CN114588951A - Carbon-based multi-metal-site ultra-rare high-entropy alloy catalyst and preparation method and application thereof - Google Patents
Carbon-based multi-metal-site ultra-rare high-entropy alloy catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN114588951A CN114588951A CN202210298430.0A CN202210298430A CN114588951A CN 114588951 A CN114588951 A CN 114588951A CN 202210298430 A CN202210298430 A CN 202210298430A CN 114588951 A CN114588951 A CN 114588951A
- Authority
- CN
- China
- Prior art keywords
- salt
- entropy alloy
- carbon
- metal
- based multi
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 58
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 52
- 239000000956 alloy Substances 0.000 title claims abstract description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 74
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229910052751 metal Inorganic materials 0.000 claims abstract description 55
- 239000002184 metal Substances 0.000 claims abstract description 55
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 24
- 238000001354 calcination Methods 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 239000012298 atmosphere Substances 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 150000002815 nickel Chemical class 0.000 claims abstract description 13
- 150000001868 cobalt Chemical class 0.000 claims abstract description 11
- 150000001879 copper Chemical class 0.000 claims abstract description 11
- 150000003751 zinc Chemical class 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000012266 salt solution Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 9
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 6
- 150000002505 iron Chemical class 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 238000006555 catalytic reaction Methods 0.000 claims description 11
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 10
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 6
- 239000004246 zinc acetate Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 claims description 2
- JNODDICFTDYODH-UHFFFAOYSA-N 2-hydroxytetrahydrofuran Chemical compound OC1CCCO1 JNODDICFTDYODH-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000002243 precursor Substances 0.000 description 9
- 238000005303 weighing Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000012153 distilled water Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910003266 NiCo Inorganic materials 0.000 description 3
- 229910006030 NiCoCu Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 239000012263 liquid product Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- -1 Nickel acetate Acetic acid cobalt salt Chemical compound 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229940076286 cupric acetate Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into 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
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/06—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
- C07D307/08—Preparation of tetrahydrofuran
-
- 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
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
- C07D307/44—Furfuryl alcohol
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a carbon-based multi-metal site ultra-rare high-entropy alloy catalyst and a preparation method and application thereof. The method comprises the following steps: (1) adding 5 metal salts of nickel salt, cobalt salt, copper salt, zinc salt and iron salt into water, and uniformly stirring to obtain a mixed metal salt solution; adding citric acid into water, and uniformly stirring to obtain a citric acid solution; adding the mixed metal salt solution into the citric acid solution, continuously stirring and uniformly mixing, and drying to obtain a catalyst precursor; (2) and heating the catalyst precursor to 600-900 ℃ in the protective gas atmosphere for calcination, continuing calcination in the reducing gas atmosphere, taking out and cooling to room temperature to obtain the carbon-based multi-metal-site ultra-rare high-entropy alloy catalyst. The catalyst prepared by the invention can be used for catalyzing furfural hydrogenation to prepare high-value compounds, such as furfuryl alcohol, tetrahydrofuryl alcohol and the like.
Description
Technical Field
The invention belongs to the field of catalyst and biomass conversion and utilization, and particularly relates to a carbon-based multi-metal site ultra-dilute high-entropy alloy catalyst, and a preparation method and application thereof.
Background
Furfuryl alcohol is used primarily in the production of adhesives, lubricants and corrosion resistant coatings, a key intermediate in the manufacture of many fine chemicals and basic industrial compounds. The production of furfuryl alcohol used 65% of the total furfural. Meanwhile, furfural is mainly generated from direct dehydration reaction of C5 sugar, so that furfural is generated from biomass rich in lignocellulose and is converted into furfuryl alcohol, and the method is an economic and green industrial production route. Wherein, the key step of synthesizing the furfural hydrogenation furfuryl alcohol catalyst with high efficiency and high selectivity catalytic activity is the key step.
The high-entropy alloy as a novel metal material shows huge catalytic potential. High entropy alloys have received much attention due to their multi-metallic sites consisting of five or more elements, heat resistance and corrosion resistance. At present, the synthesis method of the high-entropy alloy mainly comprises an electric arc melting method, a hot carbon impact method, an aerosol spray pyrolysis method, a melt spinning technology, a ball milling technology, a solvothermal method and the like. These methods require strict synthesis conditions, which limits the further popularization of high-entropy alloys. Therefore, it is also important to develop a new synthesis method of the high-entropy alloy. The rare alloy is widely researched as a catalyst with atomic site adsorption reactants, and the surface atomic arrangement and d-band center of the high-entropy alloy can be effectively adjusted, so that the catalytic activity and the product selectivity are improved to the maximum extent.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of a carbon-based multi-metal-site ultra-rare high-entropy alloy catalyst.
