CN118122302A - Preparation method for improving acid resistance of gamma-alumina - Google Patents
Preparation method for improving acid resistance of gamma-alumina Download PDFInfo
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- CN118122302A CN118122302A CN202410554463.6A CN202410554463A CN118122302A CN 118122302 A CN118122302 A CN 118122302A CN 202410554463 A CN202410554463 A CN 202410554463A CN 118122302 A CN118122302 A CN 118122302A
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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 162
- 239000002253 acid Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000011159 matrix material Substances 0.000 claims abstract description 41
- 239000011258 core-shell material Substances 0.000 claims abstract description 30
- 229920001690 polydopamine Polymers 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 21
- 239000002002 slurry Substances 0.000 claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 13
- 238000011068 loading method Methods 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 37
- 239000004005 microsphere Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 28
- 239000011248 coating agent Substances 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000012752 auxiliary agent Substances 0.000 claims description 14
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- 238000004519 manufacturing process Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 9
- JOSWYUNQBRPBDN-UHFFFAOYSA-P ammonium dichromate Chemical compound [NH4+].[NH4+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O JOSWYUNQBRPBDN-UHFFFAOYSA-P 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
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- 238000005406 washing Methods 0.000 claims description 9
- 229910021389 graphene Inorganic materials 0.000 claims description 8
- 238000007731 hot pressing Methods 0.000 claims description 8
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 7
- 239000002070 nanowire Substances 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 239000002041 carbon nanotube Substances 0.000 claims description 6
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- 229960003638 dopamine Drugs 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
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- 238000012986 modification Methods 0.000 claims description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 241000283073 Equus caballus Species 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 239000007853 buffer solution Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 230000001276 controlling effect Effects 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- 238000004070 electrodeposition Methods 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000003475 lamination Methods 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical class [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000002296 pyrolytic carbon Substances 0.000 claims description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 238000007740 vapor deposition Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229920000193 polymethacrylate Polymers 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 17
- 239000003054 catalyst Substances 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000005299 abrasion Methods 0.000 abstract description 3
- 238000005054 agglomeration Methods 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
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- 229910015189 FeOx Inorganic materials 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
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- 239000003513 alkali Substances 0.000 description 1
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Landscapes
- Catalysts (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a preparation method for improving acid resistance of gamma-alumina, which comprises the following steps: s1, preparing a gamma-alumina matrix; s2, preparing an alumina precursor; s3, preparing a core-shell alumina modified carrier-silicon dioxide, a double-layer core-shell alumina precursor-silicon dioxide-polydopamine compound and double-layer core-shell activated alumina-silicon dioxide-carbonized polydopamine powder; s4, preparing alumina matrix slurry. In the invention, a gamma-alumina with high acid resistance is researched, and can keep a stable pore structure of the gamma-alumina under a strong acid environment with pH less than 4 and at a high temperature of more than 700 ℃ so that the catalyst keeps the original activity and catalytic performance, and the catalyst carrier prepared by taking the gamma-alumina as a raw material has the advantages of low abrasion, high crushing strength and the like, and can greatly improve the stability and the loading performance of the catalyst carrier.
Description
Technical Field
The invention relates to the technical field of alumina preparation, in particular to a preparation method for improving acid resistance of gamma-alumina.
Background
The gamma-crystalline phase alumina plays a role in the production of various types of alumina, mainly because a large amount of gamma-crystalline phase alumina is used in the production of catalyst carriers for petrochemical industry, the carrier has good catalytic environment by utilizing a special pore structure and an ultra-large specific surface area, the catalytic efficiency can be greatly improved, along with the improvement of the catalytic production efficiency, the requirements on the carrier are more and more severe, the requirement on the stable pore structure and acid and alkali resistance at high temperature are also more and more severe, in particular, the strength of the acid resistance of the gamma-alumina directly determines the watershed of the carrier, so that various national research institutions invest a great deal of effort to develop carriers with higher acid resistance, in particular, the acid resistance of the gamma-alumina is the basic raw material for preparing the high-end acid catalyst carrier.
