CN117619388A - Core-shell structure NiFe@C catalyst for preparing 3-phenylpropionaldehyde by hydrogenating cinnamaldehyde and preparation method and application thereof - Google Patents
Core-shell structure NiFe@C catalyst for preparing 3-phenylpropionaldehyde by hydrogenating cinnamaldehyde and preparation method and application thereof Download PDFInfo
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- CN117619388A CN117619388A CN202311637746.9A CN202311637746A CN117619388A CN 117619388 A CN117619388 A CN 117619388A CN 202311637746 A CN202311637746 A CN 202311637746A CN 117619388 A CN117619388 A CN 117619388A
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- phenylpropionaldehyde
- cinnamaldehyde
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- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- YGCZTXZTJXYWCO-UHFFFAOYSA-N 3-phenylpropanal Chemical compound O=CCCC1=CC=CC=C1 YGCZTXZTJXYWCO-UHFFFAOYSA-N 0.000 title claims abstract description 80
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 title claims abstract description 42
- 229940117916 cinnamic aldehyde Drugs 0.000 title claims abstract description 42
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000011258 core-shell material Substances 0.000 title claims abstract description 33
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 26
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 15
- 239000000956 alloy Substances 0.000 claims abstract description 15
- 230000003197 catalytic effect Effects 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 239000002105 nanoparticle Substances 0.000 claims abstract description 8
- 238000000975 co-precipitation Methods 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 31
- 239000002244 precipitate Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- 239000000725 suspension Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 8
- 239000008103 glucose Substances 0.000 claims description 8
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 claims description 8
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 229960002089 ferrous chloride Drugs 0.000 claims description 7
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 239000012300 argon atmosphere Substances 0.000 claims description 6
- 238000010000 carbonizing Methods 0.000 claims description 6
- 239000007810 chemical reaction solvent Substances 0.000 claims description 6
- 238000010335 hydrothermal treatment Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 229930091371 Fructose Natural products 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 238000005259 measurement Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 239000002638 heterogeneous catalyst Substances 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 229910000510 noble metal Inorganic materials 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- VAJVDSVGBWFCLW-UHFFFAOYSA-N 3-Phenyl-1-propanol Chemical compound OCCCC1=CC=CC=C1 VAJVDSVGBWFCLW-UHFFFAOYSA-N 0.000 description 4
- 238000004587 chromatography analysis Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- OOCCDEMITAIZTP-QPJJXVBHSA-N (E)-cinnamyl alcohol Chemical compound OC\C=C\C1=CC=CC=C1 OOCCDEMITAIZTP-QPJJXVBHSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- OOCCDEMITAIZTP-UHFFFAOYSA-N allylic benzylic alcohol Natural products OCC=CC1=CC=CC=C1 OOCCDEMITAIZTP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 239000004030 hiv protease inhibitor Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
-
- 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
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/69—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by addition to carbon-to-carbon double or triple bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/20—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms
- C07C47/228—Unsaturated compounds having —CHO groups bound to acyclic carbon atoms containing six-membered aromatic rings, e.g. phenylacetaldehyde
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention provides a core-shell structure NiFe@C catalyst for catalyzing cinnamaldehyde hydrogenation to prepare 3-phenylpropionaldehyde, and a preparation method and application thereof. The catalyst takes nano-sized NiFe alloy as a core, an amorphous carbon layer is coated on the surface of the nano-sized NiFe alloy as a shell, ni is an active component, fe is an auxiliary agent, the NiFe alloy is prepared by a coprecipitation method, and the amorphous carbon layer is coated on a core body by a hydrothermal synthesis method. The catalyst has high catalytic activity and target product 3-phenylpropionaldehyde selectivity in the reaction of preparing 3-phenylpropionaldehyde by catalyzing the hydrogenation of cinnamaldehyde, and can effectively inhibit the deep oxidation of active metal due to the existence of a carbon layer, so that the catalyst has excellent stability. And because the catalyst is a heterogeneous catalyst, the catalyst has the advantages of easy separation, multiple recycling and the like, and has high industrial application value.
Description
Technical Field
The invention belongs to the field of heterogeneous catalysts, and particularly relates to a core-shell structure NiFe@C catalyst for preparing 3-phenylpropionaldehyde by catalyzing cinnamaldehyde hydrogenation, a preparation method and application thereof.