The invention also aims to provide the carbon-based multi-metal site ultra-dilute high-entropy alloy catalyst prepared by the method.
The invention further aims to provide application of the carbon-based polymetallic site ultra-rare high-entropy alloy catalyst.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a carbon-based multi-metal site ultra-rare high-entropy alloy catalyst comprises the following steps:
(1) adding 5 metal salts of nickel salt, cobalt salt, copper salt, zinc salt and iron salt into water, and uniformly stirring to obtain a mixed metal salt solution (metal precursor); adding citric acid into water, and stirring uniformly to obtain a citric acid solution (ligand solution); adding the mixed metal salt solution into the citric acid solution, continuously stirring and uniformly mixing, and drying to obtain a catalyst precursor;
(2) and heating the catalyst precursor to 600-900 ℃ in the protective gas atmosphere for calcination, continuing calcination in the reducing gas atmosphere, taking out and cooling to room temperature to obtain the carbon-based multi-metal-site ultra-rare high-entropy alloy catalyst.
The nickel salt in the step (1) is soluble nickel salt; preferably nickel acetate.
The cobalt salt in the step (1) is soluble cobalt salt; cobalt acetate is preferred.
The copper salt in the step (1) is soluble copper salt; preferably copper acetate.
The zinc salt in the step (1) is soluble zinc salt; preferably zinc acetate.
The ferric salt in the step (1) is soluble ferric salt; preferably ferric nitrate.
The molar ratio of the nickel salt, the cobalt salt, the copper salt, the zinc salt and the iron salt in the step (1) is 1-1.2: 1-1.2: 1-1.2: 1-1.2: 1 to 1.2; preferably 1: 1: 1: 1: 1 (i.e. five metal salts are added in equimolar amounts).
The water in the step (1) is preferably distilled water.
The amount of water in the mixed metal salt solution in the step (1) is calculated according to the proportion of 30-40 ml of water to 0.005mol of nickel salt; preferably 40ml of water per 0.005mol of nickel salt.
The molar ratio of the total molar amount of the 5 metal salts to the citric acid in the step (1) is 1: 2 (citric acid added twice the total molar amount of metal).
The amount of water in the citric acid solution in the step (1) is calculated according to the proportion of 400-20 ml-30 ml of water in every 0.05mol of citric acid; preferably 20ml of water per 0.05mol of citric acid.
The condition of uniform stirring in the step (1) is as follows: stirring for 5-10 min at 200-400 r/min; preferably, the following components are used: stirring at 300r/min for 5 min.
The condition of continuous stirring in the step (1) is as follows: stirring at 200-400 r/min for 20 min-1 h; preferably: stirring at 300r/min for 0.5 h.
The drying temperature in the step (1) is 100-110 ℃; preferably 105 deg.c.
The drying time in the step (1) is 3-5 days; preferably 3 days.
The protective gas in step (2) is preferably nitrogen.
The temperature rise rate in the step (2) is 5-10 ℃/min; preferably 5 deg.C/min.
The temperature of the calcination in the step (2) is preferably 800 ℃.
The calcining time in the step (2) is 0-2 h (excluding 0); preferably 1 h.
The reducing gas in the step (2) is H2Or H2And N2The mixed gas of (3); preferably H2And N2Mixing the obtained reducing gases according to the volume ratio of 1: 9.
The continuous calcining time in the step (2) is 0-4 h (excluding 0); preferably for 2 hours.
The cooling in the step (2) is cooling in a reducing gas atmosphere.
The preparation method of the carbon-based multi-metal site ultra-dilute high-entropy alloy catalyst further comprises a step of further grinding after the step (2), and specifically comprises the following steps: grinding the catalyst obtained in the step (2) by a 60-mesh sieve to obtain the ground carbon-based multi-metal site ultra-dilute high-entropy alloy catalyst.
A carbon-based multi-metal site ultra-dilute high-entropy alloy catalyst is prepared by any one of the methods.
The carbon-based multi-metal site ultra-dilute high-entropy alloy catalyst is applied to preparation of high-value compounds by catalyzing hydrogenation of furfural.
