CN108940270B - Palladium-alumina-cordierite composite material and preparation method and application thereof - Google Patents
Palladium-alumina-cordierite composite material and preparation method and application thereof Download PDFInfo
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- CN108940270B CN108940270B CN201810626969.8A CN201810626969A CN108940270B CN 108940270 B CN108940270 B CN 108940270B CN 201810626969 A CN201810626969 A CN 201810626969A CN 108940270 B CN108940270 B CN 108940270B
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- 229910052878 cordierite Inorganic materials 0.000 title claims abstract description 83
- 239000002131 composite material Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 66
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 65
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000000758 substrate Substances 0.000 claims abstract description 20
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 12
- 150000004056 anthraquinones Chemical class 0.000 claims abstract description 10
- 239000012452 mother liquor Substances 0.000 claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- 239000011148 porous material Substances 0.000 claims abstract description 5
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 claims description 20
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 17
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 10
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 229910017639 MgSi Inorganic materials 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 229920001400 block copolymer Polymers 0.000 claims description 3
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 abstract description 29
- 238000000034 method Methods 0.000 abstract description 10
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 abstract description 8
- 239000006185 dispersion Substances 0.000 abstract description 6
- 238000011068 loading method Methods 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 description 32
- 229910001845 yogo sapphire Inorganic materials 0.000 description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000001878 scanning electron micrograph Methods 0.000 description 10
- SJEBAWHUJDUKQK-UHFFFAOYSA-N 2-ethylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC=C3C(=O)C2=C1 SJEBAWHUJDUKQK-UHFFFAOYSA-N 0.000 description 8
- 238000003917 TEM image Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 5
- 239000011800 void material Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000000576 coating method Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- PCFMUWBCZZUMRX-UHFFFAOYSA-N 9,10-Dihydroxyanthracene Chemical compound C1=CC=C2C(O)=C(C=CC=C3)C3=C(O)C2=C1 PCFMUWBCZZUMRX-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000012224 working solution Substances 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth 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
- 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
- B01J35/393—Metal or metal oxide crystallite size
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0217—Pretreatment of the substrate before coating
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/06—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation
- C07C37/07—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by conversion of non-aromatic six-membered rings or of such rings formed in situ into aromatic six-membered rings, e.g. by dehydrogenation with simultaneous reduction of C=O group in that ring
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Abstract
The invention discloses a palladium-alumina-cordierite composite material, which comprises the following components in percentage by weight: a cordierite substrate having a plurality of honeycomb cells; a porous alumina layer grown on the surfaces of the honeycomb-shaped pore canals, wherein metal palladium particles are dispersed on the porous alumina layer, and the porous alumina layer also contains MgSixO2x+1(x ═ 1, 2, 3) species. The invention also discloses a preparation method of the palladium-alumina-cordierite composite material, which comprises the following steps: the cordierite matrix is immersed in the synthesis mother liquor in the reactor, and then the reactor is closed and reacted for 2-4 days at 110-140 ℃. The synthesis method integrates the growth of the alumina layer and the loading and dispersion processes of the palladium particles, simplifies the preparation process, and has high bonding strength of the alumina layer and high palladium dispersion level. When the palladium-alumina-cordierite composite material is used for carrying out catalytic hydrogenation on anthraquinone and substitutes thereof, the hydrogenation rate can be doubled, the selectivity of a target product is improved, and the service life of a catalyst is prolonged.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a palladium-alumina-cordierite composite material, and a preparation method and application thereof.
