CN114768856A - Heterogeneous catalyst and preparation method and application thereof - Google Patents
Heterogeneous catalyst and preparation method and application thereof Download PDFInfo
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- CN114768856A CN114768856A CN202210539553.9A CN202210539553A CN114768856A CN 114768856 A CN114768856 A CN 114768856A CN 202210539553 A CN202210539553 A CN 202210539553A CN 114768856 A CN114768856 A CN 114768856A
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- 239000002638 heterogeneous catalyst Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 34
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- VKLGKDZCKSMSHG-UHFFFAOYSA-N [5-(aminomethyl)furan-2-yl]methanamine Chemical compound NCC1=CC=C(CN)O1 VKLGKDZCKSMSHG-UHFFFAOYSA-N 0.000 claims abstract description 23
- PXJJKVNIMAZHCB-UHFFFAOYSA-N 2,5-diformylfuran Chemical compound O=CC1=CC=C(C=O)O1 PXJJKVNIMAZHCB-UHFFFAOYSA-N 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 12
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052796 boron Inorganic materials 0.000 claims abstract description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 8
- 239000011574 phosphorus Substances 0.000 claims abstract description 8
- 238000011068 loading method Methods 0.000 claims abstract description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 24
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 229910021645 metal ion Inorganic materials 0.000 description 10
- 239000002028 Biomass Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 150000004985 diamines Chemical class 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- UQYIJQXDRBKHBG-UHFFFAOYSA-N [5-(acetyloxymethyl)furan-2-yl]methyl acetate Chemical compound CC(=O)OCC1=CC=C(COC(C)=O)O1 UQYIJQXDRBKHBG-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- 229910021538 borax Inorganic materials 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- 239000004328 sodium tetraborate Substances 0.000 description 3
- 235000010339 sodium tetraborate Nutrition 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- CYJRNFFLTBEQSQ-UHFFFAOYSA-N 8-(3-methyl-1-benzothiophen-5-yl)-N-(4-methylsulfonylpyridin-3-yl)quinoxalin-6-amine Chemical compound CS(=O)(=O)C1=C(C=NC=C1)NC=1C=C2N=CC=NC2=C(C=1)C=1C=CC2=C(C(=CS2)C)C=1 CYJRNFFLTBEQSQ-UHFFFAOYSA-N 0.000 description 1
- -1 Amine compounds Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- JXBHQYZANKJVGW-UHFFFAOYSA-N [2-(aminomethyl)furan-3-yl]methanamine Chemical compound NCC=1C=COC=1CN JXBHQYZANKJVGW-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 229920000249 biocompatible polymer Polymers 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- BTVFCJZKQFDRHI-UHFFFAOYSA-N n,n-dimethylfuran-2-amine Chemical compound CN(C)C1=CC=CO1 BTVFCJZKQFDRHI-UHFFFAOYSA-N 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000011846 petroleum-based material Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Images
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a heterogeneous catalyst which is prepared by loading hydrogenation metal on a doped non-metal carrier, wherein the hydrogenation metal is selected from one of Ru, Pd, Pt and Ni, and the doped non-metal carrier is selected from one of nitrogen-doped carbon, nitrogen-doped boron, nitrogen-doped phosphorus, boron/nitrogen-doped carbon and phosphorus/nitrogen-doped carbon. The invention also provides an application of the heterogeneous catalyst, which takes 2, 5-furan dicarbaldehyde as a raw material and methanol as a solvent to react in the presence of the heterogeneous catalyst and hydrogen and a nitrogen source to generate 2, 5-furan dimethylamine. The method provided by the invention has the advantages that the conversion rate of the 2, 5-furandicarboxaldehyde reaches 100%, and the yield of the 2, 5-furandimethylamine can reach more than 96%, so that a brand new way is provided for producing the 2, 5-furandimethylamine by catalyzing the 2, 5-furandicarboxaldehyde. The invention also provides a preparation method of the heterogeneous catalyst.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a heterogeneous catalyst, a preparation method and application thereof, in particular to a heterogeneous catalyst and a method for preparing 2, 5-furandimethylamine from 2, 5-furandimethaldehyde.
Background
Amine compounds are an important class of nitrogen-containing compounds and are widely used in the synthesis of drugs, pesticides, surfactants, dyes, polymers and bioactive compounds. Primary diamines are among the most useful monomers for producing polyamides and polyurethanes. Polyamides and polyurethanes are widely used in everyday life, including automotive, aerospace, electrical and electronic, construction and biomedical applications. In conventional industrial processes, they are produced and synthesized from carbonyl and alcohol compounds derived from fossil resources. However, the consumption of fossil resources and the environmental impact associated with their use are both major issues. Therefore, there is an urgent need to replace fossil resources with renewable resources for the production of primary diamines.
