CN111185147B - Preparation method of catalyst carrier - Google Patents
Preparation method of catalyst carrier Download PDFInfo
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- CN111185147B CN111185147B CN202010204542.6A CN202010204542A CN111185147B CN 111185147 B CN111185147 B CN 111185147B CN 202010204542 A CN202010204542 A CN 202010204542A CN 111185147 B CN111185147 B CN 111185147B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 53
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000000758 substrate Substances 0.000 claims abstract description 28
- 238000001179 sorption measurement Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 66
- 238000000034 method Methods 0.000 claims description 40
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 39
- 239000010407 anodic oxide Substances 0.000 claims description 34
- 238000007254 oxidation reaction Methods 0.000 claims description 34
- 230000003647 oxidation Effects 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 230000008569 process Effects 0.000 claims description 29
- 238000005406 washing Methods 0.000 claims description 29
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 28
- 239000000463 material Substances 0.000 claims description 27
- 229910000838 Al alloy Inorganic materials 0.000 claims description 26
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000011282 treatment Methods 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 14
- 230000001681 protective effect Effects 0.000 claims description 14
- 235000006408 oxalic acid Nutrition 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 12
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 11
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- GJCXHYNLSNVSQZ-UHFFFAOYSA-L [Cu](Cl)Cl.Cl Chemical compound [Cu](Cl)Cl.Cl GJCXHYNLSNVSQZ-UHFFFAOYSA-L 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 29
- 239000011148 porous material Substances 0.000 abstract description 23
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 230000007797 corrosion Effects 0.000 abstract description 16
- 238000005260 corrosion Methods 0.000 abstract description 16
- 239000000126 substance Substances 0.000 abstract description 5
- 239000010408 film Substances 0.000 description 95
- 239000010410 layer Substances 0.000 description 68
- 239000002585 base Substances 0.000 description 16
- 230000004888 barrier function Effects 0.000 description 14
- 239000007788 liquid Substances 0.000 description 14
- 238000002791 soaking Methods 0.000 description 12
- 238000005238 degreasing Methods 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 238000004090 dissolution Methods 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 10
- 238000007743 anodising Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- 238000009777 vacuum freeze-drying Methods 0.000 description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000001488 sodium phosphate Substances 0.000 description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 3
- 229910002706 AlOOH Inorganic materials 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- -1 aluminum ions Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000013043 chemical agent Substances 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000001509 sodium citrate Substances 0.000 description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- 241000565357 Fraxinus nigra Species 0.000 description 1
- 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 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 238000011328 necessary treatment Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- 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
- B01J37/009—Preparation by separation, e.g. by filtration, decantation, screening
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
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Abstract
The invention provides a preparation method of a through-hole type alumina catalyst carrier, which comprises the steps of effectively removing a shielding layer at the bottom of a pore canal through a selective adsorption reaction of gamma-chloropropyl trimethylsilane on a porous layer and a shielding layer and a subsequent alkaline corrosion reaction, and removing an aluminum substrate through a chemical replacement reaction to obtain the through-hole type alumina catalyst carrier.
Description
Technical Field
The invention relates to a through-hole type alumina catalyst carrier and a preparation method thereof, which belong to the field of electrochemistry and catalysts, and are particularly suitable for the fields of catalyst carriers and preparation methods thereof.
Background
Anodic oxidation of aluminum or aluminum alloy means that aluminum or aluminum alloy is immersed in a suitable electrolyte to be electrified as an anode, and a layer of oxide film (Al) is formed on the surface of aluminum or aluminum alloy 2 O 3 Layer) of the substrate. The existence of the oxide film can improve the corrosion resistance of the aluminum alloy, and meanwhile, by means of the special structure of the oxide film and the post treatment process, such as the anodic oxide film can be matched with surface painting and other further treatments, so that the substrate can achieve better protection effect in a harsher environment, or the aluminum and aluminum alloy parts can be decorated by dyeing, so that the film layer has decorative and other protective properties. Common anodic oxidation processes are sulfuric acid anodic oxidation, chromic acid anodic oxidation, and the like.
From the thermodynamic conditions of the chemical reaction, aluminum can produce stable oxide film layers over a considerable pH range (ph=4.45-8.38). From the mechanism of electrochemical reaction, anodic oxide film formation is actually the result of the combined action of the two processes of film growth and film dissolution.
