CN117943066A - Alpha-alumina carrier and preparation method and application thereof - Google Patents
Alpha-alumina carrier and preparation method and application thereof Download PDFInfo
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- CN117943066A CN117943066A CN202211267352.4A CN202211267352A CN117943066A CN 117943066 A CN117943066 A CN 117943066A CN 202211267352 A CN202211267352 A CN 202211267352A CN 117943066 A CN117943066 A CN 117943066A
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- alumina
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 239000008187 granular material Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000008247 solid mixture Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 150000004684 trihydrates Chemical class 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 13
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 150000004682 monohydrates Chemical class 0.000 claims description 12
- 239000003575 carbonaceous material Substances 0.000 claims description 11
- 239000002210 silicon-based material Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000004898 kneading Methods 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 7
- 238000006735 epoxidation reaction Methods 0.000 claims description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 229910052709 silver Inorganic materials 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- -1 vaseline Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- 238000010521 absorption reaction Methods 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 6
- KZNNRLXBDAAMDZ-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane trihydrate Chemical compound O.O.O.O=[Al]O[Al]=O KZNNRLXBDAAMDZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 5
- 150000001345 alkine derivatives Chemical class 0.000 claims description 5
- 239000011260 aqueous acid Substances 0.000 claims description 5
- 150000001993 dienes Chemical class 0.000 claims description 5
- 238000005984 hydrogenation reaction Methods 0.000 claims description 5
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 4
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 4
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- 229910001610 cryolite Inorganic materials 0.000 claims description 2
- 239000010433 feldspar Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- 239000002006 petroleum coke Substances 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 238000006057 reforming reaction Methods 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 2
- 229940099259 vaseline Drugs 0.000 claims description 2
- 239000000969 carrier Substances 0.000 abstract description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 10
- 239000000463 material Substances 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 239000012752 auxiliary agent Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004134 energy conservation Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 238000002407 reforming Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004438 BET method Methods 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 244000275012 Sesbania cannabina Species 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000005465 channeling Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- UOCIZHQMWNPGEN-UHFFFAOYSA-N dialuminum;oxygen(2-);trihydrate Chemical compound O.O.O.[O-2].[O-2].[O-2].[Al+3].[Al+3] UOCIZHQMWNPGEN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000008262 pumice Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
- B01J27/055—Sulfates with alkali metals, copper, gold or silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/08—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase
- C07D301/10—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the gaseous phase with catalysts containing silver or gold
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Electromagnetism (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of catalyst carriers, and discloses an alpha-alumina carrier, a preparation method and application thereof. The standard deviation of the strength of the alpha-alumina carrier is 1-40N/grain; preferably 5 to 30N/granule; more preferably 10 to 30N/granule. The alpha-alumina carrier provided by the invention is obtained by microwave high-temperature roasting, and has the characteristic of high uniformity.
Description
Technical Field
The invention relates to the technical field of catalyst carriers, in particular to an alpha-alumina carrier, a preparation method and application thereof.
Background
In the reaction of producing epoxy compound by olefin epoxidation, under certain reaction condition, the reaction mixture gas containing olefin and oxygen reacts under the action of catalyst to produce epoxy compound and small amount of carbon dioxide, water and other side products. The catalyst consists of a carrier, an active center and an auxiliary agent, wherein the active center and the auxiliary agent are loaded on the carrier, and the carrier enables the catalyst to have specific physical properties.
Common catalyst supports are alumina supports, silica gel supports, activated carbon supports, and certain natural products such as pumice, diatomaceous earth, and the like. Improving the dispersibility of the active component; the consumption of active components is reduced, and the cost is lowered; increasing the effective specific surface area, providing a suitable pore volume; improving the thermal stability of the catalyst; so that the catalyst has proper shape, size and mechanical strength to meet the operation requirement of industrial reactor; the heat of reaction is removed and localized overheating of the catalyst surface is avoided. Among them, the most common catalyst support is an alumina support, and an alpha-alumina support is currently the only effective support for ethylene epoxidation to ethylene oxide.
Materials for preparing the α -alumina support generally include: alpha-alumina powder and/or a precursor thereof; a binder for reducing the sintering time to bind the particles together; a thermally decomposable burn-out material for use as a channeling material; a lubricant, which is beneficial to the molding of the carrier; and an auxiliary agent for improving the performance of the alpha-alumina carrier and/or the silver catalyst. In general, the method for preparing the alpha-alumina carrier is to mix and knead the raw materials, then mold the raw materials according to molding blanks with different shapes, and finally prepare the alpha-alumina carrier by high-temperature sintering.