Biomass, as a renewable, ubiquitous resource, is considered the next generation feedstock for the chemical industry. The use of biomass as a feedstock for the production of bulk chemicals helps to reduce the dependence on petroleum-based materials and reduce pollution. In addition, biomass-derived diamine monomers will meet the increasing demand for biocompatible polymers. Therefore, the development of an effective method for preparing diamine by utilizing bio-based renewable materials plays an important role in establishing the sustainable development of society.
2, 5-Furanyldimethylamine (BAMF), a diamine derived from biomass, has the potential to replace p-xylylenediamine. The selective synthesis of 2, 5-furandimethylamine is therefore a challenging task. The current method for preparing 2, 5-furandimethylamine still has great space for improvement in product yield, so that a high-efficiency catalyst is required to be searched, and the BAMF has higher yield.
Disclosure of Invention
In view of the above, the present invention provides a heterogeneous catalyst, a preparation method and an application thereof, and the heterogeneous catalyst provided by the present invention has a high yield when used for preparing 2, 5-furandimethylamine.
The present invention provides a heterogeneous catalyst comprising:
a doped non-metallic carrier;
a hydrogenation metal supported on the doped non-metallic support.
Preferably, the doped non-metal carrier is selected from one or more of nitrogen-doped carbon, nitrogen-doped boron, nitrogen-doped phosphorus, boron/nitrogen-co-doped carbon and phosphorus/nitrogen-co-doped carbon.
Preferably, the hydrogenation metal is selected from one or more of Ru, Pd, Pt and Ni.
Preferably, the mass content of the hydrogenation metal in the heterogeneous catalyst is 1-20%.
Preferably, the hydrogenation metal is in the elemental state in the heterogeneous catalyst.
The invention provides a preparation method of the heterogeneous catalyst in the technical scheme, which comprises the following steps:
loading hydrogenation metal on a doped non-metal carrier to obtain a heterogeneous catalyst;
the supporting method is selected from a dipping method or a precipitation method.
The invention provides a preparation method of 2, 5-furandimethylamine, which comprises the following steps:
reacting 2, 5-furan dicarbaldehyde with hydrogen and a nitrogen source in a solvent under the action of a heterogeneous catalyst to obtain 2, 5-furan dimethylamine;
the heterogeneous catalyst is the heterogeneous catalyst in the technical scheme.
Preferably, the mass ratio of the heterogeneous catalyst to the 2, 5-furandicarboxaldehyde is 1 (1-30).
Preferably, the pressure of the hydrogen is 0.1-3 MPa.
Preferably, the reaction temperature is 50-200 ℃.
The invention provides a heterogeneous catalyst, and the heterogeneous catalyst can be used for efficiently preparing 2, 5-furandimethylamine from 2, 5-furandimethaldehyde under mild conditions. The preparation method of the 2, 5-furandimethylamine provided by the invention has the advantages of simple process, simple reaction equipment, simple and convenient operation, mild reaction conditions, cheap and easily-obtained catalyst, high catalytic efficiency and stable recycling performance, is suitable for industrial production, and has very wide application prospect.
Drawings
FIG. 1 is a NMR spectrum of 2, 5-furandimethylamine prepared in example 78 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The present invention provides a heterogeneous catalyst comprising:
a doped non-metallic carrier;
a hydrogenation metal supported on the doped non-metallic support.
In the present invention, the heterogeneous catalyst is obtained by loading a hydrogenation metal on a doped non-metal carrier.
In the present invention, the doped non-metallic carrier is preferably selected from one or more of nitrogen-doped Carbon (CN), nitrogen-doped Boron (BN), nitrogen-doped Phosphorus (PN), boron/nitrogen-doped carbon (BNC), and phosphorus/nitrogen-doped carbon (PNC).
The source of the doped non-metallic carrier is not particularly limited in the present invention and can be prepared by methods well known to those skilled in the art, e.g., BNCs are preferably prepared as follows:
and mixing cellulose, melamine and borax, and heating to obtain BNC.