Background
Hydrogen peroxide, also known as hydrogen peroxide, is an important chemical raw material. The anthraquinone process is the main process for producing hydrogen peroxide at home and abroad at present, and has the advantages of low energy consumption, low cost, mature process and easy large-scale production compared with other preparation methods. The technical principle of the anthraquinone method for producing the hydrogen peroxide is as follows: dissolving the substitute of anthraquinone in proper solvent, reducing the substitute of anthraquinone in the working liquid with hydrogen in the presence of catalyst to obtain corresponding anthrahydroquinone, and oxidizing the anthrahydroquinone with oxygen to obtain the substitute of anthraquinone and hydrogen peroxide. And extracting and separating the obtained oxidation working solution with water to obtain aqueous hydrogen peroxide solution, further refining and concentrating to obtain hydrogen peroxide products with different concentrations, and treating the extracted raffinate to return to a hydrogenation stage for recycling.
The hydrogenation of anthraquinone substitute is generally carried out by using granular supported catalyst. In addition, a class of composite materials (structural catalysts) taking cordierite as a matrix to load active components are widely proved to be capable of remarkably optimizing the hydrodynamic behavior of a solid catalyst bed layer and improving the heat transfer/mass transfer performance in the catalyst bed layer, so that the composite materials are more and more concerned in the heterogeneous catalysis field and become a hotspot and an international leading edge in the current cross field of catalysis and chemical engineering. The structural catalyst substrate is a block type substance with macroscopic size and regular structure, and fluid channels with certain sizes are uniformly distributed in the structural catalyst substrate. However, such substrates are mostly high-temperature sintered bodies, such as cordierite honeycomb ceramics, alpha-Al2O3Foamed ceramics and the like, which have a small specific surface area and are disadvantageous in that the catalytically active components are highly dispersed.
In order to increase the specific surface area of the structural catalyst carrier, a layer of porous oxide, such as mesoporous alumina, molecular sieve, etc., is often coated on the surface of the substrate. However, it has been found that porous oxide layers prepared by coating methods have high density, non-uniform thickness, and poor mechanical strength, which characteristics reduce the performance of the structured catalyst. Then, an active component precursor is loaded on the oxide coating grown on the cordierite surface by a dipping method, and finally, the active component particles in an elementary state are obtained by a hydrogen reduction method. However, the impregnation method easily causes the active components to be aggregated into large particles, cannot realize high dispersion of the active components, and is easy to lose in the catalytic reaction process due to weak acting force between the active components and the coating.
The present invention is directed to solving the above problems.
Disclosure of Invention
A first aspect of the present invention relates to a palladium-alumina-cordierite composite material comprising:
a cordierite substrate having a plurality of honeycomb cells;
a porous alumina layer grown on the surfaces of the honeycomb-shaped pore canals, wherein metal palladium particles are dispersed on the porous alumina layer, and the porous alumina layer also contains MgSixO2x+1(x ═ 1, 2, 3) species.
Preferably, the total mass of the palladium and the porous alumina layer accounts for 0.5-5% of the mass of the composite material, and the mass ratio of the palladium to the porous alumina is not less than 0.4%.
Preferably, the cordierite substrate has a length of 50 mm, a diameter of 30 mm, a mesh number of honeycomb-shaped cells of 120 mesh, and a corresponding pore diameter of 0.125 mm; the thickness of the alumina active layer is 0.6-3.0 μm, the diameter of the metal palladium particles is 3-5nm, and the metal palladium particles are highly dispersed.
Preferably, MgSi is also contained in the porous alumina layerxO2x+1(x ═ 1, 2, 3) species, the content of which is from 1 to 10% by mass of the porous alumina.
The second aspect of the present invention relates to a method for producing the palladium-alumina-cordierite composite material according to the first aspect, which comprises the steps of: immersing a cordierite substrate in a synthetic mother liquor located within a reactor, wherein the synthetic mother liquor comprises a polyoxyethylene polyoxypropylene ether block copolymer (trade name F127), aluminum isopropoxide, magnesium nitrate hexahydrate, PdCl2HCl, citric acid and ethanol, wherein the mass ratio of the HCl to the citric acid to the ethanol is F127: aluminium isopropoxide: magnesium nitrate hexahydrate: PdCl2: HCl: citric acid: ethanol ═ 1: (0.9-1.2): (0.225-0.3): (0.002-0.02): (1.6-2.0): (0.5-0.9): (8-14), then closing the reactor and carrying out reaction for 2-4 days at the temperature of 110-140 ℃ to obtain the palladium-alumina-cordierite composite material.
