CN113101956A - Preparation of high-dispersion load type Ni by one-step heat treatment2Method for preparing P catalyst - Google Patents
Preparation of high-dispersion load type Ni by one-step heat treatment2Method for preparing P catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000006185 dispersion Substances 0.000 title claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 104
- 239000002243 precursor Substances 0.000 claims abstract description 74
- 238000010438 heat treatment Methods 0.000 claims abstract description 71
- 238000000034 method Methods 0.000 claims abstract description 54
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000012298 atmosphere Substances 0.000 claims abstract description 28
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000011144 upstream manufacturing Methods 0.000 claims abstract description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 14
- 239000011574 phosphorus Substances 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 44
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 40
- FMQXRRZIHURSLR-UHFFFAOYSA-N dioxido(oxo)silane;nickel(2+) Chemical compound [Ni+2].[O-][Si]([O-])=O FMQXRRZIHURSLR-UHFFFAOYSA-N 0.000 claims description 39
- 229910052681 coesite Inorganic materials 0.000 claims description 37
- 229910052906 cristobalite Inorganic materials 0.000 claims description 37
- 239000000377 silicon dioxide Substances 0.000 claims description 37
- 229910052682 stishovite Inorganic materials 0.000 claims description 37
- 229910052905 tridymite Inorganic materials 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 29
- 239000001257 hydrogen Substances 0.000 claims description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims description 29
- 238000001816 cooling Methods 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 26
- 239000011259 mixed solution Substances 0.000 claims description 26
- 239000000725 suspension Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000000706 filtrate Substances 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 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 22
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 22
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 17
- 239000004202 carbamide Substances 0.000 claims description 17
- 229910017604 nitric acid Inorganic materials 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 14
- 230000007935 neutral effect Effects 0.000 claims description 13
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000000967 suction filtration Methods 0.000 claims description 11
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 8
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 8
- 229940078494 nickel acetate Drugs 0.000 claims description 8
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 8
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 8
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 7
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 7
- GJYJYFHBOBUTBY-UHFFFAOYSA-N alpha-camphorene Chemical compound CC(C)=CCCC(=C)C1CCC(CCC=C(C)C)=CC1 GJYJYFHBOBUTBY-UHFFFAOYSA-N 0.000 claims description 5
- 150000002815 nickel Chemical class 0.000 claims description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 10
- 239000002245 particle Substances 0.000 description 12
- 238000005303 weighing Methods 0.000 description 12
- 230000008021 deposition Effects 0.000 description 11
- 238000001556 precipitation Methods 0.000 description 11
- 238000001228 spectrum Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- DGUACJDPTAAFMP-UHFFFAOYSA-N 1,9-dimethyldibenzo[2,1-b:1',2'-d]thiophene Natural products S1C2=CC=CC(C)=C2C2=C1C=CC=C2C DGUACJDPTAAFMP-UHFFFAOYSA-N 0.000 description 3
- MYAQZIAVOLKEGW-UHFFFAOYSA-N 4,6-dimethyldibenzothiophene Chemical compound S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—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
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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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
- 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
- B01J37/031—Precipitation
- B01J37/035—Precipitation on carriers
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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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
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/28—Phosphorising
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/12—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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Abstract
The invention discloses a method for preparing high-dispersion load type Ni by one-step heat treatment2Method of P catalyst, stepThe following were used: placing a nickel source and a phosphorus source in a tubular furnace reactor in an isolated manner, wherein the phosphorus source is positioned at the upstream and is phosphated for 2 hours in an oxygen-free atmosphere to obtain a load type nickel phosphide precursor; putting the load type phosphide precursor into a tubular furnace reactor, and carrying out heat treatment for 2h in an oxygen-free atmosphere to obtain Ni2And (3) a P catalyst. The preparation method adopted by the invention has simple steps, mild conditions and stable nickel phosphide precursor, and only one-step heat treatment is needed to obtain Ni2The P catalyst has high activity and good industrial application prospect.
Description
Technical Field
The invention relates to the field of preparation of nickel phosphide catalysts, in particular to simple, feasible, high-stability and high-activity Ni2A preparation method of the P catalyst.
Background
With Ni2P, MoP and WP, etc. has wide application foreground in hydrorefining field due to its high activity and high stability. Temperature Programmed Reduction (TPR) is currently the most common method for preparing phosphides. Preparation of Ni by TPR method2P, the temperature rise rate is slow (1 ℃/min), the reduction temperature is high (550-.
Disclosure of Invention
The present invention provides a novel Ni2The catalyst precursor prepared by the method has good stability, and the catalyst precursor can be prepared into a high-activity catalyst through simple operation, so that the preparation method has good industrial application prospect.