Disclosure of Invention
In order to solve the technical problems mentioned in the background art, a preparation method for improving the acid resistance of gamma-alumina is provided. The invention researches a gamma-alumina with high acid resistance, which can ensure that the gamma-alumina still maintains a stable pore structure at a high temperature of more than 700 ℃ under a strong acid environment with pH less than 4, so that the catalyst maintains the original activity and catalytic performance, and the catalyst carrier prepared by taking the gamma-alumina as a raw material has the advantages of low abrasion, high crushing strength and the like, can greatly improve the stability and the loading performance of the catalyst carrier, has good compatibility with inorganic nonmetallic materials, can be mixed and impregnated at random, is easy to disperse and mix in the forming process, has smooth surface, no bubbles and coarse particles, has no waste water and waste gas emission in the production process, has green and environment-friendly whole production process flow, high production efficiency and good economic benefit.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a preparation method for improving acid resistance of gamma-alumina comprises the following steps:
s1, preparing a gamma-alumina matrix;
S2, preparing a carrier modification auxiliary agent solution, loading an auxiliary agent on a gamma-alumina matrix by an impregnation method or spray powder, and then aging, drying and roasting to prepare an alumina precursor;
s3, sequentially adding the alumina precursor into an ethyl orthosilicate solution, magnetically stirring for 16-20h, and centrifuging, washing and drying to obtain a core-shell alumina modified carrier-silicon dioxide;
S4, adding core-shell alumina precursor-silicon dioxide into PB buffer solution, regulating the pH value to 7.8-8.5 by using sodium hydroxide aqueous solution, performing ultrasonic dispersion for 1-3 hours, then adding dopamine, magnetically stirring for 25-30 hours, and performing centrifugation, washing and drying to obtain a double-layer core-shell alumina precursor-silicon dioxide-polydopamine compound;
In the reaction process, because silicon dioxide is easy to agglomerate under the high-temperature condition, dopamine is polymerized on the surface of a core-shell alumina precursor-silicon dioxide to form a polydopamine layer, so that agglomeration can be inhibited, the polydopamine layer can be carbonized into carbonized polydopamine at high temperature through subsequent high-temperature calcination, agglomeration is inhibited, and active alumina is well dispersed, so that the specific surface area of the active alumina is improved;
S5, placing the double-layer core-shell alumina precursor-silicon dioxide-polydopamine compound into a calciner to be calcined to 900 ℃ and preserving heat for 4 hours, and cooling and crushing to obtain double-layer core-shell active alumina-silicon dioxide-carbonized polydopamine powder;
S6, placing the double-layer core-shell activated alumina-silica-carbonized polydopamine powder, graphene, carbon nano tubes, a solvent, a dispersing agent, a binder, a pore-forming agent and a grain inhibitor in a ball milling tank according to a proportion, ball milling and mixing uniformly, then adding an acid solution to adjust the pH value to 3-5, and stirring uniformly to prepare alumina matrix slurry;
S7, adding the gamma-alumina matrix obtained in the step S1 into alumina matrix slurry for pressure impregnation, then placing the gamma-alumina matrix in a vacuum bag after lamination in a mould, vacuumizing and pressurizing, taking out, and then placing the gamma-alumina matrix on a hot press for hot pressing at the hot pressing temperature of 50-500 ℃ for 2-10 hours to obtain an alumina blank;
s8, sintering the alumina blank in a high-temperature furnace at the sintering temperature of 1000-1400 ℃ for 2-5 h.
As a further description of the above technical solution:
In step S1, the preparation method of the γ -alumina matrix includes a preparation method of alumina microspheres, and the preparation method of the alumina microspheres includes the steps of:
S11, mixing aluminum hydroxide powder and a sodium hydroxide solution, pressurizing to 0.1-0.4MPa, heating to 110-140 ℃, and reacting for 2x 6h to obtain a sodium metaaluminate solution;
S12, adding the sodium metaaluminate solution obtained in the step S11 and the aluminum sulfate solution into a stirring reaction kettle in parallel, heating to 30-60 ℃, starting to react, adding the sodium metaaluminate solution, controlling the pH of the reaction solution to 8.5-9.5, continuing to react until the reaction is finished, heating to 70-90 ℃, standing and aging;
And S13, washing, drying and crushing the product obtained in the step S12 to obtain the alumina microspheres.
