CN118237057A - Supported nickel phosphide-based catalyst with oxygen vacancy regulation - Google Patents
Supported nickel phosphide-based catalyst with oxygen vacancy regulation Download PDFInfo
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- CN118237057A CN118237057A CN202410355470.3A CN202410355470A CN118237057A CN 118237057 A CN118237057 A CN 118237057A CN 202410355470 A CN202410355470 A CN 202410355470A CN 118237057 A CN118237057 A CN 118237057A
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- titanium dioxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 59
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000001301 oxygen Substances 0.000 title claims abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 29
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 title claims abstract description 27
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 100
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims abstract description 37
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000002057 nanoflower Substances 0.000 claims abstract description 27
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 230000001105 regulatory effect Effects 0.000 claims abstract description 15
- GSNUFIFRDBKVIE-UHFFFAOYSA-N 2,5-dimethylfuran Chemical compound CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 37
- 239000002243 precursor Substances 0.000 claims description 21
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 230000007547 defect Effects 0.000 claims description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 238000005470 impregnation Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 150000002815 nickel Chemical class 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-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
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 13
- 239000002028 Biomass Substances 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 239000002551 biofuel Substances 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000007598 dipping method Methods 0.000 abstract 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 abstract 1
- 238000000197 pyrolysis Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 14
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000001132 ultrasonic dispersion Methods 0.000 description 5
- 238000003837 high-temperature calcination Methods 0.000 description 4
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 4
- 238000004435 EPR spectroscopy Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- OXMIDRBAFOEOQT-UHFFFAOYSA-N 2,5-dimethyloxolane Chemical compound CC1CCC(C)O1 OXMIDRBAFOEOQT-UHFFFAOYSA-N 0.000 description 2
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000005291 magnetic effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- KOUDKOMXLMXFKX-UHFFFAOYSA-N sodium oxido(oxo)phosphanium hydrate Chemical compound O.[Na+].[O-][PH+]=O KOUDKOMXLMXFKX-UHFFFAOYSA-N 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005303 weighing 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or 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
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J37/0201—Impregnation
-
- 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
- B01J37/0201—Impregnation
- B01J37/0207—Pretreatment of the support
-
- 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
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/36—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
-
- 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 Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses preparation of a supported nickel phosphide-based catalyst regulated by oxygen vacancies and application of the supported nickel phosphide-based catalyst in preparing biofuel by hydrodeoxygenation of 5-Hydroxymethylfurfural (HMF), and belongs to the technical field of biomass energy chemical industry. The three-dimensional titanium dioxide nanoflower prepared by an acid heating method is used as a carrier, then oxygen vacancies are constructed on the surface of the three-dimensional titanium dioxide nanoflower, and then a dipping method is combined with a gas-phase phosphating method, and hydrogen phosphide gas generated by hypophosphite pyrolysis is used for reduction, so that the supported nickel phosphide-based catalyst is prepared. The active component nickel phosphide in the catalyst prepared by the invention is uniformly dispersed, the structure of carrier oxygen vacancies promotes the formation of more metal active sites, and the adsorption configuration of HMF and the supported nickel phosphide-based catalyst is optimized. The supported catalyst is applied to hydrodeoxygenation reaction of HMF, the conversion rate of HMF is 100% at the reaction temperature of 180 ℃, and the selectivity of target product 2, 5-Dimethylfuran (DMF) is as high as 97%.
Description
Technical Field
The invention belongs to the technical field of biomass energy chemical industry, and particularly relates to preparation of a supported nickel phosphide-based catalyst with oxygen vacancy regulation and control and application of the supported nickel phosphide-based catalyst in hydrodeoxygenation of 5-hydroxymethylfurfural.
Background
Over-exploitation and use of traditional fossil energy causes a series of environmental problems such as atmospheric pollution, greenhouse effect, etc. Biomass is widely regarded as a new renewable energy source which is expected to replace petroleum resources, wherein 5-Hydroxymethylfurfural (HMF), which is described by the U.S. department of energy as one of 12 key platform molecules from biomass, is a tie connecting biomass resources and petrochemical resources, is widely used for producing liquid fuels and high value-added chemicals, and the like, and one of its hydrogenation products, 2, 5-Dimethylfuran (DMF), has an ideal boiling point (93 ℃), high energy density (31.5 MJ ·l -1) and high octane number (119), is considered as a very potential biomass fuel, and can also be used for synthesizing high value polymers such as para-xylene.