In order to achieve the aim, the invention provides a method for preparing high-dispersion supported Ni by one-step heat treatment2A process for the preparation of a P catalyst comprising the steps of: s1, placing a nickel source and a phosphorus source in a tubular furnace reactor in an isolated manner, wherein the phosphorus source is located at the upstream and is phosphated for 2 hours in an oxygen-free atmosphere to obtain a supported nickel phosphide precursor; s2, placing the load type nickel phosphide precursor in a tubular furnace reactor, and carrying out heat treatment for 2h in an oxygen-free atmosphere to obtain Ni2And (3) a P catalyst.
Wherein, the oxygen-free atmosphere can be nitrogen atmosphere or hydrogen atmosphere, inert gas atmosphere or other atmosphere.
In addition, the preparation of the nickel source in step S1: the carrier is SiO2MCM-41, SBA-15, Silicalite-1 or TS-1; the nickel salt is nickel nitrate, nickel sulfate, nickel acetate or nickel chloride. In step S1, the phosphorus source is sodium hypophosphite, ammonium hypophosphite, red phosphorus or phosphine. However, the carrier, nickel salt and phosphorus source are not limited thereto, and any carrier or nickel salt that can implement the present invention is applicable.
Preferably, the phosphating temperature of the step S1 is 300-500 ℃; step S2 the heat treatment temperature is 300-.
In a preferred mode, the nickel source in step S1 is layered nickel silicate. The preparation method comprises the following steps: dissolving 2.62g of nickel nitrate in deionized water to prepare a nickel nitrate solution, and taking 2.40g of SiO2Adding the carrier into 4/5 the nickel nitrate solution, heating to 70 ℃ under continuous stirring to form a suspension A, weighing 7.56g of urea and 0.56g of concentrated nitric acid, adding into the rest 1/5 nickel nitrate solution to form a mixed solution B, dropwise adding the mixed solution B into the suspension A at the temperature of 70 ℃ at the speed of 2 drops/second, heating to 90 ℃ after dropwise adding, and reacting for 4 hours. And after the reaction is finished, carrying out suction filtration on the liquid, washing the liquid with deionized water until the filtrate is neutral, and drying the filtrate in an oven at 110 ℃ for 12 hours to obtain the layered nickel silicate. Wherein the nickel nitrate can be replaced by nickel sulfate, nickel acetate and nickel chloride.
In an optimal mode, the supported Ni with high activity is stable2The preparation method of the P catalyst comprises the following steps: respectively placing 0.50g of layered nickel silicate and 0.72g of sodium hypophosphite in a tubular furnace reactor, wherein the sodium hypophosphite is positioned at the upstream, phosphorizing at 350 ℃ for 2 hours in a nitrogen atmosphere at the nitrogen flow rate of 10mL/min, and cooling to room temperature to obtain a load-type nickel phosphide precursor; placing the load type phosphide precursor in a tubular furnace reactor, carrying out heat treatment for 2h at 400 ℃ in hydrogen atmosphere with the hydrogen flow rate of 150mL/min, and cooling to room temperature to obtain Ni2P/SiO2A catalyst. Here, SiO2As a carrierThe supported catalyst is supported on the carrier.
Compared with the prior art, the invention has the beneficial effects that:
1. ni preparation by the invention2The P catalyst has lower phosphorization temperature and heat treatment temperature, so that the agglomeration of particles in the catalyst preparation process is weakened, and the Ni content is improved2The dispersion of P particles is high, so that Ni2Ni in P catalyst2The particle size of P is small, the reaction activity is high, and the stability is good.
2. The supported nickel phosphide precursor prepared by the method has high stability, and Ni obtained by heat treatment after being exposed in air for 6 months2The P catalyst still shows higher reaction activity in hydrogenation reaction.
The invention discloses a stable high-activity load type Ni2The preparation method of the P catalyst comprises the following steps: placing a nickel source and a phosphorus source in a tubular furnace reactor in an isolated manner, wherein the phosphorus source is positioned at the upstream and is phosphated for 2 hours in an oxygen-free atmosphere to obtain a load type nickel phosphide precursor; putting the load type phosphide precursor into a tubular furnace reactor, and carrying out heat treatment for 2h in an oxygen-free atmosphere to obtain Ni2And (3) a P catalyst. The preparation method adopted by the invention has simple steps, mild conditions and stable nickel phosphide precursor, and only one-step heat treatment is needed to obtain Ni2The P catalyst has high activity and good industrial application prospect.
Drawings
FIG. 1 shows supported Ni on different carriers2XRD spectrum of P catalyst.
FIG. 2 shows Ni in example 12P/SiO2TEM photograph of the catalyst.
FIG. 3 shows Ni in FIG. 22P/SiO2Particle size distribution of the catalyst.
