CN114950474B - Method for regulating and controlling metal active center dispersity of metal supported catalyst by using complex precursor - Google Patents
Method for regulating and controlling metal active center dispersity of metal supported catalyst by using complex precursor Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 87
- 239000002184 metal Substances 0.000 title claims abstract description 87
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 31
- 230000001276 controlling effect Effects 0.000 title claims abstract description 21
- 239000002243 precursor Substances 0.000 title claims abstract description 21
- 230000001105 regulatory effect Effects 0.000 title claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000001035 drying Methods 0.000 claims abstract description 41
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000008367 deionised water Substances 0.000 claims abstract description 32
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 32
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 31
- 239000010941 cobalt Substances 0.000 claims abstract description 31
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 24
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 24
- 238000001914 filtration Methods 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 23
- 239000012266 salt solution Substances 0.000 claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 20
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 11
- 230000004048 modification Effects 0.000 claims abstract description 10
- 238000012986 modification Methods 0.000 claims abstract description 10
- 238000010992 reflux Methods 0.000 claims abstract description 10
- 239000002270 dispersing agent Substances 0.000 claims abstract description 5
- 239000006185 dispersion Substances 0.000 claims description 16
- 238000005470 impregnation Methods 0.000 claims description 16
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 238000011068 loading method Methods 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 24
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 10
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000012752 auxiliary agent Substances 0.000 description 3
- 230000007547 defect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- SFMJNHNUOVADRW-UHFFFAOYSA-N n-[5-[9-[4-(methanesulfonamido)phenyl]-2-oxobenzo[h][1,6]naphthyridin-1-yl]-2-methylphenyl]prop-2-enamide Chemical compound C1=C(NC(=O)C=C)C(C)=CC=C1N1C(=O)C=CC2=C1C1=CC(C=3C=CC(NS(C)(=O)=O)=CC=3)=CC=C1N=C2 SFMJNHNUOVADRW-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005303 weighing Methods 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
- 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
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J37/0213—Preparation of the impregnating solution
-
- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
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- 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
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Abstract
The invention discloses a method for regulating and controlling the dispersity of metal active centers of a metal supported catalyst by using a complex precursor, which comprises the following steps: (1) Adding soluble salt of cobalt into deionized water, and then adding soluble salt of auxiliary metal to obtain a metal salt solution; (2) Adding ammonia water, and performing ultrasonic treatment to obtain a metal complex solution; (3) Introducing water vapor into the carrier at 280-350 ℃ for 8-24 hours for modification, adding the carrier into a dispersing agent after drying, adding deionized water into the carrier, refluxing, filtering, washing and drying to obtain a modified carrier; (4) Adding the carrier into the metal complex solution, regulating the pH of the system to 9-11 with ammonia water, ultrasonic impregnating, washing with absolute ethyl alcohol, filtering, drying and roasting. The catalyst prepared by the method provided by the invention has high loading of metallic cobalt and high dispersity of the active center of the metal on the surface of the catalyst, so that the reaction efficiency is greatly improved.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a method for regulating and controlling the dispersity of metal active centers of a metal-supported catalyst by using a complex precursor.
Background
With the rapid development of the chemical industry, the catalyst is increasingly widely applied to the chemical industry. The improvement of the catalyst performance can improve the production and reduce the environmental pollution and the production cost. Typical methods for preparing the metal supported catalyst include impregnation, ion exchange, precipitation by deposition, coprecipitation, and the like. The method for preparing the catalyst by the impregnation method has the advantages of simple steps, easy industrial operation, low cost and the like, so that the catalyst prepared by the impregnation method becomes the catalyst with the most wide application in industrial production, but the catalyst prepared by the impregnation method also has the defects of uneven distribution, easy aggregation, low dispersion degree when the loading amount is higher, and the like.
Therefore, how to improve the dispersibility of metals on a highly supported metal catalyst to greatly improve the catalytic activity of the catalyst is a problem to be solved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for regulating and controlling the dispersity of the metal active center of a metal supported catalyst by using a complex precursor, and the metal catalyst prepared by the method can also improve the dispersity of the metal active center on the premise of high load.