At present, noble metal catalysts Pd, pt, ru, etc. (Angew. Chem. Int. Ed. 2021, 60, 6807-6815; ACS Sustin. Chem. Eng. 2020, 8, 8692-8699) are widely used in the catalytic reaction of HMF to prepare DMF, but the high cost of noble metals prevents their large-scale application. While inexpensive non-noble metal Ni, co, cu and Fe based catalysts (appl. Catalyst. B, 2021, 295, 120270-120282; chemsuschem.2017, 10, 1436-1447) often require harsh reaction conditions of high temperature (200-300 ℃), high pressure (4-8 MPa), long time (> 12 h), faced the dilemma of poor catalytic activity and selectivity at low temperatures.
In recent years, metal phosphides have been widely studied in Hydrodesulfurization (HDS), hydrodenitrogenation (HDN) and Hydrodeoxygenation (HDO) reactions due to their good catalytic properties. Studies have shown that Ni 2 P, due to its higher density of surface metal sites and electron density, exhibits excellent hydrodeoxygenation properties and may be a good candidate for selective hydrogenolysis of HMF, but has not been reported previously. In addition, some reducible oxide supports, such as TiO 2, and Co 3O4, etc. (appl. Catalyst. B, 2018, 237, 649-659) are also widely used in hydrodeoxygenation reactions due to the ease of surface oxygen vacancies build. Research shows that the catalyst active site can be regulated, the adsorption configuration and strength of reactant molecules can be optimized, and the like by regulating the morphology of the carrier or constructing rich oxygen vacancies on the surface of the carrier, so that the selectivity of the hydrodeoxygenation product of the catalyst can be regulated. Therefore, the invention utilizes the structure and property characteristics of TiO 2 nanoflower, prepares the high-activity Ni 2P/TiO2 catalyst by constructing and regulating oxygen vacancy defects and adopting a low-temperature gas-phase phosphating method, creatively uses nickel phosphide in the reaction, provides a high-efficiency green way for preparing DMF by catalyzing and reducing HMF under mild conditions, and provides a new idea for green preparation of titanium dioxide supported nickel phosphide-based catalyst for biomass fuel and other chemicals.
Disclosure of Invention
The invention aims to provide a preparation method of a supported nickel phosphide-based catalyst regulated by oxygen vacancies, which can be applied to the preparation of 2, 5-dimethylfuran by high-efficiency hydrodeoxygenation reaction of 5-hydroxymethylfurfural.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the preparation method of the supported nickel phosphide-based catalyst with oxygen vacancy regulation comprises the following steps:
(1) Preparation of titanium dioxide nanoflower:
Tetrabutyl titanate is dispersed in glacial acetic acid solution and reacts at 140 ℃ for 14 h; and cooling to room temperature after the reaction is finished, washing the precipitate by using deionized water, and drying and calcining at room temperature to obtain the three-dimensional titanium dioxide nanoflower.
(2) Preparation of oxygen vacancy defects on the surface of titanium dioxide:
Placing the three-dimensional titanium dioxide nanoflower prepared in the step (1) into a tubular furnace filled with Ar/H 2 mixed gas (95:5, v/v), and carrying out high-temperature reduction at 400-600 ℃ for 2-6H to obtain the titanium dioxide nanoflower with oxygen vacancy defects on the surface.
(3) Preparing a NiO/TiO 2 precursor by an impregnation method:
Taking 0.2-1.5 g of titanium dioxide nanoflower carrier with oxygen vacancy defects on the surface, which is prepared in the step (2), dissolving a certain amount of metal nickel salt with a certain amount of deionized water, performing ultrasonic dispersion to prepare a solution, and impregnating the carrier with the solution for 12-24 h; and (3) drying the precursor in an oven after the impregnation is finished, grinding the precursor uniformly, and calcining the precursor in a muffle furnace at high temperature to obtain the supported NiO/TiO 2 precursor, wherein the nickel load is 10-20: 20 wt percent.