FIG. 4 shows Ni in FIG. 22P/SiO2Lattice parameter diagram of the catalyst.
FIG. 5 is Ni2P/SiO2Experimental results on the reaction stability of the catalyst at 340 ℃.
Detailed Description
The present invention is further illustrated below with reference to experimental subjects, but the scope of the present invention is not limited thereto.
Example 1
Preparing layered nickel silicate by deposition precipitation method, preparing supported nickel phosphide precursor by phosphating method, and preparing Ni by heat treatment method2P/SiO2A catalyst.
Dissolving 2.62g of nickel nitrate in deionized water to prepare a nickel nitrate solution, and taking 2.40g of SiO2Adding the carrier into 4/5 the nickel nitrate solution, heating to 70 ℃ under continuous stirring to form a suspension A, weighing 7.56g of urea and 0.56g of concentrated nitric acid, adding into the rest 1/5 nickel nitrate solution to form a mixed solution B, dropwise adding the mixed solution B into the suspension A at the temperature of 70 ℃ at the speed of 2 drops/second, heating to 90 ℃ after dropwise adding, and reacting for 4 hours. After the reaction is finished, carrying out suction filtration on the liquid, washing the liquid with deionized water until the filtrate is neutral, and drying the filtrate in an oven at 110 ℃ for 12 hours to prepare a layered nickel silicate precursor; respectively placing 0.50g of layered nickel silicate precursor and 0.72g of sodium hypophosphite in a tubular furnace reactor, wherein the sodium hypophosphite is positioned at the upstream, phosphorizing at 350 ℃ for 2h under a nitrogen atmosphere at the nitrogen flow rate of 10mL/min, and cooling to room temperature to obtain a supported nickel phosphide precursor; placing the load type phosphide precursor in a tubular furnace reactor, carrying out heat treatment for 2h at 400 ℃ in hydrogen atmosphere with the hydrogen flow rate of 150mL/min, and cooling to room temperature to obtain Ni2P/SiO2A catalyst.
XRD spectra and Ni of the comparative catalysts2Standard spectrum of P (PDF #03-0953) (FIG. 1), without Ni2The characteristic peak of P appears, which indicates that the prepared catalyst Ni2The P particles are smaller. From Ni2P/SiO2The small particles, which are uniformly dispersed, can be seen in the TEM image of the catalyst (FIG. 2) and their lattice parameters are assigned to Ni2Crystal plane (111) of P (FIG. 3), catalyst particle size distribution diagram showing Ni2The average particle size of P was 3.9nm (FIG. 4).
Example 2
Preparing layered nickel silicate by deposition precipitation method, preparing supported nickel phosphide precursor by phosphating method, and preparing Ni by heat treatment method2P/MCM-41 catalyst.
Dissolving 2.62g of nickel nitrate in deionized water to prepare a nickel nitrate solution, adding 4/5 g of MCM-41 carrier into the nickel nitrate solution, heating to 70 ℃ under continuous stirring to form a suspension A, weighing 7.56g of urea and 0.56g of concentrated nitric acid, adding the urea and the concentrated nitric acid into the rest 1/5 nickel nitrate solution to form a mixed solution B, dropwise adding the mixed solution B into the suspension A at the temperature of 70 ℃ at the speed of 2 drops/second, heating to 90 ℃ after dropwise adding, and reacting for 4 hours. After the reaction is finished, carrying out suction filtration on the liquid, washing the liquid with deionized water until the filtrate is neutral, and drying the filtrate in an oven at 110 ℃ for 12 hours to prepare a layered nickel silicate precursor; respectively placing 0.50g of layered nickel silicate precursor and 0.72g of sodium hypophosphite in a tubular furnace reactor, wherein the sodium hypophosphite is positioned at the upstream, phosphorizing at 350 ℃ for 2h under a nitrogen atmosphere at the nitrogen flow rate of 10mL/min, and cooling to room temperature to obtain a supported nickel phosphide precursor; placing the load type phosphide precursor in a tubular furnace reactor, carrying out heat treatment for 2h at 400 ℃ in hydrogen atmosphere with the hydrogen flow rate of 150mL/min, and cooling to room temperature to obtain Ni2P/MCM-41 catalyst.
XRD spectra and Ni of the comparative catalysts2Standard spectrum of P (PDF #03-0953) (FIG. 1), with obvious Ni2The characteristic peak of P appears, and Ni is calculated by using the Sherle formula2The average particle size of P was 12.6 nm.
Example 3
Preparing layered nickel silicate by deposition precipitation method, preparing supported nickel phosphide precursor by phosphating method, and preparing Ni by heat treatment method2P/SBA-15 catalyst.