In the invention, the mass ratio of the cellulose to the melamine to the borax is preferably 1: (0.5-1.5): (0.3 to 0.7), more preferably 1: (0.8-1.2): (0.4 to 0.6), most preferably 1: 1: 0.5.
in the present invention, the mixing is preferably a grinding mixing; the time for grinding and mixing is preferably 25-35 min, and more preferably 30 min. In the present invention, the heating is preferably performed in a tube furnace; the heating is preferably performed under a nitrogen atmosphere; the heating rate in the heating process is preferably 1-3 ℃/min, and more preferably 2 ℃/min; the heating temperature is preferably 700-900 ℃, more preferably 750-850 ℃ and most preferably 800 ℃; the heat preservation time in the heating process is preferably 2-4 h, and more preferably 3 h.
In the present invention, it is preferable that the heating further includes:
the heated product is washed and dried to obtain BNCs.
In the present invention, the washing is preferably carried out with water and methanol, respectively, and the water is preferably deionized water; the number of the respective washing is preferably 2 to 4, and more preferably 3; the drying temperature is preferably 70-90 ℃, and more preferably 80 ℃; the drying is preferably overnight.
In the present invention, the hydrogenation metal is preferably one or more selected from Ru, Pd, Pt and Ni.
In the present invention, the hydrogenation metal is preferably in the elemental state in the heterogeneous catalyst.
In the present invention, the mass of the hydrogenation metal is preferably 1 to 20%, more preferably 5 to 15%, and most preferably 10% of the mass of the heterogeneous catalyst, from the viewpoint of catalyst activity and cost.
The invention provides a preparation method of the heterogeneous catalyst in the technical scheme, which comprises the following steps:
loading a hydrogenation metal on the doped non-metal carrier;
the method for supporting is selected from an impregnation method or a precipitation method.
In the present invention, the method of the impregnation method preferably includes:
and mixing, drying and reducing the doped non-metal carrier and the solution containing the hydrogenation metal ions to obtain the heterogeneous catalyst.
In the present invention, the solution containing a hydrogenation metal ion preferably includes:
contains soluble salt of hydrogenation metal ion and solvent.
In the present invention, the soluble salt is preferably selected from one or more of nitrate, chloride and sulfate. In the present invention, the solvent is preferably formaldehyde.
In the present invention, the mixing is preferably performed under stirring; the temperature of the mixing is preferably room temperature; the mixing time is preferably 12-24 hours, and more preferably 15-20 hours.
In the present invention, the mixing preferably further comprises:
the solvent was removed and dried.
In the present invention, the method for removing the solvent is preferably distillation under reduced pressure, and the solvent is preferably removed by distillation under reduced pressure using a rotary evaporator.
In the present invention, the drying is preferably performed in a drying oven; the drying temperature is preferably 60-100 ℃, more preferably 70-90 ℃, and most preferably 80 ℃; the drying time is preferably 6-12 hours, and more preferably 8-10 hours.
In the present invention, the reduction is preferably heated under the condition of hydrogen gas; the heating temperature is preferably 300-500 ℃, more preferably 350-450 ℃, and most preferably 400 ℃. After reduction treatment, the state of the hydrogenation metal is in a metal simple substance state.
In the present invention, the method of the precipitation method preferably includes:
and mixing the doped non-metal carrier and the solution containing the hydrogenation metal ions, and adding a sodium borohydride solution to obtain the heterogeneous catalyst.
In the invention, the selection range of the solution of the hydrogenation metal ions is consistent with that of the technical scheme, and is not described again; the mixing method is the same as the mixing method in the dipping process in the technical scheme, and is not repeated herein.
In the present invention, it is preferred to carry out vigorous stirring after the addition of sodium borohydride. In the invention, the time of vigorous stirring is preferably 15-25 min, and more preferably 20 min.
In the present invention, after the adding of the sodium borohydride solution, the method preferably further comprises:
the resulting product was filtered, washed and dried.
In the present invention, the washing and drying method is the same as the washing and drying method in the dipping process described in the above technical solution, and is not described herein again.
The hydrogenation metal and the carrier substance in the heterogeneous catalyst provided by the invention mutually promote and disperse, so that the metal particles are uniformly dispersed on the non-metal carrier. Therefore, the heterogeneous catalyst provided by the invention has high catalytic activity in the reaction process of preparing 2, 5-furandimethylamine by catalytic hydrogenation of 2, 5-furandimethaldehyde.