Preferably, the cordierite matrix is pretreated prior to hydrothermal reaction as follows: firstly, calcining for not less than 1h in an air atmosphere at the temperature of not less than 500 ℃; boiling in xylene for at least 10min, treating in hydrogen peroxide at 80 deg.C or higher for at least 15min, and washing with deionized water; finally, after ultrasonic treatment in deionized water, drying at a temperature of not lower than 110 ℃ for standby.
A third aspect of the invention relates to the use of the palladium-alumina-cordierite composite material of the first aspect for catalytically hydrogenating anthraquinones and their substitutes, for multiplying the hydrogenation rate, for increasing the selectivity of hydroanthraquinones and their substitutes, and for extending the catalyst life.
The invention has the advantages of
1. Through in-situ reaction, the growth of the porous alumina layer on the surfaces of cordierite honeycomb channels and the loading and dispersion of metal palladium on the porous alumina layer are synchronously completed. Compared with the traditional method of growing the porous alumina layer before loading palladium, the preparation process is greatly simplified, the palladium dispersion degree is higher, and the alumina layer stability is higher.
2. When the palladium-alumina-cordierite composite material is used as an anthraquinone hydrogenation catalyst, the hydrogenation rate is doubled, the selectivity of hydroanthraquinone and substitutes thereof is improved, and the amount of byproducts is greatly reduced.
3. The porous alumina layer also contains MgSixO2x+1The (x ═ 1, 2, 3) species can extend the life of the catalyst, making it reusable.
Drawings
FIG. 1 is Pd-Al prepared in example 12O3-the X-ray diffraction pattern of the cordierite composite (minus the matrix);
FIG. 2 is Pd-Al prepared in example 12O3-scanning electron micrographs of the cordierite composite surface;
FIG. 3 is Pd-Al prepared in example 12O3Transmission electron micrographs of cordierite composites (matrix subtracted);
FIG. 4 is Pd-Al prepared in example 22O3-the X-ray diffraction pattern of the cordierite composite (minus the matrix);
FIG. 5 is Pd-Al prepared in example 22O3-scanning electron micrographs of the cordierite composite surface;
FIG. 6 is Pd-Al prepared in example 22O3Transmission electron micrographs of cordierite composites (matrix subtracted);
FIG. 7 is Pd-Al prepared in example 32O3-the X-ray diffraction pattern of the cordierite composite (minus the matrix);
FIG. 8 is Pd-Al prepared in example 32O3-scanning electron micrographs of the cordierite composite surface;
FIG. 9 is Pd-Al prepared in example 42O3-the X-ray diffraction pattern of the cordierite composite (minus the matrix);
FIG. 10 is Pd-Al prepared in example 42O3-scanning electron micrographs of the cordierite composite surface;
FIG. 11 is Pd-Al prepared in example 42O3Transmission electron micrographs of cordierite composites (matrix subtracted);
FIG. 12 is Pd/Al prepared in comparative example 12O3The X-ray diffraction pattern of the cordierite material (minus the matrix);
FIG. 13 is Pd/Al prepared in comparative example 12O3-scanning electron micrographs of the cordierite material surface;
FIG. 14 is Pd/Al prepared in comparative example 12O3Transmission electron micrographs of cordierite material (substrate subtracted);
FIG. 15 shows Pd-Al prepared in each example and comparative example2O3And-the hydrogenation activity result of catalyzing 2-ethyl anthraquinone by the cordierite composite material.
FIG. 16 shows various embodimentsPd-Al prepared in examples and comparative examples2O3And-the distribution result of the byproduct of 2-ethyl anthraquinone hydrogenation catalyzed by the cordierite composite material.