Dissolving 2.62g of nickel nitrate in deionized water to prepare a nickel nitrate solution, adding 4/5 g of SBA-15 carrier into the nickel nitrate solution, heating to 70 ℃ under continuous stirring to form a suspension A, weighing 7.56g of urea and 0.56g of concentrated nitric acid, adding the urea and the concentrated nitric acid into the rest 1/5 nickel nitrate solution to form a mixed solution B, dropwise adding the mixed solution B into the suspension A at the temperature of 70 ℃ at the speed of 2 drops/second, heating to 90 ℃ after dropwise adding, and reacting for 4 hours. After the reaction is finished, carrying out suction filtration on the liquid, washing the liquid with deionized water until the filtrate is neutral, and drying the filtrate in an oven at 110 ℃ for 12 hours to prepare a layered nickel silicate precursor; 0.50g of layered nickel silicate precursor and 0.72g of sodium hypophosphite were placed in a tube furnace reactor, respectively, whereinThe sodium phosphite is positioned at the upstream, phosphorized for 2h at 350 ℃ in a nitrogen atmosphere, the nitrogen flow rate is 10mL/min, and cooled to room temperature to obtain a load type nickel phosphide precursor; placing the load type phosphide precursor in a tubular furnace reactor, carrying out heat treatment for 2h at 400 ℃ in hydrogen atmosphere with the hydrogen flow rate of 150mL/min, and cooling to room temperature to obtain Ni2P/SBA-15 catalyst.
XRD spectra and Ni of the comparative catalysts2Standard spectrum of P (PDF #03-0953) (FIG. 1), with obvious Ni2The characteristic peak of P appears, and Ni is calculated by using the Sherle formula2The average particle size of P was 10.0 nm.
Example 4
Preparing layered nickel silicate by deposition precipitation method, preparing supported nickel phosphide precursor by phosphating method, and preparing Ni by heat treatment method2P/Silicalite-1 catalyst.
Dissolving 2.62g of nickel nitrate in deionized water to prepare a nickel nitrate solution, adding 4/5 g of Silicalite-1 carrier into the nickel nitrate solution, heating to 70 ℃ under continuous stirring to form a suspension A, weighing 7.56g of urea and 0.56g of concentrated nitric acid, adding the urea and the concentrated nitric acid into the rest 1/5 nickel nitrate solution to form a mixed solution B, dropwise adding the mixed solution B into the suspension A at the temperature of 70 ℃ at the speed of 2 drops/second, heating to 90 ℃ after dropwise adding, and reacting for 4 hours. After the reaction is finished, carrying out suction filtration on the liquid, washing the liquid with deionized water until the filtrate is neutral, and drying the filtrate in an oven at 110 ℃ for 12 hours to prepare a layered nickel silicate precursor; respectively placing 0.50g of layered nickel silicate precursor and 0.72g of sodium hypophosphite in a tubular furnace reactor, wherein the sodium hypophosphite is positioned at the upstream, phosphorizing at 350 ℃ for 2h under a nitrogen atmosphere at the nitrogen flow rate of 10mL/min, and cooling to room temperature to obtain a supported nickel phosphide precursor; placing the load type phosphide precursor in a tubular furnace reactor, carrying out heat treatment for 2h at 400 ℃ in hydrogen atmosphere with the hydrogen flow rate of 150mL/min, and cooling to room temperature to obtain Ni2P/Silicalite-1 catalyst.
XRD spectra and Ni of the comparative catalysts2Standard spectrum of P (PDF #03-0953) (FIG. 1), with obvious Ni2The characteristic peak of P appears, and Ni is calculated by using the Sherle formula2The average particle size of P was 26.5 nm.
Example 5
Preparing layered nickel silicate by deposition precipitation method, preparing supported nickel phosphide precursor by phosphating method, and preparing Ni by heat treatment method2P/TS-1 catalyst.
Dissolving 2.62g of nickel nitrate in deionized water to prepare a nickel nitrate solution, adding 4/5 g of TS-1 carrier into the nickel nitrate solution, heating to 70 ℃ under continuous stirring to form a suspension A, weighing 7.56g of urea and 0.56g of concentrated nitric acid, adding the urea and the concentrated nitric acid into the rest 1/5 nickel nitrate solution to form a mixed solution B, dropwise adding the mixed solution B into the suspension A at the speed of 2 drops/second at 70 ℃, heating to 90 ℃ after dropwise adding, and reacting for 4 hours. After the reaction is finished, carrying out suction filtration on the liquid, washing the liquid with deionized water until the filtrate is neutral, and drying the filtrate in an oven at 110 ℃ for 12 hours to prepare a layered nickel silicate precursor; respectively placing 0.50g of layered nickel silicate precursor and 0.72g of sodium hypophosphite in a tubular furnace reactor, wherein the sodium hypophosphite is positioned at the upstream, phosphorizing at 350 ℃ for 2h under a nitrogen atmosphere at the nitrogen flow rate of 10mL/min, and cooling to room temperature to obtain a supported nickel phosphide precursor; placing the load type phosphide precursor in a tubular furnace reactor, carrying out heat treatment for 2h at 400 ℃ in hydrogen atmosphere with the hydrogen flow rate of 150mL/min, and cooling to room temperature to obtain Ni2P/TS-1 catalyst.
