CN113101910A - Large-pore-volume aluminum oxide material with reducibility and preparation method thereof - Google Patents
Large-pore-volume aluminum oxide material with reducibility and preparation method thereof Download PDFInfo
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- CN113101910A CN113101910A CN202110344322.8A CN202110344322A CN113101910A CN 113101910 A CN113101910 A CN 113101910A CN 202110344322 A CN202110344322 A CN 202110344322A CN 113101910 A CN113101910 A CN 113101910A
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- 239000000463 material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 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 64
- 239000003054 catalyst Substances 0.000 claims abstract description 56
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 47
- 239000011148 porous material Substances 0.000 claims abstract description 34
- 238000010899 nucleation Methods 0.000 claims abstract description 32
- 230000006911 nucleation Effects 0.000 claims abstract description 32
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 238000002425 crystallisation Methods 0.000 claims abstract description 22
- 230000008025 crystallization Effects 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 21
- 150000003839 salts Chemical class 0.000 claims abstract description 19
- 238000002955 isolation Methods 0.000 claims abstract description 11
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 41
- 239000008367 deionised water Substances 0.000 claims description 34
- 229910021641 deionized water Inorganic materials 0.000 claims description 34
- 238000003756 stirring Methods 0.000 claims description 18
- 239000000725 suspension Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 239000002002 slurry Substances 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000012467 final product Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 8
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 7
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 229910003244 Na2PdCl4 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- WPUINVXKIPAAHK-UHFFFAOYSA-N aluminum;potassium;oxygen(2-) Chemical compound [O-2].[O-2].[Al+3].[K+] WPUINVXKIPAAHK-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910001414 potassium ion Inorganic materials 0.000 claims description 2
- 229910002093 potassium tetrachloropalladate(II) Inorganic materials 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- 229910001415 sodium ion Inorganic materials 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 230000002829 reductive effect Effects 0.000 abstract description 10
- 150000004056 anthraquinones Chemical class 0.000 abstract description 9
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 9
- 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 7
- 230000009467 reduction Effects 0.000 abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 abstract description 4
- 229920002521 macromolecule Polymers 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 229910052763 palladium Inorganic materials 0.000 abstract description 2
- 229910052697 platinum Inorganic materials 0.000 abstract description 2
- 238000009827 uniform distribution Methods 0.000 abstract description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract 2
- 238000007598 dipping method Methods 0.000 abstract 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 15
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 15
- 238000005303 weighing Methods 0.000 description 14
- 230000001603 reducing effect Effects 0.000 description 12
- 229910020639 Co-Al Inorganic materials 0.000 description 10
- 229910020675 Co—Al Inorganic materials 0.000 description 10
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 8
- 238000005086 pumping Methods 0.000 description 7
- 239000012224 working solution Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 229910052593 corundum Inorganic materials 0.000 description 6
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 229910018657 Mn—Al Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- SNDGLCYYBKJSOT-UHFFFAOYSA-N 1,1,3,3-tetrabutylurea Chemical compound CCCCN(CCCC)C(=O)N(CCCC)CCCC SNDGLCYYBKJSOT-UHFFFAOYSA-N 0.000 description 1
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000000547 structure data Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6562—Manganese
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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
- B01J23/70—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J37/16—Reducing
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Abstract
The invention provides a large pore volume aluminum oxide material with reducibility and a preparation method thereof, which utilize the reducibility of variable valence transition metal elements, inject aluminum salt, variable valence metal salt and alkali solution into a nucleation/crystallization isolation reactor by a three-strand parallel flow method, uniformly disperse variable valence metals into pseudo-boehmite under the action of forced micro-mixing, and obtain pure phase gamma-type aluminum oxide with reducibility after roasting. The prepared aluminum oxide material can reduce noble metals Pd and Pt by dipping without adding a reducing agent to obtain a supported noble metal catalyst, and the dispersity of spontaneously reduced noble metals is obviously improved due to the uniform distribution of surface reduction sites of the supported noble metal catalyst. In addition, the macroporous structure of the alumina provides a good mass transfer space for reaction macromolecules, the obtained noble metal catalyst can catalyze the anthraquinone hydrogenation reaction at room temperature, and the excellent production capacity of preparing hydrogen peroxide by an anthraquinone method is shown.