FIG. 17 is Pd-Al prepared in example 22O3Repeated experiments on the hydrogenation performance of the cordierite composite material for catalyzing 2-ethyl anthraquinone.
Detailed Description
The present invention will be further illustrated by the following examples. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
Example 1
Placing the pretreated cordierite substrate into a reactor, and adding an activating agent F127, aluminum isopropoxide, magnesium nitrate hexahydrate and PdCl2And the synthesis mother liquor comprises HCl, citric acid and ethanol, wherein the mass ratio of the HCl to the citric acid is F127: aluminum isopropoxide: magnesium nitrate hexahydrate: PdCl2: HCl: citric acid: ethanol ═ 1: 1.1: 0.275: 0.006: 1.8: 0.7: and (3) sealing the reactor, reacting for 2 days at 120 ℃, taking out, washing, drying and calcining to obtain the composite material of the invention, wherein the mother liquor of the 11 is 70 ml.
FIG. 1 shows the X-ray diffraction pattern of the obtained composite material (with the diffraction peak of cordierite matrix subtracted), and the Pd-Al can be confirmed to be prepared by XRD phase identification2O3Cordierite composite, and in Pd-Al2O3The active layer contains MgSixO2x+1(x ═ 1, 2, 3) species with diffraction peaks at 23 ° and reported as Pd — Al2O3-M-1; weighing to obtain: pd and Al in the composite material2O3The total mass percent of the metal Pd is 0.87 percent, wherein the mass percent of the metal Pd is 0.58 percent, and the metal MgSi is MgSixO2x+1The mass ratio of (x ═ 1, 2, 3) species to the porous alumina was 5.2%.
Macroscopic measurements revealed that: composite Material (Pd-Al) prepared in this example2O3in-M-1), Pd-Al2O3The active layer accounts for 0.60 percent by volume, the cordierite matrix accounts for 50 percent by volume, and the void ratio is 49.4 percent.
Fig. 2 is a scanning electron micrograph of the surface of the composite obtained, as can be seen from fig. 2: Pd-Al2O3The active layer discontinuously grows on the surface of the cordierite matrix and has a large number of cracks; Pd-Al2O3The thickness of the active layer is about 0.7 μm.
FIG. 3 shows Pd-Al in the obtained composite2O3Transmission electron micrograph of active layer (image with cordierite matrix subtracted) from fig. 3, it can be seen that: the alumina layer has a large number of worm-like mesopores, and the Pd particles are uniformly dispersed in the Al2O3In (3), the particle size is about 4.0 nm.
Example 2
The composite material prepared in example 1 was used as a raw material, the procedure of example 1 was repeated twice more, and the prepared Pd-Al2O3The-cordierite composite material is marked as Pd-Al2O3-M-2. The product obtained in this example 2 was subjected to a total of 3 reactions starting from pretreated cordierite.
FIG. 4 shows an X-ray diffraction pattern of the obtained composite material (diffraction peaks of cordierite matrix are subtracted), and it can be confirmed that Pd-Al is obtained2O3Cordierite composite, and in Pd-Al2O3The active layer contains MgSixO2x+1(x ═ 1, 2, 3) species. Weighing to obtain: the composite material contains Pd and Al2O3The total mass percent is 2.58 percent, wherein the mass percent of Pd metal is 0.50 percent, the mass percent of cordierite-containing matrix is 97.42 percent, and the mass percent of MgSi isxO2x+1The mass ratio of (x ═ 1, 2, 3) species to the porous alumina was 5.0%.
Macroscopic measurements revealed that: composite Material (Pd-Al) prepared in this example2O3in-M-2), Pd-Al2O3The volume percentage of the active layer is 1.8 percent, the volume percentage of the cordierite matrix is 50 percent, and the void ratio is 48.2 percent.