XRD spectra and Ni of the comparative catalysts2Standard spectrum of P (PDF #03-0953) (FIG. 1), with obvious Ni2The characteristic peak of P appears, and Ni is calculated by using the Sherle formula2The average particle size of P was 16.2 nm.
Example 6
Preparing layered nickel silicate by deposition precipitation method, preparing supported nickel phosphide precursor by phosphating method, and preparing Ni by heat treatment method2P/SiO2A catalyst.
Dissolving 2.37g of nickel sulfate in deionized water to prepare a nickel sulfate solution, and taking 2.40g of SiO2Adding the carrier into 4/5 the nickel sulfate solution, heating to 70 ℃ under continuous stirring to form a suspension A, weighing 7.56g of urea and 0.56g of concentrated nitric acid, adding into the rest 1/5 nickel sulfate solution to form a mixed solution B, dropwise adding the mixed solution B into the suspension A at the temperature of 70 ℃ at the speed of 2 drops/second, heating to 90 ℃ after dropwise adding, and reacting for 4 hours. After the reaction is finished, the liquid is filtered,washing with deionized water until the filtrate is neutral, and drying in an oven at 110 deg.C for 12h to obtain layered nickel silicate precursor; respectively placing 0.50g of layered nickel silicate precursor and 0.72g of sodium hypophosphite in a tubular furnace reactor, wherein the sodium hypophosphite is positioned at the upstream, phosphorizing at 350 ℃ for 2h under a nitrogen atmosphere at the nitrogen flow rate of 10mL/min, and cooling to room temperature to obtain a supported nickel phosphide precursor; placing the load type phosphide precursor in a tubular furnace reactor, carrying out heat treatment for 2h at 400 ℃ in hydrogen atmosphere with the hydrogen flow rate of 150mL/min, and cooling to room temperature to obtain Ni2P/SiO2A catalyst.
Example 7
Preparing layered nickel silicate by deposition precipitation method, preparing supported nickel phosphide precursor by phosphating method, and preparing Ni by heat treatment method2P/SiO2A catalyst.
Dissolving 2.24g of nickel acetate in deionized water to prepare a nickel acetate solution, and taking 2.40g of SiO2Adding the carrier into 4/5 the nickel acetate solution, heating to 70 ℃ under continuous stirring to form a suspension A, weighing 7.56g of urea and 0.56g of concentrated nitric acid, adding into the rest 1/5 nickel acetate solution to form a mixed solution B, dropwise adding the mixed solution B into the suspension A at the temperature of 70 ℃ at the speed of 2 drops/second, heating to 90 ℃ after dropwise adding, and reacting for 4 hours. After the reaction is finished, carrying out suction filtration on the liquid, washing the liquid with deionized water until the filtrate is neutral, and drying the filtrate in an oven at 110 ℃ for 12 hours to prepare a layered nickel silicate precursor; respectively placing 0.50g of layered nickel silicate precursor and 0.72g of sodium hypophosphite in a tubular furnace reactor, wherein the sodium hypophosphite is positioned at the upstream, phosphorizing at 350 ℃ for 2h under a nitrogen atmosphere at the nitrogen flow rate of 10mL/min, and cooling to room temperature to obtain a supported nickel phosphide precursor; placing the load type phosphide precursor in a tubular furnace reactor, carrying out heat treatment for 2h at 400 ℃ in hydrogen atmosphere with the hydrogen flow rate of 150mL/min, and cooling to room temperature to obtain Ni2P/SiO2A catalyst.
Example 8
Preparing layered nickel silicate by deposition precipitation method, preparing supported nickel phosphide precursor by phosphating method, and preparing Ni by heat treatment method2P/SiO2A catalyst.