As a further description of the above technical solution:
The preparation method of the gamma-alumina also comprises a preparation method of high-temperature-resistant alumina, and the preparation method of the high-temperature-resistant alumina comprises the following steps of:
S14, placing the alumina microspheres obtained in the step S13 into a mixed solution of ammonium dichromate and anhydrous oxalic acid, vacuumizing and soaking for 2-4 hours, placing the soaked alumina microspheres into a high-temperature furnace for heat treatment, wherein the heat treatment temperature is 100-300 ℃, then repeating the mixed solution soaking-heat treatment process of the ammonium dichromate and the anhydrous oxalic acid for 1-4 times to obtain alumina microspheres with 10-500 nm of surface coating, and performing the mixed solution soaking-heat treatment process of the ammonium dichromate and the anhydrous oxalic acid again;
S15, placing the alumina microsphere with the surface coated by the step S14 into a vapor deposition furnace, depositing a prefabricated coating of 10-500 nm on the surface of the coated film, wherein the prefabricated coating is a pyrolytic carbon coating or a BN coating, then growing nanowires in situ on the surface deposited with the prefabricated coating by adopting an electrodeposition method, and obtaining a nanowire coating on the surface of the alumina microsphere to obtain the gamma-alumina matrix.
As a further description of the above technical solution:
In the step S2, the auxiliary agent is soluble nitrate, chloride, sulfate, phosphate or acetate, and is decomposed into metal oxides after roasting, wherein the mass ratio of the sum of the obtained metal oxides to the modified carrier is 0.5:100-2:100.
As a further description of the above technical solution:
the metal oxide includes ferric oxide, cerium oxide and lanthanum oxide.
As a further description of the above technical solution:
In the step S2, the aging time is 5-24 hours, the roasting temperature is 500-800 ℃ and the time is 2-6 hours.
As a further description of the above technical solution:
In the step S6, the ratio of the dispersing agent to the solvent is 1-8 mg/mL, the ratio of the binder to the solvent is 0.1-10 vol%, the ratio of the grain inhibitor to the solvent is 1-6 mg/mL, the graphene content is 5-15 wt% of the double-layer core-shell activated alumina-silica-carbonized polydopamine powder content, the carbon nanotube content is 0.1-5 wt% of the double-layer core-shell activated alumina-silica-carbonized polydopamine powder content, the ratio of the pore-forming agent to the solvent is 5-15 mg/mL, and the solid content of the alumina matrix slurry is 35-80 vol%.
As a further description of the above technical solution:
the dispersing agent is one of citrate, carbonate, polymethyl methacrylate, polyethylene glycol or equine petroleum polyethylene glycol, the binder is one of polyvinyl alcohol, polyvinyl butyral and amide-ammonium salt, and the solvent is one of distilled water, aluminum sol or silica sol.
As a further description of the above technical solution:
The particle size of the pore-forming agent is 0.01-1 mu m, and the pore-forming agent is one of carbon powder or starch.
As a further description of the above technical solution:
The grain size of the grain inhibitor is 0.01-1 mu m, and the grain inhibitor is one or more of organic salts or inorganic salts of iron, manganese, magnesium, yttrium, lanthanum, indium, chromium, titanium, zirconium, nickel, boron and copper.
In summary, due to the adoption of the technical scheme, the beneficial effects of the invention are as follows:
1. In the invention, the gamma-alumina with high acid resistance is researched, the gamma-alumina can still keep a stable pore structure at the high temperature of more than 700 ℃ under the strong acid environment with the pH value less than 4, so that the catalyst keeps the original activity and catalytic performance, the catalyst carrier prepared by taking the gamma-alumina as the raw material has the advantages of low abrasion, high crushing strength and the like, the stability and the loading performance of the catalyst carrier can be greatly improved, the compatibility of the powder is also good, the powder can be mixed with inorganic nonmetallic materials in any proportion and in impregnation, the mixture is easy to disperse and mix in the forming process, the surface is smooth, no bubbles and coarse particles are generated, the production process has no waste water and waste gas emission, the whole production process flow is green and environment-friendly, and the production efficiency is high and the economic benefit is good.
2. In the invention, because silicon dioxide is easy to agglomerate under the high-temperature condition, dopamine is polymerized on the surface of the core-shell alumina precursor-silicon dioxide to form the polydopamine layer, so that the agglomeration can be inhibited, and the polydopamine layer can be carbonized into carbonized polydopamine at high temperature through subsequent high-temperature calcination; agglomeration is inhibited, and the activated alumina is well dispersed, so that the specific surface area of the activated alumina is increased.
