CN111229230A - Ellipsoidal alumina supported metal catalyst and preparation method and application thereof - Google Patents
Ellipsoidal alumina supported metal catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN111229230A CN111229230A CN202010165779.8A CN202010165779A CN111229230A CN 111229230 A CN111229230 A CN 111229230A CN 202010165779 A CN202010165779 A CN 202010165779A CN 111229230 A CN111229230 A CN 111229230A
- Authority
- CN
- China
- Prior art keywords
- ellipsoidal
- alumina
- ellipsoidal alumina
- metal catalyst
- supported
- 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 48
- 239000002184 metal Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 29
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 14
- 150000002736 metal compounds Chemical class 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 239000003513 alkali Substances 0.000 claims 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 230000004913 activation Effects 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 3
- 239000002923 metal particle Substances 0.000 abstract description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 8
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229940063656 aluminum chloride Drugs 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 2
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 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 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100001081 no carcinogenicity Toxicity 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001291 vacuum drying Methods 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/51—
-
- B01J35/615—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
- C07C5/11—Partial hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/74—Iron group metals
- C07C2523/755—Nickel
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/10—One of the condensed rings being a six-membered aromatic ring the other ring being six-membered, e.g. tetraline
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/14—All rings being cycloaliphatic
- C07C2602/26—All rings being cycloaliphatic the ring system containing ten carbon atoms
- C07C2602/28—Hydrogenated naphthalenes
-
- 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention relates to the technical field of catalysts, in particular to an ellipsoidal alumina supported metal catalyst and a preparation method and application thereof. The invention discloses an ellipsoidal alumina supported metal catalyst, which comprises ellipsoidal alumina and metal supported on the ellipsoidal alumina; the major axis of the ellipsoidal alumina is 2-3 μm, and the minor axis is 1 &1.5 μm, a specific surface area of 150m2/g～200m2(ii) in terms of/g. The ellipsoidal alumina supported metal catalyst provided by the invention has a higher specific surface area, so that the metal dispersion degree on the surface of alumina is improved, more active sites can be provided, and the activation of hydrogen on the surface of metal particles in a catalytic hydrogenation reaction is facilitated. Therefore, the alumina supported metal catalyst with the ellipsoidal alumina structure has higher catalytic activity and stability of catalytic hydrogenation of polycyclic aromatic hydrocarbons.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to an ellipsoidal alumina supported metal catalyst and a preparation method and application thereof.
Background
Polycyclic Aromatic Hydrocarbons (PAHs) are aromatic hydrocarbon components having a two-ring or multi-ring structure, which are substances existing in petroleum in large amounts, and are yellow flaky or needle-shaped crystals precipitated from light petroleum, and have light green fluorescence. Such substances are of no value in industry, have a strong carcinogenic effect and reduce the fuel value in oil products. In recent years, strict limitations are imposed on PAHs and 8 kinds of strong carcinogenic polycyclic aromatic hydrocarbons in 2005/69/EC in European Union, and the standard of no carcinogenicity must be achieved, so that the research on catalytic hydrogenation of polycyclic aromatic hydrocarbons is urgent. The metal-supported catalyst is commonly used for the catalytic hydrogenation reaction of the polycyclic aromatic hydrocarbon, but the carrier specific surface area of the existing supported catalyst is small, so that the metal active sites are few, the catalytic activity of the supported catalyst is low, the reaction conditions of the hydrogenation of the polycyclic aromatic hydrocarbon are harsh, and the requirement of reducing the reaction cost cannot be met.
Disclosure of Invention
The invention provides an ellipsoidal alumina supported metal catalyst, a preparation method and application thereof, and solves the problem of low catalytic activity caused by small specific surface area of the existing supported catalyst carrier.
The specific technical scheme is as follows:
the invention provides an ellipsoidal alumina supported metal catalyst, which comprises ellipsoidal alumina and metal supported on the ellipsoidal alumina;
the long axis of the ellipsoidal alumina is 2-3 μm, the short axis is 1-1.5 μm, and the specific surface area is 150-200 m2Preferably 180 to 200 m/g2(ii) g, more preferably 200m2/g。
The ellipsoidal alumina supported metal catalyst provided by the invention has a higher specific surface area, so that the metal dispersion degree on the surface of alumina is improved, more active sites can be provided, and the activation of hydrogen on the surface of metal particles in a catalytic hydrogenation reaction is facilitated. Therefore, the alumina supported metal catalyst with the ellipsoidal structure has higher catalytic activity and stability of catalytic hydrogenation of polycyclic aromatic hydrocarbons.