Fig. 5 is a scanning electron micrograph of the surface of the composite material obtained, from fig. 5 it can be seen that: Pd-Al2O3The active layer is continuously grown on the surface of the cordierite substrate;Pd-Al2O3the thickness of the active layer is about 1.9 μm.
FIG. 6 shows Pd-Al in the obtained composite2O3Transmission electron micrograph of active layer (image with cordierite matrix subtracted) seen in fig. 6: al (Al)2O3Contains a large number of worm-like mesopores, and Pd particles are uniformly dispersed in Al2O3In (3), the particle size is about 4.3 nm.
Example 3
Placing the pretreated cordierite substrate into a reactor, and adding a catalyst containing a surfactant F127, aluminum isopropoxide, magnesium nitrate hexahydrate and PdCl2And the synthesis mother liquor of HCl, citric acid and ethanol is prepared from the following raw materials in a mass ratio of F127: aluminum isopropoxide: magnesium nitrate hexahydrate: PdCl2: HCl: citric acid: ethanol ═ 1: 1.1: 0.275: 0.006: 1.8: 0.7: 11, sealing the reactor, placing the reactor in an oven at 120 ℃ for reacting for 4 days, taking out, washing, drying and calcining to obtain the composite material marked as Pd-Al2O3-M-3。
FIG. 7 shows the X-ray diffraction pattern of the obtained composite material (excluding the diffraction peak of cordierite matrix), and the phase identification by XRD confirms that Pd-Al is prepared2O3Cordierite composite, and in Pd-Al2O3The active layer contains MgSixO2x+1(x ═ 1, 2, 3) species. Weighing to obtain: pd and Al in the composite material2O3The total mass percent is 0.99 percent, wherein the Pd metal accounts for Pd and Al2O3The total mass percentage is 0.60 percent, the mass percentage of the cordierite-containing matrix is 99.01 percent, and the MgSixO2x+1The mass ratio of (x ═ 1, 2, 3) species to the porous alumina was 8.1%.
Macroscopic measurements revealed that: composite Material (Pd-Al) prepared in this example2O3in-M-3), Pd-Al2O3The active layer accounts for 0.70 percent by volume, the cordierite matrix accounts for 50 percent by volume, and the void ratio is 49.3 percent.
Fig. 8 is a scanning electron micrograph of the surface of the composite material obtained, from which fig. 8 it can be seen: Pd-Al2O3The active layer grows on the surface of the cordierite substrate continuously, and a small amount of cracks exist; Pd-Al2O3The thickness of the active layer is about 0.76 μm.
Example 4
Placing the pretreated cordierite substrate into a reactor, and adding a surfactant F127, aluminum isopropoxide, magnesium nitrate hexahydrate and PdCl2And the synthesis mother liquor comprises HCl, citric acid and ethanol, wherein the mass ratio of the HCl to the citric acid is F127: aluminum isopropoxide: magnesium nitrate hexahydrate: PdCl2: HCl: citric acid: ethanol ═ 1: 1.1: 0.275: 0.018: 1.8: 0.7: 11, sealing the reactor, placing the reactor in an oven at 120 ℃ for reacting for 2 days, taking out, washing, drying and calcining to obtain the composite material marked as Pd-Al2O3-M-4。
FIG. 9 shows the X-ray diffraction pattern of the obtained composite material (excluding the diffraction peak of cordierite matrix), and the phase identification by XRD confirms that Pd-Al is prepared2O3Cordierite composite, and Pd-Al2O3The active layer contains MgSixO2x+1(x ═ 1, 2, 3) compound, a diffraction peak at 40.1 ° ascribed to metal Pd; weighing to obtain: pd and Al in the composite material2O3The total mass percent is 0.88 percent, wherein the Pd metal accounts for Pd and Al2O3The total mass percentage is 1.41 percent, the mass percentage of the cordierite-containing matrix is 99.12 percent, and the MgSixO2x+1The mass ratio of (x ═ 1, 2, 3) species to the porous alumina was 5.0%.