Background
Cinnamaldehyde is an important chemical raw material in industrial application, and due to its unique molecular composition, the product 3-phenylpropionaldehyde (HCAL) and cinnamyl alcohol are generated by the hydrogenation sites of c=c bond and c=o bond. The 3-phenylpropionaldehyde as a partial hydrogenation product is a key intermediate for synthesizing high-added-value products such as perfume, essence, medicine and the like. In particular, in the pharmaceutical industry, 3-phenylpropionaldehyde produced by hydrogenation of cinnamaldehyde can be used as an intermediate for synthesizing HIV protease inhibitors. However, achieving controlled hydrogenation of specific functional groups while retaining other functional groups remains a complex task. Therefore, the selective hydrogenation of cinnamaldehyde to prepare 3-phenylpropionaldehyde has both theoretical research value and industrial application prospect.
Cinnamaldehyde selective hydrogenation catalysts can be classified into noble metal catalysts and non-noble metal catalysts. For noble metal catalysts, pd-based catalysts and Pt-based catalysts have been widely studied. For example, team Sun Baochang (Separation and Purification Technology,2023, 315:123631.) reduced the synthesized Ni-Pt nanoparticle catalyst with surfactant-free liquid in a rotating packed bed, resulting in 97.1% cinnamaldehyde conversion and 88.4% selectivity to 3-phenylpropionaldehyde. The Pd-Ag bimetallic catalyst disclosed in the patent CN108435167A realizes the conversion rate of cinnamaldehyde of 99 percent and the selectivity of 3-phenylpropionaldehyde of 98 percent. The palladium/carbon catalyst disclosed in patent CN115957794a achieves conversions up to 100% and selectivities above 80% under mild reaction conditions. The La2O2CO3 nano-triangular plate supported Pd catalyst disclosed in patent CN109999871a exhibits higher catalytic activity in the selective hydrogenation of cinnamaldehyde than conventional Pd supported catalysts. For non-noble metal catalysts, metallic Ni has received considerable attention for its ability to favor c=c hydrogenation (Applied Catalysis A: general,2005, 292:1-49.). For example, the silicon oxide limited-area nickel-based catalyst disclosed in patent CN108525670A has low preparation cost, nickel oxide particles are uniformly distributed on a carrier, and the catalyst has better activity and 3-phenylpropionaldehyde selectivity under the action of a limited-area effect.
In summary, the existing noble metal-based catalyst for preparing 3-phenylpropionaldehyde by selective hydrogenation of cinnamaldehyde has the problems of high production cost and the like, and limits the application of the noble metal-based catalyst in industrial production. While the cheaper non-noble metal Ni-based catalyst has excellent catalytic activity, the catalyst often generates a complete hydrogenation product 3-phenylpropanol in the catalytic hydrogenation process, and has lower selectivity for a partial hydrogenation product 3-phenylpropanol. Secondly, the surface is easy to oxidize due to the active nature of the metal Ni, so that the catalyst is easy to deactivate. The present inventors have found through extensive studies that adding a second metal (e.g., fe) on the basis of a Ni-based catalyst can effectively improve the selectivity of the catalyst through an electronic effect and a geometric effect. In addition, the carbon layer is coated on the surface of the bimetallic Ni-based catalyst, so that oxidation of surface metal can be effectively inhibited, and the stability of the catalyst can be improved.
Disclosure of Invention
In view of the defects of the prior art, the technical problem to be solved by the invention is to provide a core-shell structure NiFe@C catalyst for preparing 3-phenylpropionaldehyde by catalyzing cinnamaldehyde hydrogenation, and a preparation method and application thereof. The catalyst is a non-noble metal alloy catalyst, has lower production cost, not only has good catalytic activity and high 3-phenylpropionaldehyde selectivity in the hydrogenation reaction of cinnamaldehyde, but also has excellent catalytic stability and recyclability, and is convenient for industrial large-scale application.
