CN112705271B - Hollow spherical carrier and preparation method and application thereof - Google Patents
Hollow spherical carrier and preparation method and application thereof Download PDFInfo
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- CN112705271B CN112705271B CN201911018485.6A CN201911018485A CN112705271B CN 112705271 B CN112705271 B CN 112705271B CN 201911018485 A CN201911018485 A CN 201911018485A CN 112705271 B CN112705271 B CN 112705271B
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- spherical particles
- porous material
- spherical
- soluble salt
- catalyst
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 33
- 239000011148 porous material Substances 0.000 claims abstract description 27
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 72
- 235000002639 sodium chloride Nutrition 0.000 claims description 54
- 239000012798 spherical particle Substances 0.000 claims description 38
- 239000011780 sodium chloride Substances 0.000 claims description 35
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 24
- 239000011230 binding agent Substances 0.000 claims description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 19
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 19
- 238000005096 rolling process Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 10
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 5
- 239000003377 acid catalyst Substances 0.000 claims description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 4
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000003125 aqueous solvent Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims 1
- 150000001342 alkaline earth metals Chemical class 0.000 claims 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims 1
- 238000005299 abrasion Methods 0.000 abstract description 8
- 239000000843 powder Substances 0.000 description 24
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 18
- 239000002245 particle Substances 0.000 description 16
- 239000008188 pellet Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 229910021529 ammonia Inorganic materials 0.000 description 9
- 238000004140 cleaning Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000011949 solid catalyst Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000008093 supporting effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- -1 fields of refining Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8876—Arsenic, antimony or bismuth
-
- 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
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- 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
- B01J35/60—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
-
- 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
- B01J35/60—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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a hollow spherical carrier and a preparation method and application thereof, wherein the carrier comprises a shell layer of porous material and a spherical cavity surrounded by the shell layer. The carrier has high strength, long service life and low abrasion, and can be effectively combined with the active components of the catalyst to efficiently and stably catalyze the selective oxidation reaction.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a catalyst containing a hollow spherical carrier.
Background
The catalyst has extremely important position in modern chemical industry, more than nine chemical reaction processes need to be used in the catalyst, including fields of refining, chemical industry, environmental protection and the like, wherein the heterogeneous solid catalyst is most commonly used in the industry, and has the advantages of continuous production, easy recovery and the like.
The carrier is an important component of heterogeneous solid catalyst, can play a role in supporting and dispersing active components of the catalyst, is beneficial to improving catalytic performance and physical indexes and reduces the production cost of the catalyst.
In the prior art, the catalyst carrier is often powder or solid spheres, the powder carrier and the active components are mixed and then formed into a solid particle catalyst, and the supported active components are difficult to sinter together because the activation temperature of the supported active components is not too high, so that the catalyst carrier has small supporting effect on the catalyst and the integral mechanical strength of the catalyst is low; or the solid spherical carrier surface is coated with the active component to prepare the spherical catalyst, and the active component only exists on the surface of the catalyst, so that the problems of spalling of the active component and deactivation of the catalyst are easy to occur in the later use process.
Disclosure of Invention
One of the technical problems to be solved by the invention is that the solid catalyst in the prior art has lower mechanical strength and shorter service life, so that the hollow spherical carrier with high mechanical strength and long service life is provided, and has higher porosity and low abrasion.
The second technical problem to be solved by the invention is to provide a preparation method for obtaining the hollow spherical carrier, which has simple process and lower cost.
The third technical problem to be solved by the invention is to provide the application of the hollow spherical carrier.
The invention firstly provides a hollow spherical carrier which comprises a shell layer of porous material and a spherical cavity surrounded by the shell layer. The hollow spherical carrier of the present invention has a hollow core and a porous open shell.
According to some embodiments of the invention, the ratio of the average diameter of the cavity to the average thickness of the shell layer is 0.1-3.5, e.g. 0.1, 0.2, 0.3, 0.38, 0.4, 0.5, 0.6, 0.7, 0.77, 0.8, 0.83, 0.89, 0.9, 0.96, 1.0, 1.8, 2.0, 2.5, 3.0, etc.
According to some embodiments of the invention, the cavity has an average diameter of 0.5-5mm, e.g., 1.0mm, 1.5mm, 2.0mm, 2.5mm,3.0 mm, 3.5mm, 4.0mm, 4.5mm, etc.
