CN113967479A - Reductive amination catalyst and method for synthesizing furan amine compound by selective reductive amination of furan alcohol or furan aldehyde - Google Patents
Reductive amination catalyst and method for synthesizing furan amine compound by selective reductive amination of furan alcohol or furan aldehyde Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000006268 reductive amination reaction Methods 0.000 title claims abstract description 44
- -1 furan amine compound Chemical class 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 230000002194 synthesizing effect Effects 0.000 title claims description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- 229910052751 metal Inorganic materials 0.000 claims abstract description 48
- 239000002184 metal Substances 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052586 apatite Inorganic materials 0.000 claims abstract description 27
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 claims abstract description 27
- 239000003960 organic solvent Substances 0.000 claims abstract description 21
- 239000012046 mixed solvent Substances 0.000 claims abstract description 12
- UTVVREMVDJTZAC-UHFFFAOYSA-N furan-2-amine Chemical class NC1=CC=CO1 UTVVREMVDJTZAC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001412 amines Chemical class 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 25
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims description 18
- 238000011068 loading method Methods 0.000 claims description 18
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical class OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 12
- DSLRVRBSNLHVBH-UHFFFAOYSA-N 2,5-furandimethanol Chemical class OCC1=CC=C(CO)O1 DSLRVRBSNLHVBH-UHFFFAOYSA-N 0.000 claims description 9
- 229910052707 ruthenium Inorganic materials 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 229910052741 iridium Inorganic materials 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 150000002596 lactones Chemical class 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- PXJJKVNIMAZHCB-UHFFFAOYSA-N 2,5-diformylfuran Chemical class O=CC1=CC=C(C=O)O1 PXJJKVNIMAZHCB-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Chemical class COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims description 3
- GYQBROOJXNICMZ-UHFFFAOYSA-N 4-(hydroxymethyl)furan-2-carbaldehyde Chemical class OCC1=COC(C=O)=C1 GYQBROOJXNICMZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052785 arsenic Inorganic materials 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 238000002474 experimental method Methods 0.000 abstract description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 21
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 18
- 238000004811 liquid chromatography Methods 0.000 description 18
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 18
- 230000003197 catalytic effect Effects 0.000 description 14
- 150000001299 aldehydes Chemical class 0.000 description 12
- 239000012295 chemical reaction liquid Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- VKLGKDZCKSMSHG-UHFFFAOYSA-N [5-(aminomethyl)furan-2-yl]methanamine Chemical compound NCC1=CC=C(CN)O1 VKLGKDZCKSMSHG-UHFFFAOYSA-N 0.000 description 11
- 229910021529 ammonia Inorganic materials 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- 238000007865 diluting Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000005576 amination reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- DDRPCXLAQZKBJP-UHFFFAOYSA-N furfurylamine Chemical compound NCC1=CC=CO1 DDRPCXLAQZKBJP-UHFFFAOYSA-N 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- CADZRPOVAQTAME-UHFFFAOYSA-L calcium;hydroxy phosphate Chemical compound [Ca+2].OOP([O-])([O-])=O CADZRPOVAQTAME-UHFFFAOYSA-L 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- ZWRLWJAFBLTMSQ-UHFFFAOYSA-N Docosa-7,10,14-triensaeure Natural products C1C(C)=C2CC(C)(C)CC2C(O)C2=COC=C21 ZWRLWJAFBLTMSQ-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229910052587 fluorapatite Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- YKASHPSKFYVZRC-UHFFFAOYSA-M furan-2-ylmethyl(trimethyl)azanium;iodide Chemical compound [I-].C[N+](C)(C)CC1=CC=CO1 YKASHPSKFYVZRC-UHFFFAOYSA-M 0.000 description 1
- 150000002241 furanones Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- BSIDXUHWUKTRQL-UHFFFAOYSA-N nickel palladium Chemical compound [Ni].[Pd] BSIDXUHWUKTRQL-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
-
- 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)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a reductive amination catalyst and a method for selectively reducing amines by using furan alcohol or furan aldehyde to synthesize furan amine compounds, wherein the reductive amination catalyst is a metal catalyst loaded on an apatite carrier; the apatite carrier has a general formula Ma(XOb)c(Z)dThe apatite carrier can be a mixture of one or more of the above general formulas. Experiments prove that under the action of a hydroxyapatite-supported metal catalyst, the furan amine compound can be prepared with high conversion rate and high selectivity in an organic solvent or a mixed solvent system consisting of water and the organic solvent, the conversion rate of the furan alcohol or aldehyde and the selectivity of different reductive amination products of the furan amine compound reach 100 percent, and the method is provided for efficiently producing the furan amine compound.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a reductive amination catalyst and a method for synthesizing furan amines compounds by selectively reducing amines with furan alcohols or furan aldehydes.