The patent application with publication number CN107398303A kneads pseudo-boehmite, peptizing agent, extrusion aid and pore-forming agent in a kneader, and then forms and dries after being stirred into uniform bulk, and then the alpha-alumina carrier is obtained by high temperature roasting 1150-1350 ℃ in a muffle furnace, a tunnel kiln or a bell jar. The patent CN103372466B is prepared by mixing, kneading and forming alpha-Al 2O3 with trihydrate, al 2O3 with pseudomonohydrate, burnout lubricating material, fluoride and heavy alkaline earth metal compound, and roasting at 1280-1430 ℃ by using a bell jar kiln to obtain the alpha-alumina carrier. The patent CN108855129B is to mix and pinch the pseudo-boehmite containing nickel, nitric acid, sesbania powder, auxiliary agent, water and the like into a plastic body, squeeze the plastic body to form strips, and bake the plastic body by adopting a vertical furnace and a mesh belt kiln to obtain the composite crystalline phase alumina carrier containing alpha-alumina. The roasting kilns adopt heavy oil, residual oil, natural gas or coal and the like as fuels, and heat generated by burning the fuels is used for sintering to prepare products, but the energy utilization rate of the kilns is low, and a large amount of polluted gas is generated in the combustion process, so that the requirements of energy conservation and emission reduction promoted by the state are not met.
Disclosure of Invention
The invention aims at solving the problems of the prior art, and the inventor of the invention carries out intensive experimental research in the field of alpha-alumina carriers, and prepares the alpha-alumina carrier by adopting a microwave high-temperature roasting process, wherein the carrier prepared by the roasting process has good uniformity, low standard deviation of carrier strength and uniform morphology of alumina inside and outside the carrier.
In order to achieve the above object, a first aspect of the present invention provides an α -alumina carrier having a standard deviation of strength of 1 to 40N/particle; preferably 5 to 30N/granule; more preferably 10 to 30N/granule.
In a second aspect, the present invention provides a method for producing an α -alumina carrier, the method comprising: and kneading, forming, drying and microwave roasting the raw materials for preparing the alpha-alumina carrier to obtain the alpha-alumina carrier.
A third aspect of the present invention provides an α -alumina support prepared by the above-described preparation method.
In a fourth aspect, the present invention provides the use of the above alpha-alumina support in a silver catalyst for olefin epoxidation, selective hydrogenation of alkynes and dienes, or methane reforming.
The technical scheme of the invention has the following beneficial effects:
(1) The alpha-alumina carrier provided by the invention is obtained by microwave high-temperature roasting, and has the characteristic of high uniformity.
(2) The microwave roasting process has the characteristics of rapidness, energy conservation and small pollution. Compared with the roasting modes of kilns such as tunnel kiln, bell kiln, shuttle kiln and the like, the microwave roasting has the characteristics of low pollution and low cost, meets the requirements of environmental protection and energy saving, and has good application prospect.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the preferred embodiments of the present invention are described below, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein.
The first aspect of the present invention provides an α -alumina carrier having a standard deviation of strength of 1 to 40N/particle; preferably 5 to 30N/granule; more preferably 10 to 30N/granule.
According to the present invention, preferably, the α -alumina support further has at least one of the following features: the content of alpha-alumina is more than or equal to 95wt%; the specific surface area is 0.8-5.0 m 2/g, preferably 1.3-4m 2/g; the water absorption rate is more than or equal to 35 percent.
According to the invention, the alpha-alumina is preferably produced by a preparation process comprising the following process steps: and kneading, forming, drying and microwave roasting the raw materials for preparing the alpha-alumina carrier to obtain the alpha-alumina carrier.
The invention prepares the alpha-alumina carrier by using the raw materials for preparing the alpha-alumina carrier and adopting a microwave high-temperature roasting process, the carrier prepared by the roasting process has good uniformity, low standard deviation of carrier strength and uniform appearance of alumina inside and outside the carrier. And the microwave roasting process has the characteristics of rapidness, energy conservation and small pollution.
According to the invention, preferably, the temperature of the microwave roasting is 800-1600 ℃ and the time is 0.1-50 h; further preferably, the microwave roasting temperature is 900-1550 ℃ and the time is 0.2-30 h; still more preferably, the microwave roasting temperature is 950-1550 ℃ and the time is 0.5-20 h.