According to some embodiments of the invention, the shell layer has a thickness of 1-5mm, e.g., 1.0mm, 1.5mm, 2.0mm, 2.5mm,3.0 mm, 3.5mm, 4.0mm, 4.5mm, 5mm, etc.
According to some embodiments of the invention, the carrier has a crush strength of 25-500N.
According to some embodiments of the invention, the carrier has an attrition rate of 0.1 to 5%.
According to some embodiments of the invention, the overall porosity (volume content) of the support is 20-80%, e.g., 20%, 30%, 40%, 50%, 60%, 70%, 80%, etc.
According to some embodiments of the invention, the porosity of the shell layer is 30-75%, e.g., 30%, 40%, 50%, 60%, 70%, etc.
According to some embodiments of the invention, the shell has a specific surface area of 1-200m 2 /g, e.g. 10m 2 /g、20m 2 /g、30m 2 /g、40m 2 /g、50m 2 /g、60m 2 /g、70m 2 /g、80m 2 /g、90m 2 /g、100m 2 /g、110m 2 /g、120m 2 /g、130m 2 /g、140m 2 /g, etc.
According to some embodiments of the invention, the average pore size of the shell layer is in the range of 0.5-500nm, preferably 1-100nm, e.g. 1nm, 5nm, 10nm, 15nm, 20nm, 30nm, 50nm, etc.
According to some embodiments of the invention, the porous material is selected from inorganic oxides, further preferably containing SiO 2 And/or Al 2 O 3 Is an inorganic oxide of (a). In a preferred embodiment, the porous material is SiO 2 And Al 2 O 3 Is a mixture of (a) and (b).
The invention also provides a preparation method of the hollow spherical carrier, which comprises the following steps:
1) Mixing a first soluble salt with a first binder to form first spherical particles;
2) Mixing a second soluble salt with the porous material precursor to form a mixture;
3) Coating the mixture formed in the step 2) on the surfaces of the first spherical particles by using a second binder to form second spherical particles;
4) Roasting the second spherical particles;
5) Removing the first and second soluble salts from the calcined second spherical particles with benign solvents for the first and second soluble salts.
According to some embodiments of the invention, the first soluble salt is the same or different from the second soluble salt and is selected from the group consisting of alkali metal or alkaline earth metal chloride, bromide, carbonate, bicarbonate, preferably from the group consisting of sodium chloride, potassium chloride, sodium carbonate, sodium bicarbonate, sodium bromide and potassium bromide.
According to some embodiments of the invention, the first binder is the same as or different from the second binder and is selected from inorganic sols, preferably from one or more of silica sols and alumina sols.
According to some embodiments of the invention, the porous material precursor comprises one or more of inorganic oxides, preferably one or more of silicon-containing compounds, aluminum-containing compounds and titanium-containing compounds, preferably one or more selected from the group consisting of aluminum oxide, titanium oxide and silicon oxide. For example SiO 2 、γ-Al 2 O 3 Aluminosilicate, and the like.
According to some embodiments of the invention, the benign solvent is an aqueous solvent, preferably water, more preferably deionized water.
According to some embodiments of the invention, the ratio of the average diameter of the first spherical particles to the second spherical particles is 1: (1-16), preferably 1 (2-10).
According to some embodiments of the invention, the mass ratio of the second soluble salt to the porous material precursor is (0.1-2.0): 1, preferably (0.3-1.8): 1, more preferably (0.6-1.5): 1, most preferably (0.8-1.3): 1.
according to some embodiments of the invention, the first spherical particles have a particle size of 1-7mm, for example 2.0-2.5mm,3.0-3.5mm.
According to some embodiments of the invention, the second spherical particles have a particle size of 3-8mm, preferably 4.0-4.5mm,5.0-5.5mm,6.0-6.5mm,7.0-7.5mm.
According to some embodiments of the invention, the mixing of step 1) is performed in a ball mill; the coating in step 3) is carried out in a ball rolling machine.
According to some embodiments of the invention, the firing temperature is 500-800 ℃, preferably 600-750 ℃.
According to some embodiments of the invention, the calcination time is 1-48 hours, preferably 2-10 hours.
By the above preparation method, a hollow spherical carrier can be obtained, which comprises a shell layer of porous material and a spherical cavity surrounded by the shell layer, wherein the diameter of the cavity is 0.5-5mm, and/or the thickness of the shell layer is 1-5mm. The support may have a crush strength of 25-500N and/or an attrition rate of 0.1-5%, and/or the support may have an overall porosity of 20-80%.