Macroscopic measurements revealed that: composite Material (Pd-Al) prepared in this example2O3in-M-4), Pd-Al2O3The active layer accounts for 0.61 percent by volume, the cordierite matrix accounts for 50 percent by volume, and the void ratio is 49.39 percent.
Fig. 10 is a scanning electron micrograph of the surface of the obtained composite material, as can be seen from fig. 10: Pd-Al2O3The active layer discontinuously grows on the surface of the cordierite substrate, and a large number of cracks exist; Pd-Al2O3The thickness of the active layer is about 0.7 μm.
FIG. 11 shows Pd-Al in the obtained composite2O3Transmission electron micrograph of active layer (image with cordierite matrix subtracted) and can be seen in fig. 11: al (Al)2O3Contains a large number of worm-like mesopores, and Pd particles are uniformly dispersed in Al2O3In (3), the particle size is about 4.8 nm.
Comparative example 1
The raw materials used in this comparative example were the same as those used in example 2 except that, in the production process, the cordierite honeycomb channels were coated with alumina gel on the surfaces thereof and then oxidized to form Al2O3Layer, then impregnated with Pd (NO)3)2Solution to Al2O3The layer supported Pd. The comparative example is denoted as Pd/CO-M.
FIG. 12 shows the X-ray diffraction pattern of the obtained composite material (excluding the diffraction peak of cordierite matrix), and the Pd/Al can be confirmed to be obtained by XRD phase identification2O3An active layer; weighing to obtain: Pd/Al contained in the Pd/CO-M material2O3The mass percent of the active layer is 2.60%, wherein the mass percent of Pd metal in the active layer is 0.49%, and the mass percent of the cordierite-containing substrate is 97.40%.
Macroscopic measurements revealed that: in the material (Pd/CO-M) prepared in this comparative example, Pd/Al2O3The volume percentage of the active layer is 1.10 percent, the volume percentage of the cordierite matrix is 50 percent, and the void ratio is 48.9 percent.
FIG. 13 is a scanning electron micrograph of the surface of the obtained Pd/CO-M material, as can be seen from FIG. 13: the Pd/CO-M surface has a large number of gaps and is not flat, and Pd/Al2O3Filled in the gap and Pd/Al2O3The integrity of the active layer is not apparent; Pd-Al2O3The thickness of the active layer is about 0.9 μm.
FIG. 14 is a transmission electron micrograph (excluding images of cordierite matrix) of Pd/CO-M in the obtained material, as seen from FIG. 14: the alumina is in a rod-like structure, and Pd particles are dispersed in Al2O3The rod surface, particle size was about 8.0 nm.
Experiment of catalytic Effect
Will be at the topPd-Al prepared in the examples2O3Carrying out 2-ethyl anthraquinone catalytic hydrogenation reaction on the cordierite composite material and Pd/CO-M prepared in the comparative example: adopting a fixed bed reactor, firstly introducing hydrogen to carry out in-situ reduction, then adding 150mL of working solution with the concentration of 0.26mol/L of 2-ethylanthraquinone under the condition of continuously introducing hydrogen, and carrying out in-situ reduction at the temperature of 60 ℃ under the condition of 0.1MPaH2The reaction was carried out, and the experimental results are shown in FIG. 15, FIG. 16 and FIG. 17.
As can be seen from FIG. 15, the Pd-Al provided by the present invention2O3The cordierite composite material is used in the catalytic hydrogenation reaction of 2-ethyl anthraquinone, and the hydrogenation conversion rate of the 2-ethyl anthraquinone is improved by nearly 600 percent compared with Pd/CO-M prepared by traditional coating and dipping. In addition, as can be seen from FIG. 16, the present invention provides Pd-Al in comparison to Pd/CO-M2O3The cordierite composite material can effectively inhibit the generation of byproducts in the hydrogenation reaction of 2-ethyl anthraquinone, and the selectivity of the reaction is improved. As can be seen from FIG. 17, the present invention provides Pd-Al2O3After 8 times of tests, the catalytic activity of the cordierite composite material is not obviously reduced, and the catalytic activity characterized by the conversion rate of reactants is always kept above 94%, which shows that the catalytic performance of the composite material is stable.