Specifically, the invention is realized through the following technical schemes:
in a first aspect, the invention provides a NiFe@C catalyst with a core-shell structure for preparing 3-phenylpropionaldehyde by catalyzing cinnamaldehyde hydrogenation, wherein a nano-sized NiFe alloy is taken as a core, an amorphous carbon layer is coated on the surface of the catalyst as a shell, ni is taken as an active component in the nano-sized NiFe alloy, fe is taken as an auxiliary agent, the NiFe alloy is prepared by a coprecipitation method, and the amorphous carbon layer is coated on a nuclear body by a hydrothermal synthesis method.
In the catalyst, the average grain diameter of the nano NiFe alloy is 10-35 nm, and the thickness of the amorphous carbon layer shell is 1-4 nm.
In the catalyst, the molar ratio of the Ni element of the catalytic active component to the Fe element of the auxiliary agent is 1:0.2-1.2.
In a second aspect, the invention provides a preparation method of the nife@c catalyst with the core-shell structure, which comprises the following steps:
(1) Mixing water-soluble Fe salt, water-soluble Ni salt and glycol according to a certain metering, stirring at a certain temperature of 100-200 ℃ for 0.5-2 h;
(2) Metering, namely dropwise adding a sodium carbonate aqueous solution with a certain concentration into the mixed solution in the step (1), keeping stirring in the adding process, keeping the rotating speed at 500-1000 r/min, and keeping the stirring temperature at 100-200 ℃; after the dripping is finished, maintaining the temperature and the rotating speed, aging for 0.5-5 h to obtain a suspension, filtering and washing the suspension to obtain a reddish brown or yellowish green precipitate;
(3) Adding the reddish brown or yellowish green precipitate obtained in the step (2) into a hydrothermal synthesis kettle, adding a carbon source precursor and deionized water according to the measurement, stirring, performing ultrasonic treatment, and performing hydrothermal treatment at a hydrothermal temperature of 150-200 ℃ for 12-24 hours;
(4) Filtering, washing and drying the hydrothermal product obtained in the step (3) to obtain a black precipitate, wherein the drying temperature is 100-130 ℃ and the drying time is 10-20 h;
(5) And (3) carbonizing the black precipitate obtained in the step (4) at a high temperature for a plurality of hours in an argon atmosphere to obtain the NiFe@C catalyst with the core-shell structure.
In the step (1), the water-soluble Fe salt is selected from one or more of ferrous chloride tetrahydrate, ferrous sulfate and ferrous nitrate, preferably ferrous chloride tetrahydrate; the water-soluble Ni salt is selected from one or more of nickel nitrate, nickel chloride and nickel acetate tetrahydrate, preferably nickel acetate tetrahydrate.
In the step (3), the carbon source precursor is one or more selected from glucose, maltose and fructose, preferably glucose.
In the step (5), the carbonization temperature is 500-700 ℃ and the carbonization time is 3-8 h.
In a third aspect, the invention provides the use of the above-mentioned core-shell structure NiFe@C catalyst or the core-shell structure NiFe@C catalyst prepared by the above-mentioned method, wherein the catalyst is used for catalyzing cinnamaldehyde hydrogenation to prepare 3-phenylpropionaldehyde.
In a fourth aspect, the invention provides a method for preparing 3-phenylpropionaldehyde by hydrogenating cinnamaldehyde, which adopts the NiFe@C catalyst with a core-shell structure or the NiFe@C catalyst with a core-shell structure prepared by the method.
The reaction temperature of the reaction for preparing 3-phenylpropionaldehyde by hydrogenating cinnamaldehyde is 80-120 ℃, and the reaction pressure is 0.5-3.0 Mpa; the reaction solvent is selected from one or more of isopropanol, toluene, ethylbenzene, tetrahydrofuran and cyclohexane, preferably isopropanol.
The reaction for preparing 3-phenylpropionaldehyde by hydrogenating cinnamaldehyde can be intermittently produced by using a reaction kettle, and can also be carried out by using a fixed bed.