(1) Film growth:
cathode, hydrogen evolution reaction 2H + +2e→H 2
Anode, oxidation reaction H 2 O-2e→O+2H +
Oxygen generated in the anode reaction can form oxygen molecules to be separated out in a gaseous form, and an aluminum oxide film layer can be formed on the surface of the anode:
2Al+3O→Al 2 O 3 +Q。
the reaction is exothermic, the speed of the anodic oxidation process is high, a layer of oxide film which is thin, nonporous, compact, strong in adhesive force and high in insulativity can be generated after a few seconds of electrifying, the film grows continuously, the thickness is increased continuously, the resistance is increased correspondingly, and the reaction speed for generating the film is reduced continuously until the film stops.
(2) And (3) dissolving the film. It is the dissolution of the film that allows the film to grow continuously. During the reaction, both the aluminum and the resulting aluminum oxide film may dissolve in the acidic electrolyte solution.
2Al+6H + →2Al 3+ +3H 2
Al 2 O 3 +6H + →2Al 3+ +3H 2 O
The dissolution reaction causes a large number of pinholes to form in the surface of the aluminum. The dissolution process of the film is synchronous with the film generation process, because the primary film layer is uneven, the thin film layer is easy to dissolve to generate pores, electrolyte solution can pass through the pores to enter the film, an oxide film is continuously generated on an aluminum matrix, and meanwhile, the pores (pinholes) which finally form the oxide film form a conical structure from the surface to the inside, and the dissolution of the film is related to factors such as the property of electrolyte, the structure of a reaction product, current, voltage, solution temperature, electrifying time and the like.
The porous honeycomb structure of the anodic oxide film of aluminum and aluminum alloy has the film layer with micropores perpendicular to the surface, and the parameters of the structural unit, such as size, aperture, wall thickness, barrier layer thickness, etc. can be controlled by the electrolyte component and the technological parameters, i.e. the anodic oxide film of aluminum has two main types, namely barrier anodic oxide film and porous anodic oxide film. The barrier type anodic oxide film is a compact and nonporous thin anodic oxide film closely attached to the metal surface, and is short for barrier film, the thickness of the barrier type anodic oxide film is generally very thin and not more than 0.1 μm depending on the applied anodic oxidation voltage, and the barrier type anodic oxide film is mainly used for manufacturing electrolytic capacitors. Barrier type anodic oxide films are also known as barrier layer anodic oxide films, and in brief, porous anodic oxide films include a barrier layer and a plurality of layersPore layers, which differ significantly in specific structure and composition, wherein the barrier layer is a dense, non-porous amorphous oxide, typically gamma-Al 2 O 3 The porous layer is composed of amorphous alumina, and the main component of the porous layer is alpha-AlOOH alumina.
As described above, in the anodic oxide film material, the aluminum substrate, the shielding layer and the porous layer are sequentially arranged from bottom to top, and the porous layer has controllable pore diameter and uniform array, so that the anodic oxide film material is very suitable for being used as a catalyst carrier, and various technical means are generally adopted to remove the aluminum substrate and the shielding layer so as to obtain the porous alumina material, and the main method is as follows:
(a) Chemical method: directly adopt CuCl 2 -HCl solution or SnCl 4 And removing the aluminum material at the bottom of the anodic oxide film by replacement, soaking the anodic aluminum oxide in phosphoric acid solution, dissolving and removing the shielding layer, and obviously corroding and dissolving part of the anodic oxide porous layer.
(b) Step-by-step pressurization: the principle is that the thickness of the anodized shielding layer is in direct proportion to the voltage, the thickness of the shielding layer is reduced in the voltage reducing process, and the shielding layer is considered to be removed when the voltage is reduced to 0V, but the nano pore structure is necessarily damaged in the voltage reducing process because the voltage is closely related to the structural aperture and uniformity of the pore channel, and the shielding layer is removed.
(c) Back pressure process: the main principle is that after the anodic oxidation is finished, a reverse voltage is provided in the electrolyte, H + Migration to the bottom of the well, localized high concentrations of H + The ions accelerate the dissolution of the barrier alumina, and once the barrier is dissolved, H+ ions are reduced on the metal cathode to form H 2 The generated gas pressure promotes the peeling of the porous film from the aluminum substrate. Although theoretically simple, the actual operation process is extremely difficult to control.