(4) Preparing a Ni 2P/TiO2 catalyst by a low-temperature gas-phase phosphating method:
placing a certain amount of NiO/TiO 2 precursor prepared in the step (3) and sodium hypophosphite (the molar ratio of Ni to P is 1:9-1:3) in an alumina magnetic boat, transferring to a tube furnace, respectively placing the tube furnace at the downstream and upstream of the tube furnace, keeping a certain space distance, calcining under the protection of nitrogen, introducing nitrogen at a flow rate of 30-50 mL/min before heating to discharge air in the tube furnace, and after introducing 15-30min, regulating the gas flow rate to 40-60 mL/min. Heating to 300-350deg.C at a heating rate of 2deg.C/min and maintaining 2-4 h; in the process, nitrogen is continuously introduced until the temperature of the tube furnace naturally drops to the room temperature, and the tube furnace is opened to take out the sample.
The metal nickel salt in the step (3) is at least one of nickel nitrate, nickel chloride, nickel acetate and nickel oxalate.
The supported nickel phosphide-based catalyst prepared by the method can be used for catalytic hydrodeoxygenation of HMF to prepare DMF. The application method specifically comprises the following steps: weighing HMF with certain mass, dissolving the HMF in 40 mL tetrahydrofuran organic solvent, then adding the solution and the supported nickel phosphide-based catalyst into a high-pressure reaction kettle, carrying out hydrogenation reaction for 1-4 h under the conditions of 110-180 ℃ and hydrogen pressure of 1-2 MPa and stirring speed of 600-800 rpm, cooling the solution obtained by the reaction to room temperature and centrifuging.
The mass ratio of the used supported nickel phosphide-based catalyst to HMF is as follows: 0.1-1.
The invention has the beneficial effects that:
(1) The Ni 2P/TiO2 prepared by the method is of a three-dimensional flower-shaped structure, active metal is uniformly dispersed on the surface of the carrier, and full contact between HMF and the active metal is facilitated. The catalyst active site can be regulated, the adsorption configuration, strength and the like of reactant molecules can be optimized, and the selectivity of the hydrodeoxygenation product of the catalyst can be regulated and controlled.
(2) According to the invention, the nickel phosphide catalyst contains more active Ni δ+ species by regulating and controlling the surface defect of the carrier titanium dioxide, and the adsorption configuration, strength and the like of reactant molecules are optimized, so that the selectivity of the hydrodeoxygenation target product of the catalyst is regulated and controlled.
(3) The catalyst prepared by the method has mild conditions and low catalyst cost, and has excellent performance when being applied to HMF low-temperature hydrodeoxygenation.
(4) No research on the nickel phosphide-based catalyst for the reaction exists before, and a certain reference value can be provided for the research on the nickel phosphide-based catalyst for preparing high-added-value chemicals by HMF hydrodeoxygenation to a certain extent.
Drawings
FIG. 1 is an SEM image of a TiO 2 nanoflower carrier prepared in the examples;
FIG. 2 is an EPR diagram of the titania nanoflower carrier obtained by high temperature pretreatment in examples 1-3;
FIG. 3 is an XRD pattern of the supported nickel phosphide-based catalyst prepared in examples 1-3;
FIG. 4 is a graph comparing the performance of the catalysts prepared in examples 1-3 and comparative example 1 for HMF hydrodeoxygenation products.
Detailed Description
In order that the technical contents, features and effects of the present invention may be clearly and clearly illustrated, the present invention will be more specifically and fully described by the following examples, but is not to be construed as limiting the scope of the present invention. The method of the invention is a conventional method in the art unless specifically stated otherwise.
Example 1
(1) Preparation of titanium dioxide nanoflower:
Slowly and dropwise dripping tetrabutyl titanate 3mL into a glacial acetic acid 60 mL solution under the condition of continuous stirring, stirring for 10min, transferring the obtained mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and reacting at 140 ℃ for 14 h; cooling to room temperature after the reaction is finished, removing supernatant liquid by a suction filtration mode, washing the obtained white precipitate with deionized water until the precipitate is neutral, drying the precipitate at room temperature, grinding the precipitate into a uniform powdery sample, and placing the uniform powdery sample in a muffle furnace to calcine 1h at 400 ℃ at a heating rate of 2 ℃/min to obtain the anatase type three-dimensional titanium dioxide nanoflower carrier.
Fig. 1 is an SEM image of a titania support, which is a three-dimensional flower-like structure of stacked adjacent nanoplatelets, and is porous and fluffy.