Description
Technical Field
The invention belongs to the field of catalytic materials, and particularly relates to a large pore volume aluminum oxide material with reducibility and a preparation method thereof.
Background
The pseudoboehmite is an alumina with fine particles, incomplete crystals and a space network structure, the water-containing state of the pseudoboehmite is thixotropic gel, and a product gamma-Al calcined at 400-2O3Widely used as catalyst carrier, catalyst, adsorbent, etc. The pseudo-boehmite produced by different routes and methods endows alumina with different properties and purposes, and particularly when the pseudo-boehmite is used as a catalyst carrier, surface sites and a pore structure of the pseudo-boehmite have important influence on the dispersion of active components of a supported catalyst and the diffusion of macromolecular reactants. The most common preparation method of supported metal catalysts is a liquid phase impregnation method, and due to the presence of surface tension of a solvent, active metal components are not easily uniformly dispersed and agglomerated and inactivated in the subsequent roasting and reduction processes, thereby reducing the atom utilization rate of the active metal, particularly for the supported metal catalystsIn the case of the noble metal catalyst, the agglomeration of the noble metal active component brings about a great increase in the catalyst cost, and therefore, it is of great significance to develop the regulation of the surface structure of the carrier based on the impregnation method which is most widely used in industry, thereby improving the dispersion degree of the catalyst active component. In addition, for the serial catalytic reaction process involving macromolecules, the large pore volume characteristic of the carrier material can provide enough space for the transfer of reaction molecules, reduce the collision frequency of the reaction molecules and active components in pores, and obviously improve the selectivity of intermediate products in the serial catalytic reaction. However, in the preparation process of the alumina carrier material, how to realize the adjustment of the pore volume of the metal active component while realizing high dispersion of the metal active component in the loading process through the construction of the surface site of the carrier still has great challenges.
The structure and the appearance of the pseudo-boehmite have important influence on the pore volume of the alumina in the process of synthesizing the alumina. The Kamylar Keyvanolo, Maryam Khosravi Markkhe, Todd M.Alam, Calvin H.Bartholomew, Brian F.Woodfield, William C.Hecker, ACS Catalysis 2014,4, 1071-. The application of the adjustable chemical composition of layered composite metal hydroxide (LDH) laminates in the documents Haiping Li, Tianxing Yang, Yiwei Jiang, Shuai Chen, Yufei He, Junting Feng, Dianqing Li, Journal of Catalysis 2020,385, 313-doped 323 for reducing Co2+The LDH is introduced with ions to obtain a reductive carrier, and the Pd is reduced by using the carrier under the condition of not adding a reducing agent to prepare the sub-nanometer supported catalyst, and an active component in the catalyst can be stably anchored at the periphery of a reduction site of the carrier, so that the catalyst has the advantage of high dispersion. However, LDH materials are inferior to alumina in terms of shape, strength and stability, which limits their application in industrial catalysis. Although catalysis can be enhanced by impregnation with reducing metal ionsThe dispersion degree of the catalyst can cause the blockage of the pore channels of the carrier in the introduction process, reduce the pore volume of the carrier and influence the catalytic mass transfer efficiency.
Disclosure of Invention
The invention aims to provide a large-pore-volume aluminum oxide material with reducibility, and the invention also aims to provide a preparation method of the large-pore-volume aluminum oxide material with reducibility, wherein the aluminum oxide is obtained by roasting the pseudoboehmite provided by the invention at high temperature, has the characteristics of large pore volume, high purity and uniform reduction site distribution on the surface, and the noble metal catalyst prepared by the carrier is expressed as xM/yN-Al2O3Wherein M represents a noble metal and is one or two of Pd and Pt; n represents doped variable valence transition metal and is one or two of Co and Mn; x and y respectively represent the loading amounts of the noble metal and the variable valence metal in the catalyst, and the active components of the catalyst are highly dispersed, can catalyze the hydrogenation reaction of the anthraquinone at normal temperature, and have good catalytic activity and catalytic selectivity.