2.14g of nickel chloride is dissolved in deionized water to prepare chlorideNickel solution, 2.40g SiO2Adding the carrier into 4/5 the nickel chloride solution, heating to 70 ℃ under continuous stirring to form a suspension A, weighing 7.56g of urea and 0.56g of concentrated nitric acid, adding into the rest 1/5 nickel chloride solution to form a mixed solution B, dropwise adding the mixed solution B into the suspension A at the temperature of 70 ℃ at the speed of 2 drops/second, heating to 90 ℃ after dropwise adding, and reacting for 4 hours. After the reaction is finished, carrying out suction filtration on the liquid, washing the liquid with deionized water until the filtrate is neutral, and drying the filtrate in an oven at 110 ℃ for 12 hours to prepare a layered nickel silicate precursor; respectively placing 0.50g of layered nickel silicate precursor and 0.72g of sodium hypophosphite in a tubular furnace reactor, wherein the sodium hypophosphite is positioned at the upstream, phosphorizing at 350 ℃ for 2h under a nitrogen atmosphere at the nitrogen flow rate of 10mL/min, and cooling to room temperature to obtain a supported nickel phosphide precursor; placing the load type phosphide precursor in a tubular furnace reactor, carrying out heat treatment for 2h at 400 ℃ in hydrogen atmosphere with the hydrogen flow rate of 150mL/min, and cooling to room temperature to obtain Ni2P/SiO2A catalyst.
Example 9
Preparing layered nickel silicate by deposition precipitation method, preparing supported nickel phosphide precursor by phosphating method, and preparing Ni by heat treatment method2P/SiO2A catalyst.
Dissolving 2.62g of nickel nitrate in deionized water to prepare a nickel nitrate solution, and taking 2.40g of SiO2Adding the carrier into 4/5 the nickel nitrate solution, heating to 70 ℃ under continuous stirring to form a suspension A, weighing 7.56g of urea and 0.56g of concentrated nitric acid, adding into the rest 1/5 nickel nitrate solution to form a mixed solution B, dropwise adding the mixed solution B into the suspension A at the temperature of 70 ℃ at the speed of 2 drops/second, heating to 90 ℃ after dropwise adding, and reacting for 4 hours. After the reaction is finished, carrying out suction filtration on the liquid, washing the liquid with deionized water until the filtrate is neutral, and drying the filtrate in an oven at 110 ℃ for 12 hours to prepare a layered nickel silicate precursor; respectively placing 0.50g of layered nickel silicate precursor and 0.57g of ammonium hypophosphite in a tubular furnace reactor, wherein the ammonium hypophosphite is positioned at the upstream, phosphorizing for 2 hours at 350 ℃ in a nitrogen atmosphere at the nitrogen flow rate of 10mL/min, and cooling to room temperature to obtain a supported nickel phosphide precursor; placing the load type phosphide precursor in a tubular furnace reactor, carrying out heat treatment for 2h at 400 ℃ in hydrogen atmosphere at the hydrogen flow rate of 150mL/min, and cooling to room temperatureWarm to obtain Ni2P/SiO2A catalyst.
Example 10
Preparing layered nickel silicate by deposition precipitation method, preparing supported nickel phosphide precursor by phosphating method, and preparing Ni by heat treatment method2P/SiO2A catalyst.
Dissolving 2.62g of nickel nitrate in deionized water to prepare a nickel nitrate solution, and taking 2.40g of SiO2Adding the carrier into 4/5 the nickel nitrate solution, heating to 70 ℃ under continuous stirring to form a suspension A, weighing 7.56g of urea and 0.56g of concentrated nitric acid, adding into the rest 1/5 nickel nitrate solution to form a mixed solution B, dropwise adding the mixed solution B into the suspension A at the temperature of 70 ℃ at the speed of 2 drops/second, heating to 90 ℃ after dropwise adding, and reacting for 4 hours. After the reaction is finished, carrying out suction filtration on the liquid, washing the liquid with deionized water until the filtrate is neutral, and drying the filtrate in an oven at 110 ℃ for 12 hours to prepare a layered nickel silicate precursor; respectively placing 0.50g of layered nickel silicate precursor and 0.05g of red phosphorus in a tubular furnace reactor, wherein the red phosphorus is positioned at the upstream, phosphorizing at 350 ℃ for 2 hours under the nitrogen atmosphere at the nitrogen flow rate of 10mL/min, and cooling to room temperature to obtain a supported nickel phosphide precursor; placing the load type phosphide precursor in a tubular furnace reactor, carrying out heat treatment for 2h at 400 ℃ in hydrogen atmosphere with the hydrogen flow rate of 150mL/min, and cooling to room temperature to obtain Ni2P/SiO2A catalyst.
Example 11
Preparing layered nickel silicate by deposition precipitation method, preparing supported nickel phosphide precursor by phosphating method, and preparing Ni by heat treatment method2P/SiO2A catalyst.