A method for controlling the dispersion of metal active centers of a metal-supported catalyst using a complex precursor, comprising the steps of:
(1) Adding soluble salt of cobalt into deionized water, and then adding soluble salt of auxiliary metal to obtain a metal salt solution;
(2) Adding ammonia water into the metal salt solution, and performing ultrasonic treatment for 0.5-2h to obtain a metal complex solution;
(3) Introducing water vapor into the carrier at 280-350 ℃ for 8-24 hours for modification, adding the carrier into a dispersing agent after drying, adding deionized water into the carrier, refluxing the carrier for 8-12 hours at 80-120 ℃, filtering, washing and drying to obtain a modified carrier;
(4) Adding a carrier into a metal complex solution, regulating the pH of the system to 9-11 by ammonia water, then carrying out ultrasonic impregnation for 2-8 hours, then adding absolute ethyl alcohol for washing, filtering, drying and roasting to obtain a metal supported catalyst;
wherein the auxiliary metal is one or more of chromium, palladium and copper.
Preferably, the carrier is gamma-Al 2 O 3 One of a carrier, a silica carrier, a ZSM-5 carrier and an S-1 carrier.
Preferably, the mole ratio of the soluble salt of cobalt, the soluble salt of the auxiliary metal and the deionized water in the step (1) is (3-10): (0.3-1): (5-30).
Preferably, the mass ratio of the soluble salt of cobalt to the carrier is (1-3): 1.
Preferably, the concentration of the aqueous ammonia is 25-35wt%.
Preferably, the mass ratio of the soluble salt of cobalt in the step (1) to the ammonia water in the step (2) is (4-10): 1.
preferably, the dispersing agent is at least one of absolute ethyl alcohol, cyclohexanol, isobutanol and hexanediol.
Preferably, the drying temperature is 80-130 ℃ and the drying time is 8-24h.
Preferably, the roasting temperature is 400-650 ℃, and the roasting time is 4-8h.
The invention has the advantages that:
the catalyst prepared by the method provided by the invention has high loading of metallic cobalt and high dispersity of the active center of the metal on the surface of the catalyst, so that the reaction efficiency is greatly improved.
Detailed Description
Example 1
A method for controlling the dispersion of metal active centers of a metal-supported catalyst using a complex precursor, comprising the steps of:
(1) 5.25g (0.01804 mol) of cobalt nitrate hexahydrate is added into 3g (0.1667 mol) of deionized water, and then 0.33g (0.00186 mol) of auxiliary palladium chloride is added to obtain a metal salt solution;
(2) Adding 0.6g of 30wt% ammonia water into the metal salt solution, and performing ultrasonic treatment for 1h to obtain a metal complex solution;
(3) Taking 5g of gamma-Al 2 O 3 Introducing water vapor into the carrier at 300 ℃ for 8 hours for modification, adding the carrier into 200mL of absolute ethyl alcohol after drying, adding deionized water into the carrier, refluxing the carrier at 80 ℃ for 8 hours, filtering, washing the carrier with the deionized water, and drying the carrier at 120 ℃ for 12 hours to obtain a modified carrier;
(4) Adding the carrier obtained in the step (3) into the metal complex solution obtained in the step (2), regulating the pH of the system to 11 by using 30wt% ammonia water, then carrying out ultrasonic impregnation for 8 hours, then adding absolute ethyl alcohol for washing, filtering, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ for 6 hours to obtain the metal supported catalyst, wherein the load of the metal cobalt (calculated by cobaltosic oxide) is 21.38%.
Example 2
A method for controlling the dispersion of metal active centers of a metal-supported catalyst using a complex precursor, comprising the steps of:
(1) 5.25g (0.01804 mol) of cobalt nitrate hexahydrate is added into 3g (0.1667 mol) of deionized water, and then 0.33g (0.00186 mol) of auxiliary palladium chloride is added to obtain a metal salt solution;
(2) Adding 0.6g of 30wt% ammonia water into the metal salt solution, and performing ultrasonic treatment for 1h to obtain a metal complex solution;
(3) Taking 5g of gamma-Al 2 O 3 Introducing water vapor into the carrier at 300 ℃ for 12 hours for modification, adding the carrier into 200mL of absolute ethyl alcohol after drying, adding deionized water into the carrier, refluxing the carrier at 80 ℃ for 8 hours, filtering, washing the carrier with the deionized water, and drying the carrier at 120 ℃ for 12 hours to obtain a modified carrier;
(4) Adding the carrier obtained in the step (3) into the metal complex solution obtained in the step (2), regulating the pH of the system to 10 by using 30wt% ammonia water, then carrying out ultrasonic impregnation for 8 hours, then adding absolute ethyl alcohol for washing, filtering, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ for 6 hours to obtain the metal supported catalyst, wherein the load of the metal cobalt (calculated by cobaltosic oxide) is 21.38%.