The carbon-based multi-metal site ultra-dilute high-entropy alloy catalyst is applied to preparation of a high-value compound by catalyzing furfural hydrogenation, and is characterized in that the carbon-based multi-metal site ultra-dilute high-entropy alloy catalyst and furfural are added into isopropanol to perform catalytic reaction at the temperature of 60-180 ℃ and the hydrogen pressure of 0-4 MPa (excluding 0) to obtain the high-value compound.
The high-value compound comprises at least one of furfuryl alcohol and tetrahydrofurfuryl alcohol; furfuryl alcohol is preferred.
The temperature of the catalytic reaction is preferably 90-120 ℃; further preferably 90 ℃.
The hydrogen pressure is preferably 1-3 Mpa; more preferably 2 to 3 MPa; still more preferably 3 MPa.
The rotating speed of the catalytic reaction is preferably 800 r/min.
The mass space velocity of the catalytic reaction is 0.1h-1~1h-1(ii) a Preferably 0.6h-1。
The time of the catalytic reaction is 0-24 h (excluding 0); preferably 9 h.
Compared with the prior art, the invention has the following advantages and effects:
the carbon-based ultra-dilute high-entropy alloy catalyst containing multiple metal sites is prepared by preparing a precursor from five cheap transition metals by a sol-gel method, and calcining the precursor in a common atmosphere furnace to form the multi-metal-site ultra-dilute high-entropy alloy catalyst with atom-dispersed Zn active sites.
Drawings
FIG. 1 is a flow diagram of ultra-dilute high-entropy alloy catalyst preparation.
FIG. 2 is a schematic diagram of the synthesis of an ultra-dilute high-entropy alloy.
FIG. 3 is a structural representation of a NiCoCuZnFe/C-800 catalyst; wherein, (a), (b) and (c) are SEM spectra with the sizes of 2 μm, 500nm and 100nm respectively; (d) (e), (f), (g), (i), (j) and (k) are respectively a dark field map, an EDS map of the Ni-Co-Fe-Cu-Zn, and a mixed map; (h) is XRD pattern; (l) And (m), (m) and (o) are respectively a 500nm size TEM pattern, a 10nm size TEM pattern, a Fourier transform processed pattern and a schematic diagram of lattice fringes.
FIG. 4 is a graph of the effect of catalytic furfural hydrogenation to furfuryl alcohol in example 1.
FIG. 5 is a graph of the effect of catalytic hydrogenation of furfural to furfuryl alcohol in example 2 (hydrogenation of furfural by HEA of varying content of constituent elements); wherein a is the hydrogenation reaction of high-entropy alloy with different component element contents on furfural at 90 ℃; b is hydrogenation reaction of high-entropy alloy with different component element contents on furfural at 120 ℃; c is the hydrogenation reaction of furfural on NiCoCuZnFe/C-800 at different reaction temperatures; d is furfural in different H2Hydrogenation under pressure on NiCoCuZnFe/C-800.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated. The following examples are given without reference to specific experimental conditions, and are generally in accordance with conventional experimental conditions. Unless otherwise specified, reagents and starting materials for use in the present invention are commercially available.
Example 1: preparation of ultra-dilute high-entropy alloy at different calcination temperatures and application of ultra-dilute high-entropy alloy in furfural hydrogenation conversion into furfuryl alcohol
In the embodiment, five metals are added according to an equal molar ratio to prepare a metal precursor, and the metal precursor is calcined and reduced at different temperatures to prepare the ultra-dilute high-entropy alloy catalyst which is applied to furfural catalytic hydrogenation to prepare furfuryl alcohol.
Catalyst preparation (catalyst preparation flow is shown in figure 1, and synthesis schematic is shown in figure 2)
(1) Preparing a precursor: respectively weighing 0.005mol of five metal salts of nickel acetate, cobalt acetate, copper acetate, zinc acetate and ferric nitrate, adding the five metal salts into a 500ml beaker, adding 40ml of distilled water, and stirring for 5min at 300r/min to prepare a metal salt solution; weighing 0.05mol of citric acid, adding 20ml of distilled water, stirring at 300r/min for 5min, slowly adding the metal salt solution, continuously stirring for 0.5h, putting into a drying oven at 105 ℃, starting a fan, and drying for 3 days.