The large pore volume aluminum oxide material with reducibility and the preparation method thereof comprise the following specific steps:
A. respectively dissolving soluble meta-aluminate and aluminum salt in different deionized water according to a molar ratio of about 1:6, dissolving metal salt containing variable valence metal elements in the deionized water, and balancing to the same volume.
The metaaluminate can be one or two of sodium metaaluminate and potassium metaaluminate, and the aluminum salt can be one or more of aluminum sulfate, aluminum nitrate and aluminum chloride.
The variable valence metal elements are all low oxidation state divalent transition metals, and can be Co2+And Mn2+One or two of (1).
The metal salt may be one or more of a sulfate, a nitrate, a chloride.
The mass of the variable valence metal salt is 1-20 wt% of the variable valence metal content in the final product.
B. And C, injecting the three solutions in the step A into a nucleation/crystallization isolation reactor with the rotation speed of 1500-. The alkali solution is one or more of sodium hydroxide, ammonia water and potassium hydroxide, and the concentration is 0.1-1M. Cooling the slurry after crystallization, washing the slurry with deionized water until no sodium/potassium ions are contained, filtering the slurry, and drying the filtered slurry at the temperature of between 80 and 120 ℃ until the weight of the filtered slurry is constant to obtain the pseudo-boehmite powder. The pseudo-boehmite is roasted at the temperature of 600-1000 ℃ to obtain the gamma-alumina material with the reducibility and large pore volume.
C. And B, dispersing the alumina powder obtained in the step B in deionized water to prepare a suspension with the solid content of 100-200ml/g, and stirring at room temperature for 5-15min to uniformly disperse the suspension. And (3) dropwise adding a noble metal salt solution, and determining the dosage of the noble metal salt according to the mass ratio of the noble metal in the catalyst to the alumina carrier of 0.05-2%. And stirring at room temperature for 5-9 hours, finishing the reaction, filtering, washing with deionized water to neutrality, and performing vacuum freeze drying at-60-30 ℃ for 6-9 hours to obtain the reducing and large pore volume alumina material-based supported catalyst.
The noble metal salt is K2PdCl4、Na2PdCl4、H2PtCl6The concentration of one or two of (1) is 25-50 mmol/L.
The invention has the beneficial effects that:
on the basis of preparing pseudo-boehmite by a precipitation method widely adopted in China, the invention proposes that reducible heteroatoms are uniformly introduced into an alumina precursor by a bulk phase doping method, the reduction characteristic is utilized to realize the improvement of the dispersity of a noble metal catalyst, meanwhile, the uniform doping of the heteroatoms in an alumina unit cell can change the structural property of alumina without generating an impurity phase, and particularly in a high-temperature environment, the surface Al is prevented from being doped3+Diffusion of ions to octahedral sites allows the alumina to remain porous after firing. By utilizing the reducibility of variable valence transition metal elements, aluminum salt, variable valence metal salt and alkali solution are injected into a nucleation/crystallization isolation reactor by a three-strand parallel flow method, and the variable valence metals are uniformly dispersed into pseudo-boehmite under the action of forced micro-mixingAnd calcining the mixture to obtain pure-phase gamma-type alumina with reducibility. The internal structure of the alumina can be changed by doping the transition metal element, so that the thermal stability and the pore volume of the alumina are influenced, and the alumina still has larger pore volume and specific surface after being roasted. The obtained alumina with reducibility and large pore volume is used as a carrier, a supported noble metal catalyst is prepared by adopting an impregnation method, the alumina and noble metal can carry out spontaneous redox reaction through self reducibility, the noble metal is reduced to obtain the supported catalyst on the premise of not adding a reducing agent, and the dispersion degree of the spontaneously reduced noble metal is obviously improved due to the uniform distribution of reduction sites on the surface of the supported catalyst. In addition, the macroporous structure of the alumina provides a good mass transfer space for reaction macromolecules, and the obtained noble metal catalyst shows good catalytic performance in the anthraquinone hydrogenation reaction, and the hydrogenation efficiency is improved by more than 30% compared with that of an industrial catalyst.