3. According to the invention, the slurry can be fully homogenized by the dispersing agent and the pH value is adjusted, and under the action of pore-forming agent carbon powder or starch, the microporous alumina microsphere reinforced alumina matrix ceramic with more uniform size and distribution can be obtained after hot-pressing sintering, so that the alumina microsphere reinforced alumina matrix composite with high physical properties is obtained. Graphene is added, the components are fully mixed with components such as alumina ceramic powder, pore-forming agent and the like, and after high-temperature and high-pressure treatment, uniformly distributed nano holes are obtained, and the toughness and strength of an alumina microsphere reinforced alumina matrix are improved, so that the strength and toughness of the composite material are improved. After the grain inhibitor is added into the alumina matrix slurry, the growth of alumina grains in the fiber and alumina grains in the slurry can be effectively inhibited, so that the reduction of the mechanical property of the fiber is avoided.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a technical scheme: a preparation method for improving acid resistance of gamma-alumina comprises the following steps:
S1, preparing a gamma-alumina matrix, wherein the preparation method of the gamma-alumina matrix comprises the following steps: (1) a preparation method of alumina microspheres; (2) a preparation method of high-temperature-resistant alumina, in particular:
(1) The preparation method of the alumina microsphere comprises the following steps:
S11, mixing aluminum hydroxide powder and a sodium hydroxide solution, pressurizing to 0.1-0.4MPa, heating to 110-140 ℃, and reacting for 2x 6h to obtain a sodium metaaluminate solution;
S12, adding the sodium metaaluminate solution obtained in the step S11 and the aluminum sulfate solution into a stirring reaction kettle in parallel, heating to 30-60 ℃, starting to react, adding the sodium metaaluminate solution, controlling the pH of the reaction solution to 8.5-9.5, continuing to react until the reaction is finished, heating to 70-90 ℃, standing and aging;
s13, washing, drying and crushing the product obtained in the step S12 to obtain alumina microspheres;
The pore diameter of the macroporous active alumina powder prepared by the method is 10-20nm, the specific surface area is 250-320m 2/g, and the pore volume is 0.9-1.2ml/g. If the specific surface area, pore volume and average pore diameter of the carrier are too small, the pore structure of the prepared alumina precursor is easily blocked during the subsequent auxiliary loading and active component loading, the catalytic activity is influenced, if the indexes are too large, the pore diameter of the carrier is inevitably large, the effective adsorption and activation of the active alumina to reactant molecules are restricted due to the pore channel adsorption effect, and the catalytic activity of the active alumina is also influenced.
(2) The preparation method of the high-temperature-resistant alumina comprises the following steps:
S14, placing the alumina microspheres obtained in the step S13 into a mixed solution of ammonium dichromate and anhydrous oxalic acid, vacuumizing and soaking for 2-4 hours, placing the soaked alumina microspheres into a high-temperature furnace for heat treatment, wherein the heat treatment temperature is 100-300 ℃, then repeating the mixed solution soaking-heat treatment process of the ammonium dichromate and the anhydrous oxalic acid for 1-4 times to obtain alumina microspheres with 10-500 nm of surface coating, and performing the mixed solution soaking-heat treatment process of the ammonium dichromate and the anhydrous oxalic acid again;
S15, placing the alumina microsphere with the surface coated with the film obtained in the step S14 into a vapor deposition furnace, depositing a 10-500 nm prefabricated coating on the surface of the coated film, wherein the prefabricated coating is a pyrolytic carbon coating or a BN coating, then growing nanowires in situ on the surface deposited with the prefabricated coating by adopting an electrodeposition method, and obtaining a nanowire coating on the surface of the alumina microsphere to obtain a gamma-alumina matrix;
Specifically, the film is coated on the surface of the alumina microsphere and the nanowire coating is prepared, so that the thickness of the alumina microsphere is increased, and the alumina microsphere has good strength.