Compared with the prior art, the invention has the following beneficial effects:
(1) The catalyst provided by the invention adopts nano-sized NiFe alloy as a core, an amorphous carbon layer is coated on the surface of the NiFe alloy as a shell, and the core-shell components act synergistically to catalyze cinnamaldehyde hydrogenation to prepare 3-phenylpropionaldehyde. The introduction of the catalyst auxiliary agent Fe is beneficial to the modulation of the electronic property of the active component Ni, and the high selectivity of the target product 3-phenylpropionaldehyde is realized through the influence of the active component Ni on the intermediate product. And the introduction of the auxiliary agent Fe can promote the high dispersion of the active component Ni, and is beneficial to improving the adsorption capacity and agglomeration sintering resistance of the reaction raw material gas, thereby improving the stability of the catalyst. In addition, the carbon layer coating designed by the invention can further inhibit the deep oxidation of the active metal, so that the stability, the repeatable cycle use performance and the use performance after regeneration of the catalyst are improved.
(2) The preparation method of the catalyst provided by the invention creatively combines a coprecipitation method and a hydrothermal synthesis method, realizes the combination of the active component Ni, the auxiliary agent Fe and the carbon layer of the coating material, and realizes the high catalytic activity, the high stability and the high selectivity of the catalyst.
(3) The catalyst provided by the invention is a non-noble metal alloy catalyst, has the advantages of lower production cost and higher economical efficiency, and the preparation method is easy to regulate and control, and can realize industrial production, so that the industrial application of preparing 3-phenylpropionaldehyde by hydrogenating cinnamaldehyde can be satisfied.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention. In the drawings:
FIG. 1 shows a core-shell Ni structure prepared in example 1 of the present invention 1 Fe 0.7 Transmission electron microscopy of catalyst @ C.
FIG. 2 shows a core-shell Ni structure prepared in example 1 of the present invention 1 Fe 0.7 The catalyst @ C is used for catalyzing the reaction of preparing 3-phenylpropionaldehyde by hydrogenating cinnamaldehyde, and the catalyst is circulated for 5 times.
Detailed Description
The following detailed description of the embodiments of the present invention is provided for better illustration of the present invention, but is not to be construed as limiting the invention.
The specific techniques or conditions are not identified in the examples and are described in the literature in this field or are carried out in accordance with the product specifications. The reagents or equipment used were conventional products available for purchase through regular channels, with no manufacturer noted.
The product analysis method in the embodiment of the invention adopts an Agilent chromatograph to analyze, and the specific detection method for preparing the 3-phenylpropionaldehyde product by hydrogenating cinnamaldehyde comprises the following steps:
sample injection amount: 0.5. Mu.L; the chromatographic column is as follows: agilent HP-5 model (30 m.320 um.0.25 um); column temperature: maintaining at 40deg.C for 5min, heating to 100deg.C at 3deg.C/min, maintaining for 3min, heating to 240 deg.C at 10deg.C/min, and maintaining for 10min; the temperature of the sample inlet is 250 ℃; detector temperature: 250 ℃.
Spacer purge gas flow rate: 3ml/min; chromatographic column flow rate (N2): 54ml/min; split sample introduction, wherein the split ratio is 50:1; hydrogen flow rate: 30ml/min; air flow rate: 400ml/min; tail gas purge flow: 25ml/min.
Example 1
Ni of core-shell structure 1 Fe 0.7 The preparation method of the @ C catalyst (the molar ratio of Ni element to Fe element is 1:0.7) comprises the following steps:
(1) 7g of nickel acetate tetrahydrate, 3.9g of ferrous chloride tetrahydrate and 100ml of ethylene glycol are mixed and stirred for 0.5h at 160 ℃;
(2) Dissolving 6g of sodium carbonate into 160ml of deionized water, dropwise adding the solution into the mixed solution obtained in the step (1), keeping stirring in the adding process, keeping the rotating speed at 500r/min, and keeping the stirring temperature at 160 ℃; after the dripping is finished, maintaining the temperature and the rotating speed, aging for 1h to obtain a suspension, filtering and washing the suspension to obtain a reddish brown precipitate;
(3) Adding the reddish brown precipitate obtained in the step (2) into a hydrothermal synthesis kettle, adding 1.06g of glucose and 40ml of deionized water, stirring, performing ultrasonic treatment, and performing hydrothermal treatment at a hydrothermal temperature of 175 ℃ for 18 hours;
(4) Filtering, washing and drying the hydrothermal product obtained in the step (3) to obtain a black precipitate, wherein the drying temperature is 120 ℃ and the drying time is 12 hours;
(5) Carbonizing the black precipitate obtained in the step (4) for 4 hours at 600 ℃ in an argon atmosphere to obtain the Ni with the core-shell structure 1 Fe 0.7 The @ C catalyst, designated catalyst 1#. The transmission electron microscope of catalyst 1# is shown in fig. 1.