(d) A complete oxidation method: the overoxidation method is to extend the electrolysis time, so that the aluminum sheet is completely anodized from one side to penetrate to the lower metal layer, and a self-supporting through hole film is directly obtained.
Disclosure of Invention
Based on the problems of the prior art, the invention provides a through-hole type alumina catalyst carrier and a preparation method thereof, and the through-hole type alumina catalyst carrier comprises the following processing steps.
(1) Selecting aluminum alloy as a base material;
(2) Pretreating an aluminum substrate;
(3) Performing anodic oxidation treatment on the treated aluminum substrate to form an oxide film on the surface;
(4) Adsorbing a protective film on the surface of the porous layer of the anodic oxide film, wherein the protective film is not adsorbed on the shielding layer;
(5) Removing the shielding layer at the bottom of the anodic oxide film to expose the aluminum base material;
(6) The aluminum substrate was removed to obtain a catalyst support containing only the anodized film porous layer.
Further, in the step (1), the aluminum alloy substrate is preferably a 5-series aluminum alloy, and the thickness of the aluminum alloy is less than 0.5cm.
Further, in the step (2), the pretreatment removal includes an alkaline degreasing-hot water washing-alkaline washing-hot water washing-cold water washing-acid washing-water washing step.
Further, in the step (3), the solution used for the anodic oxidation is a mixed solution of oxalic acid, phosphoric acid and sulfosalicylic acid, the concentration of oxalic acid is 0.25-0.3M, the concentration of phosphoric acid is 0.2-0.4M, the concentration of sulfosalicylic acid is 0.05-0.15M, the voltage in the anodic oxidation process is 20-30V, the temperature is 30 ℃ and the current density is 2-3A/dm 2 The time is 20-30min.
Further, the solution adopted in the step (4) is mixed solution of gamma-chloropropyl trimethoxysilane and anhydrous toluene, the concentration of the gamma-chloropropyl trimethoxysilane is 10-20wt.%, the dosage of the gamma-chloropropyl trimethoxysilane is 3-5% of the weight of the anodized aluminum material, and the vacuumizing treatment is assisted in the step (4), so that the vacuum degree is 90-100Pa.
Further, the solution used for removing the shielding layer in the step (5) is a mixed solution of NaOH, naF and ethanol.
Further, the NaOH: naF: the mass ratio of the ethanol is (2-5): 1-2): 7.
Further, the solution used for removing the aluminum substrate in the step (6) is a copper chloride-hydrochloric acid aqueous solution, the concentration of hydrochloric acid is 7-10wt.%, and the concentration of copper chloride is 0.1-0.15M.
Further, the through-hole alumina catalyst carrier is used for preferential oxidation of CO under the hydrogen-rich condition or CO oxidation reaction.
Further, the porous alumina catalyst carrier obtained by the above method is obtained by a preparation method.
The reagents, concentrations, and principles used in the above preparation methods are explained in detail as follows:
(1) The choice of the base material is not particularly limited, but is preferably a 5-series aluminum alloy based on the superiority of the anodic oxidation treatment, the aluminum alloy is a magnesium aluminum alloy, the anodic oxidation is convenient, and the subsequent replacement treatment is easy.
(2) Regarding the pretreatment: firstly, pretreatment is a necessary treatment means, if grease on the surface of the aluminum alloy is not removed to seriously affect the binding force between an oxide film and a base material, if alkali acid does not remove the oxide film, the subsequent anodic oxidation cannot be performed, specifically:
(a) Alkaline degreasing: the invention adopts alkaline solution degreasing, can saponify vegetable oil and animal oil on the surface of the substrate to generate soap dissolved in water, and removes the soap, and the following reactions are carried out:
(C17H35COO) 3 C 3 H 5 +3NaOH→3C 17 H 35 COONa+C 3 H 5 (OH) 3
the degreasing liquid is a mixed aqueous solution of 20-25 g/L sodium carbonate and 2-3g/L sodium phosphate, the temperature is 65-70 ℃, the soaking time is 5-6min, the alkalinity of the sodium carbonate is weaker than that of sodium hydroxide, the sodium carbonate has certain saponification capacity, the pH value of the solution is buffered, the corrosiveness to metals and the skin irritation are lower than those of sodium hydroxide, the price is low, the sodium carbonate is often used as main salt in aluminum alloy degreasing liquid, the sodium phosphate is slightly alkaline, the sodium phosphate has certain saponification capacity and the buffering function to the pH value, and can complex metal ions in water to soften the water quality, and the sodium carbonate is an emulsifier with high solubility and good washing property. The alkaline degreasing includes a primary water washing and a secondary water washing, for example, the primary water washing can be performed by hot water at 60-70 ℃, so that pollutants remained on the surface of the workpiece after degreasing can be effectively removed.