Dissolving 2.62g of nickel nitrate in deionized water to prepare a nickel nitrate solution, and taking 2.40g of SiO2Adding the carrier into 4/5 the nickel nitrate solution, heating to 70 ℃ under continuous stirring to form a suspension A, weighing 7.56g of urea and 0.56g of concentrated nitric acid, adding into the rest 1/5 nickel nitrate solution to form a mixed solution B, dropwise adding the mixed solution B into the suspension A at the temperature of 70 ℃ at the speed of 2 drops/second, heating to 90 ℃ after dropwise adding, and reacting for 4 hours. After the reaction is finished, filtering the liquid, washing the liquid with deionized water until the filtrate is neutral, and drying the filtrate in a drying oven for 12 hours at 110 ℃ to prepare the layered nickel silicateA precursor; placing 0.50g of layered nickel silicate precursor in a tubular furnace reactor, phosphorizing for 2h at 350 ℃ in the atmosphere of 10% phosphine/hydrogen, wherein the gas flow rate is 10mL/min, and cooling to room temperature to obtain a supported nickel phosphide precursor; placing the load type phosphide precursor in a tubular furnace reactor, carrying out heat treatment for 2h at 400 ℃ in hydrogen atmosphere with the hydrogen flow rate of 150mL/min, and cooling to room temperature to obtain Ni2P/SiO2A catalyst.
Example 12
Preparation of Ni as in example 12P/SiO2Catalyst, then 0.2g of catalyst is placed in a high-pressure fixed bed tubular reactor with the inner diameter of 10mm, the reaction pressure is 4.0MPa, the reaction temperature is 300--1The hydrogen/oil volume ratio was 750: 1. After the reaction was stabilized for 2h, a liquid sample was taken and analyzed by gas chromatography, type Aglient 6890N, using FID as the detector and commercial HP-5(30 m.times.320. mu.m.times.0.5 μm) as the column. The reaction results are shown in Table 1.
As can be seen from Table 1, the conversion rate of 4, 6-dimethyldibenzothiophene reached 80.0% at 320 ℃ and 99.4% at 340 ℃, indicating that the prepared catalyst has good catalytic activity.
TABLE 14, 6-Diethyldibenzothiophene in Ni2P/SiO2Hydrodesulfurization reaction performance on catalyst
Example 13
Preparation of Ni as in example 12P/SiO2The reaction temperature of the catalyst in this example was 340 ℃ and the other examples were conducted in the same manner as in example 2. The reaction results are shown in FIG. 5.
As can be seen from FIG. 5, the conversion rate of 4, 6-dimethyldibenzothiophene is stabilized at 100% within 100h, indicating that the prepared catalyst has good stability.
Example 14
In this example, the prepared supported nickel phosphide precursor was exposed to air and left for 6 months, and the other preparation conditions were the same as in example 1 and the reaction conditions were the same as in example 2. The reaction results are shown in Table 2.
As can be seen from Table 2, the conversion rate of 4, 6-dimethyldibenzothiophene reached 93.9% at 340 ℃, indicating that the prepared supported nickel phosphide precursor had good stability.
TABLE 24, 6-Diethyldibenzothiophene in Ni2P/SiO2Hydrodesulfurization reaction performance on catalyst
In combination with the above embodiments, the present invention provides a simple, easy, highly stable, highly active Ni2The preparation method of the P catalyst comprises the following steps:
s1, placing a nickel source and a phosphorus source in a tubular furnace reactor in an isolated manner, wherein the phosphorus source is located at the upstream, carrying out phosphating for 2 hours in an oxygen-free atmosphere, and cooling to room temperature to obtain a supported nickel phosphide precursor;
s2, placing the supported phosphide precursor in a tubular furnace reactor, carrying out heat treatment for 2h in an oxygen-free atmosphere, and cooling to room temperature to obtain supported Ni2And (3) a P catalyst.
Further, the carrier is preferably SiO when preparing the nickel source in step 12MCM-41, SBA-15, Silicalite-1 or TS-1.
Further, the nickel salt in preparing the nickel source in step 1 is preferably nickel nitrate, nickel sulfate, nickel acetate or nickel chloride.
Further, the phosphorus source in step 1 is preferably sodium hypophosphite, ammonium hypophosphite, red phosphorus or phosphine.
Further, the phosphating temperature of the step S1 is 300-500 ℃; the phosphating temperature is preferably 400 ℃ or lower.
Further, the heat treatment temperature in step S1 is 300-500 ℃; the heat treatment temperature is preferably 400 ℃ or lower.
The present invention also provides the above-mentioned Ni as in example 122P catalyst in hydrogenation reactionThe application has the characteristics of high activity and high stability. The application of the catalyst of the invention is not limited to the manner of use of this example.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be able to cover the technical solutions and the inventive concepts of the present invention within the technical scope of the present invention.