S2, preparing a carrier modification auxiliary agent solution, loading an auxiliary agent on the gamma-alumina matrix by an impregnation method or spray powder, and then aging, drying and roasting to prepare the alumina precursor. Wherein (1) the auxiliary agent is soluble nitrate, chloride, sulfate, phosphate or acetate, the auxiliary agent is decomposed into metal oxides of ferric oxide, cerium oxide and lanthanum oxide after roasting, the mass ratio of the obtained metal oxides to the modified carrier is 0.5:100-2:100, and the auxiliary agent cerium oxide has a hole structure and has a flowable oxygen vacancy (with oxygen storage and release function) to release lattice oxygen and carboxylic acid on the surface in reaction to generate HCO 3 -, so that the decomposition is avoided, the carbon deposit is prevented from covering active components, and the humidity enhancement effect is realized; (2) Aging for 5-24h, roasting at 500-800 ℃ for 2-6h; (3) Because of the limitation of the pore structure of the carrier, the content of the auxiliary agent selected by the application is low, the loading is too high, the pore canal is blocked, the preparation cost is increased, and meanwhile, the auxiliary agent is accumulated in the pore canal of the carrier so as to be difficult to exert the advantage of the nano structure; (4) The transition metal oxide has an ability to activate oxygen (to excite oxygen into reactive oxygen atoms). The rare earth metal oxide and the transition metal oxide are coupled to form a multi-metal composite structure, so that the respective effects are enhanced, and the catalytic activity is enhanced; (5) The coupling structure modification is carried out on the catalyst initial carrier by the rare earth metal oxide cerium oxide and lanthanum oxide, and the composite transition metal oxides FeOx, mnO2 and CuO2, so that the effective dispersion of the noble metal active component in the modified carrier is enhanced, and the acting force between the active component and the carrier is enhanced. When the catalyst has the same catalytic activity, compared with a catalyst with an unmodified carrier, the catalyst has the advantages of effectively reducing the load of the noble metal active component, having smaller microscopic size of the noble metal active component and having poisoning resistance.
S3, sequentially adding the alumina precursor into an ethyl orthosilicate solution, magnetically stirring for 16-20h, and centrifuging, washing and drying to obtain a core-shell alumina modified carrier-silicon dioxide;
S4, adding core-shell alumina precursor-silicon dioxide into PB buffer solution, regulating the pH value to 7.8-8.5 by using sodium hydroxide aqueous solution, performing ultrasonic dispersion for 1-3 hours, then adding dopamine, magnetically stirring for 25-30 hours, and performing centrifugation, washing and drying to obtain a double-layer core-shell alumina precursor-silicon dioxide-polydopamine compound;
In the reaction process, considering that silicon dioxide is easy to agglomerate under the high-temperature condition, dopamine is polymerized on the surface of a core-shell alumina precursor-silicon dioxide to form a polydopamine layer, so that agglomeration can be inhibited, and the polydopamine layer can be carbonized into carbonized polydopamine at high temperature through subsequent high-temperature calcination; agglomeration is inhibited, and the activated alumina is well dispersed, so that the specific surface area of the activated alumina is increased.
S5, placing the double-layer core-shell alumina precursor-silicon dioxide-polydopamine compound into a calciner to be calcined to 900 ℃ and preserving heat for 4 hours, and cooling and crushing to obtain double-layer core-shell active alumina-silicon dioxide-carbonized polydopamine powder;
S6, placing double-layer core-shell activated alumina-silica-carbonized polydopamine powder, graphene, carbon nano tubes, a solvent, a dispersing agent, a binder, a pore-forming agent and a grain inhibitor in a ball milling tank in proportion, ball milling and mixing uniformly, then adding an acid solution to adjust the pH value to 3-5, and stirring uniformly to prepare alumina matrix slurry, wherein the proportion of the dispersing agent to the solvent is 1-8 mg/mL, and the dispersing agent is one of citrate, carbonate, polymethacrylate, polyethylene glycol or equine petroleum polyethylene glycol; (2) The proportion of the binder to the solvent is 0.1-10vol%, and the binder is one of polyvinyl alcohol, polyvinyl butyral and amide-ammonium salt; (3) The ratio of the grain inhibitor to the solvent is 1-6 mg/mL, the grain size of the grain inhibitor is 0.01-1 mu m, and the grain inhibitor is one or more of organic salts or inorganic salts of iron, manganese, magnesium, yttrium, lanthanum, indium, chromium, titanium, zirconium, nickel, boron and copper; (4) The content of the graphene is 5-15 wt% of the content of the double-layer core-shell activated alumina-silicon dioxide-carbonized polydopamine powder; (5) The content of the carbon nano tube is 0.1 to 5 weight percent of the content of the double-layer core-shell activated alumina-silicon dioxide-carbonized polydopamine powder; (6) The ratio of the pore-forming agent to the solvent is 5-15 mg/mL, the particle size of the pore-forming agent is 0.01-1 mu m, and the pore-forming agent is one of carbon powder or starch; (7) the solid content of the alumina matrix slurry is 35-80 vol%; (8) The solvent is one of distilled water, aluminum sol or silica sol.