According to some embodiments of the invention, the hollow spherical support produced by this method has a shell porosity of 30-75%; and/or the specific surface area of the shell layer is 1-200m 2 And/or the shell has an average pore size in the range of 0.5 to 500nm.
The invention further provides application of the hollow spherical carrier and/or the hollow spherical carrier prepared by the preparation method in a catalyst.
Preferably, the catalyst is used in a selective oxidation catalytic reaction, more preferably, the catalyst is a catalyst for preparing acrolein by selective oxidation of propylene, an acrylic acid catalyst by selective oxidation of acrolein, a methacrolein by selective oxidation of isobutylene, or a methacrylic acid catalyst by selective oxidation of methacrolein.
The calculation method of the average diameter of the carrier cavity is as follows:
average diameter of cavity = average diameter of support- (average thickness of shell x 2)
Herein, the average diameter test method is: 30 particles were randomly selected, their diameters were individually tested using a vernier caliper, and the average value was calculated. The method for testing the average thickness of the shell layer comprises the following steps: 30 particles are randomly selected, smashed one by one, the shell thicknesses of the particles are respectively tested by using a vernier caliper, and an average value is calculated.
Herein, the strength and the abrasion rate are both the crushing resistance strength and the abrasion rate of the carrier, which can be tested according to the national standard HG/T2782-1996 and the national standard HG/T2976-2011, respectively.
Herein, the porosity of the carrier refers to the ratio of the volume of all pores (including pores of the shell layer and the cavities) in the carrier to the total volume of the carrier (i.e., the total volume enclosed by the shell layer).
Herein, the porosity of the porous material refers to the ratio of the volume of all pores in the porous material to the total volume of the porous material.
The porosity P can be obtained by the following calculation formula:
P＝(1-ρ 0 /ρ)×100％
wherein ρ is 0 Is the bulk density (g/cm) 3 ) The method comprises the steps of carrying out a first treatment on the surface of the ρ is the actual density of the material (g/cm 3 )，
At the time of testing ρ 0 The average value can be calculated by measuring a plurality of mass data and diameter data, for example, when calculating the porosity of the carrier, the average diameter of 30 hollow carriers is measured, the total volume V is calculated, the total weight m of the 30 carriers is measured, and the average actual carrier density is calculated from ρ=m/V.
Herein, the specific surface area was measured and calculated using the American microphone company Tristar-3000 (model) N2 adsorption and desorption tester BET method.
The hollow spherical carrier has high porosity, high strength and low abrasion, can be effectively combined with the active components of the catalyst to catalyze the oxidation reaction with high activity and stability, prolongs the service life of the catalyst, improves the mechanical strength of the catalyst, accelerates the heat dissipation of the catalytic reaction, inhibits the overheat of the reaction, enhances the selectivity of the catalytic reaction, and obviously improves the catalytic efficiency and the product yield.
Detailed Description
The present invention will be described in detail with reference to examples. It should be understood that the embodiments and examples described herein are for the purpose of illustration and explanation only and are not intended to limit the present invention.
The porosity test method comprises the following steps:
P＝(1-ρ 0 /ρ)×100％
p is the material porosity (%); ρ 0 Is the bulk density (g/cm) 3 ) The method comprises the steps of carrying out a first treatment on the surface of the ρ is the actual density (g/cm) of the material 3 )。
Wherein ρ is 0 Using a true densitometer to test, the calculation method of ρ is: the average diameter of the 30 spherical catalysts was measured, and the total volume V was calculated, and the total weight m, ρ=m/V of the 30 spherical catalysts was weighed.
The abrasion rate testing method comprises the following steps:
taking 100g of carrier, putting into an abrasion tester, rotating for 30min at a rotating speed of 60rmp/min, taking out the carrier, sieving out fine powder at 40 meshes, and testing the weight m of the rest carrier, wherein the abrasion is (100-m)%.