(b) Alkali washing: after degreasing, the aluminum alloy workpiece cannot be subjected to conversion film treatment, and the surface of the aluminum alloy workpiece generally has the defects of natural oxide film, processing stripes and the like, and the aluminum alloy workpiece needs to be subjected to corrosion treatment to remove the natural oxide film and activate the surface. Alkaline corrosion is the most commonly used corrosion process, the main components are NaOH solution, alkali washing liquid is sodium citrate aqueous solution of 20-30g/LNaOH and 3-5g/L, the temperature is 10-20 ℃, the soaking time is 15-20min, wherein a natural aluminum oxide film reacts with sodium hydroxide to form sodium metaaluminate, and the corrosion speed of aluminum is in direct proportion to the total content of sodium hydroxide in the solution and rises with the rise of temperature. Wherein, the main function of the sodium citrate is complexing agent, which can effectively mask aluminum ions and avoid the generation of aluminum hydroxide precipitation.
(c) Acid washing: the surface of the aluminum alloy workpiece subjected to alkaline degreasing and alkaline corrosion is generally provided with a layer of black ash. In order to obtain a bright metal surface, it is necessary to carry out the light-emitting treatment with an acidic solution. Even the pure aluminum workpiece has alkali solution on the surface, which is difficult to be completely cleaned by water and needs to be neutralized by acid solution, the acid washing ash removal liquid of the invention is 50-70g/L HNO 3 And 4-8g/LNaF, at normal temperature for 2-3min.
(d) Washing: any aluminum workpiece treated by the chemical solution should be immediately washed after being removed from the treatment solution, and the faster and better. Because the workpiece is exposed to the air leaving the treatment fluid, the surface is in a non-uniform state and the chemical agent needs to be immediately rinsed away with water to terminate the chemical reaction. And at the same time, prevents the chemical agent from being brought into the next treatment liquid to pollute the next chemical treatment tank.
(3) Regarding anodic oxidation: the thickness of the barrier layer depends on the anodic oxidation voltage, and the size of the pores and pore bodies of the porous layer is related to the composition, concentration and operating conditions of the electrolyte, and the invention usesOxalic acid is used as main acid, and phosphoric acid and sulfosalicylic acid are compounded, wherein the dissolution capacity of oxalic acid to aluminum is smaller than that of sulfuric acid, so that a film layer which is more stable than that of sulfuric acid anodic oxidation is easily obtained, and the thickness of an anodic oxidation film is 0.5-1 mu m; when phosphoric acid is used for anodic oxidation, the porosity of the anodic oxidation film can be effectively improved, and the pore diameter is larger, for example, the pore number of the anodic oxidation film is 80-150/mu m 2 The addition of the sulfosalicylic acid organic acid can effectively reduce the use amount of oxalic acid and phosphoric acid, and has a slight improvement effect on the reduction of the thickness of the shielding layer of the anodic oxide film.
Voltage: in the oxalic acid oxidation process, the voltage is slowly increased, the current concentration at the uneven part of the newly generated oxide film is caused, the serious electric breakdown occurs at the uneven part, the corrosion of metal aluminum is caused, the voltage is preferably 20-30V, the pore number of the pore canal of the anodic oxide film is obviously reduced along with the increase of the voltage, and the pore canal of the anodic oxide film is enlarged and the porosity is reduced along with the increase of the voltage.
Current density: the current density is proportional to the rate of alumina formation, and the higher the current density, the faster the rate of alumina formation. However, the formation rate of the oxide film is not completely proportional to the current density. The rate of formation of the oxide film is equal to the rate of formation of aluminum minus the rate of dissolution of aluminum oxide in the electrolyte, which is a chemical process independent of the electrolysis current density, depending on the concentration of the electrolyte and the local temperature of the solution. The higher the concentration of the electrolyte, the higher the local temperature of the solution and the faster the dissolution rate of alumina. Thus, the dissolution rate of alumina is unchanged under the same electrolyte concentration and temperature conditions. The current density is increased, the generation speed of the oxide film is increased, and the porosity of the oxide film is reduced.