Background
The continuous rise of oil price and the increasing shortage of oil resources seriously threaten the whole chemical industry based on oil and influence the development of national economy. The organic chemical intermediate with important application prospect is obtained from renewable biomass sources through efficient biological and chemical conversion, a reasonable and effective way is found for the utilization of biomass resources and the substitution of petrochemical products, and the method is an effective measure for solving the problem.
The furan amine compounds (2, 5-furandimethylamine, furfurylamine, etc.) are a new chemical product with wide market application prospect. The furan amine compound can be used as a monomer raw material to produce a novel biodegradable polyurethane material or a polyamide material and the like. Therefore, developing a synthetic process for producing environment-friendly furan amine compounds with industrial prospects is one of the most urgent key problems to be solved in the biomass-based material industry at present. However, at present, the reductive amination of the functional group C ═ O or C-O in the furan ring to C-NH with high selectivity is possible2There are also significant challenges. Some reports have attempted to achieve this by a stepwise amination process, for example, Le et al proposed a redox amination route in which HMF is first oxidized to DFF and then C ═ O is reductively aminated over raney nickel catalyst, resulting in a final yield of 2, 5-furandimethylamine of only 42.6%. They concluded that the low yield of the target product is caused by the formation of by-products by condensation between aldehyde and amino groups. To prevent condensation, Qi et al introduced more nucleophilic n-butylamine to inhibit side reactions from proceeding, and finally gave diamine yields of 93%. However, it uses an additional expensive reagent which complicates the reaction and is not favorable for atom economy. In addition, Schaub et al propose a reductive amination strategy, first reducing HMF to DHMF, and then generating 2, 5-furandimethylamine by catalyzing the amination of two C-OH groups using a homogeneous Ru catalyst. The activity of the catalyst prepared by the reaction in the complicated steps still has a great space for improving.
Disclosure of Invention
In view of the above-mentioned deficiencies of the prior art, the present invention provides a reductive amination catalyst and a method for synthesizing furan amines from furan alcohols or furan aldehydes by selective reductive amination. The method can efficiently catalyze, reduce and aminate the furan alcohol or aldehyde into the furan amine compound to obtain the furan amine compound with high selectivity and high yield, and the whole operation process is simple, mild in condition, green and environment-friendly, and the catalyst has good stability.
The reductive amination catalyst is a metal catalyst loaded on an apatite carrier.
The apatite carrier has a general formula Ma(XOb)c(Z)dThe apatite carrier can be a mixture of one or more of the above general formulas. Wherein M is one or more metal cations selected from Ca, Mg, Ce, Na and K, X is one or more of Si, P, S, V and As, and Z is OH-、CO3 2-、HCO3 -、F-、Cl-One or more negatively charged groups; a. b, c and d are each independently an integer of 3 to 10 under the condition that the valences of the formulae are balanced.
The metal is one of transition metals of VIIIB or IB groups or a plurality of transition metals combined in any proportion, preferably Ru, Pd, Ir, Pt, Co, Cu and Ni.