The cinnamaldehyde hydrogenation reaction of the catalyst 1# prepared above is adopted to prepare 3-phenylpropionaldehyde: 1mmol of reaction substrate cinnamaldehyde, 5ml of isopropanol reaction solvent and 0.02g of catalyst No. 1 are sequentially placed in an autoclave; by H 2 Replacing air in the autoclave for multiple times, and filling hydrogen with total pressure of 1Mpa after the replacement is finished; the reaction was carried out at 100℃for 3h, and the mixture was subjected to quantitative chromatography after the reaction vessel was cooled to room temperature. The reaction results of the catalyst 1# prepared above for catalyzing the hydrogenation of cinnamaldehyde to prepare 3-phenylpropionaldehyde are shown in table 1. The reaction results of catalyst 1# for 5 cycles are shown in FIG. 2. As can be seen from FIG. 2, the core-shell Ni prepared by the invention 1 Fe 0.7 After recycling 5 times, the catalyst at the temperature of C can still keep high catalytic activity and high product selectivity.
Example 2
Ni of core-shell structure 1 Fe 0.3 The preparation method of the @ C catalyst (the molar ratio of Ni element to Fe element is 1:0.3) comprises the following steps:
(1) 7g of nickel acetate tetrahydrate, 1.7g of ferrous chloride tetrahydrate and 100ml of ethylene glycol are mixed and stirred for 0.5h at 160 ℃;
(2) Dissolving 6g of sodium carbonate into 160ml of deionized water, dropwise adding the solution into the mixed solution obtained in the step (1), keeping stirring in the adding process, keeping the rotating speed at 600r/min, and keeping the stirring temperature at 180 ℃; after the dripping is finished, maintaining the temperature and the rotating speed, aging for 3 hours to obtain a suspension, filtering and washing the suspension to obtain a reddish brown precipitate;
(3) Adding the reddish brown precipitate obtained in the step (2) into a hydrothermal synthesis kettle, adding 1.06g of glucose and 40ml of deionized water, stirring, performing ultrasonic treatment, and performing hydrothermal treatment at 190 ℃ for 12 hours;
(4) Filtering, washing and drying the hydrothermal product obtained in the step (3) to obtain a black precipitate, wherein the drying temperature is 120 ℃ and the drying time is 12 hours;
(5) Carbonizing the black precipitate obtained in the step (4) at 650 ℃ for 3 hours in an argon atmosphere to obtain the Ni with the core-shell structure 1 Fe 0.3 The @ C catalyst, designated catalyst 2#.
The reaction of preparing 3-phenylpropionaldehyde by hydrogenating cinnamaldehyde of the catalyst No. 2 prepared by the method comprises the following steps: 1mmol of reaction substrate cinnamaldehyde, 5ml of toluene reaction solvent and 0.02g of catalyst No. 2 are sequentially placed in an autoclave; by H 2 Replacing air in the autoclave for multiple times, and filling hydrogen with total pressure of 2Mpa after the replacement is finished; the reaction was carried out at 110℃for 5h, and the mixture was subjected to quantitative chromatography after the reaction vessel was cooled to room temperature. The reaction results of the catalyst 2# prepared above for catalyzing the hydrogenation of cinnamaldehyde to prepare 3-phenylpropionaldehyde are shown in table 1.