Temperature: the temperature is increased and the film is thinned, and if the pH value of the electrolyte is increased at a higher temperature, the thickness of the film can be increased, and the optimal temperature is between 25 and 40 ℃, preferably 30 ℃.
(4) Regarding the adsorption protective film and the selective removal of the shielding layer: the anodic oxide film generally comprises a shielding layer and a nano array which are positioned at the bottom of the pore canal of the anodic oxide filmWherein the main component of the shielding layer is gamma-Al 2 O 3 I.e. no water, very few hydroxyl groups, whereas the porous layer is typically alpha-AlOOH alumina, rich in crystal water and hydroxyl groups, based on the difference between the barrier layer and the porous layer, vacuum is applied to the inside of the anodized film to introduce gamma-chloropropyl trimethoxysilane, 75 o Under C, the gamma-chloropropyl trimethoxysilane reacts with hydroxyl to form a tri-tripod silica bond with strong binding force, and the specific reaction formula is as follows:
the gamma-chloropropyl trimethoxysilane is not stuck to the surface of the shielding layer, so that the accurate cladding of the gamma-chloropropyl trimethoxysilane is realized, in addition, an auxiliary vacuumizing means is used for conveniently and effectively overcoming the capillary effect of the anodic oxide film nanotube in the process of positioning and marking the protective film, in addition, the nano pore canal of the anodic oxide film is an opening at one end and an aluminum base at one end, and the vacuumizing is more convenient for the gamma-chloropropyl trimethoxysilane to enter the nano pore canal, so that the invention is an indispensable auxiliary means.
Then, the shielding layer is corroded by using an corrosive liquid, wherein the corrosive liquid is alkaline corrosive liquid instead of acidic corrosive liquid, protons in the acidic corrosive liquid are easy to dissociate silicon oxygen bonds adsorbed on the surface of the porous layer, so that gamma-chloropropyl trimethoxysilane is desorbed from the surface of the porous layer, the function of a protective layer is finally lost, alkaline sodium hydroxide does not influence gamma-chloropropyl trimethoxysilane, and meanwhile, the alkaline sodium hydroxide can effectively contact the shielding layer to generate NaOH+Al 2 O 3 →NaAlO 2 +H 2 O, further, the reaction for effectively removing alumina is realized, and the corrosion reaction can occur at normal temperature without heating.
In addition, the corrosive liquid of the invention consists of NaOH, naF and ethanol, does not contain any moisture, and is mainly due to the existence of waterUnder the condition, al+NaOH+H is very easy to occur 2 O—NaAlO 2 +3H 2 The loss of the base material is caused, when no moisture exists in the corrosion process (less water is generated in the corrosion shielding layer process and can be ignored), the reaction of Al and NaOH only occurs difficultly, in addition, nitrogen protection is assisted in the corrosion process, the corrosion of alkali and the base material is not or hardly caused, the positioning corrosion is simpler and easier, the damage of the base material does not occur, and in addition, naF is a penetrating agent, so that the corrosion reaction of sodium hydroxide and a compact nonporous shielding layer is facilitated.
(5) Regarding removal of the aluminum substrate, a simple chemical substitution reaction CuCl was used 2 +Al (Mg) → AlCl3 (MgCl 2) +Cu, in the whole process, aluminum material participates in the displacement reaction, aluminum oxide does not participate in the reaction, and finally the base material is removed, and notably hydrochloric acid is added into copper chloride to prevent copper chloride from being hydrolyzed to form copper hydroxide precipitate and influence the displacement reaction effect, so hydrochloric acid is added to reduce the hydrolysis reaction, but the addition amount of hydrochloric acid cannot be too high, otherwise, an anodic oxide film reacts with hydrochloric acid to influence the performance of the catalyst carrier.
In addition, it is noted that the anode substrate does not need single-sided anodic oxidation, but double-sided anodic oxidation, and after the anodic oxidation is finished, the copper chloride can react with the aluminum material positioned in the middle by removing the pore canal of the shielding layer, so that the through-hole alumina substrate is finally obtained.