The invention provides a preparation method of 2, 5-furandimethylamine, which comprises the following steps:
reacting 2, 5-furan dicarbaldehyde with hydrogen and a nitrogen source in a solvent under the action of a heterogeneous catalyst to obtain 2, 5-furan dimethylamine;
the heterogeneous catalyst is the heterogeneous catalyst in the technical scheme.
In the present invention, the heterogeneous catalyst is preferably pulverized by a mill to increase a reaction contact area, thereby accelerating the reaction.
The source of the 2, 5-furandicarboxaldehyde in the present invention is not particularly limited, but is preferably biomass-derived 2, 5-furandicarboxaldehyde.
In the present invention, the solvent is preferably one or more selected from tetrahydrofuran, water and methanol.
In the present invention, the nitrogen source is preferably selected from one or both of ammonia gas and hydrazine hydrate.
In the present invention, the mass ratio of the heterogeneous catalyst to 2, 5-furandicarboxaldehyde is preferably 1: (1 to 30), more preferably 1: (1-20), most preferably 1: (1-10).
In the present invention, the molar amount of the nitrogen source is preferably 1 to 10 times, and more preferably 4 to 6 times the molar amount of 2, 5-furandicarboxaldehyde.
In the present invention, the pressure of the hydrogen gas is preferably 0.1 to 3MPa, more preferably 0.5 to 2.5MPa, and most preferably 1 to 2 MPa.
In the present invention, the reaction is preferably carried out in a reactor in which 2, 5-furandicarboxaldehyde is reacted with hydrogen and a nitrogen source in the presence of a heterogeneous catalyst to hydrogenate 2, 5-furandimethylamine in high yield; the reactor can realize the catalytic hydrogenation reaction of the 2, 5-furan dicarbaldehyde in hydrogen atmosphere; such as a reaction vessel or autoclave.
In the invention, the reaction temperature is preferably 50-200 ℃, more preferably 60-150 ℃, and most preferably 60-100 ℃; the reaction time is preferably 2-24 h, more preferably 4-18 h, and most preferably 6-12 h.
The heterogeneous catalyst provided by the invention can be used for preparing 2, 5-furandimethylamine from 2, 5-furandimethaldehyde, wherein the conversion rate of the raw material 2, 5-furandimethaldehyde reaches 100%, and the yield of the 2, 5-furandimethylamine reaches more than 96%, so that a brand new way is provided for catalytically producing the 2, 5-furandimethylamine from the 2, 5-furandimethaldehyde. In addition, the method provided by the invention has the advantages of simple process, simple reaction equipment, simple and convenient operation, mild reaction conditions, low price and easy obtainment of the catalyst, high catalytic efficiency, recycling, suitability for industrial production and very wide application prospect.
EXAMPLE 110 preparation of a heterogeneous catalyst of wt% Ru/NBC
1g of cellulose, 1g of melamine and 0.5g of borax are ground together for 30min, then the mixture is placed into a tubular furnace, heated to 800 ℃ at a heating rate of 2 ℃/min in a nitrogen atmosphere and kept for 3h, after cooling, the mixture is washed respectively for 3 times by using deionized water and methanol, and then dried overnight at 80 ℃ to obtain a BNC carrier;
mixing soluble nitrate (nickel nitrate, nickel sulfate, palladium chloride, ruthenium chloride and the like) containing metal ions of hydrogenation metals with methanol to obtain an alcoholic solution of the metal ions; the mass of the hydrogenation metal in the solution is 5%, 10% and 15% of the mass of the carrier;
adding 0.1-1 g of BNC carrier into the alcoholic solution of the metal ions, and stirring for 2-12 h at room temperature; then, carrying out reduced pressure distillation by using a rotary evaporator to remove the solvent, and drying in a drying oven at 105 ℃ for 12 hours to obtain a catalyst precursor;
and (3) carrying out reduction treatment on the catalyst precursor for 3h at 400 ℃ in a hydrogen atmosphere to enable the metal state of the hydrogenation metal in the catalyst precursor to be a metal elementary substance state, thereby obtaining the heterogeneous catalyst.
TEM-EDS examination of the heterogeneous catalyst prepared in example 1 shows that Ru is homogeneously dispersed on the surface of the catalyst support BNC.
Examples 2 to 77
A heterogeneous catalyst was prepared according to the method of example 1, which is different from example 1 in that heterogeneous catalysts of different hydrogenation metals and hydrogenation metal contents were obtained using different amounts of the carrier and the solution of metal ions, and the solution of metal ions of different hydrogenation metals, as shown in table 1.