Drawings
FIG. 1 is an X-ray diffraction analysis (XRD) spectrum of a sample prepared in example 1;
FIG. 2 shows 0.5Pd/5Co-Al obtained in example 42O3X-ray photoelectron spectroscopy (XPS) of Pd element in the catalyst;
FIG. 3 shows 0.2Pd/10Co-Al obtained in example 52O3X-ray photoelectron spectroscopy (XPS) of Pd element in the catalyst;
FIG. 4 is a High Resolution Transmission Electron Microscope (HRTEM) image of example 4;
fig. 5 is a High Resolution Transmission Electron Microscope (HRTEM) image of example 5.
Detailed Description
The invention provides a large pore volume alumina material with reducibility and a preparation method thereof, which are explained in detail by the following specific examples:
example 1
A. Weighing a certain mass of sodium metaaluminate and aluminum sulfate, respectively dissolving in 200mL of deionized water to prepare the solution with the concentration of 0.72 mol.L-1，0.12moL·L-1The solution of (1); weighing a certain mass of cobalt nitrate, and dissolving the cobalt nitrate in deionized water, wherein the mass of the cobalt nitrate is calculated by the Co content in the final product being 5 wt%.
B. Pumping the three solutions in the step A into a nucleation/crystallization isolation reactor simultaneously by adopting three parallel flows, controlling the nucleation temperature at 70 ℃, controlling the nucleation time at 30min, transferring the solution into a 90 ℃ water bath for crystallization for 90min after nucleation is finished, drying the solution for 4h to constant weight after 5 times of washing to obtain pseudo-boehmite powder, and roasting the pseudo-boehmite for 4h at 960 ℃ to obtain the reductive large-pore-volume gamma-type alumina material (5 Co-Al)2O3)。
C. 0.5g of 5Co-Al from step B2O3Dispersing in 100mL deionized water to prepare suspension, and stirring at room temperature for 10min to uniformly disperse the suspension. And (3) dropwise adding a noble metal Pd solution, and determining the dosage of the noble metal salt according to the mass ratio of the noble metal in the catalyst to the alumina carrier of 1.5%. Stirring at room temperature for 8 hr, filtering, washing with deionized water to neutrality, and vacuum freeze drying at-50 deg.C for 8 hr to obtain reducing and macroporous alumina material-based supported catalyst (1.5Pd/5 Co-Al)2O3)。
Example 2
A. Weighing a certain mass of sodium metaaluminate and aluminum nitrate, respectively dissolving in 200mL of deionized water to prepare the solution with the concentration of 0.72 mol.L-1，0.12moL·L-1The solution of (1); weighing a certain mass of manganese nitrate, and dissolving the manganese nitrate in an aluminum nitrate solution, wherein the mass of the manganese nitrate is calculated by the Mn content in a final product being 9 wt%.
B. Pumping the three solutions in the step A into a nucleation/crystallization isolation reactor simultaneously by adopting a three-strand parallel flow method, controlling the nucleation temperature at 70 ℃, controlling the nucleation time at 50min, transferring to a water bath at 80 ℃ for crystallization for 120min after nucleation is finished, drying the washed precipitate at 120 ℃ to constant weight to obtain pseudo-boehmite powder, and roasting the pseudo-boehmite at 960 ℃ for 4h to obtain the reductive large-pore-volume gamma-type aluminum oxide material (9 Mn-Al)2O3)。
C. 0.5g of the 9Mn-Al obtained in step B2O3Dispersing in 100mL deionized water to prepare suspension, and stirring at room temperature for 10min to uniformly disperse the suspension. And (3) dropwise adding a noble metal Pt solution, and determining the dosage of the noble metal salt according to the mass ratio of the noble metal in the catalyst to the alumina carrier of 0.5%. Stirring was continued at room temperature for 6 hoursThen the reaction is finished, the mixture is filtered, washed to be neutral by deionized water and vacuum freeze-dried for 8 hours at the temperature of minus 50 ℃ to obtain the load type catalyst (0.5Pt/9 Mn-Al) based on the reducing and large pore volume alumina material2O3)。
Example 3
A. Weighing a certain mass of sodium metaaluminate and aluminum sulfate, respectively dissolving in 200mL of deionized water to prepare the solution with the concentration of 0.72 mol.L-1，0.12moL·L-1The solution of (1); weighing a certain mass of cobalt nitrate, and dissolving the cobalt nitrate in deionized water, wherein the mass of the cobalt nitrate is calculated by the Co content in the final product being 5 wt%.