Example 3
Ni of core-shell structure 1 Fe 0.9 The preparation method of the @ C catalyst (the molar ratio of Ni element to Fe element is 1:0.9) comprises the following steps:
(1) 7g of nickel acetate tetrahydrate, 5g of ferrous chloride tetrahydrate and 100ml of ethylene glycol are mixed and stirred for 0.5h at 160 ℃;
(2) Dissolving 6g of sodium carbonate into 160ml of deionized water, dropwise adding the solution into the mixed solution obtained in the step (1), keeping stirring in the adding process, keeping the rotating speed at 500r/min, and keeping the stirring temperature at 170 ℃; after the dripping is finished, maintaining the temperature and the rotating speed, aging for 0.5h to obtain a suspension, filtering and washing the suspension to obtain a reddish brown precipitate;
(3) Adding the reddish brown precipitate obtained in the step (2) into a hydrothermal synthesis kettle, adding 1.06g of glucose and 40ml of deionized water, stirring, performing ultrasonic treatment, and performing hydrothermal treatment at a hydrothermal temperature of 180 ℃ for 15 hours;
(4) Filtering, washing and drying the hydrothermal product obtained in the step (3) to obtain a black precipitate, wherein the drying temperature is 120 ℃ and the drying time is 12 hours;
(5) Carbonizing the black precipitate obtained in the step (4) for 8 hours at 550 ℃ in an argon atmosphere to obtain the Ni with the core-shell structure 1 Fe 0.9 The @ C catalyst, designated catalyst 3#.
The reaction of preparing 3-phenylpropionaldehyde by hydrogenating cinnamaldehyde with the catalyst 3# prepared above: 1mmol of reaction substrate cinnamaldehyde, 10ml of tetrahydrofuran reaction solvent and 0.04g of catalyst 3# are sequentially placed in an autoclave; by H 2 Replacing air in the autoclave for multiple times, and filling hydrogen with total pressure of 2.5Mpa after the replacement is finished; the reaction was carried out at 90℃for 12h, and the mixture was subjected to quantitative chromatography after the autoclave was cooled to room temperature. The reaction results of the catalyst 3# prepared above for catalyzing the hydrogenation of cinnamaldehyde to prepare 3-phenylpropionaldehyde are shown in table 1.
Comparative example 1
The preparation method of the Ni@C catalyst with the core-shell structure comprises the following steps:
(1) 7g of nickel acetate tetrahydrate and 100ml of ethylene glycol are mixed and stirred for 0.5h at 160 ℃;
(2) Dissolving 6g of sodium carbonate into 160ml of deionized water, dropwise adding the solution into the mixed solution obtained in the step (1), keeping stirring in the adding process, keeping the rotating speed at 500r/min, and keeping the stirring temperature at 160 ℃; after the dripping is finished, maintaining the temperature and the rotating speed, aging for 1h to obtain a suspension, filtering and washing the suspension to obtain a green precipitate;
(3) Adding the green precipitate obtained in the step (2) into a hydrothermal synthesis kettle, adding 1.06g of glucose and 40ml of deionized water, stirring, performing ultrasonic treatment, and performing hydrothermal treatment at a hydrothermal temperature of 175 ℃ for 18 hours;
(4) Filtering, washing and drying the hydrothermal product obtained in the step (3) to obtain a black precipitate, wherein the drying temperature is 120 ℃ and the drying time is 12 hours;
(5) Carbonizing the black precipitate obtained in the step (4) for 4 hours at 600 ℃ in an argon atmosphere to obtain a core-shell structure Ni@C catalyst, which is taken as a comparative catalyst 1#.
The reaction of preparing 3-phenylpropionaldehyde by hydrogenating cinnamaldehyde by using the prepared comparative catalyst No. 1: 1mmol of reaction substrate cinnamaldehyde, 2ml of isopropanol reaction solvent and 0.02g of comparative catalyst # 1 are placed in an autoclave in sequence; by H 2 Replacing air in the autoclave for multiple times, and filling hydrogen with total pressure of 1Mpa after the replacement is finished; the reaction was carried out at 200℃for 1h, and the mixture was subjected to quantitative chromatography after the reaction vessel was cooled to room temperature. The reaction results of the comparative example catalyst 1# prepared above for catalyzing the hydrogenation of cinnamaldehyde to 3-phenylpropionaldehyde are shown in table 1.
Table 1: the catalyst prepared by the invention catalyzes the reaction result of preparing 3-phenylpropionaldehyde by cinnamaldehyde hydrogenation
As shown in Table 1, the core-shell structure NiFe@C catalyst disclosed by the invention is used for catalyzing the reaction of preparing 3-phenylpropionaldehyde by hydrogenating cinnamaldehyde, has high catalytic activity, high selectivity and excellent stability, and has high industrial application value.
It is apparent that the above examples are only illustrative of the present invention and are not limiting of the embodiments of the present invention. Various modifications and alterations of this invention may be made by those skilled in the art without departing from the spirit and scope of this invention. Thus, it is intended that the present invention also include such modifications and alterations insofar as they come within the scope of the appended claims or the equivalents thereof.