Example 78
500mg of 2, 5-furandicarboxaldehyde was added to a 25mL reaction vessel, 250mg of the heterogeneous catalyst prepared in examples 1 to 77 was added, 15mL of a solvent (methanol), 4 equivalents of hydrazine hydrate, and 1MPa of hydrogen were added, and the reaction was heated to 80 ℃ with stirring for 12 hours, followed by cooling, degassing, and filtration to separate the catalyst from the reaction solution.
Diluting the obtained reaction solution with methanol to a certain concentration, and analyzing by gas chromatography; the results of gas chromatography analysis of three replicates are shown in table 1.
The product produced in inventive example 78 (using the heterogeneous catalyst produced in example 1) was subjected to nmr spectroscopy, and the results are shown in fig. 1, from which fig. 1 shows that the obtained product, furandimethylamine, was produced.
TABLE 1 heterogeneous catalyst prepared in example and reaction conditions and yields of 2, 5-furandimethylamine
As can be seen from table 1, the hydrogenation metal is supported on the heterogeneous catalyst doped with the nonmetal carrier, and the 2, 5-furandimethaldehyde can be catalytically hydrogenated in one step to prepare 2, 5-furandimethylamine by using methanol as a solvent; meanwhile, the catalyst has a very good catalytic effect, and 2, 5-furandimethaldehyde can be catalyzed to obtain 2, 5-furandimethylamine with high conversion rate (100%) and high yield (> 96%).
Preferred reaction conditions in the present invention are as follows: the reaction temperature is 50-200 ℃, the molar weight of the nitrogen source is 4-6 times that of DFF, the hydrogen pressure is 0.1-2 MPa, and the reaction time is 12-16 h; the 2, 5-furan dimethylamine product can be prepared with high conversion rate and yield.
The hydrogenation metal in the heterogeneous catalyst provided by the invention is uniformly distributed on the doped non-metal carrier, so that the catalyst has high catalytic activity and selectivity in the reaction process of preparing 2, 5-furandimethylamine by catalytically hydrogenating 2, 5-furandimethaldehyde. The invention realizes a novel method for preparing 2, 5-furandimethylamine with high selectivity by utilizing a simple, green and efficient catalyst to catalytically convert 2, 5-furandicarboxaldehyde under mild conditions, and can better meet the requirements of industrial application. The method for preparing 2, 5-furandimethylamine from 2, 5-furandimethaldehyde has the advantages of simple process, simple reaction equipment, simple and convenient operation, mild reaction conditions, cheap and easily-obtained catalyst, high hydrothermal stability of the catalyst, recyclability, suitability for industrial production and very wide application prospect.
The above embodiments are only intended to help the understanding of the method of the present invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (10)
1. A heterogeneous catalyst comprising:
a doped non-metallic carrier;
a hydrogenation metal supported on the doped non-metallic support.
2. The heterogeneous catalyst according to claim 1, wherein the doped non-metallic carrier is selected from one or more of nitrogen-doped carbon, nitrogen-doped boron, nitrogen-doped phosphorus, boron/nitrogen-co-doped carbon, and phosphorus/nitrogen-co-doped carbon.
3. The heterogeneous catalyst of claim 1 wherein the hydrogenation metal is selected from one or more of Ru, Pd, Pt and Ni.
4. The heterogeneous catalyst according to claim 1, wherein the hydrogenation metal is present in the heterogeneous catalyst in an amount of 1 to 20% by mass.
5. The heterogeneous catalyst of claim 1 wherein the hydrogenation metal is in the elemental state in the heterogeneous catalyst.
6. A method of preparing the heterogeneous catalyst of claim 1, comprising:
loading hydrogenation metal on a doped non-metal carrier to obtain a heterogeneous catalyst;
the supporting method is selected from a dipping method or a precipitation method.
7. A method for producing 2, 5-furandimethylamine, comprising:
under the action of a heterogeneous catalyst, reacting 2, 5-furan dicarbaldehyde with hydrogen and a nitrogen source in a solvent to obtain 2, 5-furan dimethylamine;
the heterogeneous catalyst is the heterogeneous catalyst of claim 1.
8. The method according to claim 7, wherein the mass ratio of the heterogeneous catalyst to the 2, 5-furandicarboxaldehyde is 1 (1 to 30).
9. The method according to claim 7, wherein the pressure of the hydrogen gas is 0.1 to 3 MPa.
10. The method according to claim 7, wherein the reaction temperature is 50 to 200 ℃.
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