The selective reductive amination catalyst is prepared by an impregnation method. The loading of the metal is 0.5-10%, preferably 1-5% of the mass of the catalyst.
The invention discloses a method for synthesizing furan amine compounds by selective reductive amination of furan alcohol or furan aldehyde.
The above reaction is carried out in an organic solvent or a mixed solvent of an organic solvent and water. The organic solvent comprises alkane organic solvent, lactone organic solvent, tetrahydrofuran and the like. Water or a mixed solvent system consisting of water and a lactone solvent is preferably used as the reaction solvent.
In the reaction system, the pressure of hydrogen and the pressure of ammonia gas are controlled to be 0.1 to 4MPa, preferably 0.5 to 2MPa, and more preferably 0.5 to 1MPa, respectively.
During the reaction, the reaction temperature is controlled to be 0-250 ℃, preferably 60-160 ℃, and more preferably 80-140 ℃; the reaction time is 1-24h, preferably 6-12 h.
In the reaction catalytic system, the dosage of the reaction catalyst is controlled to be 1-30%, preferably 5-30%, and more preferably 5-20% of the mass of the input raw materials.
The furan alcohol or furan aldehyde mainly comprises some furan ring substituted alcohol or aldehyde, and representative compounds are furfuryl alcohol, furfural, alkyl substituted furfuryl alcohol, alkyl substituted furfural, 5-hydroxymethyl furfural, 4-hydroxymethyl furfural, 2, 5-furandimethanol, 2, 5-furandicarboxaldehyde and the like.
The typical reaction for preparing the furan amine compound by the high-efficiency catalytic reductive amination of the furan alcohol or furan aldehyde is to react 5-hydroxymethylfurfural or 2, 5-furandicarboxaldehyde to prepare 2, 5-furandimethylamine, and the reaction route is shown as follows:
the invention has the beneficial effects that:
the invention uses an impregnation method to prepare a metal catalyst loaded on a hydroxyapatite carrier, and the furan amine compound can be prepared with high conversion rate (100%) and high selectivity (100%) by catalyzing raw material furan alcohol or furan aldehyde under quite mild conditions. The main reason why the catalyst has higher catalytic activity in the process of catalyzing the reaction from the furan alcohol or aldehyde to the furan amine compound is that the raw materials are not easy to polymerize under the condition of mild reaction temperature, the Hydroxyapatite (HAP) as the carrier presents alkalinity, the coking formation in the process of converting the furan alcohol or aldehyde can be obviously inhibited, the target product with high selectivity of furan ring opening can be inhibited, and the metal has very good dispersion effect on the carrier, so that the catalyst shows higher catalytic activity.
Drawings
FIG. 1 is a schematic representation of the product1H-NMR spectrum.
FIG. 2 is calcium hydroxyphosphate (Ca)5(PO4)3(OH), HAP) and Ni/HAP and Ru/HAP catalysts prepared by taking nickel and ruthenium metal loaded in calcium hydroxy phosphate as a carrier as an example. In FIG. 2The morphology comparison before and after the hydroxyapatite carrier loads the metal shows that no diffraction peak of any metal species is observed on the XRD spectrogram of the hydroxyapatite after the metal is loaded, which shows that the metal is dispersed on the HAP carrier very uniformly, and simultaneously also shows that the stability of the morphology structure of the hydroxyapatite carrier is very good.
Detailed Description
The technical scheme of the invention is further fully explained in detail by combining specific embodiments. In the following examples, unless otherwise specified, all methods used are conventional and all reagents used are commercially available. The following examples are illustrative only and are not to be construed as limiting the invention.
Example 1: preparation of supported metal catalyst
0.126-1.265mg RuCl per ml is adopted3·xH20.50-1.00g of apatite carrier is soaked in 50-150mL of acetone solution of O, stirred for 12-24h at 25-55 ℃, then the acetone dispersant is removed by rotary evaporation, and the supported ruthenium catalyst with the supported ruthenium mass fraction of 0.5-5% is obtained after drying for 6-12h at 20-100 ℃.