According to the present invention, preferably, the raw materials for preparing the α -alumina carrier include: a solid mixture and a binder;
The solid mixture comprises: alumina trihydrate, alumina pseudomonohydrate, optionally a mineralizer, optionally a silicon-containing compound, optionally an alkaline earth metal compound, and optionally a burnout carbonaceous material;
Preferably, the mass content of the alumina trihydrate is 20-90%, the mass content of the pseudo-alumina monohydrate is 5-50%, the mass content of the optional mineralizer is 0-10%, the mass content of the optional silicon-containing compound is 0-5%, the mass content of the optional alkaline earth metal compound is 0-3.5%, and the mass content of the optional burnout carbonaceous material is 0-15% based on the total mass of the solid mixture; the solid mixture comprises the components with the sum of the mass percentages of 100 percent.
In a second aspect, the present invention provides a method for producing an α -alumina carrier, the method comprising: and kneading, forming, drying and microwave roasting the raw materials for preparing the alpha-alumina carrier to obtain the alpha-alumina carrier.
In the present invention, calcination is almost the last step in the preparation of most supports and catalysts therefor. The roasting mode and condition have important influence on the properties of the catalyst and the carrier thereof, such as phase, grain size, surface acidity and alkalinity, strength, specific surface, pore distribution and the like. The invention adopts a microwave roasting mode to prepare the alpha-alumina carrier. Microwave roasting is a method for densification by generating heat by coupling a special wave band of microwaves with a basic microstructure of a material and heating the material to a sintering temperature as a whole by dielectric loss in an electromagnetic field carried by the material. The alpha-alumina carrier prepared by the invention has the characteristic of uniform performance.
According to the invention, preferably, the temperature of the microwave roasting is 800-1600 ℃ and the time is 0.1-50 h;
Further preferably, the microwave roasting temperature is 900-1550 ℃ and the time is 0.2-30 h;
still more preferably, the microwave roasting temperature is 950-1550 ℃ and the time is 0.5-20 h.
According to the present invention, preferably, the raw materials for preparing the α -alumina carrier include: a solid mixture and a binder;
The solid mixture comprises: alumina trihydrate, alumina pseudomonohydrate, optionally a mineralizer, optionally a silicon-containing compound, optionally an alkaline earth metal compound, and optionally a burnout carbonaceous material;
Preferably, the mass content of the alumina trihydrate is 20-90%, the mass content of the pseudo-alumina monohydrate is 5-50%, the mass content of the optional mineralizer is 0-10%, the mass content of the optional silicon-containing compound is 0-5%, the mass content of the optional alkaline earth metal compound is 0-3.5%, and the mass content of the optional burnout carbonaceous material is 0-15% based on the total mass of the solid mixture; the solid mixture comprises the components with the sum of the mass percentages of 100 percent.
In the present invention, preferably, the raw materials for preparing the α -alumina carrier are prepared by the following method: uniformly mixing aluminum oxide trihydrate, pseudo-aluminum oxide monohydrate, an optional mineralizer, an optional silicon-containing compound, an optional alkaline earth metal compound and an optional burnout carbonaceous material to obtain a solid mixture; the solid mixture is then mixed with a binder.
In the present invention, the pseudo-alumina monohydrate is converted to alpha-alumina upon calcination.
According to the invention, the alumina trihydrate is converted to alpha-alumina after calcination as an aluminium source, preferably the alumina trihydrate comprises alpha-alumina trihydrate and/or beta-alumina trihydrate;
The silicon-containing compound is at least one selected from silicon dioxide, silicate, silicon carbide, kieselguhr, feldspar and ethyl silicate;
The alkaline earth metal compound is selected from at least one of alkaline earth metal oxides, nitrates, sulfates, carbonates, oxalates and chlorides;
The burnout carbonaceous material is at least one of graphite, carbon powder, rosin, petroleum coke, vaseline, polyethylene and polypropylene;
the mineralizer comprises at least one of fluoride, chloride, boric acid, and metal oxide;
the fluoride preferably comprises at least one of aluminum fluoride, ammonium fluoride, cryolite and zinc fluoride;
The chloride preferably comprises at least one of ammonium chloride, magnesium chloride and calcium chloride;
the metal oxide preferably comprises magnesium oxide and/or titanium oxide;
The binder is an aqueous acid solution, and the volume ratio of the acid to the water is 1 (1-10);
the acid is preferably at least one selected from the group consisting of citric acid, nitric acid, formic acid, acetic acid, propionic acid and hydrochloric acid.
In the present invention, the alkaline earth metal compound can improve the mechanical strength of the alumina carrier.