(2) Calcining and reducing: respectively selecting temperature gradients of 600 ℃, 700 ℃, 800 ℃ and 900 ℃ (the samples are respectively named NiCoCuZnFe/C-600, NiCoCuZnFe/C-700, NiCoCuZnFe/C-800 and NiCoCuZnFe/C-900), calcining by using an atmosphere furnace, raising the temperature to a target temperature at 5 ℃/min under the nitrogen atmosphere, keeping the temperature for 1H, and reducing the temperature in a reducing gas (10% (v/v) H2I.e. H2And N2Reducing gas obtained by mixing according to the volume ratio of 1: 9) for 2 hours, immediately taking out, cooling at room temperature (the cooling at room temperature is carried out under the atmosphere of the reducing gas), and grinding and sieving by a 60-mesh sieve to obtain the carbon-based multi-metal site ultra-thin high-entropy alloy catalyst.
TABLE 1ICP-OES analysis of Metal content of ultra-dilute high-entropy alloys at different calcination temperatures
Sample name | Ni(%) | Co(%) | Cu(%) | Zn(%) | Fe(%) |
NiCoCuZnFe/C-600 | 20.22 | 21.03 | 20.43 | 19.97 | 18.35 |
NiCoCuZnFe/C-700 | 23.06 | 23.49 | 22.98 | 9.86 | 20.61 |
NiCoCuZnFe/C-800 | 24.94 | 25.13 | 26.38 | 0.45 | 23.10 |
NiCoCuZnFe/C-900 | 25.44 | 26.01 | 25.41 | 0.15 | 23.00 |
(II) structural characterization of the catalyst
The prepared catalyst sample NiCoCuZnFe/C-800 is characterized, namely, a Scanning Electron Microscope (SEM), an energy spectrometer (EDS), an X-ray diffraction (XRD), a Transmission Electron Microscope (TEM), a Fourier transform infrared spectrometer and the like are used for detection, and the result is shown in figure 3.
(III) evaluation of catalyst reaction
Liquid phase conversion of furfural hydrogenation into furfuryl alcohol is carried out in a six-linked parallel reaction kettle. Respectively weighing 50mg of carbon-based multi-metal site ultra-rare high-entropy alloy catalyst (NiCoCuZnFe/C-600, NiCoCuZnFe/C-700, NiCoCuZnFe/C-800 and NiCoCuZnFe/C-900) and 300mg of furfural into a quartz lining, adding 20ml of isopropanol as a solvent, setting the rotating speed of 800r/min under 3MPa of hydrogen pressure, timing from 90 ℃ to react for 9h, naturally cooling and collecting. After filtration through an organic 13mm x 0.22um filter, the product was analyzed for liquid product type by testing with a gas chromatograph-mass spectrometer (Thermo Trace1300-ISQ) equipped with a TG-5MS column (30m x 0.25mm x 0.25 μm). Standard sample calibration of furfural and furfuryl alcohol was configured by quantitative testing of the product using a gas chromatograph (Agilent) with the same capillary column. The temperature rising procedure is as follows: held at 40 ℃ for 5min and then raised to 280 ℃ at a rate of 10 ℃/min for 3 min. The operation steps are as follows:
(1) weighing 50mg of catalyst by a weighing balance, adding the catalyst into the quartz lining, dripping about 300mg of furfural, adding 20ml of isopropanol solution, and recording data.
(2) Adding stirrer, putting the liner into the kettle, packaging, checking the opening and closing of gas and liquid valves, and connecting thermocouple.
(3) Introducing hydrogen, sealing, waiting for 5min, observing gas tightness again, and discharging hydrogen.
(4) And introducing hydrogen again, and discharging the residual gas in the kettle.
(5) Most preferablyThen introducing hydrogen needed by the reaction, and sealing. Starting the reaction kettle, setting conditions such as reaction temperature, reaction time, rotation speed and the like (hydrogen pressure: 3MPa, rotation speed: 800 r/min; timing from 90 ℃ to 90 ℃ (maintaining the reaction temperature at 90 ℃), reacting for 9h, and setting the mass space velocity at 0.6h-1) And the reaction is carried out.
(6) After the reaction is finished, naturally cooling to room temperature, discharging gas, and collecting liquid products.
(7) After filtration using an organic 13mm x 0.22um filter head, the sample was diluted 20 times with isopropanol and tested by on-line gas chromatography.
The reaction effect is shown in figure 4: the carbon-based ultra-dilute high-entropy alloy catalyst prepared at the calcination reduction temperature of 800 ℃ has optimal activity for preparing furfuryl alcohol by furfural hydrogenation under the design condition.