The scheme of the invention has the following beneficial effects:
(1) The shielding layer at the bottom of the pore canal of the anodic oxide film can be effectively corroded through the selective adsorption reaction of gamma-chloropropyl trimethoxysilane on the porous layer and the shielding layer and the subsequent alkaline corrosion reaction;
(2) Can be anodized on both sides without a single-sided alumina substrate.
(3) The alumina pore canal array obtained by removing aluminum base through displacement reaction has complete and uniform pore canal structure.
(4) The whole preparation process is simple to operate, convenient to implement and high in repetition rate.
Description of the drawings:
FIG. 1 is a schematic illustration of the process of the present invention.
Fig. 2 is a TEM image of a through-hole alumina catalyst support.
Fig. 3 is a TEM image of a through-hole alumina catalyst support.
Fig. 4 is an SEM image of a through-hole alumina catalyst support.
Fig. 5 is an SEM magnified view of the through-hole alumina catalyst support.
The specific embodiment is as follows:
example 1
A through-hole alumina catalyst support, as shown in fig. 1, comprising the following processing steps:
(1) Selecting 5 series aluminum alloy smaller than 0.5cm as a base material;
(2) The method comprises the steps of pretreatment of aluminum substrates, namely alkaline degreasing, hot water washing, alkaline washing, hot water washing, cold water washing, acid washing and water washing.
(3) Anodizing the treated aluminum substrate to form an oxide film on the surface, wherein the solution used for anodizing is mixed solution of oxalic acid, phosphoric acid and sulfosalicylic acid, the concentration of oxalic acid is 0.25M, the concentration of phosphoric acid is 0.2M, the concentration of sulfosalicylic acid is 0.05M, the voltage in the anodizing process is 20V, the temperature is 30 ℃, and the current density is 2A/dm 2 The time is 20min.
(4) The protective film is adsorbed on the surface of the porous layer of the anodic oxidation film, the protective film is not adsorbed on the shielding layer, the solution adopted in the step (4) is mixed liquid of gamma-chloropropyl trimethoxysilane and anhydrous toluene, the concentration of the gamma-chloropropyl trimethoxysilane is 10 wt%, the dosage of the gamma-chloropropyl trimethoxysilane is 3% of the weight of the anodized aluminum material, and the vacuumizing treatment is assisted in the process of the step (4), so that the vacuum degree is 90-100Pa.
(5) Removing the shielding layer at the bottom of the anodic oxide film to expose the aluminum base material; the solution used for removing the shielding layer in the step (5) is a mixed solution of NaOH, naF and ethanol, and the solution is NaOH: naF: the mass ratio of the ethanol is (2) to (1) to (7), and the whole process is under the protection of nitrogen.
(6) Vacuum freeze drying the above sample, soaking in copper chloride-hydrochloric acid aqueous solution with concentration of 7wt.%, concentration of copper chloride of 0.1M, soaking time of more than 24 hr and soaking temperature of 25deg.C
(7) And (5) performing vacuum freeze drying to obtain the through-hole type alumina catalyst carrier.
Example 2
A through-hole alumina catalyst support comprising the following processing steps:
(1) Selecting 5 series aluminum alloy smaller than 0.5cm as a base material;
(2) The method comprises the steps of pretreatment of aluminum substrates, namely alkaline degreasing, hot water washing, alkaline washing, hot water washing, cold water washing, acid washing and water washing.
(3) Anodizing the treated aluminum substrate to form an oxide film on the surface, wherein the solution used for anodizing is mixed solution of oxalic acid, phosphoric acid and sulfosalicylic acid, the concentration of oxalic acid is 0.275M, the concentration of phosphoric acid is 0.3M, the concentration of sulfosalicylic acid is 0.1M, the voltage in the anodizing process is 25V, the temperature is 30 ℃, and the current density is 2.5A/dm 2 Time 25min.
(4) The protective film is adsorbed on the surface of the porous layer of the anodic oxidation film, the protective film is not adsorbed on the shielding layer, the solution adopted in the step (4) is mixed liquid of gamma-chloropropyl trimethoxysilane and anhydrous toluene, the concentration of the gamma-chloropropyl trimethoxysilane is 15 wt%, the dosage of the gamma-chloropropyl trimethoxysilane is 4% of the weight of the anodized aluminum material, and the vacuumizing treatment is assisted in the step (4), so that the vacuum degree is 90-100Pa.