In the present invention, the amount of the metal supported is 20 to 30 wt%, more preferably 20 wt%.
The invention also provides a preparation method of the ellipsoidal alumina supported metal catalyst, which comprises the following steps:
step 1: mixing aluminum chloride, an alkaline reagent and a solvent, and then carrying out hydrothermal reaction to obtain an ellipsoidal alumina precursor;
step 2: drying and roasting the ellipsoidal alumina precursor in sequence to obtain ellipsoidal alumina;
and step 3: and dipping the ellipsoidal alumina in a solution containing a metal compound, and then drying and calcining to obtain the ellipsoidal alumina supported metal catalyst.
In the step 1 of the invention, aluminum chloride and an alkaline reagent are mixed and then undergo hydrothermal reaction to obtain an ellipsoidal alumina precursor;
step 1, the aluminum chloride is specifically aluminum chloride hexahydrate;
the alkaline reagent is selected from urea or ammonia water, and is preferably urea;
the solvent is deionized water;
the molar ratio of the aluminum chloride to the alkaline agent is (1: 1) to (1: 2), preferably 1: when the alkaline agent is urea, the molar ratio of the aluminum chloride to the urea is preferably 1: 1;
the temperature of the hydrothermal reaction is 170 ℃, the time is 3-6 h, and the alumina formed by the hydrothermal reaction under the condition is ellipsoidal;
after the hydrothermal reaction is finished and before the ellipsoidal alumina precursor is obtained, the method further comprises the following steps: filtering and washing a product obtained by the hydrothermal reaction;
the liquid used for washing is water and ethanol in sequence, and the washing frequency is preferably 3 times.
In the step 2 of the invention, the ellipsoidal alumina precursor is dried and roasted to obtain ellipsoidal alumina;
the drying is preferably vacuum drying, the drying temperature is 60-80 ℃, the drying time is 10-12 h, and preferably 80 ℃ and 12 h;
the roasting specifically comprises the following steps: heating to 550-600 ℃ at a heating rate of 2-10 ℃/min, and roasting for 2-4 h, preferably at a heating rate of 5 ℃/min to 600 ℃ for 2 h.
In step 3 of the invention, after the ellipsoidal alumina is immersed in the solution containing the metal compound, the metal is loaded on the ellipsoidal alumina through drying and calcining;
the solution containing the metal compound comprises a metal compound and a dispersant;
the metal in the metal compound is nickel, palladium, platinum or ruthenium, preferably nickel, the nickel-containing compound is preferably nickel nitrate, nickel chloride or nickel sulfate, and the nickel nitrate is preferably nickel nitrate because the nickel chloride can leave chlorine atoms on the catalyst and the nickel sulfate can leave sulfur on the catalyst;
the dispersant is ethylene glycol, the solvent in the metal compound solution is water, and in the present invention, the metal compound and the dispersant are preferably mixed in a molar ratio of 1: 1 is dissolved in water, the selection of the solvent amount is determined according to the mass of the used ellipsoidal alumina carrier, and the mass ratio of the carrier to the water is 1: 1. the dipping time is 20-40 minutes, and preferably 30 minutes.
The molar ratio of the ellipsoidal alumina to the metal compound is (0.34: 1) to (0.5: 1), preferably 0.34: 1;
the drying temperature is 100-110 ℃, the drying time is 12-14 h, and preferably the drying time is 12h at 110 ℃;
the calcination is specifically as follows: heating to 400-450 ℃ at the heating rate of 5-10 ℃/min, calcining for 2-4 h, preferably heating to 400 ℃ at the heating rate of 5 ℃/min, and calcining for 2 h.
The invention also provides the application of the ellipsoidal alumina supported metal catalyst or the ellipsoidal alumina supported metal catalyst prepared by the preparation method in the catalytic hydrogenation reaction of polycyclic aromatic hydrocarbons.