B. Pumping the three solutions in the step A into a nucleation/crystallization isolation reactor simultaneously by adopting a three-strand parallel flow method, controlling the nucleation temperature at 70 ℃, controlling the nucleation time at 30min, transferring to a 90 ℃ water bath for crystallization for 90min after nucleation is finished, drying the washed precipitate at 110 ℃ to constant weight to obtain pseudo-boehmite powder, and roasting the pseudo-boehmite at 960 ℃ for 4h to obtain the reductive large-pore-volume gamma-type aluminum oxide material (5 Co-Al)2O3)。
C. 0.5g of 5Co-Al from step B2O3Dispersing in 100mL deionized water to prepare suspension, and stirring at room temperature for 10min to uniformly disperse the suspension. And (3) dropwise adding a noble metal Pt solution, and determining the dosage of the noble metal salt according to the mass ratio of the noble metal in the catalyst to the alumina carrier of 0.5%. Stirring at room temperature for 8 hr, filtering, washing with deionized water to neutrality, and vacuum freeze drying at-50 deg.C for 8 hr to obtain load type catalyst (0.5Pt/5 Co-Al) based on reducing and macroporous alumina material2O3)。
Example 4
A. Weighing a certain mass of sodium metaaluminate and aluminum sulfate, respectively dissolving in 200mL of deionized water to prepare the solution with the concentration of 0.72 mol.L-1，0.12moL·L-1The solution of (1); weighing a certain mass of cobalt nitrate, and dissolving the cobalt nitrate in an aluminum sulfate solution, wherein the mass of the cobalt nitrate is calculated by the Co content in a final product being 5 wt%.
B. Pumping the three solutions in the step A into a nucleation/crystallization isolation reactor simultaneously by adopting a three-strand parallel flow method, controlling the nucleation temperature at 70 ℃, and controlling the nucleationThe crystallization is carried out for 30min, the crystal is transferred to a water bath with the temperature of 90 ℃ for crystallization for 90min after nucleation is finished, the washed precipitate is dried to constant weight at the temperature of 100 ℃ to obtain pseudo-boehmite powder, and the pseudo-boehmite is roasted for 4h at the temperature of 960 ℃ to obtain the gamma-alumina material (5 Co-Al) with the reducibility and large pore volume2O3)。
C. 0.5g of 5Co-Al from step B2O3Dispersing in 100mL deionized water to prepare suspension, and stirring at room temperature for 10min to uniformly disperse the suspension. And (3) dropwise adding a noble metal Pd solution, and determining the dosage of the noble metal salt according to the mass ratio of the noble metal in the catalyst to the alumina carrier of 0.5%. Stirring at room temperature for 6 hr, filtering, washing with deionized water to neutrality, and vacuum freeze drying at-50 deg.C for 8 hr to obtain load type catalyst (0.5Pd/5 Co-Al) based on reducing and macroporous alumina material2O3)。
Example 5
A. Weighing a certain mass of sodium metaaluminate and aluminum sulfate, respectively dissolving in 200mL of deionized water to prepare the solution with the concentration of 0.72 mol.L-1，0.12moL·L-1The solution of (1); weighing a certain mass of cobalt nitrate, and dissolving the cobalt nitrate in an aluminum sulfate solution, wherein the mass of the cobalt nitrate is calculated by the Co content in a final product being 10 wt%.