Example 2: preparation of ultra-dilute high-entropy alloy by different metal proportions and application of ultra-dilute high-entropy alloy in furfural hydrogenation conversion into furfuryl alcohol
In this example, catalysts with equal metal molar ratios and catalysts in which five metals are increased to 1.2 times each were prepared, and the influence of the metal change ratio on the catalyst action was investigated.
(one) catalyst preparation
(1) Preparing a precursor: respectively weighing five metal salts of nickel acetate, cobalt acetate, copper acetate, zinc acetate and ferric nitrate with calculated amounts (shown in table 2), adding the five metal salts into a 500ml beaker, adding 40ml of distilled water, and stirring at 300r/min for 5min to prepare a metal precursor; weighing 0.05mol (or 0.052mol) of citric acid, adding 20ml of distilled water, stirring at 300r/min for 5min, slowly adding the metal precursor, continuously stirring for 0.5h, putting into a 105 ℃ oven, and drying for 3 days. The catalyst samples were designated NiCoCuZnFe, (1.2Ni) CoCuZnFe, Ni (1.2Co) CuZnFe, NiCo (1.2Cu) ZnFe, NiCoCu (1.2Zn) Fe and NiCoCuZn (1.2Fe), respectively.
TABLE 2 dosage table for preparing ultra-dilute high-entropy alloy with different metal ratios
Sample name | Nickel acetate | Acetic acid cobalt salt | Cupric acetate | Zinc acetate | Ferric nitrate | Citric acid |
NiCoCuZnFe | 0.005mol | 0.005mol | 0.005mol | 0.005mol | 0.005mol | 0.05mol |
(1.2Ni)CoCuZnFe | 0.006mol | 0.005mol | 0.005mol | 0.005mol | 0.005mol | 0.052mol |
Ni(1.2Co)CuZnFe | 0.005mol | 0.006mol | 0.005mol | 0.005mol | 0.005mol | 0.052mol |
NiCo(1.2Cu)ZnFe | 0.005mol | 0.005mol | 0.006mol | 0.005mol | 0.005mol | 0.052mol |
NiCoCu(1.2Zn)Fe | 0.005mol | 0.005mol | 0.005mol | 0.006mol | 0.005mol | 0.052mol |
NiCoCuZn(1.2Fe) | 0.005mol | 0.005mol | 0.005mol | 0.005mol | 0.006mol | 0.052mol |
(2) Calcining and reducing: the calcination temperature was determined to be 800 ℃ by screening. Calcining in an atmosphere furnace, heating to 800 deg.C at 5 deg.C/min in nitrogen atmosphere, maintaining for 1 hr, maintaining for 2 hr in reducing gas atmosphere, taking out immediately, and cooling at room temperature.
(II) evaluation of catalyst reaction
And carrying out liquid phase conversion of furfural hydrogenation into furfuryl alcohol in a six-joint parallel reaction kettle. Respectively weighing 50mg of catalyst and 300mg of furfural, adding the catalyst and the furfural into a quartz lining, adding 20ml of isopropanol as a solvent, setting the rotating speed of 800r/min, timing from the temperature rise to the target temperature, reacting for 9 hours, naturally cooling, and collecting. After filtration through an organic 13mm by 0.22um filter, the liquid product species of the product was analyzed by a gas chromatograph-mass spectrometer (Thermo Trace1300-ISQ) equipped with a TG-5MS chromatography column (30m by 0.25mm by 0.25 μm). Standard sample calibration of furfural and furfuryl alcohol was configured by quantitative testing of the product using a gas chromatograph (Agilent) with the same capillary column. The temperature rising procedure is as follows: held at 40 ℃ for 5min and then raised to 280 ℃ at a rate of 10 ℃/min for 3 min.