Example 3
A method for controlling the dispersion of metal active centers of a metal-supported catalyst using a complex precursor, comprising the steps of:
(1) 8.0g (0.02749 mol) of cobalt nitrate hexahydrate is added into 3g (0.1667 mol) of deionized water, and then 0.62g (0.00349 mol) of auxiliary palladium chloride is added to obtain a metal salt solution;
(2) Adding 1.0 g of 30wt% ammonia water into the metal salt solution, and performing ultrasonic treatment for 1h to obtain a metal complex solution;
(3) Taking 5g of gamma-Al 2 O 3 Introducing water vapor into the carrier at 300 ℃ for 12 hours for modification, adding the carrier into 200mL of absolute ethyl alcohol after drying, adding deionized water into the carrier, refluxing the carrier at 80 ℃ for 8 hours, filtering, washing the carrier with the deionized water, and drying the carrier at 120 ℃ for 12 hours to obtain a modified carrier;
(4) Adding the carrier obtained in the step (3) into the metal complex solution obtained in the step (2), regulating the pH of the system to 11 by using 30wt% ammonia water, then carrying out ultrasonic impregnation for 8 hours, then adding absolute ethyl alcohol for washing, filtering, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ for 6 hours to obtain the metal supported catalyst, wherein the load of the metal cobalt (calculated by cobaltosic oxide) is 32.58%.
Example 4
A method for controlling the dispersion of metal active centers of a metal-supported catalyst using a complex precursor, comprising the steps of:
(1) 8.0g (0.02749 mol) of cobalt nitrate hexahydrate is added into 3g (0.1667 mol) of deionized water, and then 0.62g (0.00349 mol) of auxiliary palladium chloride is added to obtain a metal salt solution;
(2) Adding 1.0 g of 30wt% ammonia water into the metal salt solution, and performing ultrasonic treatment for 1h to obtain a metal complex solution;
(3) Taking 5g of gamma-Al 2 O 3 Introducing water vapor into the carrier at 300 ℃ for 12 hours for modification, adding the carrier into 200mL of absolute ethyl alcohol after drying, adding deionized water into the carrier, refluxing the carrier at 80 ℃ for 8 hours, filtering, washing the carrier with the deionized water, and drying the carrier at 120 ℃ for 12 hours to obtain a modified carrier;
(4) Adding the carrier obtained in the step (3) into the metal complex solution obtained in the step (2), regulating the pH of the system to 9 by using 30wt% ammonia water, then carrying out ultrasonic impregnation for 8 hours, then adding absolute ethyl alcohol for washing, filtering, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ for 6 hours to obtain the metal supported catalyst, wherein the load of the metal cobalt (calculated by cobaltosic oxide) is 32.58%.
Example 5
A method for controlling the dispersion of metal active centers of a metal-supported catalyst using a complex precursor, comprising the steps of:
(1) 5.25g g (0.01804 mol) of cobalt nitrate hexahydrate is added into 0.54 g (0.03000 mol) of deionized water, and then 0.32g (0.001804 mol) of auxiliary palladium chloride is added to obtain a metal salt solution;
(2) Adding 1.31g of 25wt% ammonia water into the metal salt solution, and performing ultrasonic treatment for 1h to obtain a metal complex solution;
(3) Taking a 5.25g silica carrier, introducing water vapor for 24 hours at 280 ℃ for modification, adding the silica carrier into 200mL of cyclohexanol after drying, adding deionized water into the cyclohexanol, refluxing for 8 hours at 120 ℃, filtering, washing with deionized water, and drying at 80 ℃ for 24 hours to obtain a modified carrier;
(4) Adding the carrier obtained in the step (3) into the metal complex solution obtained in the step (2), regulating the pH of the system to 9 by using 25wt% ammonia water, then carrying out ultrasonic impregnation for 2 hours, then adding absolute ethyl alcohol for washing, filtering, drying at 80 ℃ for 24 hours, and roasting at 400 ℃ for 8 hours to obtain the metal supported catalyst, wherein the load of the metal cobalt (calculated by cobaltosic oxide) is 21.38%.