In the present invention, the polycyclic aromatic hydrocarbon is preferably naphthalene, and the WHSV (mass space velocity) of a 1% naphthalene/n-heptane solution is 20.52h-1～41.04h-1The space velocity is preferably 20.52h-1。
According to the technical scheme, the invention has the following advantages:
the invention provides an ellipsoidal alumina supported metal catalyst, which comprises ellipsoidal alumina and metal supported on the ellipsoidal alumina; the major axis of the ellipsoidal alumina is 2-3 μm, the minor axis is 1-1.5 μm, and the specific surface area is 150-200 m2/g。
The ellipsoidal alumina supported metal catalyst provided by the invention has a higher specific surface area, so that the metal dispersion degree on the surface of alumina is improved, more active sites can be provided, and the activation of hydrogen on the surface of metal particles in a catalytic hydrogenation reaction is facilitated. Therefore, the alumina supported metal catalyst with the ellipsoidal structure has higher catalytic activity and stability of catalytic hydrogenation of polycyclic aromatic hydrocarbons. According to experimental data, the conversion rate of naphthalene in the catalytic naphthalene hydrogenation reaction of the ellipsoidal alumina supported metal catalyst provided by the invention is 99.6%, and the selectivity to tetrahydronaphthalene is 82.2%.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without inventive exercise.
FIG. 1 is an XRD pattern of an ellipsoidal alumina provided in example 1 of the present invention;
FIG. 2 is an XRD pattern of an ellipsoidal alumina-supported metallic nickel catalyst provided in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of the ellipsoidal alumina supported metallic nickel catalyst provided in example 1 of the present invention;
FIG. 4 is a TEM image of the catalyst comprising metal nickel and ellipsoidal alumina provided in example 1 of the present invention.
Detailed Description
The embodiment of the invention provides an ellipsoidal alumina supported metal catalyst, and a preparation method and application thereof, which are used for solving the problem of low catalytic activity caused by small specific surface area of the existing supported catalyst carrier.
In order to make the objects, features and advantages of the present invention more obvious and understandable, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it should be apparent that the embodiments described below are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In comparative example 1 of the present invention, commercial alumina was purchased from Zibo Heng aluminum industries, Inc.
Example 1
This example provides the first ellipsoidal γ -Al2O3The supported metal Ni catalyst is prepared by the following specific steps:
step 1: mixing and stirring 0.0064mol of aluminum chloride hexahydrate and 60mL of 0.0064mol of urea for 10 minutes until the mixture is uniform to obtain a first solution;
transferring the first solution into a 100mL hydrothermal reaction kettle, putting the kettle into an oven with the temperature of 170 ℃, carrying out hydrothermal reaction for 6h, cooling to normal temperature after the hydrothermal reaction is finished, washing the obtained solid for 3 times with water and ethanol respectively, and carrying out suction filtration to obtain an alumina precursor.
Step 2: drying the alumina precursor for 12h at the temperature of 80 ℃ in vacuum, then heating to 600 ℃ at the heating rate of 5 ℃/min in a muffle furnace, and roasting for 2h to obtain gamma-Al2O3。
And step 3: mixing gamma-Al2O3Immersing in the aqueous solution of nickel nitrate hexahydrate and glycol for 30 minutes, drying the sample at 110 ℃ for 12 hours, heating to 400 ℃ at the heating rate of 5 ℃/min, calcining for 2 hours to obtain gamma-Al2O3A supported metallic Ni catalyst, wherein the molar ratio of nickel nitrate hexahydrate to ethylene glycol is 1: 1, water and gamma-Al2O3The mass ratio of (1): 1, gamma-Al2O3And nickel nitrate in a molar ratio of 0.34: 1.
in this example, the amount of Ni supported was 20%.
Fig. 1 is an XRD pattern of the ellipsoidal alumina provided in this example. FIG. 1 illustrates the success of this example in producing ellipsoidal γ -Al2O3。
Fig. 2 is an XRD pattern of the metal nickel catalyst supported on the ellipsoidal alumina provided in this example. FIG. 2 illustrates the successful preparation of gamma-Al in this example2O3A metallic Ni catalyst is supported.