B. Pumping the three solutions in the step A into a nucleation/crystallization isolation reactor simultaneously by adopting a three-strand parallel flow method, controlling the nucleation temperature at 70 ℃, controlling the nucleation time at 30min, transferring into a 90 ℃ water bath for crystallization for 120min after nucleation is finished, drying the washed precipitate at 90 ℃ to constant weight to obtain pseudo-boehmite powder, and roasting the pseudo-boehmite at 960 ℃ for 4h to obtain the reductive large-pore-volume gamma-type aluminum oxide material (10 Co-Al)2O3)。
C. 0.5g of 10Co-Al from step B2O3Dispersing in 100mL deionized water to prepare suspension, and stirring at room temperature for 10min to uniformly disperse the suspension. And (3) dropwise adding a noble metal Pd solution, and determining the dosage of the noble metal salt according to the mass ratio of the noble metal in the catalyst to the alumina carrier of 0.2%. Stirring at room temperature for 6 hr, filtering, washing with deionized water to neutrality, vacuum freeze drying at-50 deg.C for 8 hr to obtain aluminum oxide material with reducibility and large pore volumeSupported catalyst for catalyst (0.2Pd/10 Co-Al)2O3)。
Example 6
A. Weighing a certain mass of sodium metaaluminate and aluminum sulfate, respectively dissolving in 200mL of deionized water to prepare the solution with the concentration of 0.72 mol.L-1，0.12moL·L-1The solution of (1); weighing a certain mass of cobalt nitrate, and dissolving the cobalt nitrate in an aluminum sulfate solution, wherein the mass of the cobalt nitrate is calculated by the Co content in a final product being 9 wt%.
B. Pumping the three solutions in the step A into a nucleation/crystallization isolation reactor simultaneously by adopting a three-strand parallel flow method, controlling the nucleation temperature at 80 ℃, controlling the nucleation time at 30min, transferring to a 90 ℃ water bath for crystallization for 60min after nucleation is finished, drying the washed precipitate at 90 ℃ to constant weight to obtain pseudo-boehmite powder, and roasting the pseudo-boehmite at 900 ℃ for 4h to obtain the gamma-type alumina material (9 Co-Al) with reducibility with large pore volume2O3)。
C. 0.5g of the 9Co-Al obtained in step B2O3Dispersing in 100mL deionized water to prepare suspension, and stirring at room temperature for 10min to uniformly disperse the suspension. And (3) dropwise adding a noble metal Pd solution, and determining the dosage of the noble metal salt according to the mass ratio of the noble metal in the catalyst to the alumina carrier of 1.5%. Stirring at room temperature for 6 hr, filtering, washing with deionized water to neutrality, and vacuum freeze drying at-50 deg.C for 8 hr to obtain reducing and macroporous alumina material-based supported catalyst (1.5Pd/9 Co-Al)2O3)。
Example 7
A. Weighing a certain mass of sodium metaaluminate and aluminum nitrate, respectively dissolving in 200mL of deionized water to prepare the solution with the concentration of 0.72 mol.L-1，0.12moL·L-1The solution of (1); weighing a certain mass of manganese nitrate, and dissolving the manganese nitrate in an aluminum nitrate solution, wherein the mass of the manganese nitrate is calculated by that the Mn content in a final product is 15 wt%.
B. Pumping the three solutions in the step A into a nucleation/crystallization isolation reactor simultaneously by adopting a three-strand parallel flow method, controlling the nucleation temperature at 80 ℃, controlling the nucleation time at 60min, transferring to 80 ℃ water bath for crystallization for 120min after nucleation is finished, drying the washed precipitate at 100 ℃ to constant weight to obtain the pseudo-weightBaking boehmite powder and pseudo-boehmite at 800 deg.C for 4h to obtain reducing gamma-type alumina material (15 Mn-Al)2O3)。
C. 0.5g of the 15Mn-Al obtained in step B2O3Dispersing in 100mL deionized water to prepare suspension, and stirring at room temperature for 10min to uniformly disperse the suspension. And (3) dropwise adding a noble metal Pt solution, and determining the dosage of the noble metal salt according to the mass ratio of the noble metal in the catalyst to the alumina carrier of 0.5%. Stirring at room temperature for 6 hr, filtering, washing with deionized water to neutrality, and vacuum freeze drying at-50 deg.C for 8 hr to obtain load type catalyst (0.5Pt/15 Mn-Al) based on reducing and macroporous alumina material2O3)。
The drawings illustrate in detail:
FIG. 1 is an X-ray diffraction analysis (XRD) spectrum of a sample prepared in example 1, from which it can be seen that the Co-introduced sample after firing at 960 ℃ is gamma-Al2O3Crystal form, no impurity phase.