In the experimental process, the Pd-Al is also discovered unexpectedly2O3-no MgSi is contained in the cordierite composite materialxO2x+1(x is 1, 2, 3) species, catalytic activity, as characterized by reactant conversion, will gradually decrease to around 85% after 8 trial and error runs in the same manner. This indicates MgSixO2x+1The (x ═ 1, 2, 3) species may help to maintain high dispersion of the metallic palladium or to maintain stability of the porous alumina layer structure.
In summary, it can be seen that: the invention provides Pd-Al2O3Compared with the prior art, the cordierite composite material has obvious progress and excellent catalytic effect, and the preparation method is simple, has a controllable structure, is suitable for industrial production, and has use value and application prospect.
The above embodiments are only used for further detailed description of the technical solutions of the present invention, but should not be understood as limiting the scope of the present invention, and the conventional modifications and adjustments made by those skilled in the art according to the above descriptions of the present invention are within the scope of the present invention.
Claims (4)
1. A palladium-alumina-cordierite composite, comprising:
a cordierite substrate having a plurality of honeycomb cells; the cordierite substrate is 50 mm in length, 30 mm in diameter and 0.125 mm in aperture of a honeycomb pore channel;
a porous alumina layer grown on the surfaces of the honeycomb-shaped pore canals, wherein metal palladium particles are dispersed on the porous alumina layer, and the porous alumina layer also contains MgSixO2x+1A species, wherein x =1, 2, 3; the thickness of the porous alumina active layer is 0.6-3.0 μm, and the diameter of the metal palladium particles is 3-5 nm;
the preparation method of the palladium-alumina-cordierite composite material comprises the following steps: immersing a cordierite substrate in a synthesis mother liquor located within a reactor, wherein the synthesis mother liquor comprises a polyoxyethylene polyoxypropylene ether block copolymer, aluminum isopropoxide, magnesium nitrate hexahydrate, PdCl2HCl, citric acid and ethanol, wherein the mass ratio of the HCl to the citric acid to the ethanol is that the polyoxyethylene polyoxypropylene ether block copolymer: aluminum isopropoxide: magnesium nitrate hexahydrate: PdCl2: HCl: citric acid: ethanol = 1: (0.9-1.2): (0.225-0.3): (0.002-0.02): (1.6-2.0): (0.5-0.9): (8-14), then sealing the reactor and reacting for 2-4 days at the autogenous pressure at the temperature of 110-140 ℃ to obtain the palladium-alumina-cordierite composite material.
2. The palladium-alumina-cordierite composite material according to claim 1, wherein the total mass of the palladium and the porous alumina layer is 0.5 to 5% by mass of the composite material, the mass ratio of the palladium to the porous alumina is not less than 0.4%, and the MgSi isxO2x+1The mass ratio of species to the porous alumina is 1.0-10%, wherein x =1, 2, 3.
3. The palladium-alumina-cordierite composite material of claim 1 wherein the cordierite substrate is pretreated prior to hydrothermal reaction by: firstly, calcining for not less than 1h in an air atmosphere at the temperature of not less than 500 ℃; boiling in xylene for at least 10min, treating in hydrogen peroxide at 80 deg.C or higher for at least 15min, and washing with deionized water; finally, after ultrasonic treatment in deionized water, drying at a temperature of not lower than 110 ℃ for standby.
4. Use of the palladium-alumina-cordierite composite material according to claim 1 for the catalytic hydrogenation of anthraquinones and their substitutes, for doubling the hydrogenation rate, for increasing the selectivity of hydroanthraquinones and their substitutes and for extending the catalyst life.
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