Claims (9)
1. The catalyst is characterized in that the catalyst takes nano-sized NiFe alloy as a core and coats an amorphous carbon layer on the surface of the catalyst as a shell, ni in the nano-sized NiFe alloy is an active component, fe is an auxiliary agent, the NiFe alloy is prepared by coprecipitation, and the amorphous carbon layer coats a nuclear body by a hydrothermal synthesis method.
2. The NiFe@C catalyst with the core-shell structure according to claim 1, wherein the average particle size of the nano NiFe alloy is 10-35 nm, and the amorphous carbon layer shell thickness is 1-4 nm.
3. The NiFe@C catalyst with the core-shell structure according to claim 1, wherein the molar ratio of the Ni element serving as the catalytic active component to the Fe element serving as an auxiliary agent is 1:0.2-1.2.
4. The method for preparing the NiFe@C catalyst with a core-shell structure as claimed in claim 1, which is characterized by comprising the following steps:
(1) Mixing water-soluble Fe salt, water-soluble Ni salt and glycol according to a certain metering, stirring at a certain temperature of 100-200 ℃ for 0.5-2 h;
(2) Metering, namely dropwise adding a sodium carbonate aqueous solution with a certain concentration into the mixed solution in the step (1), keeping stirring in the adding process, keeping the rotating speed at 500-1000 r/min, and keeping the stirring temperature at 100-200 ℃; after the dripping is finished, maintaining the temperature and the rotating speed, aging for 0.5-5 h to obtain a suspension, filtering and washing the suspension to obtain a reddish brown or yellowish green precipitate;
(3) Adding the reddish brown or yellowish green precipitate obtained in the step (2) into a hydrothermal synthesis kettle, adding a carbon source precursor and deionized water according to the measurement, stirring, performing ultrasonic treatment, and performing hydrothermal treatment at a hydrothermal temperature of 150-200 ℃ for 12-24 hours;
(4) Filtering, washing and drying the hydrothermal product obtained in the step (3) to obtain a black precipitate, wherein the drying temperature is 100-130 ℃ and the drying time is 10-20 h;
(5) And (3) carbonizing the black precipitate obtained in the step (4) at a high temperature for a plurality of hours in an argon atmosphere to obtain the NiFe@C catalyst with the core-shell structure.
5. The method of claim 4, wherein in step (1), the water-soluble Fe salt is selected from one or more of ferrous chloride tetrahydrate, ferrous sulfate, ferrous nitrate, preferably ferrous chloride tetrahydrate; the water-soluble Ni salt is selected from one or more of nickel nitrate, nickel chloride and nickel acetate tetrahydrate, preferably nickel acetate tetrahydrate;
in the step (3), the carbon source precursor is selected from one or more of glucose, maltose and fructose, preferably glucose;
in the step (5), the carbonization temperature is 500-700 ℃ and the carbonization time is 3-8 h.
6. The use of the nife@c catalyst with a core-shell structure according to any one of claims 1 to 3 or the nife@c catalyst with a core-shell structure prepared by the method according to claim 4 or 5, wherein the catalyst is used for catalyzing cinnamaldehyde hydrogenation to prepare 3-phenylpropionaldehyde.
7. A method for preparing 3-phenylpropionaldehyde by hydrogenating cinnamaldehyde, which is characterized in that the method adopts the nife@c catalyst with a core-shell structure according to any one of claims 1 to 3 or the nife@c catalyst with a core-shell structure prepared by the method according to claim 4 or 5.
8. The method according to claim 7, wherein the reaction temperature of the reaction for preparing 3-phenylpropionaldehyde by hydrogenating cinnamaldehyde is 80-120 ℃, and the reaction pressure is 0.5-3.0 Mpa; the reaction solvent is selected from one or more of isopropanol, toluene, ethylbenzene, tetrahydrofuran and cyclohexane, preferably isopropanol.
9. The method according to claim 7 or 8, wherein the reaction for preparing 3-phenylpropionaldehyde by hydrogenating cinnamaldehyde can be carried out in batch mode by using a reaction kettle or can be carried out by using a fixed bed.
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