Example 1
Silica sol (ammonia content 40 wt%) is used as adhesive, naCl powder passed through 200 meshes is firstly rolled into granules whose average diameter is 2.5mm in ball-rolling machine, then passed through 200 meshes of gamma-Al powder 2 O 3 Uniformly mixing with NaCl powder according to the mass ratio of 55:45, still using silica sol as a binder, and roll-coating NaCl and gamma-Al on the surface of the NaCl pellets 2 O 3 Until the average diameter of the particles reaches 5.5mm, and taking out and drying. Roasting the obtained spherical particles for 4 hours at 750 ℃, putting the roasted spherical particles into deionized water for cleaning for 6 times, and airing to obtain hollow spherical Al after NaCl is completely dissolved 2 O 3 A carrier. The results of the test are shown in Table 1.
Example 2
Silica sol (ammonia content 40 wt%) is used as adhesive, KBr powder passing through 200 meshes is firstly rolled into small balls with average diameter of 2.5mm in a ball rolling machine, and then gamma-Al passing through 200 meshes is obtained 2 O 3 Uniformly mixing KBr powder and silica sol serving as a binder according to the mass ratio of 50:50, and then, after the mixture is uniformly mixed with KBr powderKBr and gamma-Al are coated on the surface of KBr pellet in a rolling way 2 O 3 Until the average diameter of the particles reaches 5.5mm, and taking out and drying. Roasting the obtained spherical particles for 4 hours at 700 ℃, putting the roasted spherical particles into deionized water for cleaning for 6 times, and airing to obtain hollow spherical Al after KBr is completely dissolved 2 O 3 A carrier. The results of the test are shown in Table 1.
Example 3
Firstly rolling KBr powder which is sieved by a 200-mesh sieve into pellets with the average diameter of 2.5mm in a ball rolling machine by using silicasol (ammonia type and solid content of 40 wt%) as a binder, uniformly mixing the 200-mesh sieve pseudo-boehmite and KBr powder according to the mass ratio of 60:40, and then rolling KBr and gamma-Al on the surfaces of the KBr pellets by using the silicasol as the binder 2 O 3 Until the average diameter of the particles reaches 5.5mm, and taking out and drying. Roasting the obtained spherical particles for 4 hours at 650 ℃, putting the roasted spherical particles into deionized water for cleaning for 6 times, and airing to obtain hollow spherical Al after KBr is completely dissolved 2 O 3 A carrier. The results of the test are shown in Table 1.
Example 4
Silica sol (ammonia content, solid content 40 wt%) was used as binder, and NaCl powder having been sieved with 200 mesh was first rolled into pellets having an average diameter of 2.5mm in a ball rolling machine, and then sieved with 200 mesh silica micropowder (SiO) 2 ) Mixing with NaCl powder at a mass ratio of 55:45, rolling coating NaCl and silicon micropowder (SiO) on the surface of NaCl pellet with silica sol as binder 2 ) Until the average diameter of the particles reaches 5.5mm, and taking out and drying. Roasting the obtained spherical particles for 4 hours at 750 ℃, putting the roasted spherical particles into deionized water for cleaning for 6 times, and airing to obtain hollow spherical SiO after NaCl is completely dissolved 2 A carrier. The results of the test are shown in Table 1.
Example 5
Silica sol (ammonia content 40 wt%) is used as adhesive, naCl powder passed through 200 meshes is firstly rolled into granules whose average diameter is 2.5mm in ball-rolling machine, then passed through 200 meshes and passed through silicon micro-sievePowder (SiO) 2 ) Uniformly mixing with NaCl powder according to the mass ratio of 80:20, still using silica sol as a binder, and roll-coating NaCl and silica micropowder (SiO) on the surface of the NaCl pellets 2 ) Until the average diameter of the particles reaches 5.5mm, and taking out and drying. Roasting the obtained spherical particles for 4 hours at 750 ℃, putting the roasted spherical particles into deionized water for cleaning for 6 times, and airing to obtain hollow spherical SiO after NaCl is completely dissolved 2 A carrier. The results of the test are shown in Table 1.
Example 6
Silica sol (ammonia content, solid content 40 wt%) was used as binder, and NaCl powder having been sieved with 200 mesh was first rolled into pellets having an average diameter of 3.5mm in a ball rolling machine, and then sieved with 200 mesh silica micropowder (SiO) 2 ) Uniformly mixing with NaCl powder according to the mass ratio of 30:70, still using silica sol as a binder, and roll-coating NaCl and silica micropowder (SiO) on the surface of the NaCl pellets 2 ) Until the average diameter of the particles reaches 5.5mm, and taking out and drying. Roasting the obtained spherical particles for 4 hours at 750 ℃, putting the roasted spherical particles into deionized water for cleaning for 6 times, and airing to obtain hollow spherical SiO after NaCl is completely dissolved 2 A carrier. The results of the test are shown in Table 1.