In the invention, the binder is an aqueous acid solution, and the aqueous acid solution has the function of forming an aluminum sol with the pseudo-alumina monohydrate, and binding the raw materials together to form the paste capable of being extruded and molded.
The amount of the aqueous acid solution used in the present invention is not particularly limited, and is used in an amount that can form an alumina sol with the pseudo-alumina monohydrate in the solid mixture to bond the raw materials together and form an extrudable paste.
According to the present invention, the drying is preferably performed at a temperature of 20 to 120 ℃ for 24 hours or longer, preferably 24 to 48 hours.
In the present invention, in order to uniformly mix the raw materials for preparing the α -alumina carrier, the raw materials are kneaded in a kneader for a kneading time of 5 to 90 minutes. After the raw materials are sufficiently kneaded, the carrier can be formed into a certain shape including a sphere, a block, a cylinder, a porous cylinder, a raschig ring, a clover, a honeycomb, etc., and the molding is performed in a molding machine.
After molding, the molded article is dried, and the moisture content in the molded article is controlled to 10% or less, and the drying is preferably oven drying.
A third aspect of the present invention provides an α -alumina support prepared by the above-described preparation method.
In a fourth aspect, the present invention provides the use of the above alpha-alumina support in a silver catalyst for olefin epoxidation, selective hydrogenation of alkynes and dienes, or methane reforming.
The alpha-alumina carrier of the invention can be applied to olefin epoxidation reaction, selective hydrogenation reaction of alkyne and diene or methane reforming reaction. The alpha-alumina carrier has low standard deviation of strength, and uniform morphology of alumina inside and outside the carrier, so that the active components and the auxiliary agent loaded during the preparation of the silver catalyst are distributed more uniformly in the carrier, and the dispersibility of the active components and the auxiliary agent is good, so that the silver catalyst prepared by using the carrier has good catalyst activity and selectivity, and therefore, the silver catalyst prepared by using the carrier of the invention has good selectivity and reactivity in olefin epoxidation reaction, alkyne and diene selective hydrogenation, methane reforming and other reactions.
In order that the invention may be more readily understood, the invention will be further described in detail with reference to the following examples, which are given by way of illustration only and are not limiting in scope of application.
The method for detecting the physical properties of the alpha-alumina carrier in the invention comprises the following steps:
the detection method of the intensity standard deviation is as follows: and adopting a DL II type intelligent particle intensity tester produced by Dalian chemical engineering research institute, randomly selecting 30 carrier samples to measure the intensity, and obtaining the standard deviation of the intensity through the intensity value.
The term "water absorption" as used herein refers to the volume of saturated adsorbed water per unit mass of carrier, in mL/g. The measuring method comprises the following steps: firstly, weighing a certain amount of carrier (assuming that the mass is m 1), taking out the carrier after boiling in boiling water for 1h, standing the carrier on wet gauze with moderate water content to remove superfluous water on the surface of the carrier, finally weighing the mass of the carrier after adsorbing water (assuming that the mass is m 2), and calculating the water absorption rate of the carrier according to the following formula.
Water absorption= (m) 2-m1)/m1/ρ Water and its preparation method
Wherein ρ Water and its preparation method is the density of water at the measured temperature, atmospheric pressure.
The specific surface area was determined by the nitrogen physical adsorption BET method.
Comparative example 1
Weighing 720.0g of alpha-alumina trihydrate, 180.0g of pseudo-alumina monohydrate, 10.5g of aluminum fluoride, 2.5g of silicon dioxide, 4.0g of barium sulfate and 300g of graphite, putting into a mixer, uniformly mixing, transferring into a kneader, adding dilute nitric acid (nitric acid: water=1:3, volume ratio) until kneading into an extrudable paste, putting the paste into a strip extruder, extruding into five-hole columns with the diameter of 8.0mm and the length of 6.0mm, drying in an oven at 100 ℃ for more than 24 hours to reduce the free water content to below 10%, then putting the dried five-hole columns into a bell jar kiln for roasting at the roasting temperature of 1350 ℃ for 8 hours, and finally cooling to room temperature to obtain the alpha-alumina carrier. The data on the physical properties of this comparative example α -alumina support are shown in table 1.