(2) Preparation of oxygen vacancy defects on the surface of titanium dioxide:
Placing the three-dimensional titanium dioxide nanoflower prepared in the step (1) into a tube furnace filled with Ar/H 2 mixed gas (95:5, v/v), and reducing at a high temperature of 400 ℃ at a heating rate of 5 ℃/min for 2: 2H to obtain the titanium dioxide nanoflower carrier with oxygen vacancy defects on the surface.
(3) Preparing a NiO/TiO 2 -400 precursor by an impregnation method:
taking a titanium dioxide nanoflower carrier with oxygen vacancy defects on the surface, which is prepared in the step (2) of 1g by pre-reduction at 400 ℃, dissolving 1.2387 g nickel nitrate hexahydrate with 3mL deionized water, performing ultrasonic dispersion to prepare a solution, and impregnating the carrier with the solution for 24 h; drying the mixture in an oven at 80 ℃ for 12 h after the impregnation is finished, grinding the mixture uniformly, and then placing the mixture in a muffle furnace for high-temperature calcination at 450 ℃ for 4h at a heating rate of 2 ℃/min to obtain the supported NiO/TiO 2 -400 precursor, wherein the nickel load is 20 wt%.
(4) Preparing Ni 2P/TiO2 -400 catalyst by low-temperature gas-phase phosphating method:
and (3) placing the 0.5 g NiO/TiO 2 -400 precursor prepared in the step (3) and 1.6254 g sodium hypophosphite monohydrate in an alumina magnetic boat, transferring the precursor to a tube furnace, respectively placing the precursor at the downstream and upstream of the tube furnace, keeping a certain space distance, calcining under the protection of nitrogen, introducing nitrogen at a flow rate of 30 mL/min before heating to discharge air in the tube furnace, and after introducing for 30min, regulating the gas flow rate to 60 mL/min. Heating to 300 ℃ at a heating rate of 5 ℃/min and maintaining 2 h; in the process, nitrogen is continuously introduced until the temperature of the tube furnace naturally drops to the room temperature, and the tube furnace is opened to take out a sample, thus obtaining the Ni 2P/TiO2 -400 catalyst.
(5) Catalytic hydrodeoxygenation of HMF:
0.2000 g of HMF was weighed and dissolved in 40 mL of tetrahydrofuran organic solvent, then the solution and 0.1000 g Ni 2P/TiO2 -400 of catalyst were added into a high-pressure reaction kettle, hydrogenation reaction was carried out for 3h under the conditions of 180 ℃ and hydrogen pressure of 2 MPa and stirring rate of 600 rpm, and the solution obtained by the reaction was cooled to room temperature and centrifuged. The conversion rate of the Ni 2P/TiO2 -400 catalyst to HMF under the condition is 100% by using a gas chromatograph-mass spectrometer (GC-MS), and the selectivity of the target product DMF is 92%.
Example 2
The titania nanoflower carrier was prepared in the same manner as in steps (1) and (2) of example 1.
(3) Preparing a NiO/TiO 2 -500 precursor by an impregnation method:
Taking a titanium dioxide nanoflower carrier with oxygen vacancy defects on the surface, which is prepared in the step (2) of 1 g by pre-reduction at 500 ℃, dissolving 1.2387 g nickel nitrate hexahydrate with 2.6 mL deionized water, performing ultrasonic dispersion to prepare a solution, and impregnating the carrier with the solution for 24 h; drying the mixture in an oven at 80 ℃ for 12 h after the impregnation is finished, grinding the mixture uniformly, and then placing the mixture in a muffle furnace for high-temperature calcination at 450 ℃ for 4h at a heating rate of 2 ℃/min to obtain the supported NiO/TiO 2 -500 precursor, wherein the nickel load is 20 wt%.
Ni 2P/TiO2 -500 catalyst was prepared in the same manner as in step (4) of example 1.
(5) Catalytic hydrodeoxygenation of HMF:
0.2000 g of HMF was weighed and dissolved in 40 mL of tetrahydrofuran organic solvent, then the solution and 0.1000 g Ni 2P/TiO2 -500 of catalyst were added into a high-pressure reaction kettle, hydrogenation reaction was carried out for 3h under the conditions of 180 ℃ and hydrogen pressure of 2 MPa and stirring rate of 600 rpm, and the solution obtained by the reaction was cooled to room temperature and centrifuged. The conversion rate of the Ni 2P/TiO2 -500 catalyst to HMF under the condition is 100% by using a gas chromatograph-mass spectrometer (GC-MS), and the selectivity of the target product DMF is 94%.