Example 7
Silica sol (ammonia content, solid content 40 wt%) was used as binder, and NaCl powder having been sieved with 200 mesh was first rolled into pellets having an average diameter of 2.5mm in a ball rolling machine, and then sieved with 200 mesh silica micropowder (SiO) 2 ) Uniformly mixing with NaCl powder according to the mass ratio of 85:15, still using silica sol as a binder, and roll-coating NaCl and silica micropowder (SiO) on the surface of the NaCl pellets 2 ) Until the average diameter of the particles reaches 5.5mm, and taking out and drying. Roasting the obtained spherical particles for 4 hours at 750 ℃, putting the roasted spherical particles into deionized water for cleaning for 6 times, and airing to obtain hollow spherical SiO after NaCl is completely dissolved 2 A carrier. The results of the test are shown in Table 1.
Example 8
Silica sol (ammonia, solids content 40 wt%) was used as binder, and was first appliedRolling NaCl powder passing through a 200-mesh sieve into small balls with the average diameter of 2.5mm in a ball rolling machine, uniformly mixing the 200-mesh sieve silicon micro powder (SiO 2) and the NaCl powder according to the mass ratio of 20:80, still using silica sol as a binder, and rolling NaCl and the silicon micro powder (SiO 2 ) Until the average diameter of the particles reaches 4.5mm, and taking out and drying. And roasting the obtained spherical particles for 4 hours at 750 ℃, putting the roasted spherical particles into deionized water for cleaning for 6 times, and after NaCl is completely dissolved, completely dissolving the NaCl, and failing to perform experimental molding.
Example 9
Silica sol (ammonia content, solid content 40 wt%) was used as binder, and NaCl powder having been sieved with 200 mesh was first rolled into pellets having an average diameter of 3.5mm in a ball rolling machine, and then sieved with 200 mesh silica micropowder (SiO) 2 ) Mixing with NaCl powder at a mass ratio of 55:45, rolling coating NaCl and silicon micropowder (SiO) on the surface of NaCl pellet with silica sol as binder 2 ) Until the average diameter of the particles reaches 4.5mm, and taking out and drying. And roasting the obtained spherical particles for 4 hours at 750 ℃, putting the roasted spherical particles into deionized water for cleaning for 6 times, and performing experiment forming failure after NaCl is completely dissolved.
TABLE 1
200 g of ammonium heptamolybdate ((NH) 4 ) 6 Mo 7 O 24 ·4H 2 O), 91.6 g of bismuth nitrate, 57.8 g of ferric nitrate and 49.5 g of cobalt nitrate are dissolved in 500ml of deionized water to obtain an aqueous dispersion of an active component compound, 250g of the carrier prepared in spherical examples 1-7 are added into the aqueous dispersion, the carrier is filtered and dried until the carrier is saturated in adsorption, the concentrated solution is added again until the carrier is saturated in adsorption, the carrier is filtered and dried, and the SiO2 carrier cannot adsorb the concentrated solution after the total of five times of repetition. And roasting and activating the impregnated and dried catalyst particles at 550 ℃ for 4 hours to obtain a final catalyst product.
The catalyst evaluation method used in the above examples was:
introducing reactants isobutene and air into a fixed bed reactor filled with a catalyst to be detected, absorbing the reacted product by using dilute acid at 0 ℃, analyzing by using gas chromatography, calculating carbon balance in the analysis process, and selecting data when the carbon balance is 95-105% as effective data, wherein the reaction conditions are as follows:
the reactor comprises: a fixed bed reactor with an inner diameter of 25.4 mm and a length of 750 mm;
catalyst loading: 130ml;
reaction temperature: 380-420 ℃;
reaction time: 10 hours;
the volume ratio of the raw materials is as follows: isobutene: air: steam = 1:7.5:1.7;
isobutene volume space velocity: 90mL h -1 ·g -1 。
The evaluation results are shown in Table 2.