FIG. 3 is a scanning electron microscope image of the catalyst of this example with metal nickel supported on ellipsoidal alumina; FIG. 4 is a transmission electron microscope image of the catalyst of this example with metal nickel supported on ellipsoidal alumina. As shown in FIGS. 3 and 4, γ -Al was obtained in this example2O3Is ellipsoidal, and metal Ni is successfully loaded on ellipsoidal gamma-Al2O3The above. Ellipsoidal gamma-Al2O3The major axis of the supported metal Ni catalyst is 2-3 μm, the minor axis is 1-1.5 μm, and the specific surface area is 200m2/g。
Example 2
The ellipsoidal gamma-Al provided in example 12O3The supported metal Ni catalyst was subjected to naphthalene hydrogenation test.
Ellipsoidal gamma-Al2O30.4g of supported metallic Ni catalyst was mixed with 2mL of silica sand, and the catalyst wasBefore use, the agent is reduced for 4h at the temperature of 450 ℃ under hydrogen of 30mL/min, in the subsequent reaction, the pressure is 4Mpa, the temperature is 350 ℃, the reaction liquid is 1wt percent of naphthalene/n-heptane, and the WHSV (mass space velocity) is 20.52h-1，H2When the oil phase (V/V) ═ 150, the catalyst had a naphthalene conversion of 99.6%, a decalin selectivity of 17.8%, and a tetralin selectivity of 82.2%.
Comparative example 1
This comparative example used a commercial alumina supported metallic nickel catalyst (nickel loading of 20%) for naphthalene hydrogenation testing
This comparative example was the same as example 2 under the same test conditions.
The specific surface area of the commercial alumina supported metallic nickel catalyst was 143m2The conversion of naphthalene was 63.8%, the selectivity to decalin was 2.45% and the selectivity to tetralin was 97.55%.
The above-mentioned embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. An ellipsoidal alumina-supported metal catalyst characterized by comprising an ellipsoidal alumina and a metal supported on the ellipsoidal alumina;
the long axis of the ellipsoidal alumina is 2-3 μm, the short axis is 1-1.5 μm, and the specific surface area is 150-200 m2/g。
2. The ellipsoidal alumina supported metal catalyst of claim 1, wherein the loading of the metal in the ellipsoidal alumina supported metal catalyst is 20 to 30 wt%.
3. A preparation method of an ellipsoidal alumina supported metal catalyst is characterized by comprising the following steps:
step 1: mixing aluminum chloride, an alkaline reagent and a solvent, and then carrying out hydrothermal reaction to obtain an ellipsoidal alumina precursor;
step 2: drying and roasting the ellipsoidal alumina precursor in sequence to obtain ellipsoidal alumina;
and step 3: and dipping the ellipsoidal alumina in a solution containing a metal compound, and then drying and calcining to obtain the ellipsoidal alumina supported metal catalyst.
4. The production method according to claim 3, wherein the metal in the metal compound is selected from nickel, palladium, platinum or ruthenium;
the alkaline reagent is selected from urea or ammonia water.
5. The production method according to claim 3, wherein the molar ratio of the aluminum chloride to the alkali agent is (1: 1) to (1: 2);
the molar ratio of the ellipsoidal alumina to the metal compound is (0.34: 1) - (0.5: 1).
6. The preparation method according to claim 3, wherein the temperature of the hydrothermal reaction in the step 1 is 170 ℃ and the time is 3-6 h.
7. The preparation method according to claim 3, wherein the roasting temperature in the step 2 is 550-600 ℃ and the roasting time is 2-4 h;
the calcining temperature in the step 3 is 400-450 ℃, and the time is 2-4 h.
8. The method of claim 3, wherein the solution containing the metal compound further comprises: a dispersant;
the molar ratio of the metal compound to the dispersant is 1: 1;
the dipping time is 20-40 min.
9. The production method according to claim 3, wherein the solvent of the solution containing the metal compound is water;
the mass ratio of the water to the ellipsoidal alumina is 1: 1.