Example 3
The titania nanoflower carrier was prepared in the same manner as in steps (1) and (2) of example 1.
Fig. 2 is an electron paramagnetic resonance chart (EPR) of the titania nanoflower carrier obtained by high temperature pretreatment of examples 1-3 (2), showing that the carrier samples each show a signal peak concerning oxygen vacancies at g=2.007, and that the signal peak intensity increases with increasing treatment temperature and has a relative maximum at 600 ℃, indicating that the oxygen vacancy concentration increases with increasing reduction temperature and reaches a maximum at 600 ℃.
(3) Preparing a NiO/TiO 2 -600 precursor by an impregnation method:
Taking a titanium dioxide nanoflower carrier with oxygen vacancy defects on the surface, which is prepared in the step (2) of 1 g by pre-reduction at 600 ℃, dissolving 1.2387 g nickel nitrate hexahydrate with 2.1 mL deionized water, performing ultrasonic dispersion to prepare a solution, and impregnating the carrier with the solution for 24 h; drying the mixture in an oven at 80 ℃ for 12 h after the impregnation is finished, grinding the mixture uniformly, and then placing the mixture in a muffle furnace for high-temperature calcination at 450 ℃ for 4h at a heating rate of 2 ℃/min to obtain the supported NiO/TiO 2 -600 precursor, wherein the nickel loading amount is 20 wt%.
Ni 2P/TiO2 -600 catalyst was prepared in the same manner as in step (4) of example 1.
FIG. 3 is an X-ray diffraction pattern (XRD) of the supported nickel phosphide-based catalyst prepared in examples 1-3 (4), showing that the catalyst samples each contain characteristic diffraction peaks of Ni 2 P and anatase TiO 2, demonstrating successful preparation of the catalyst.
(5) Catalytic hydrodeoxygenation of HMF:
0.2000 g of HMF was weighed and dissolved in 40 mL of tetrahydrofuran organic solvent, then the solution and 0.1000 of g Ni 2P/TiO2 -600 catalyst were added into a high-pressure reaction kettle, hydrogenation reaction was carried out for 3h under the conditions of 180 ℃ and hydrogen pressure of 2 MPa and stirring rate of 600 rpm, and the solution obtained by the reaction was cooled to room temperature and centrifuged. The conversion rate of the Ni 2P/TiO2 -600 catalyst to HMF under the condition is 100% by using a gas chromatograph-mass spectrometer (GC-MS), and the selectivity of the target product DMF is 97%.
Comparative example 1
The titania nanoflower support was prepared in the same manner as in step (1) of example 1.
(2) Preparation of NiO/TiO 2 -air precursor by impregnation method:
Taking the titanium dioxide nanoflower carrier prepared in the step (1) of 1 g without pre-reduction, dissolving 1.2387 g nickel nitrate hexahydrate with 3.1 mL deionized water, performing ultrasonic dispersion to prepare a solution, and impregnating the carrier with the solution for 24 h; drying the mixture in an oven at 80 ℃ for 12 h after the impregnation is finished, grinding the mixture uniformly, and then placing the mixture in a muffle furnace for high-temperature calcination at 450 ℃ for 4 h at a heating rate of 2 ℃/min to obtain the supported NiO/TiO 2 -air precursor, wherein the nickel loading amount is 20: 20 wt percent.
The Ni 2P/TiO2 -air catalyst was prepared in the same manner as in step (4) of example 1.
(4) Catalytic hydrodeoxygenation of HMF:
0.2000 g of HMF was weighed and dissolved in 40 mL of tetrahydrofuran organic solvent, then the solution and 0.1000 of g Ni 2P/TiO2 -air catalyst were added into a high-pressure reaction kettle, hydrogenation reaction was carried out for 3 h under the conditions of 180 ℃ and hydrogen pressure of 2 MPa and stirring rate of 600 rpm, and the solution obtained by the reaction was cooled to room temperature and centrifuged. The conversion rate of the Ni 2P/TiO2 -air catalyst to HMF under the condition is 100% by using a gas chromatograph-mass spectrometer (GC-MS), and the selectivity of the target product DMF is 80%.