FIG. 2 shows 0.5Pd/5Co-Al obtained in example 42O3X-ray photoelectron Spectroscopy (XPS) of Pd element in catalyst, wherein Pd exists in Pd0And Pd2+Species, Pd0Presence of (2) proves 5Co-Al2O3Has reducing property, and can reduce Pd without adding a reducing agent. Pd2+Is present due to oxidation by oxygen in the air during storage.
FIG. 3 shows 0.2Pd/10Co-Al obtained in example 52O3X-ray photoelectron Spectroscopy (XPS) of Pd element in the catalyst, when the Pd/Co ratio is decreased, Pd in the catalyst is reduced as compared with FIG. 20The content of (a) is significantly increased.
FIG. 4 is a photograph taken by High Resolution Transmission Electron Microscopy (HRTEM) of example 4, wherein the Pd average particle size of the catalyst is 1.2 nm.
FIG. 5 is a photograph taken by a High Resolution Transmission Electron Microscope (HRTEM) of example 5, wherein the Pd average particle diameter of the catalyst is 0.9 nm.
The samples obtained were characterized as follows:
in Table 1 are the low temperature nitrogen adsorption characterization data for the modified alumina, the 5 wt% Co impregnated alumina, and the aluminas obtained in examples 4 and 6. It can be seen from the data in the table that bulk doping is beneficial to increase pore volume, while impregnation can plug the channels.
TABLE 1 sample well Structure data Table
| Sample (I) | Specific surface area (m)2/g) | Pore size (nm) | Pore volume (cm)3/g) |
| Al2O3 | 133.6 | 6.2 | 0.21 |
| Impregnating with 5% Co/Al2O3 | 94.9 | 17.1 | 0.40 |
| Example 4 | 123.6 | 19.8 | 0.61 |
| Example 6 | 117.1 | 22.9 | 0.67 |
| Example 7 | 118.6 | 25.4 | 0.95 |
Application example:
industrial Pd/Al2O3Catalysts of examples 1 and 6 and impregnation of 1.5Pd5Co/Al obtained by stepwise impregnation of Co and Pd2O3The catalyst is applied to anthraquinone hydrogenation reaction to evaluate the catalytic performance, and comprises the following specific steps:
a slurry bed reactor with a heating device is used as an evaluation device, the concentration of anthraquinone working solution is 120g/L, and the solvent of the working solution is prepared by mixing 1,3, 5-trimethylbenzene, trioctyl phosphate and tetrabutyl urea according to the weight ratio of 6: 2: 2, dissolving a certain mass of 2-ethyl anthraquinone in a solvent, washing for 2-3 times by using 0.01M NaOH solution after complete dissolution, then washing to be neutral by using deionized water, and finally adding a drying agent to remove moisture in the working solution. Adding 50mg of catalyst and 30mL of anthraquinone working solution into a reactor, maintaining the temperature of the reactor at 30-50 ℃, introducing hydrogen from the bottom of the reactor at the flow rate of 30mL/min, allowing the hydrogen to form micro bubbles through a sand core and flow upwards to drive the catalyst and the working solution to move, timing for 30min, taking out the working solution to evaluate the activity and the selectivity, adding fresh working solution into the reactor, continuing to react, and repeating for 5 times. The hydrogenation efficiencies of the catalysts are shown in Table 2(30 ℃ C.) and Table 3(50 ℃ C.).
TABLE 2 evaluation of hydrogenation Properties of anthraquinones at Normal temperature (30 ℃ C.)