Example 2: preparation of supported metal catalyst
0.228-2.28mg Ni (OAC) per ml is used20.50-1.00g of apatite carrier is soaked in 50-150mL of acetone solution, stirred for 12-24h at 25-55 ℃, the acetone dispersing agent is removed by rotary evaporation, and the loaded palladium catalyst with the negative nickel palladium mass fraction of 0.5-10% is obtained after drying for 6-12h at 20-100 ℃.
The preparation method of the catalyst with other metals (Ir, Pt, Co, Cu and Ni) or the combination of various metals (Ru, Pd, Ir, Pt, Co, Cu and Ni) loaded on the hydroxyapatite is similar to the preparation method of the catalyst with Ru and Pd loaded on the hydroxyapatite.
Example 3: effect of different types of Apatite Carriers on the Effect of catalytic reductive amination
Loading metals onto apatite supports of different types, e.g. Ca5(PO4)3(OH)、Mg2Ca3(PO4)3(OH)、Ce5(VO4)6(OH)2、Ca5(PO4)3(HCO3)、Ca5(PO4)3F、Na10(PO4)3(OH), and the like. The catalyst is used for catalyzing the reductive amination of HMF to prepare 2, 5-furandimethylamine by reacting hydrogen and ammonia for 3h in water solvent at 150 ℃ and 1 MPa.
Adding 50mg of HMF and a metal catalyst loaded on an apatite carrier into a 50mL reaction kettle, adding 10mL of water, setting the pressure of hydrogen and ammonia gas to be 1MPa, heating to 150 ℃, reacting for 6 hours under the condition of stirring, cooling, deflating, filtering, separating the catalyst from reaction liquid, diluting the reaction liquid with water to a fixed concentration, and analyzing by liquid chromatography. The results of the liquid chromatography analysis of the three replicates are detailed in Table 1 for run numbers 1-8.
Example 4: effect of different loadings of catalyst on catalytic reductive amination Effect
The metal catalyst with different loading amounts (0.5-5%) loaded on the apatite carrier reacts for 15h in a normal hexane solvent by hydrogen with 2MPa at 100 ℃, and the HMF is catalyzed to prepare the 2, 5-furandimethylamine through reductive amination.
Adding 50mg of HMF into a 50mL reaction kettle, adding 10mL of normal hexane into the reaction kettle, setting the pressure of hydrogen and ammonia to be 2MPa, heating the reaction kettle to 100 ℃, reacting for 15 hours under the condition of stirring, cooling, deflating and filtering to separate the catalyst from reaction liquid, diluting the reaction liquid with water to a fixed concentration, and analyzing by liquid chromatography. The results of the liquid chromatography analyses of the three replicates are detailed in Table 1 for run numbers 9-14.
Example 5: effect of different Metal Supported catalysts on the catalytic reductive amination Effect
Different metals such as Ru, Pd, Ir, Pt, Co, Cu, Ni and various metal combinations thereof are respectively loaded on an apatite carrier (the loading of the noble metal is 1 percent, and the loading of the base metal is 10 percent), and the prepared metal catalyst reacts for 4 hours in gamma-butyrolactone (GBL) solvent under the conditions of hydrogen and ammonia gas of 2MPa and the temperature of 80 ℃ to catalyze HMF for reductive amination to prepare 2, 5-furandimethylamine.
Adding 50mg of metal catalyst which is prepared by respectively loading HMF, Ru, Pd, Ir, Pt, Co, Cu, Ni and a plurality of metal combinations thereof on an apatite carrier into a 50mL reaction kettle, adding 10mL of GBL, setting the pressure of hydrogen and ammonia gas to be 2MPa, heating to 80 ℃, reacting for 24 hours under stirring, cooling, deflating, filtering, separating the catalyst from reaction liquid, diluting the reaction liquid with water to a fixed concentration, and analyzing by liquid chromatography. The results of the liquid chromatography analyses of the three replicates are detailed in Table 1 for run Nos. 15-27.