Further, the slurry can be fully homogenized by dispersing agent and regulating pH value, and under the action of pore-forming agent carbon powder or starch, microporous alumina microsphere reinforced alumina matrix ceramic with more uniform size and distribution can be obtained after hot-pressing sintering, so that the alumina microsphere reinforced alumina matrix composite with high physical property is obtained. Graphene is added, the components are fully mixed with components such as alumina ceramic powder, pore-forming agent and the like, and after high-temperature and high-pressure treatment, uniformly distributed nano holes are obtained, and the toughness and strength of an alumina microsphere reinforced alumina matrix are improved, so that the strength and toughness of the composite material are improved. After the grain inhibitor is added into the alumina matrix slurry, the growth of alumina grains in the fiber and alumina grains in the slurry can be effectively inhibited, so that the reduction of the mechanical property of the alumina matrix slurry is avoided.
S7, adding the gamma-alumina matrix obtained in the step S1 into alumina matrix slurry for pressure impregnation, then placing the gamma-alumina matrix in a vacuum bag after lamination in a mould, vacuumizing and pressurizing, taking out, and then placing the gamma-alumina matrix on a hot press for hot pressing at the hot pressing temperature of 50-500 ℃ for 2-10 hours to obtain an alumina blank;
S8, sintering the alumina blank in a high-temperature furnace at 1000-1400 ℃ for 2-5 h.
The invention, (1) high acid resistant active alumina technology: the adoption of a high corrosion resistance synthesis process ensures that the pore diameter has reasonable distribution, and the gamma-activated alumina can keep stable activity and pore structure in a high-temperature acidic environment within 900 ℃ so as to exert the maximum catalytic efficiency in the catalytic operation process; (2) catalyst activity and stability enhancement technique: in the continuous catalytic stability and efficiency test of the carrier made of the activated alumina for 3 months, the catalytic activity can be maintained to be more than 95%, and the catalytic stability is well maintained.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (10)
1. The preparation method for improving the acid resistance of gamma-alumina is characterized by comprising the following steps of:
s1, preparing a gamma-alumina matrix;
S2, preparing a carrier modification auxiliary agent solution, loading an auxiliary agent on a gamma-alumina matrix by an impregnation method or spray powder, and then aging, drying and roasting to prepare an alumina precursor;
s3, sequentially adding the alumina precursor into an ethyl orthosilicate solution, magnetically stirring for 16-20h, and centrifuging, washing and drying to obtain a core-shell alumina modified carrier-silicon dioxide;
S4, adding core-shell alumina precursor-silicon dioxide into PB buffer solution, regulating the pH value to 7.8-8.5 by using sodium hydroxide aqueous solution, performing ultrasonic dispersion for 1-3 hours, then adding dopamine, magnetically stirring for 25-30 hours, and performing centrifugation, washing and drying to obtain a double-layer core-shell alumina precursor-silicon dioxide-polydopamine compound;
S5, placing the double-layer core-shell alumina precursor-silicon dioxide-polydopamine compound into a calciner to be calcined to 900 ℃ and preserving heat for 4 hours, and cooling and crushing to obtain double-layer core-shell active alumina-silicon dioxide-carbonized polydopamine powder;
S6, placing the double-layer core-shell activated alumina-silica-carbonized polydopamine powder, graphene, carbon nano tubes, a solvent, a dispersing agent, a binder, a pore-forming agent and a grain inhibitor in a ball milling tank according to a proportion, ball milling and mixing uniformly, then adding an acid solution to adjust the pH value to 3-5, and stirring uniformly to prepare alumina matrix slurry;
S7, adding the gamma-alumina matrix obtained in the step S1 into alumina matrix slurry for pressure impregnation, then placing the gamma-alumina matrix in a vacuum bag after lamination in a mould, vacuumizing and pressurizing, taking out, and then placing the gamma-alumina matrix on a hot press for hot pressing at the hot pressing temperature of 50-500 ℃ for 2-10 hours to obtain an alumina blank;
s8, sintering the alumina blank in a high-temperature furnace at the sintering temperature of 1000-1400 ℃ for 2-5 h.