TABLE 3 evaluation of hydrogenation Properties of anthraquinones under Industrial conditions (50 ℃ C.)
| Catalyst and process for preparing same | Industrial Pd/Al2O3 | Example 1 |
| Hydrogenation efficiency (g/L) | 11.34 | 14.76 |
Claims (9)
1. The method for preparing the large-pore-volume aluminum oxide material with reducibility is characterized by comprising the following steps of:
A. respectively dissolving soluble meta-aluminate and aluminum salt in different deionized water according to a molar ratio of about 1:6, dissolving metal salt containing variable valence metal elements in the deionized water, and balancing to the same volume.
B. And C, injecting the three solutions in the step A into a nucleation/crystallization isolation reactor with the rotation speed of 1500-. Cooling the slurry after crystallization, washing the slurry with deionized water until no sodium/potassium ions are contained, filtering the slurry, and drying the filtered slurry at the temperature of between 80 and 120 ℃ until the weight of the filtered slurry is constant to obtain the pseudo-boehmite powder. The pseudo-boehmite is roasted at the temperature of 600-1000 ℃ to obtain the gamma-alumina material with the reducibility and large pore volume.
C, dispersing the alumina powder obtained in the step B in deionized water, preparing a suspension with the solid content of 100-200ml/g, stirring at room temperature for 5-15min to uniformly disperse the suspension, dropwise adding a noble metal salt solution, determining the dosage of the noble metal salt according to the mass ratio of the noble metal to the alumina in the catalyst of 0.05-2%, continuing stirring at room temperature for 5-9 hours, ending the reaction, filtering, washing with deionized water to be neutral, and performing vacuum freeze drying at-60 to-30 ℃ for 6-9 hours to obtain the macroporous alumina material with reducibility.
2. The large pore volume alumina material with reducibility and the preparation method thereof as claimed in claim 1, wherein: and step B, performing bulk phase doping of pseudo-boehmite in a nucleation/crystallization reactor in a three-strand parallel flow mode, wherein the impurity element is one or two of variable valence transition metal elements Co and Mn, the calcined pure-phase gamma-type alumina has reducibility, the dispersion degree of the noble metal can be improved by taking the pure-phase gamma-type alumina material as a carrier in the impregnation process, the particle size of the noble metal is 0.5-3nm, and the pore volume of the pure-phase gamma-type alumina material can still be kept at 0.6-1.0cm after the pure-phase gamma-type alumina material is calcined at the temperature of 600-1000 DEG C3/g。
3. The large pore volume alumina material with reducibility and the preparation method thereof as claimed in claim 1, wherein: the meta-aluminate in the step A can be one or two of sodium meta-aluminate and potassium meta-aluminate.
4. The large pore volume alumina material with reducibility and the preparation method thereof as claimed in claim 1, wherein: the aluminum salt in the step A can be one or more of aluminum sulfate, aluminum nitrate and aluminum chloride.
5. The large pore volume alumina material with reducibility and the preparation method thereof as claimed in claim 1, wherein: the metal salt in the step A can be one or more of sulfate, nitrate and chloride.
6. The large pore volume alumina material with reducibility and the preparation method thereof as claimed in claim 1, wherein: the mass of the metal salt containing variable valence metal element in the step A is 1-20 wt% of the content of variable valence metal in the final product.
7. The method of claim 2, wherein the large pore volume of the catalyst is reducedAn alumina material and a preparation method thereof are characterized in that: the variable valence transition metal elements are all low oxidation state divalent transition metals, and can be Co2+And Mn2+One or two of (1).
8. The large pore volume alumina material with reducibility and the preparation method thereof as claimed in claim 1, wherein: the alkali solution in the step B is one or more of sodium hydroxide, ammonia water and potassium hydroxide, and the concentration is 0.1-1M.
9. The large pore volume alumina material with reducibility and the preparation method thereof as claimed in claim 1, wherein: the noble metal salt in the step C is K2PdCl4、Na2PdCl4、H2PtCl6The concentration of one or two of (1) is 25-50 mmol/L.
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