Example 6: effect of different reaction solvents on the Effect of catalytic reductive amination
The catalyst prepared by loading metal on an apatite carrier reacts for 10 hours at 140 ℃ under the conditions of 3MPa hydrogen and ammonia gas and different solvents to catalyze furfural to prepare furfurylamine through reductive amination.
Adding 50mg of furfural into a 50mL reaction kettle, loading metal on a catalyst prepared on an apatite carrier, adding 10mL of solvent, setting the pressure of hydrogen and ammonia gas to be 3MPa, heating to 140 ℃, reacting for 10 hours under the condition of stirring, cooling, deflating, filtering, separating the catalyst from reaction liquid, diluting the reaction liquid with water to a fixed concentration, and analyzing by liquid chromatography. The results of the liquid chromatography analysis of the three replicates are detailed in Table 1 for run numbers 28-40.
Example 7: effect of different reaction temperatures on the Effect of catalytic reductive amination
The catalyst prepared by loading metal on an apatite carrier reacts for 12 hours under different temperature conditions (0-200 ℃) by hydrogen and ammonia under 1MPa with water as a solvent to catalyze HMF for reductive amination to prepare 2, 5-furandimethylamine.
Adding 100mg of HMF into a 50mL reaction kettle, loading metal on a catalyst prepared on an apatite carrier, adding 10mL of water, heating to a set temperature under the pressure of 1MPa of hydrogen and ammonia, reacting for 12 hours under the condition of stirring, cooling, deflating, filtering, separating the catalyst from a reaction solution, diluting the reaction solution with water to a fixed concentration, and analyzing by liquid chromatography. The results of the liquid chromatography analyses of the three replicates are detailed in Table 1 for run numbers 41-51.
Example 8: effect of different Hydrogen and Ammonia pressures on catalytic reductive amination Effect
The catalyst prepared by loading metal on an apatite carrier reacts for 8 hours in a mixed solvent of water and GVL under the conditions of different hydrogen and ammonia pressures (0.1-4MPa) and 140 ℃, and 2, 5-furandimethanol is catalyzed to prepare 2, 5-furandimethylamine through reductive amination.
Adding 100mg of 2, 5-furandimethanol into a 50mL reaction kettle, adding 10mL of water + GVL into the reaction kettle, adding hydrogen and ammonia gas under the pressure of set hydrogen pressure, heating to 140 ℃, reacting for 8 hours under the condition of stirring, cooling, deflating, filtering, separating the catalyst from the reaction liquid, diluting the reaction liquid with water to a fixed concentration, and analyzing by liquid chromatography. The results of the liquid chromatography analyses of the three replicates are detailed in Table 1 for run numbers 52-57.
Example 9: effect of different reaction times on the Effect of catalytic reductive amination
The furfuryl amine is prepared by carrying a catalyst prepared by loading metal on an apatite carrier in a DMSO solvent to catalyze furfuryl alcohol to perform reductive amination under different reaction time conditions (1-10h) and under the conditions of 160 ℃ and 1MPa of hydrogen and ammonia.
Adding 100mg of furfuryl alcohol into a 50mL reaction kettle, adding 10mL of DMSO into the reaction kettle, setting the pressure of hydrogen and ammonia to be 1MPa, heating to 160 ℃, stirring, reacting for a set time, cooling, deflating, filtering to separate the catalyst from the reaction liquid, diluting the reaction liquid with water to a set concentration, and analyzing by liquid chromatography. The results of the liquid chromatography analysis of the three replicates are detailed in Table 1 for run numbers 58-65.