The specific experimental process is as follows:
(1) hydrogenation reaction of high-entropy alloy with different component element contents on furfural
NiCoCuZnFe/C-800, (1.2Ni) CoCuZnFe/C-800, Ni (1.2Co) CuZnFe/C-800, NiCo (1.2Cu) ZnFe-800/C, NiCoCu (1.2Zn) Fe/C-800, NiCoCuZn (1.2Fe)/C-800 catalysts were weighed, respectively, according to the operation procedures in example 1, wherein the temperatures set in step (5) were 90 ℃, 120 ℃, and the mass space velocity was 0.6h-1And carrying out hydrogenation reaction on the furfural under the hydrogen pressure of 3 Mpa. Meanwhile, the reaction effect of a commercial 5% Pd/C catalyst (purchased from Aladdin reagent Co., Ltd.) tested at a reaction temperature of 120 ℃ and a hydrogen pressure of 3MPa was compared. The result of the hydrogenation reaction of the high-entropy alloy with different component element contents on the furfural at 90 ℃ is shown in figure 5a, and the result of the hydrogenation reaction on the furfural at 120 ℃ is shown in figure 5 b.
(2) Hydrogenation reaction of furfural on NiCoCuZnFe/C-800 at different reaction temperatures
NiCoCuZnFe/C-800 was weighed and the procedure of example 1 was followed, except that: the temperatures set in the step (5) are respectively 60 ℃, 90 ℃ and 120 ℃, and the hydrogenation reaction of the furfural is carried out under the hydrogen pressure of 3 Mpa. The results are shown in FIG. 5 c.
(3) Hydrogenation reaction of furfural on NiCoCuZnFe/C-800 under different hydrogen pressures
NiCoCuZnFe/C-800 was weighed and the procedure of example 1 was followed, except that: the pressure of the hydrogen gas required in the step (5) is 0MPa, 1MPa, 2MPa and 3MPa respectively, and the reaction is carried out at 90 ℃. The results are shown in FIG. 5 d.
From the above results, it can be seen that: the carbon-based ultra-thin high-entropy alloy catalyst prepared by adding five metals in equimolar amounts has the optimal catalytic effect on the reaction of preparing furfuryl alcohol by furfural hydrogenation under the design condition, and the conversion rate and the selectivity are superior to those of a 5% Pd/C catalyst.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a carbon-based multi-metal site ultra-rare high-entropy alloy catalyst is characterized by comprising the following steps:
(1) adding 5 metal salts of nickel salt, cobalt salt, copper salt, zinc salt and iron salt into water, and uniformly stirring to obtain a mixed metal salt solution; adding citric acid into water, and uniformly stirring to obtain a citric acid solution; adding the mixed metal salt solution into the citric acid solution, continuously stirring and uniformly mixing, and drying to obtain a catalyst precursor;
(2) and heating the catalyst precursor to 600-900 ℃ in the protective gas atmosphere for calcination, continuing calcination in the reducing gas atmosphere, taking out and cooling to room temperature to obtain the carbon-based multi-metal-site ultra-rare high-entropy alloy catalyst.
2. The preparation method of the carbon-based multi-metal site ultra-dilute high-entropy alloy catalyst according to claim 1, characterized in that:
the molar ratio of the nickel salt, the cobalt salt, the copper salt, the zinc salt and the iron salt in the step (1) is 1-1.2: 1-1.2: 1-1.2: 1-1.2: 1 to 1.2;
the molar ratio of the total molar amount of the 5 metal salts to the citric acid in the step (1) is 1: 2.
3. the preparation method of the carbon-based multi-metal site ultra-dilute high-entropy alloy catalyst according to claim 2, characterized in that:
the molar ratio of the nickel salt, the cobalt salt, the copper salt, the zinc salt and the iron salt in the step (1) is 1: 1: 1: 1: 1.
4. the preparation method of the carbon-based multi-metal site ultra-dilute high-entropy alloy catalyst according to claim 1, characterized in that:
the nickel salt in the step (1) is soluble nickel salt;
the cobalt salt in the step (1) is soluble cobalt salt;
the copper salt in the step (1) is soluble copper salt;
the zinc salt in the step (1) is soluble zinc salt;
the ferric salt in the step (1) is soluble ferric salt.
5. The preparation method of the carbon-based multi-metal site ultra-dilute high-entropy alloy catalyst according to claim 4, characterized in that:
the nickel salt in the step (1) is nickel acetate;
the cobalt salt in the step (1) is cobalt acetate;
the copper salt in the step (1) is copper acetate;
the zinc salt in the step (1) is zinc acetate;
the ferric salt in the step (1) is ferric nitrate.