10. use of the ellipsoidal alumina-supported metal catalyst of claim 1 or 2 or the ellipsoidal alumina-supported metal catalyst obtained by the preparation method of any one of claims 3 to 9 in a catalytic hydrogenation reaction of a condensed ring aromatic hydrocarbon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010165779.8A CN111229230B (en) | 2020-03-11 | 2020-03-11 | Ellipsoidal alumina supported metal catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010165779.8A CN111229230B (en) | 2020-03-11 | 2020-03-11 | Ellipsoidal alumina supported metal catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111229230A true CN111229230A (en) | 2020-06-05 |
| CN111229230B CN111229230B (en) | 2022-10-21 |
Family
ID=70872020
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010165779.8A Active CN111229230B (en) | 2020-03-11 | 2020-03-11 | Ellipsoidal alumina supported metal catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111229230B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1483513A (en) * | 2002-09-19 | 2004-03-24 | 北京化工大学 | High dispersing supported type nickel catalyst prepared by lamellar precursor and preparation method thereof |
| CN1583270A (en) * | 2004-06-14 | 2005-02-23 | 北京化工大学 | Magnetic microspheric high-dispersion loaded metal catalyst, preparing method and use |
| CN101543778A (en) * | 2009-05-08 | 2009-09-30 | 北京化工大学 | Noble metal catalyst based on spherical silicon-containing alumina, and preparation method thereof |
-
2020
- 2020-03-11 CN CN202010165779.8A patent/CN111229230B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1483513A (en) * | 2002-09-19 | 2004-03-24 | 北京化工大学 | High dispersing supported type nickel catalyst prepared by lamellar precursor and preparation method thereof |
| CN1583270A (en) * | 2004-06-14 | 2005-02-23 | 北京化工大学 | Magnetic microspheric high-dispersion loaded metal catalyst, preparing method and use |
| CN101543778A (en) * | 2009-05-08 | 2009-09-30 | 北京化工大学 | Noble metal catalyst based on spherical silicon-containing alumina, and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 杨永辉等: "超声浸渍法制备Pd/Al_2O_3催化剂及其催化蒽醌加氢性能", 《催化学报》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111229230B (en) | 2022-10-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9908105B2 (en) | Resid hydrotreating catalyst | |
| CA2500549A1 (en) | High hydrothermal stability catalyst support | |
| CN104475171B (en) | A kind of catalysts for hydrogenation desulfurization and dearsenication and the preparation method of carrier thereof | |
| US3210293A (en) | Hydrorefining catalyst base prepared by high ph precipitation | |
| PL89320B1 (en) | ||
| CN112004600A (en) | Method for producing bimetallic catalysts based on nickel and copper for hydrogenating aromatic compounds | |
| CN106669803A (en) | Catalyst applied to production of high-viscosity index hydrocracking tail oil and preparation method thereof | |
| CN109847793B (en) | Method for synthesizing ZSM-5 molecular sieve based non-supported hydrogenation catalyst by eutectic method | |
| CN111229230B (en) | Ellipsoidal alumina supported metal catalyst and preparation method and application thereof | |
| DK172341B1 (en) | Process for preparing hydrotreating catalyst from a hydrogel and catalyst prepared by the process | |
| US11370976B2 (en) | Method for hydrogenating aromatics using a catalyst obtained by impregnation comprising a specific support | |
| JP2018508351A (en) | Catalyst containing dispersed gold and palladium and its use in selective hydrogenation | |
| RU2691065C1 (en) | Catalytic cracking gasoline hydrotreating catalyst | |
| CN108865243B (en) | Pre-hydrogenation treatment method of carbon tetra-alkylation raw material | |
| RU2607905C1 (en) | Catalyst for hydrocracking hydrocarbon material | |
| US7056955B2 (en) | Attrition resistant bulk metal catalysts and methods of making and using same | |
| RU2626396C1 (en) | Hydrocarbons crude hydrocraking catalyst | |
| JP2567260B2 (en) | Method for producing hydrotreating catalyst from hydrogel | |
| RU2603776C1 (en) | Method of hydrocracking hydrocarbon material | |
| CN112742408B (en) | Dry gas hydrogenation saturated olefin and desulfurization catalyst, and preparation method and application thereof | |
| CN112973706B (en) | Nickel-based catalyst and preparation and application thereof | |
| CN109692696B (en) | Reforming catalyst and preparation method and application thereof | |
| CN112723977A (en) | Method for removing trace sulfide in benzene | |
| RU2626401C1 (en) | Method of hydrotreating hydrocracking feedstock | |
| CN111420670A (en) | Hydrogenation catalyst, preparation method and application thereof |
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 |