Example 10: effect of different Mixed solvent systems on the Effect of catalytic reductive amination
The catalyst prepared by loading metal on an apatite carrier is reacted for 3 hours to catalyze the reduction amination of HMF to prepare 2, 5-furandimethylamine under the conditions of hydrogen and ammonia gas at 60-160 ℃ and 2MPa and using a water and organic solvent mixed solvent system (the proportion of water and organic solvent in the mixed solvent has no specific requirement, and can be mixed at any proportion).
Adding 100mg of HMF into a 50mL reaction kettle, loading metal on a catalyst prepared on an apatite carrier, using a mixed solvent of water and an organic solvent, setting the pressure of hydrogen and ammonia gas to be 2MPa, heating to a specific temperature, reacting for 3 hours under the condition of stirring, cooling, deflating, filtering, separating the catalyst from a reaction solution, diluting the reaction solution with water to a fixed concentration, and analyzing by liquid chromatography. The results of the liquid chromatography analyses of the three replicates are detailed in Table 1 for run numbers 66-74.
TABLE 1 results of experiments for examples 3-10
According to the reaction conditions of various parameters shown in Table 1, the reaction temperature of 120-180 ℃ is more favorable for generating furan amine compounds, the reductive amination at too low temperature is insufficient, and the side reaction at too high temperature is increased; a high-polarity organic solvent such as tetrahydrofuran or DMSO in a solvent system is more favorable for generating a target product; the metal with high hydrogenation activity in the catalyst system is more beneficial to the catalytic reaction to generate a target product under a mild condition.
The review shows that the catalyst prepared by using the carrier hydroxyapatite to load metal can catalyze the furan alcohol or aldehyde to prepare the furan amine compound with high conversion rate and high selectivity under the condition of a mixed solvent system consisting of water, alkane, lactone, tetrahydrofuran and other organic solvents or the condition of a mild reaction condition of slightly high temperature (more than 80 ℃) and pressure (hydrogen and ammonia gas are more than 1 MPa).
Example 11:
the catalyst prepared by loading metal on an apatite carrier reacts for a certain time under the conditions of hydrogen and ammonia gas at 40-60 ℃ and 0.1-1MPa by using a water solvent system to catalyze HMF for reductive amination to prepare 2, 5-furandimethylamine.
Adding 100mg of HMF into a 50mL reaction kettle, loading metal on a catalyst prepared by an apatite carrier, setting certain hydrogen and ammonia pressure by using a water solvent, heating to a specific temperature, reacting for a period of time under a stirring condition, cooling, deflating, filtering, separating the catalyst from a reaction solution, diluting the reaction solution with water to a fixed concentration, and analyzing by liquid chromatography. The results of the liquid chromatography analysis of the three replicates are detailed in Table 2 for run numbers 1-9.
Table 2 the experimental results of example 11 are as follows:
from the reaction results shown in table 2, the catalyst prepared by using the carrier hydroxyapatite to support the metal can catalyze the furan alcohol or aldehyde to prepare the furan amine compound with high conversion rate and high selectivity under the condition of an organic solvent such as water, alkanes, lactones, tetrahydrofuran and the like or a mixed solvent system consisting of water and the organic solvent and under the mild reaction conditions of a slightly low reaction temperature (less than 60 ℃) and a pressure (less than 0.5 MPa).
From the reaction results shown in tables 1 and 2, the catalyst prepared by using the carrier hydroxyapatite to load metal can catalyze the preparation of the furan amine compound with high conversion rate and high selectivity under mild reaction conditions under the conditions of organic solvents such as water, alkanes, lactones and tetrahydrofuran or a mixed solvent system consisting of water and the organic solvents and by controlling the reaction conditions.