6. The preparation method of the carbon-based multi-metal site ultra-dilute high-entropy alloy catalyst according to claim 1, characterized in that:
the condition of uniform stirring in the step (1) is as follows: stirring for 5-10 min at 200-400 r/min;
the conditions for continuously stirring in the step (1) are as follows: stirring at 200-400 r/min for 20 min-1 h;
the drying temperature in the step (1) is 100-110 ℃;
the drying time in the step (1) is 3-5 days;
the protective gas in the step (2) is nitrogen;
the temperature rise rate in the step (2) is 5-10 ℃/min;
the calcining temperature in the step (2) is 800 ℃;
the calcining time in the step (2) is 0-2 h, and 0 is not included;
the continuous calcining time in the step (2) is 0-4 h, and 0 is not included;
the reducing gas in the step (2) is H2Or H2And N2The mixed gas of (3);
the cooling in the step (2) is cooling in a reducing gas atmosphere.
7. A carbon-based multi-metal site ultra-rare high-entropy alloy catalyst is characterized in that: prepared by the method of any one of claims 1 to 6.
8. The application of the carbon-based multi-metal site ultra-dilute high-entropy alloy catalyst in preparing high-value compounds by catalyzing furfural hydrogenation.
9. Use according to claim 8, characterized in that: adding a carbon-based multi-metal site ultra-dilute high-entropy alloy catalyst and furfural into isopropanol, and carrying out catalytic reaction at 60-180 ℃ and under the hydrogen pressure of 0-4 MPa, wherein the hydrogen pressure is not 0, so as to obtain a high-value compound;
the high-value compound comprises at least one of furfuryl alcohol and tetrahydrofurfuryl alcohol;
the mass space velocity of the catalytic reaction is 0.1h-1~1h-1;
The time of the catalytic reaction is 0-24 h, and 0 is not included.
10. Use according to claim 9, characterized in that:
the high-value compound is furfuryl alcohol;
the temperature of the catalytic reaction is 90-120 ℃;
the hydrogen pressure is 1-3 Mpa;
the mass space velocity of the catalytic reaction is 0.6h-1;
The time of the catalytic reaction is 9 hours.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210298430.0A CN114588951B (en) | 2022-03-25 | 2022-03-25 | Carbon-based multi-metal site ultra-thin high-entropy alloy catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210298430.0A CN114588951B (en) | 2022-03-25 | 2022-03-25 | Carbon-based multi-metal site ultra-thin high-entropy alloy catalyst and preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114588951A true CN114588951A (en) | 2022-06-07 |
CN114588951B CN114588951B (en) | 2023-06-20 |
Family
ID=81819531
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210298430.0A Active CN114588951B (en) | 2022-03-25 | 2022-03-25 | Carbon-based multi-metal site ultra-thin high-entropy alloy catalyst and preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114588951B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115672340A (en) * | 2022-10-19 | 2023-02-03 | 华南农业大学 | Low-temperature synthesis supported high-entropy alloy catalyst and preparation method and application thereof |
CN116173983A (en) * | 2023-02-03 | 2023-05-30 | 中国工程物理研究院材料研究所 | Hydrogenation catalyst, preparation method and application thereof, and hydrogen-absorbing composite material |
CN116618047A (en) * | 2023-04-19 | 2023-08-22 | 广东工业大学 | Copper-based low-temperature catalyst and preparation method and application thereof |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB505600A (en) * | 1936-11-14 | 1939-05-15 | Deutsche Hydrierwerke Ag | Improvements in or relating to the manufacture of hydrogenation products of furfurol |
CN109261152A (en) * | 2018-10-08 | 2019-01-25 | 天津理工大学 | A kind of loaded catalyst and preparation method and application of catalysis furfural reduction |
CN111085232A (en) * | 2019-12-16 | 2020-05-01 | 西南林业大学 | Method for preparing furfuryl alcohol by catalyzing furfural through nitrogen-doped porous carbon-coated non-noble metal catalyst |
CN112475315A (en) * | 2020-11-27 | 2021-03-12 | 电子科技大学 | Method for universally preparing high-entropy alloy nanoparticles |
CN112892537A (en) * | 2021-01-25 | 2021-06-04 | 大连理工大学 | Preparation method and application of easily-recycled high-selectivity furfural hydrogenation catalyst |
-
2022
- 2022-03-25 CN CN202210298430.0A patent/CN114588951B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB505600A (en) * | 1936-11-14 | 1939-05-15 | Deutsche Hydrierwerke Ag | Improvements in or relating to the manufacture of hydrogenation products of furfurol |