Example 6
A method for controlling the dispersion of metal active centers of a metal-supported catalyst using a complex precursor, comprising the steps of:
(1) 5.25 mol g (0.01804 mol) of cobalt nitrate hexahydrate is added into 0.9742 g (0.05412 mol) of deionized water, and then 0.32g (0.001804 mol) of auxiliary palladium chloride is added to obtain a metal salt solution;
(2) Adding 0.525g of 35wt% ammonia water into the metal salt solution, and performing ultrasonic treatment for 2 hours to obtain a metal complex solution;
(3) Taking 1.75g of ZSM-5 carrier, introducing water vapor for 8 hours at 350 ℃ for modification, adding the carrier into 200mL of cyclohexanol after drying, adding deionized water into the carrier, refluxing the carrier for 12 hours at 100 ℃, filtering, washing the carrier with deionized water, and drying the carrier at 130 ℃ for 8 hours to obtain a modified carrier;
(4) Adding the carrier obtained in the step (3) into the metal complex solution obtained in the step (2), regulating the pH of the system to 9 by using 25wt% ammonia water, then carrying out ultrasonic impregnation for 4 hours, then adding absolute ethyl alcohol for washing, filtering, drying at 130 ℃ for 8 hours, and roasting at 650 ℃ for 4 hours to obtain the metal supported catalyst, wherein the load of the metal cobalt (calculated by cobaltosic oxide) is 41.30%.
Comparative example 1
5.25g of cobalt nitrate hexahydrate is weighed into 3g of deionized water, and is sonicated for 1h at room temperature, 5g of gamma-Al is added 2 O 3 Adding the carrier into the solution, carrying out ultrasonic impregnation for 8 hours, drying in a drying oven at 120 ℃ for 12 hours, then placing the solution into a muffle furnace, roasting for 4 hours at 500 ℃, washing with absolute ethyl alcohol, filtering, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ for 6 hours to obtain the metal supported catalyst, wherein the load of the metal cobalt (calculated by cobaltosic oxide) is 21.38%.
Comparative example 2
Weighing 5.25g of cobalt nitrate hexahydrate, adding into 3g of deionized water, adding 0.33g of auxiliary agent palladium chloride, and carrying out ultrasonic treatment at room temperature for 1h to obtain 5g of gamma-Al 2 O 3 Adding the carrier into the solution, carrying out ultrasonic impregnation for 8 hours, drying in a drying oven at 120 ℃ for 12 hours, then placing the solution into a muffle furnace, roasting for 4 hours at 500 ℃, washing with absolute ethyl alcohol, filtering, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ for 6 hours to obtain the metal supported catalyst, wherein the load of the metal cobalt (calculated by cobaltosic oxide) is 21.38%.
Comparative example 3
A method for controlling the dispersion of metal active centers of a metal-supported catalyst using a complex precursor, comprising the steps of:
(1) Adding 5.25g of cobalt nitrate hexahydrate into 3g of deionized water, and adding 0.22g of auxiliary agent palladium chloride to obtain a metal salt solution;
(2) Taking 5g of gamma-Al 2 O 3 Introducing water vapor into the carrier at 300 ℃ for 8 hours for modification, adding the carrier into 200mL of absolute ethyl alcohol after drying, adding deionized water into the carrier, refluxing the carrier at 80 ℃ for 8 hours, filtering, washing the carrier with the deionized water, and drying the carrier at 120 ℃ for 12 hours to obtain a modified carrier;
(3) Adding the carrier obtained in the step (2) into the metal salt solution obtained in the step (1), then carrying out ultrasonic impregnation for 8 hours, then adding absolute ethyl alcohol for washing, filtering, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ for 6 hours to obtain the metal supported catalyst, wherein the load of the metal cobalt (calculated by cobaltosic oxide) is 21.38%.
Comparative example 4
A method for controlling the dispersion of metal active centers of a metal-supported catalyst using a complex precursor, comprising the steps of:
(1) Adding 5.25g of cobalt nitrate hexahydrate into 3g of deionized water, and adding 0.22g of auxiliary agent palladium chloride to obtain a metal salt solution;
(2) Adding 0.5g 30wt% ammonia water into the metal salt solution, and performing ultrasonic treatment for 1h to obtain a metal complex solution;
(3) Taking 5g of gamma-Al 2 O 3 Adding a carrier into the metal complex solution obtained in the step (2), regulating the pH of the system to 11 by using 30wt% ammonia water, then carrying out ultrasonic impregnation for 8 hours, then adding absolute ethyl alcohol for washing, filtering, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ for 6 hours to obtain the metal supported catalyst, wherein the load of the metal cobalt (calculated by cobaltosic oxide) is 21.38%.