FIG. 4 is a graph comparing the performance of the examples and comparative examples on HMF hydrodeoxygenation products under the same conditions. It can be seen from the figure that the catalyst can completely convert HMF under the reaction conditions of 180 ℃,2 MPa H 2 pressure and 3h, but the Ni 2 P-supported catalyst Ni 2P/TiO2 -air without the pretreatment of the carrier in a reducing atmosphere has poor selectivity to DMF, only 80 percent, and the product contains higher content of excessive hydrogenation products such as 2, 5-dimethyl tetrahydrofuran, 2, 5-hexanedione and some other condensation products. The oxygen vacancy content is increased along with the pretreatment of the carrier, the selectivity of the target product 2, 5-dimethylfuran is greatly improved, and the selectivity of the DMF product is improved to 97% under the condition that the conversion rate is kept optimal along with the temperature rise from 400 ℃ to 600 ℃.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (10)
1. A preparation method of a supported nickel phosphide-based catalyst regulated by oxygen vacancies is characterized by comprising the following steps: the method comprises the following steps:
(1) Preparation of titanium dioxide nanoflower:
Tetrabutyl titanate is dispersed in glacial acetic acid solution and reacts at 140 ℃ for 14 h; cooling to room temperature after the reaction is finished, washing the precipitate by using deionized water, and drying and calcining at room temperature to obtain the three-dimensional titanium dioxide nanoflower;
(2) Preparation of oxygen vacancy defects on the surface of titanium dioxide:
Reducing the three-dimensional titanium dioxide nanoflower prepared in the step (1) in Ar/H 2 mixed gas at high temperature to prepare the titanium dioxide nanoflower with oxygen vacancy defects on the surface;
(3) Preparing a NiO/TiO 2 precursor by an impregnation method:
Immersing 12-24 h of titanium dioxide nanoflower with oxygen vacancy defects on the surface prepared in the step (2) as a carrier in a metal nickel salt solution, drying, grinding uniformly, and calcining at a high temperature to prepare a supported NiO/TiO 2 precursor;
(4) Preparing a Ni 2P/TiO2 catalyst by a low-temperature gas-phase phosphating method:
Calcining the NiO/TiO 2 precursor prepared in the step (3) and sodium hypophosphite under the protection of nitrogen to prepare the oxygen vacancy regulated supported nickel phosphide-based catalyst.
2. The method of manufacturing according to claim 1, characterized in that: and (3) the volume ratio of Ar to H 2 in the Ar/H 2 mixed gas in the step (2) is 95:5.
3. The method of manufacturing according to claim 1, characterized in that: the high temperature reduction in the step (2) is carried out at a temperature of 400-600 ℃ for a time of 2-6 h.
4. The method of manufacturing according to claim 1, characterized in that: the loading of metallic nickel in the NiO/TiO 2 precursor described in step (3) is 10-20 wt%.
5. The method of manufacturing according to claim 1, characterized in that: the metal nickel salt in the step (3) is at least one of nickel nitrate, nickel chloride, nickel acetate and nickel oxalate.
6. The method of manufacturing according to claim 1, characterized in that: the molar ratio of nickel to phosphorus in the step (4) is 1:9-1:3; the calcination temperature is 300-350 ℃ and the time is 2-4 h.
7. An oxygen vacancy-regulated supported nickel phosphide-based catalyst prepared by the method of any one of claims 1-6.
8. Use of the oxygen vacancy-controlled supported nickel phosphide-based catalyst prepared by the method of any one of claims 1-6 in the hydrodeoxygenation of 5-hydroxymethylfurfural to produce 2, 5-dimethylfuran.
9. The use according to claim 8, characterized in that: dissolving 5-hydroxymethylfurfural in an organic solvent, adding a supported nickel phosphide-based catalyst, carrying out hydrogenation reaction on the mixture at 110-180 ℃ under the conditions that the hydrogen pressure is 0.1-2 MPa and the stirring rate is 600-800 rpm, cooling the mixture to room temperature and centrifuging the mixture to obtain 2, 5-dimethylfuran.
10. The use according to claim 9, characterized in that: the mass ratio of the supported nickel phosphide-based catalyst to the 5-hydroxymethylfurfural is 0.1-1:1, a step of; the organic solvent is one or more of tetrahydrofuran, n-butanol, methyl tetrahydrofuran and methyl isobutyl ketone.
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