TABLE 2
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (21)
1. A method for preparing a hollow spherical carrier, comprising the steps of:
1) Mixing a first soluble salt with a first binder to form first spherical particles;
2) Mixing a second soluble salt with the porous material precursor to form a mixture;
3) Coating the mixture formed in the step 2) on the surfaces of the first spherical particles by using a second binder to form second spherical particles;
4) Roasting the second spherical particles;
5) Removing the first and second soluble salts from the calcined second spherical particles with benign solvents for the first and second soluble salts;
the first soluble salt is the same or different from the second soluble salt and is selected from chloride, bromide, carbonate and bicarbonate of alkali metal or alkaline earth metal;
the first binder is the same as or different from the second binder and is selected from one or more of silica sol and aluminum sol;
the porous material precursor comprises one or more of inorganic oxides, and is selected from one or more of aluminum oxide, titanium oxide and silicon oxide;
the ratio of the average diameters of the first spherical particles to the second spherical particles is 1: (1-16);
the average diameter of the first spherical particles is 0.5-5mm;
the second spherical particles have an average diameter of 3-8 mm.
2. The method of manufacturing according to claim 1, characterized in that:
the first soluble salt is the same as or different from the second soluble salt and is selected from sodium chloride, potassium chloride, sodium carbonate, sodium bicarbonate, sodium bromide and potassium bromide; and/or
The benign solvent is an aqueous solvent.
3. The preparation method according to claim 1 or 2, characterized in that:
the ratio of the average diameter of the first spherical particles to the second spherical particles is 1 (2-10).
4. The preparation method according to claim 2, characterized in that: the benign solvent is water.
5. The method of manufacturing according to claim 4, wherein: the benign solvent is deionized water.
6. The preparation method according to claim 1 or 2, characterized in that:
the mass ratio of the second soluble salt to the porous material precursor is (0.1-2.0): 1.
7. the method of manufacturing according to claim 6, wherein: the mass ratio of the second soluble salt to the porous material precursor is (0.3-1.8): 1.
8. the method of manufacturing according to claim 7, wherein: the mass ratio of the second soluble salt to the porous material precursor is (0.6-1.5): 1.
9. the method of manufacturing according to claim 8, wherein: the mass ratio of the second soluble salt to the porous material precursor is (0.8-1.3): 1.
10. the preparation method according to claim 1 or 2, characterized in that:
the mixing of step 1) is carried out in a ball mill; step 3) the coating is carried out in a ball rolling machine;
the roasting temperature is 500-800 ℃; the roasting time is 1-48h.
11. The method of manufacturing according to claim 10, wherein: the roasting temperature is 600-750 ℃; the roasting time is 2-10 hours.
12. A hollow spherical support prepared by the preparation method of any one of claims 1 to 11, comprising a shell layer of porous material and a spherical cavity surrounded by the shell layer, wherein the ratio of the average diameter of the cavity to the average thickness of the shell layer is 0.1 to 3.5.
13. The hollow sphere shaped carrier of claim 12, wherein: the average diameter of the cavity is 0.5-5mm, and/or the average thickness of the shell layer is 1-5mm.
14. Hollow sphere support according to claim 12 or 13, characterized in that: the support has an average crush strength of 25 to 500N and/or an attrition rate of 0.1 to 5%, and/or the overall porosity of the support is 20 to 80%.
15. Hollow sphere support according to claim 12 or 13, characterized in that: the porosity of the shell layer is 30-75%; and/or the specific surface area of the shell layer is 1-200 m/g, and/or the average pore diameter of the shell layer is 0.5-500nm.
16. Hollow sphere support according to claim 12 or 13, characterized in that: the porous material is selected from inorganic oxides.
17. The hollow sphere shaped carrier of claim 16, wherein: the porous material is selected from the group consisting of SiO-containing materials 2 And/or Al 2 O 3 Is an inorganic oxide of (a).
18. The hollow sphere shaped carrier of claim 17, wherein: the porous material is selected from SiO 2 And Al 2 O 3 Is a mixture of (a) and (b).
19. Use of a hollow spherical support according to any one of claims 12 to 18 or a hollow spherical support prepared according to the preparation method of any one of claims 1 to 11 in a catalyst.
20. The use according to claim 19, characterized in that: the catalyst is used in selective oxidation catalytic reactions.
21. The use according to claim 20, characterized in that: the catalyst is a catalyst for preparing acrolein by propylene selective oxidation, an acrylic acid catalyst by acrolein selective oxidation, a methacrylic acid catalyst by isobutene selective oxidation or a methacrylic acid catalyst by methacrolein selective oxidation.
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