Therefore, the experimental results of the above examples show that the supported catalyst prepared by using hydroxyapatite and metal (Ru, Pd, Ir, Pt, Co, Cu, Ni and combinations of these metals) through an impregnation method can catalyze furan alcohol or aldehyde to undergo reductive amination at a high conversion rate (100%) under relatively mild conditions (40-160 ℃, 0.1-2MPa hydrogen and ammonia, 1-12 hours), and prepare the furan amine compound at a high selectivity (100%), so that a simple, green and efficient catalyst can catalyze furan alcohol or aldehyde to undergo reductive amination at a high selectivity to prepare the furan amine compound under relatively mild conditions, and industrial application requirements can be better met. The main reason that the hydroxyapatite-supported metal catalyst has very high catalytic hydrogenation activity in the reaction process of catalyzing high-selectivity reductive amination of furan alcohol or aldehyde to furan amine compounds is as follows: in the water phase, the alkaline carrier HAP can obviously inhibit the formation of coking in the conversion process of furan alcohol or aldehyde, the dispersion capacity of metal on the carrier is higher, so that the carrier shows higher catalytic activity, and in addition, the carrier HAP presents alkalinity, so that the formation of a target product with high selectivity of furan ring opening can be obviously inhibited. These factors contribute to the very efficient catalytic reductive amination activity of the catalyst on the furanol or aldehyde to produce the industrial chemical class of furanones. The method for preparing the furan amine compound has the advantages of simple process, simple reaction equipment, simple and convenient operation, no need of extra alkali addition, very mild reaction conditions, cheap and easily-obtained catalyst, easy separation of the product from the catalyst and a solvent system, high hydrothermal stability of the catalyst, good recycling performance, short reaction period, suitability for industrial production and very wide application prospect.
Claims (9)
1. A reductive amination catalyst characterized by:
the reductive amination catalyst is a metal catalyst supported on an apatite carrier;
the apatite carrier has a general formula Ma(XOb)c(Z)dThe apatite carrier can be a mixture of one or more of the above general formulas; wherein M is one or more metal cations selected from Ca, Mg, Ce, Na and K, X is one or more of Si, P, S, V and As, and Z is OH-、CO3 2-、HCO3 -、F-、Cl-One or more negatively charged groups; a. b, c and d are each independently an integer from 3 to 10 under the condition of valence bond balance of the formula;
the metal is one of transition metals of VIIIB or IB groups or a plurality of transition metals combined in any proportion.
2. A reductive amination catalyst according to claim 1, characterized in that:
the metal is one or more of Ru, Pd, Ir, Pt, Co, Cu and Ni.
3. A reductive amination catalyst according to claim 1, characterized in that:
the loading amount of the metal is 0.5-10% of the mass of the reductive amination catalyst.
4. A method for synthesizing furan amine compounds by selectively reducing amines with furan alcohol or furan aldehyde is characterized in that:
reacting furan alcohol or furan aldehyde serving as a raw material in the presence of a catalyst in the atmosphere of hydrogen and ammonia gas, and carrying out high-selectivity reductive amination to generate a furan amine compound; the catalyst is a reductive amination catalyst as claimed in any one of claims 1 to 3.
5. The method of claim 4, wherein:
the reaction is carried out in an organic solvent or a mixed solvent consisting of the organic solvent and water; the organic solvent comprises alkane organic solvent, lactone organic solvent or tetrahydrofuran.
6. The method of claim 4, wherein:
in the reaction system, the pressure of hydrogen and ammonia gas is controlled at 0.1-4MPa respectively.
7. The method of claim 4, wherein:
in the reaction process, the reaction temperature is controlled to be 0-250 ℃, and the reaction time is 1-24 h.
8. The method of claim 4, wherein:
the furan alcohol or furan aldehyde comprises furfuryl alcohol, furfural, alkyl-substituted furfuryl alcohol, alkyl-substituted furfural, 5-hydroxymethylfurfural, 4-hydroxymethylfurfural, 2, 5-furandimethanol or 2, 5-furandicarbaldehyde.
9. The method of claim 4, wherein:
in the reaction system, the quality of the catalyst is controlled to be 1-30% of the quality of the raw materials.
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