Example 1
Weighing 720.0g of alpha-alumina trihydrate, 180.0g of pseudo-alumina monohydrate, 10.5g of aluminum fluoride, 2.5g of silicon dioxide, 4.0g of barium sulfate and 30g of graphite, putting into a mixer, uniformly mixing, transferring into a kneader, adding dilute nitric acid (nitric acid: water=1:3, volume ratio) until kneading into an extrudable paste, putting the paste into a strip extruder, extruding into five-hole columns with the diameter of 8.0mm and the length of 6.0mm, drying in an oven at 100 ℃ for more than 24 hours to reduce the free water content to below 10%, then putting the dried five-hole columns into a microwave oven for roasting at the roasting temperature of 1350 ℃ for 8 hours, and finally cooling to room temperature to obtain the alpha-alumina carrier. The data on the physical properties of the α -alumina support of this example are shown in Table 1.
Example 2
780.0G of alpha-alumina trihydrate, 180.0g of pseudo-alumina monohydrate, 15.3g of ammonium fluoride, 2.8g of silicon dioxide and 4.0g of barium sulfate are weighed, put into a mixer to be uniformly mixed, transferred into a kneader, added with dilute nitric acid (nitric acid: water=1:3, volume ratio) until being kneaded into paste capable of extrusion molding, put the paste into a bar extruder to be extruded into five-hole columns with the diameter of 8.0mm and the length of 6.0mm, oven-dried for more than 24 hours at the temperature of 100 ℃ to reduce the free water content to below 10%, then put the dried five-hole columns into a microwave oven to be baked, the baking temperature is 1100 ℃ and the baking time is 4 hours, and finally cooled to room temperature to obtain the alpha-alumina carrier. The data on the physical properties of the α -alumina support of this example are shown in Table 1.
Example 3
Weighing 720g of beta-alumina trihydrate, 300.0g of pseudo-alumina monohydrate, 8.1g of ammonium chloride, 3.5g of boric acid, 2.0g of silicon dioxide, 4.0g of barium sulfate and 70g of polyethylene, putting into a mixer, uniformly mixing, transferring into a kneader, adding dilute nitric acid (nitric acid: water=1:3, volume ratio) until kneading into an extrudable paste, putting the paste into a bar extruder, extruding into five-hole columns with the diameter of 8.0mm and the length of 6.0mm, oven-drying at 100 ℃ for more than 24 hours to reduce the free water content to below 10%, then putting the dried five-hole columns into a microwave oven for roasting at 1050 ℃ for 4 hours, and finally cooling to room temperature to obtain the alpha-alumina carrier. The data on the physical properties of the α -alumina support of this example are shown in Table 1.
Example 4
200.0G of alpha-alumina trihydrate, 500.0g of beta-alumina trihydrate, 225.0g of pseudo-alumina monohydrate, 11.2g of ammonium fluoride, 3.4g of magnesium oxide, 4.5g of ethyl orthosilicate and 4.0g of barium sulfate are weighed, put into a mixer to be uniformly mixed, transferred into a kneader, added with dilute nitric acid (nitric acid: water=1:3 by volume ratio) until being kneaded into paste capable of extrusion molding, put the paste into a strip extruder, extruded into five-hole columns with the diameter of 8.0mm and the length of 6.0mm, dried in a baking oven for more than 24 hours at the temperature of 100 ℃ to reduce the free water content to below 10%, then put the dried five-hole columns into a microwave oven to be baked, the baking temperature is 1200 ℃ and the baking time is 2 hours, and finally cooled to room temperature to obtain the alpha-alumina carrier. The data on the physical properties of the α -alumina support of this example are shown in Table 1.
TABLE 1
| Specific surface area (m 2/g) | Standard deviation of intensity (N/grain) | Water absorption (%) | |
| Comparative example 1 | 1.2 | 61.7 | 47.1 |
| Example 1 | 1.3 | 24.3 | 50.4 |
| Example 2 | 1.7 | 17.1 | 52.0 |
| Example 3 | 2.3 | 24.9 | 52.8 |
| Example 4 | 1.9 | 15.9 | 52.3 |
As can be seen from comparison of the data in Table 1, the carrier obtained by microwave roasting has the characteristics of uniform appearance of internal and external aluminum oxide and low standard deviation of strength.
The foregoing description of embodiments of the invention has been presented for purposes of illustration and description, and is not intended to be exhaustive or limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the various embodiments described.
Claims (12)
1. An alpha-alumina carrier, characterized in that the standard deviation of the intensity of the alpha-alumina carrier is 1-40N/grain; preferably 5 to 30N/granule; more preferably 10 to 30N/granule.
2. The α -alumina support of claim 1, wherein the α -alumina support further has at least one of the following characteristics: the content of alpha-alumina is more than or equal to 95wt%; the specific surface area is 0.8-5.0 m 2/g, preferably 1.3-4m 2/g; the water absorption rate is more than or equal to 35 percent.