Claims (7)
1. Preparation of high-dispersion load type Ni by one-step heat treatment2A process for the preparation of a P catalyst, comprising the steps of:
s1, placing a nickel source and a phosphorus source in a tubular furnace reactor in an isolated manner, wherein the phosphorus source is located at the upstream and is phosphated for 2 hours in an oxygen-free atmosphere to obtain a supported nickel phosphide precursor;
s2, placing the load type nickel phosphide precursor in a tubular furnace reactor, and carrying out heat treatment for 2h in an oxygen-free atmosphere to obtain Ni2And (3) a P catalyst.
2. The method for preparing high-dispersion supported Ni by one-step heat treatment according to claim 12The method of P catalyst is characterized in that the nickel source is prepared in the step S1, and the carrier is SiO2MCM-41, SBA-15, Silicalite-1 or TS-1;
the nickel salt is nickel nitrate, nickel sulfate, nickel acetate or nickel chloride.
3. The method for preparing high-dispersion supported Ni by one-step heat treatment according to claim 12The method of P catalyst, characterized by, the said nickel source of step S1 is the nickel silicate of stratiform;
the preparation method of the layered nickel silicate comprises the following steps: dissolving 2.62g of nickel nitrate in deionized water to prepare a nickel nitrate solution, and taking 2.40g of SiO24/5 adding carrier into the above nickel nitrate solution, heating to 70 deg.C under stirring to form suspension A, adding 7.56g urea and 0.56g concentrated nitric acid into the rest 1/5 nickel nitrate solution to form mixed solution B, and mixing at 70 deg.CThe mixed solution B is dripped into the suspension A at the speed of 2 drops/second, and after the dripping is finished, the temperature is raised to 90 ℃ for reaction for 4 hours. And after the reaction is finished, carrying out suction filtration on the liquid, washing the liquid with deionized water until the filtrate is neutral, and drying the filtrate in an oven at 110 ℃ for 12 hours to obtain the layered nickel silicate.
4. The method for preparing high-dispersion supported Ni by one-step heat treatment according to claim 12The method of P catalyst is characterized in that the phosphorus source in the step S1 is sodium hypophosphite, ammonium hypophosphite, red phosphorus or phosphine.
5. The method for preparing high-dispersion supported Ni by one-step heat treatment according to claim 12A process for the preparation of a P catalyst, comprising the steps of:
respectively placing 0.50g of layered nickel silicate and 0.72g of sodium hypophosphite in a tubular furnace reactor, wherein the sodium hypophosphite is positioned at the upstream, phosphorizing at 350 ℃ for 2 hours in a nitrogen atmosphere at the nitrogen flow rate of 10mL/min, and cooling to room temperature to obtain a load-type nickel phosphide precursor; placing the load type phosphide precursor in a tubular furnace reactor, carrying out heat treatment for 2h at 400 ℃ in hydrogen atmosphere with the hydrogen flow rate of 150mL/min, and cooling to room temperature to obtain Ni2P/SiO2A catalyst.
6. The method for preparing high-dispersion supported Ni by one-step heat treatment according to claim 12The method of P catalyst is characterized in that the phosphating temperature in the step S1 is 300-500 ℃.
7. The method for preparing high-dispersion supported Ni by one-step heat treatment according to claim 12The method of P catalyst is characterized in that the heat treatment temperature in step S2 is 300-500 ℃.
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| CN114908376A (en) * | 2022-06-06 | 2022-08-16 | 黔南民族师范学院 | Polyaniline and nickel phosphide composite catalyst and preparation method thereof |
| CN116060049A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method and application thereof |
| CN117735500A (en) * | 2024-02-19 | 2024-03-22 | 江苏中鲈科技发展股份有限公司 | Nickel phosphide catalyst, preparation method thereof and application thereof in electrocatalytic hydrogen evolution process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116060049A (en) * | 2021-10-29 | 2023-05-05 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method and application thereof |
| CN116060049B (en) * | 2021-10-29 | 2024-05-10 | 中国石油化工股份有限公司 | Hydrogenation catalyst and preparation method and application thereof |
| CN114908376A (en) * | 2022-06-06 | 2022-08-16 | 黔南民族师范学院 | Polyaniline and nickel phosphide composite catalyst and preparation method thereof |
| CN114908376B (en) * | 2022-06-06 | 2023-09-08 | 黔南民族师范学院 | Polyaniline and nickel phosphide composite catalyst and preparation method thereof |
| CN117735500A (en) * | 2024-02-19 | 2024-03-22 | 江苏中鲈科技发展股份有限公司 | Nickel phosphide catalyst, preparation method thereof and application thereof in electrocatalytic hydrogen evolution process |
| CN117735500B (en) * | 2024-02-19 | 2024-06-04 | 江苏中鲈科技发展股份有限公司 | Nickel phosphide catalyst, preparation method thereof and application thereof in electrocatalytic hydrogen evolution process |
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