2. The method for producing an alumina according to claim 1, wherein in step S1, the method for producing a gamma-alumina matrix comprises a method for producing alumina microspheres, the method for producing alumina microspheres comprising the steps of:
S11, mixing aluminum hydroxide powder and a sodium hydroxide solution, pressurizing to 0.1-0.4MPa, heating to 110-140 ℃, and reacting for 2x 6h to obtain a sodium metaaluminate solution;
S12, adding the sodium metaaluminate solution obtained in the step S11 and the aluminum sulfate solution into a stirring reaction kettle in parallel, heating to 30-60 ℃, starting to react, adding the sodium metaaluminate solution, controlling the pH of the reaction solution to 8.5-9.5, continuing to react until the reaction is finished, heating to 70-90 ℃, standing and aging;
And S13, washing, drying and crushing the product obtained in the step S12 to obtain the alumina microspheres.
3. The method for preparing gamma-alumina with improved acid resistance according to claim 2, wherein the method for preparing gamma-alumina further comprises a method for preparing high temperature resistant alumina, the method for preparing high temperature resistant alumina comprising the steps of:
S14, placing the alumina microspheres obtained in the step S13 into a mixed solution of ammonium dichromate and anhydrous oxalic acid, vacuumizing and soaking for 2-4 hours, placing the soaked alumina microspheres into a high-temperature furnace for heat treatment, wherein the heat treatment temperature is 100-300 ℃, then repeating the mixed solution soaking-heat treatment process of the ammonium dichromate and the anhydrous oxalic acid for 1-4 times to obtain alumina microspheres with 10-500 nm of surface coating, and performing the mixed solution soaking-heat treatment process of the ammonium dichromate and the anhydrous oxalic acid again;
S15, placing the alumina microsphere with the surface coated by the step S14 into a vapor deposition furnace, depositing a prefabricated coating of 10-500 nm on the surface of the coated film, wherein the prefabricated coating is a pyrolytic carbon coating or a BN coating, then growing nanowires in situ on the surface deposited with the prefabricated coating by adopting an electrodeposition method, and obtaining a nanowire coating on the surface of the alumina microsphere to obtain the gamma-alumina matrix.
4. The method for preparing gamma-alumina with improved acid resistance according to claim 1, wherein in the step S2, the auxiliary agent is soluble nitrate, chloride, sulfate, phosphate or acetate, the auxiliary agent is decomposed into metal oxides after roasting, and the mass ratio of the sum of the obtained metal oxides to the modified carrier is 0.5:100-2:100.
5. The method for producing gamma-alumina according to claim 4, wherein the metal oxide comprises ferric oxide, cerium oxide, and lanthanum oxide.
6. The method for preparing gamma-alumina having improved acid resistance according to claim 1, wherein in the step S2, the aging time is 5-24 hours, the calcination temperature is 500-800 ℃ and the time is 2-6 hours.
7. The method according to claim 1, wherein in step S6, the ratio of the dispersant to the solvent is 1-8 mg/mL, the ratio of the binder to the solvent is 0.1-10 vol%, the ratio of the grain inhibitor to the solvent is 1-6 mg/mL, the graphene content is 5-15 wt% of the double-layer core-shell activated alumina-silica-carbonized polydopamine powder content, the carbon nanotube content is 0.1-5 wt% of the double-layer core-shell activated alumina-silica-carbonized polydopamine powder content, the ratio of the pore-forming agent to the solvent is 5-15 mg/mL, and the solid content of the alumina matrix slurry is 35-80 vol%.
8. The method for preparing gamma-alumina with improved acid resistance according to claim 7, wherein the dispersing agent is one of citrate, carbonate, polymethacrylate, polyethylene glycol or equine petroleum polyethylene glycol, the binder is one of polyvinyl alcohol, polyvinyl butyral and amide-ammonium salt, and the solvent is one of distilled water, aluminum sol or silica sol.
9. The method for preparing gamma-alumina with improved acid resistance according to claim 7, wherein the pore-forming agent has a particle size of 0.01-1 μm and is one of carbon powder and starch.
10. The method for preparing gamma-alumina with improved acid resistance according to claim 7, wherein the grain size of the grain inhibitor is 0.01-1 μm, and the grain inhibitor is one or more of organic salts or inorganic salts of iron, manganese, magnesium, yttrium, lanthanum, indium, chromium, titanium, zirconium, nickel, boron and copper.
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