3. The α -alumina support according to claim 1 or 2, wherein the α -alumina is prepared by a preparation process comprising the process steps of: and kneading, forming, drying and microwave roasting the raw materials for preparing the alpha-alumina carrier to obtain the alpha-alumina carrier.
4. The α -alumina carrier of claim 3, wherein the microwave calcination is carried out at a temperature of 800-1600 ℃ for a time of 0.1-50 hours;
Preferably, the temperature of the microwave roasting is 900-1550 ℃ and the time is 0.2-30 h;
further preferably, the microwave roasting temperature is 950-1550 ℃ and the time is 0.5-20 h.
5. The α -alumina support of claim 3, wherein the feedstock for preparing the α -alumina support comprises: a solid mixture and a binder;
The solid mixture comprises: alumina trihydrate, alumina pseudomonohydrate, optionally a mineralizer, optionally a silicon-containing compound, optionally an alkaline earth metal compound, and optionally a burnout carbonaceous material;
Preferably, the mass content of the alumina trihydrate is 20-90%, the mass content of the pseudo-alumina monohydrate is 5-50%, the mass content of the optional mineralizer is 0-10%, the mass content of the optional silicon-containing compound is 0-5%, the mass content of the optional alkaline earth metal compound is 0-3.5%, and the mass content of the optional burnout carbonaceous material is 0-15% based on the total mass of the solid mixture; the solid mixture comprises the components with the sum of the mass percentages of 100 percent.
6. A method for preparing an alpha-alumina carrier, which is characterized by comprising the following steps: and kneading, forming, drying and microwave roasting the raw materials for preparing the alpha-alumina carrier to obtain the alpha-alumina carrier.
7. The preparation method according to claim 6, wherein the microwave roasting temperature is 800-1600 ℃ and the time is 0.1-50 h;
Preferably, the temperature of the microwave roasting is 900-1550 ℃ and the time is 0.2-30 h;
further preferably, the microwave roasting temperature is 950-1550 ℃ and the time is 0.5-20 h.
8. The preparation method according to claim 6, wherein the raw materials for preparing the α -alumina carrier include: a solid mixture and a binder;
The solid mixture comprises: alumina trihydrate, alumina pseudomonohydrate, optionally a mineralizer, optionally a silicon-containing compound, optionally an alkaline earth metal compound, and optionally a burnout carbonaceous material;
Preferably, the mass content of the alumina trihydrate is 20-90%, the mass content of the pseudo-alumina monohydrate is 5-50%, the mass content of the optional mineralizer is 0-10%, the mass content of the optional silicon-containing compound is 0-5%, the mass content of the optional alkaline earth metal compound is 0-3.5%, and the mass content of the optional burnout carbonaceous material is 0-15% based on the total mass of the solid mixture; the solid mixture comprises the components with the sum of the mass percentages of 100 percent.
9. The production method according to claim 8, wherein the alumina trihydrate comprises α -alumina trihydrate and/or β -alumina trihydrate;
The silicon-containing compound is at least one selected from silicon dioxide, silicate, silicon carbide, kieselguhr, feldspar and ethyl silicate;
The alkaline earth metal compound is selected from at least one of alkaline earth metal oxides, nitrates, sulfates, carbonates, oxalates and chlorides;
The burnout carbonaceous material is at least one of graphite, carbon powder, rosin, petroleum coke, vaseline, polyethylene and polypropylene;
the mineralizer comprises at least one of fluoride, chloride, boric acid, and metal oxide;
the fluoride preferably comprises at least one of aluminum fluoride, ammonium fluoride, cryolite and zinc fluoride;
The chloride preferably comprises at least one of ammonium chloride, magnesium chloride and calcium chloride;
the metal oxide preferably comprises magnesium oxide and/or titanium oxide;
The binder is an aqueous acid solution, and the volume ratio of the acid to the water is 1 (1-10);
the acid is preferably at least one selected from the group consisting of citric acid, nitric acid, formic acid, acetic acid, propionic acid and hydrochloric acid.
10. The process according to claim 6, wherein the drying is carried out at a temperature of 20 to 120 ℃ for a period of 24 hours or more, preferably 24 to 48 hours.
11. An α -alumina support prepared by the method of any one of claims 6-10.
12. Use of the alpha-alumina support according to any one of claims 1-5, 11 in silver catalysts for olefin epoxidation, selective hydrogenation of alkynes and dienes, or methane reforming reactions.
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