Metal dispersity detection
The dispersity of the metallic cobalt is H through the metallic catalyst 2 The principle of the temperature programming reduction measurement is obtained by the ratio of the total cobalt atom number on the surface of the catalyst to all cobalt atoms on the catalyst, and the specific calculation formula is as follows:
D=；
wherein D represents the dispersity of cobalt, and V represents H of the sample 2 Consumption of H by heating reduction 2 Can be measured and calculated by a TCD detector, m represents the total mass of the catalyst, w is the mass fraction of cobalt in the catalyst and MCo is the relative atomic mass of metallic cobalt;
the calculation results are shown in table 1.
TABLE 1 dispersity of metallic cobalt in catalysts
| Catalyst | Dispersity of metallic cobalt | Loading of metallic cobalt |
| Example 1 | 52% | 21.38% |
| Example 2 | 43% | 21.38% |
| Example 3 | 45% | 32.58% |
| Example 4 | 35% | 32.58% |
| Example 5 | 53% | 21.28% |
| Example 6 | 39% | 41.30% |
| Comparative example 1 | 14% | 21.38% |
| Comparative example 2 | 25% | 21.38% |
| Comparative example 3 | 28% | 21.38% |
| Comparative example 4 | 29% | 21.38% |
In the embodiment of the invention, the loading of the metal cobalt is the percentage of the metal cobalt (calculated as cobaltosic oxide) to the sum of the mass of the metal cobalt (calculated as cobaltosic oxide) and the mass of the carrier.
Claims (7)
1. A method for regulating and controlling the dispersity of metal active centers of a metal supported catalyst by using a complex precursor is characterized by comprising the following steps of: the method comprises the following steps:
(1) Adding soluble salt of cobalt into deionized water, and then adding soluble salt of auxiliary metal to obtain a metal salt solution;
(2) Adding ammonia water into the metal salt solution, and performing ultrasonic treatment for 0.5-2h to obtain a metal complex solution;
(3) Introducing water vapor into the carrier at 280-350 ℃ for 8-24 hours for modification, adding the carrier into a dispersing agent after drying, adding deionized water into the carrier, refluxing the carrier for 8-12 hours at 80-120 ℃, filtering, washing and drying to obtain a modified carrier;
(4) Adding a carrier into a metal complex solution, regulating the pH of the system to 9-11 by ammonia water, then carrying out ultrasonic impregnation for 2-8 hours, then adding absolute ethyl alcohol for washing, filtering, drying and roasting to obtain a metal supported catalyst;
wherein the auxiliary metal is palladium;
the carrier is gamma-Al 2 O 3 One of a carrier, a silica carrier, a ZSM-5 carrier and an S-1 carrier;
the dispersing agent is at least one of absolute ethyl alcohol, cyclohexanol, isobutanol and hexanediol.
2. The method for controlling the dispersion of metal active centers of a metal-supported catalyst using a complex precursor according to claim 1, wherein: the mole ratio of the soluble salt of cobalt, the soluble salt of the auxiliary metal and the deionized water in the step (1) is (3-10): (0.3-1): (5-30).
3. The method for controlling the dispersion degree of metal active centers of metal-supported catalyst by using a complex precursor according to claim 2, wherein the method comprises the following steps: the mass ratio of the soluble salt of cobalt to the carrier is (1-3): 1.
4. A method for controlling the dispersion of metal active centers of a metal-supported catalyst using a complex precursor according to claim 3, wherein: the concentration of the ammonia water is 25-35wt%.
5. The method for controlling the dispersion of metal active centers of a metal-supported catalyst using a complex precursor according to claim 4, wherein: the mass ratio of the soluble salt of cobalt in the step (1) to the ammonia water in the step (2) is (4-10): 1.
6. the method for controlling the dispersion of metal active centers of a metal-supported catalyst using a complex precursor according to claim 5, wherein: the drying temperature is 80-130 ℃, and the drying time is 8-24h.
7. The method for controlling the dispersion of metal active centers of a metal-supported catalyst using a complex precursor according to claim 6, wherein: the roasting temperature is 400-650 ℃, and the roasting time is 4-8h.
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