CN109261152A (en) * | 2018-10-08 | 2019-01-25 | 天津理工大学 | A kind of loaded catalyst and preparation method and application of catalysis furfural reduction |
CN111085232A (en) * | 2019-12-16 | 2020-05-01 | 西南林业大学 | Method for preparing furfuryl alcohol by catalyzing furfural through nitrogen-doped porous carbon-coated non-noble metal catalyst |
CN112475315A (en) * | 2020-11-27 | 2021-03-12 | 电子科技大学 | Method for universally preparing high-entropy alloy nanoparticles |
CN112892537A (en) * | 2021-01-25 | 2021-06-04 | 大连理工大学 | Preparation method and application of easily-recycled high-selectivity furfural hydrogenation catalyst |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115672340A (en) * | 2022-10-19 | 2023-02-03 | 华南农业大学 | Low-temperature synthesis supported high-entropy alloy catalyst and preparation method and application thereof |
CN115672340B (en) * | 2022-10-19 | 2024-01-23 | 华南农业大学 | Low-temperature synthesis supported high-entropy alloy catalyst and preparation method and application thereof |
CN116173983A (en) * | 2023-02-03 | 2023-05-30 | 中国工程物理研究院材料研究所 | Hydrogenation catalyst, preparation method and application thereof, and hydrogen-absorbing composite material |
CN116618047A (en) * | 2023-04-19 | 2023-08-22 | 广东工业大学 | Copper-based low-temperature catalyst and preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CN114588951B (en) | 2023-06-20 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN114588951B (en) | Carbon-based multi-metal site ultra-thin high-entropy alloy catalyst and preparation method and application thereof | |
Abu-Zied | Structural and catalytic activity studies of silver/chromia catalysts | |
Mirzaei et al. | Preparation and optimization of mixed iron cobalt oxide catalysts for conversion of synthesis gas to light olefins | |
AU2013203123B2 (en) | Treating of catalyst support | |
CN110449189B (en) | Catalyst for synthesizing dimethyl carbonate and preparation method thereof | |
US7709541B2 (en) | Fischer-Tropsch catalysts incorporating promoter for increasing yields of C5+ hydrocarbons and methods for making and using same | |
CN101966460A (en) | Supported catalyst for synthesis of dimethyl carbonate, preparation method and using method thereof | |
CN112871200B (en) | Catalyst system for preparing light aromatic hydrocarbon from synthesis gas and application thereof | |
CN115382541B (en) | Method for regulating existence form of Rh species in rhodium-based catalyst | |
CN110575833A (en) | Catalyst for directly preparing low-carbon alpha-olefin from synthesis gas and preparation method thereof | |
Pampararo et al. | Acetaldehyde production by ethanol dehydrogenation over Cu-ZnAl2O4: Effect of catalyst synthetic strategies on performances | |
CN110354857A (en) | A kind of preparation method and applications of Ni-based heterogeneous catalyst are in catalysis aldehyde compound hydrogenation deoxidation reaction | |
CN106890665B (en) | Catalyst for producing methyl acetate by dimethyl ether carbonylation and application thereof | |
CN111054326B (en) | Supported catalyst, preparation method thereof and application of supported catalyst in catalyzing synthesis of indole from ethylene glycol and aniline | |
CN115337926B (en) | Rhodium-based catalyst and preparation method and application thereof | |
CN106316866B (en) | A kind of preparation method of N- methyl aminated compounds | |
CN103691440A (en) | Catalyst for preparing ethanol by acetic acid hydrogenation and preparation method thereof | |
CN114849720B (en) | Silica supported nickel-based trimetallic catalyst, preparation method thereof and application thereof in phenylacetylene selective hydrogenation | |
Meng et al. | Zn species decorated Pt/CeO2 catalysts for selective hydrogenation of 1, 4-butynediol in continuous-flow reactor | |
CN108047173B (en) | Method for preparing gamma-valerolactone | |
CN112237918A (en) | Dual-function supported catalyst for oxidative dehydrogenation and dry reforming of low-carbon alkane and preparation method thereof | |
CN110563585A (en) | Preparation method of dimethyl carbonate | |
CN115814794A (en) | Copper/silicon oxide catalyst and preparation method and application thereof | |
CN115672340B (en) | Low-temperature synthesis supported high-entropy alloy catalyst and preparation method and application thereof | |
An et al. | Preparation of Ni-IL/SiO 2 and its catalytic performance for one-pot sequential synthesis of 2-propylheptanol from n-valeraldehyde |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |