanediol, uniformly mixing, placing the obtained mixture as raw material liquor into high-pressure reaction kettle, making the high-pressure reaction kettle implement sealed air displacement, heating to 150 deg.C under the condition of stirring speed of 400rpm, and maintaining temperatureAfter the reaction lasts for 2 hours, the temperature is continuously raised to 200 ℃, and the reaction lasts for 3 hours, so that the 2, 5-dimethylfuran can be obtained, and the final yield is 95.5% and the conversion rate of HMF is 100% as shown by the detection of a gas chromatograph (figure 4).
Comparative example 1
The difference from the example 6 is that the single-active-center composite catalyst is adopted, and the active center loading step is as follows: 1g of magnetic inorganic-organic hybrid polymer carrier was dispersed in 200mL of a solution containing RuCl in terms of the amount of the supported RuCl3Stirring the mixture in deionized water for 45min by ultrasonic wave, and then continuing stirring the mixture for 3h at room temperature; 200mL of a solution containing 100mg of NaBH was added dropwise slowly to the above mixture under ice-bath conditions4The aqueous solution is continuously stirred for 2 hours at room temperature; washing the solid precipitate with deionized water and ethanol for 6 times, and vacuum drying at 80 deg.C for 12h to obtain magnetic inorganic-organic hybrid polymer loaded active metal catalyst (Ru/Fe)3O4@Hf-THTA）。
0.6g of 5-hydroxymethylfurfural and 0.5g of Ru/Fe3O4Adding @ Hf-THTA (the load of Ru is 5 wt%) into 19.4g of 1, 4-butanediol, uniformly mixing, placing the obtained mixture as a raw material solution into a high-pressure reaction kettle, after the high-pressure reaction kettle is sealed to displace air, firstly heating to 150 ℃ at the stirring speed of 400rpm, keeping the temperature for 2h, then continuously heating to 200 ℃ and keeping the temperature for 3h to obtain 2, 5-dimethylfuran, and detecting by a gas chromatograph, wherein the final yield is 88.1%, and the conversion rate of HMF is 100%.
Comparative example 2
The difference from the example 6 is that the single-active-center composite catalyst is adopted, and the active center loading step is as follows: 1g of magnetic inorganic-organic hybrid polymer carrier was dispersed in 200mL of a solution containing CuCl in terms of the amount of the supported catalyst2Stirring the mixture in deionized water for 45min by ultrasonic wave, and then continuing stirring the mixture for 3h at room temperature; 200mL of a solution containing 100mg of NaBH was added dropwise slowly to the above mixture under ice-bath conditions4The aqueous solution is continuously stirred for 2 hours at room temperature; washing the solid precipitate with deionized water and ethanol for 6 times, and vacuum drying at 80 deg.C for 12h to obtain magnetic inorganic-organic hybrid polymer loaded active metal catalyst (Cu/Fe)3O4@Hf-THTA）。
0.6g of 5-hydroxymethylfurfural and 0.5g of Cu/Fe3O4Adding @ Hf-THTA (Cu loading is 5 wt%) into 19.4g of 1, 4-butanediol, uniformly mixing, then placing the obtained mixture as a raw material solution into a high-pressure reaction kettle, after the high-pressure reaction kettle is sealed to displace air, firstly heating to 150 ℃ at a stirring speed of 400rpm, keeping the temperature for 2 hours, then continuously heating to 200 ℃ and keeping the temperature for 3 hours to obtain 2, 5-dimethylfuran, and detecting by a gas chromatograph, wherein the final yield is 69.7%, and the conversion rate of HMF is 100%.
It can be seen from the comparison between example 6 and comparative examples 1 and 2 that the catalyst with double active sites adopted in the present invention utilizes the metal pairs such as Cu to increase the dispersion degree of Ru, improve the atom utilization rate of Ru, and also can increase the adsorption capacity to aldehyde group and alcoholic hydroxyl group, and improve the selectivity of the target product.
Comparative example 3
The difference from example 6 is that: different temperature-rising reaction procedures are changed.
0.6g of 5-hydroxymethylfurfural and 0.5g of RuCu/Fe3O4@ Hf-THTA (Ru loading of 2wt% and Cu loading of 3 wt%) was added to 19.4g of 1, 4-butanediol, the mixture was uniformly mixed and placed in a high pressure reactor as a raw material solution, the high pressure reactor was sealed to displace air, the temperature was raised to 150 ℃ at a stirring speed of 400rpm, and the temperature was maintained for 5 hours to obtain 2, 5-dimethylfuran, which was detected by a gas chromatograph to show that the final yield was 58.3% and the conversion of HMF was 100%.
Comparative example 4
The difference from example 6 is that: different temperature-rising reaction procedures are changed.
0.6g of 5-hydroxymethylfurfural and 0.5g of RuCu/Fe3O4Adding @ Hf-THTA (Ru loading is 2wt% and Cu loading is 3 wt%) into 19.4g of 1, 4-butanediol, uniformly mixing, placing the obtained mixture as raw material liquor into a high-pressure reaction kettle, hermetically replacing air in the high-pressure reaction kettle, heating to 200 deg.C at a stirring speed of 400rpm, holding for 5h to obtain 2, 5-dimethylfuran, and detecting by a gas chromatograph to obtain the final yield of 89.2% and the conversion rate of HMFIs 100%.
It can be seen from the comparison between example 6 and comparative examples 3 and 4 that the catalytic performance and synergistic effect of the active bimetallic and magnetic inorganic-organic hybrid polymer carrier can be selectively regulated and controlled by a segmented temperature control method, the formation of byproducts is effectively avoided, and the selectivity of target products is improved.
Comparative example 5
The difference from example 6 is that: the carrier of the double active metal is changed.
1g of Fe is taken3O4@Al2O3The support was dispersed in 200mL of a solution containing RuCl in terms of loading3And CuCl2Stirring the mixture in deionized water for 45min by ultrasonic wave, and then continuing stirring the mixture for 3h at room temperature; 200mL of a solution containing 100mg of NaBH was added dropwise slowly to the above mixture under ice-bath conditions4The aqueous solution is continuously stirred for 2 hours at room temperature; washing the solid precipitate with deionized water and ethanol for 6 times, and vacuum drying at 80 deg.C for 12h to obtain magnetic inorganic-organic hybrid polymer loaded active metal catalyst (RuCu/Fe)3O4@ Al2O3）。
0.6g of 5-hydroxymethylfurfural and 0.5g of RuCu/Fe3O4@Al2O3(the Ru loading is 2wt% and the Cu loading is 3 wt%) is added into 19.4g of 1, 4-butanediol, the mixture is uniformly mixed and then is used as a raw material liquid to be placed in a high-pressure reaction kettle, the high-pressure reaction kettle is sealed to replace air, the temperature is firstly raised to 150 ℃ at the stirring speed of 400rpm, the temperature is kept for 2 hours, then the temperature is continuously raised to 200 ℃ and the temperature is kept for 3 hours, so that the 2, 5-dimethylfuran can be obtained, the final yield is 72.2% and the conversion rate of HMF is 100% as can be seen by gas chromatograph detection.
Comparative example 6
The difference from example 6 is that: the carrier of the double active metal is changed.
1g of Fe is taken3O4@ZrO2The support was dispersed in 200mL of a solution containing RuCl in terms of loading3And CuCl2Stirring the mixture in deionized water for 45min by ultrasonic wave, and then continuing stirring the mixture for 3h at room temperature; 200mL of a solution containing 100mg of NaBH was added dropwise slowly to the above mixture under ice-bath conditions4The aqueous solution is continuously stirred for 2 hours at room temperature; washing the solid precipitate with deionized water and ethanol for 6 times, and vacuum drying at 80 deg.C for 12h to obtain magnetic inorganic-organic hybrid polymer loaded active metal catalyst (RuCu/Fe)3O4@ZrO2）。
0.6g of 5-hydroxymethylfurfural and 0.5g of RuCu/Fe3O4@ZrO2(the Ru loading is 2wt% and the Cu loading is 3 wt%) is added into 19.4g of 1, 4-butanediol, the mixture is uniformly mixed and then is used as a raw material liquid to be placed in a high-pressure reaction kettle, the high-pressure reaction kettle is sealed to replace air, the temperature is firstly raised to 150 ℃ at the stirring speed of 400rpm, the temperature is kept for 2 hours, then the temperature is continuously raised to 200 ℃ and the temperature is kept for 3 hours, so that the 2, 5-dimethylfuran can be obtained, the final yield is 81.9% and the conversion rate of HMF is 100% through the detection of a gas chromatograph.
Comparative example 7
The difference from example 6 is that: the carrier of the double active metal is changed.
1g of Fe is taken3O4@C-SO3H carrier dispersed in 200mL of RuCl containing the same in terms of loading3And CuCl2Stirring the mixture in deionized water for 45min by ultrasonic wave, and then continuing stirring the mixture for 3h at room temperature; 200mL of a solution containing 100mg of NaBH was added dropwise slowly to the above mixture under ice-bath conditions4The aqueous solution is continuously stirred for 2 hours at room temperature; washing the solid precipitate with deionized water and ethanol for 6 times, and vacuum drying at 80 deg.C for 12h to obtain magnetic inorganic-organic hybrid polymer loaded active metal catalyst (RuCu/Fe)3O4@C-SO3H）。
0.6g of 5-hydroxymethylfurfural and 0.5g of RuCu/Fe3O4@C-SO3Adding H (the loading capacity of Ru is 2wt% and the loading capacity of Cu is 3 wt%) into 19.4g of 1, 4-butanediol, uniformly mixing, placing the obtained mixture as a raw material liquid into a high-pressure reaction kettle, sealing the high-pressure reaction kettle to replace air, heating to 150 ℃ at a stirring speed of 400rpm, keeping for 2 hours, then continuously heating to 200 ℃ and keeping for 3 hours to obtain 2, 5-dimethylfuran, wherein the final yield is 64.7% and the conversion rate of HMF is 100% as detected by a gas chromatograph.
It can be seen from the comparison between example 6 and comparative examples 5, 6 and 7 that the catalytic activity of the magnetic inorganic organic hybrid polymer supported active bimetallic catalyst can be enhanced by adjusting the acidity and basicity of the carrier of the active bimetallic, the formation of by-products can be effectively avoided, and the selectivity of the target product can be improved.
Claims (6)
1. The application of a composite catalytic material in the in-situ dehydrogenation-hydrogenation coupling reaction mediated preparation of 2, 5-dimethylfuran is characterized in that the composite catalytic material comprises a carrier and an active material loaded on the carrier, wherein the active material comprises a first active metal and a second active metal, the first active metal is Ru, and the second active metal is one selected from Cu, Co or Ni;
the carrier is Fe3O4A hybrid polymer of a supported third active metal and an organic acid; the third active metal is selected from zirconium or hafnium; the organic acid is selected from one or a mixture of more of iminodiacetic acid, dipicolinic acid, 2, 6-dihydroxy isonicotinic acid, phenol and 2,4, 6-trihydroxy-1, 3, 5-triazine;
the application comprises the following steps: step a, uniformly mixing 5-hydroxymethylfurfural, a composite catalytic material and 1, 4-butanediol, and placing the obtained mixture serving as a raw material liquid in a high-pressure reaction kettle; step b, heating to a first temperature to perform reaction; step c, heating to a second temperature again, and reacting to obtain 2, 5-dimethylfuran; the first temperature is 130-160 ℃, and the reaction time is 1-6 h; the second temperature is 180 ℃ and 220 ℃, and the reaction time is 2-5 h.
2. The use according to claim 1, wherein the first active metal and the second active metal are both present in an amount of 1 to 4wt% on the support.
3. Use according to claim 1, wherein the carrier is Fe3O4@Zr-INDAA、Fe3O4@ Hf-DHINA or Fe3O4@ Hf-THTA.
4. The use according to claim 1, wherein the method for preparing the composite catalytic material comprises the following steps:
step 1, preparing a magnetic carrier: FeSO (ferric oxide) is added4•7H2O and FeCl3•6H2Dissolving O in oxygen-free deionized water, and dripping NH3•H2O, performing temperature rise reaction, separating precipitates obtained by the reaction, and washing to obtain a magnetic carrier;
step 2, polymer loading of the surface of the magnetic carrier: dispersing the magnetic material in an organic solvent containing a third active metal chloride to obtain a mixed solution; dropwise adding an N, N-dimethylformamide solution containing an organic acid ligand into the mixed solution, dropwise adding triethylamine, reacting, then aging, washing and drying the precipitate to obtain a magnetic inorganic organic hybrid polymer carrier;
step 3, loading of active center: dispersing the magnetic inorganic-organic hybrid polymer carrier in deionized water containing the chloride of the first active metal and the chloride of the second active metal, stirring uniformly, and dripping NaBH4The solid precipitate is washed and dried to obtain the magnetic inorganic organic hybrid polymer loaded active bimetallic catalyst.
5. Use according to claim 4, wherein in step 1, FeSO4•7H2O and FeCl3•6H2The molar ratio of O is 1: 1-3; NH (NH)3•H2The dropwise adding amount of O is to ensure that the pH value of the solution is 9-11; the heating reaction is carried out at 75-85 ℃ for 0.5-1.5 h; in the step 2, the organic solvent is N, N-dimethylformamide; the dosage ratio of the magnetic material, the third active metal chloride, the organic acid ligand and the triethylamine is as follows: 1-2g of 10-20mmol, 15-25mmol, 100-150 mmol; the reaction refers to reaction for 2-4h at room temperature, and the aging refers to standing and aging for 4-8h at 90 ℃; in step 3, a magnetic inorganic-organic hybrid polymer support and NaBH4The dosage ratio of the components is 1-2g:80120mg, reaction at room temperature for 1-3 h.
6. The use according to claim 1, wherein the 5-hydroxymethylfurfural is used in an amount of 2 to 4wt% based on the amount of 1, 4-butanediol; the dosage of the composite catalytic material is 60-100wt% of that of 5-hydroxymethylfurfural.
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