(5) Removing the shielding layer at the bottom of the anodic oxide film to expose the aluminum base material; the solution used for removing the shielding layer in the step (5) is a mixed solution of NaOH, naF and ethanol, and the solution is NaOH: naF: the mass ratio of the ethanol is (3.5): (1.5): 7, and the whole process is under the protection of nitrogen.
(6) Vacuum freeze drying the above sample, soaking in copper chloride-hydrochloric acid aqueous solution with concentration of 8.5wt.%, copper chloride concentration of 0.15M, soaking time greater than 24 hr, and soaking temperature of 28deg.C
(7) And (5) performing vacuum freeze drying to obtain the through-hole type alumina catalyst carrier.
Example 3
A through-hole alumina catalyst support comprising the following processing steps:
(1) Selecting 5 series aluminum alloy smaller than 0.5cm as a base material;
(2) The method comprises the steps of pretreatment of aluminum substrates, namely alkaline degreasing, hot water washing, alkaline washing, hot water washing, cold water washing, acid washing and water washing.
(3) Anodizing the treated aluminum substrate to form an oxide film on the surface, wherein the solution used in the anodizing is mixed solution of oxalic acid, phosphoric acid and sulfosalicylic acid, the concentration of oxalic acid is 0.3M, the concentration of phosphoric acid is 0.4M, the concentration of sulfosalicylic acid is 0.15M, the voltage in the anodizing process is 30V, and the temperature is 30 o C, current density 3A/dm 2 The time is 30min.
(4) The protective film is adsorbed on the surface of the porous layer of the anodic oxidation film, the protective film is not adsorbed on the shielding layer, the solution adopted in the step (4) is mixed liquid of gamma-chloropropyl trimethoxysilane and anhydrous toluene, the concentration of the gamma-chloropropyl trimethoxysilane is 20 wt%, the dosage of the gamma-chloropropyl trimethoxysilane is 5% of the weight of the anodized aluminum material, and the vacuumizing treatment is assisted in the process of the step (4), so that the vacuum degree is 90-100Pa.
(5) Removing the shielding layer at the bottom of the anodic oxide film to expose the aluminum base material; the solution used for removing the shielding layer in the step (5) is a mixed solution of NaOH, naF and ethanol, and the solution is NaOH: naF: the mass ratio of the ethanol is 5:2:7, and the whole process is under the protection of nitrogen.
(6) Vacuum freeze drying the above sample, soaking in copper chloride-hydrochloric acid aqueous solution with concentration of 10wt.%, concentration of copper chloride of 0.15M, soaking time greater than 24 hr, and soaking temperature of 30deg.C
(7) And (5) performing vacuum freeze drying to obtain the through-hole type alumina catalyst carrier.
As shown in TEM results of fig. 2 and 3 and SEM results of fig. 4 and 5, the obtained shielding layer at the bottom of the oxide film pore canal is effectively removed, and the porous oxide film porous layer corrosive substrate is uniform in pore canal array and extremely high in penetrability.
Although the present invention has been described by way of example with reference to the preferred embodiments, the present invention is not limited to the specific embodiments, and may be modified appropriately within the scope of the present invention.
Claims (4)
1. The preparation method of the catalyst carrier is characterized by comprising the following processing steps:
(1) Selecting aluminum alloy as an aluminum base material;
(2) Pretreating an aluminum substrate;
(3) Performing anodic oxidation treatment on the treated aluminum substrate to form an oxide film on the surface;
(4) Adsorbing a protective film on the surface of the porous layer of the anodic oxide film, wherein the protective film is not adsorbed on the shielding layer;
(5) Removing the shielding layer at the bottom of the anodic oxide film to expose the aluminum base material;
(6) Removing the aluminum substrate to obtain a catalyst carrier containing only the anodic oxide film porous layer;
in the step (3), the solution used for the anodic oxidation is mixed solution of oxalic acid, phosphoric acid and sulfosalicylic acid, the concentration of oxalic acid is 0.25-0.3M, the concentration of phosphoric acid is 0.2-0.4M, the concentration of sulfosalicylic acid is 0.05-0.15M, the voltage in the anodic oxidation process is 20-30V, the temperature is 30 ℃, and the current density is 2-3A/dm 2 The time is 20-30min;
the solution adopted by the adsorption protective film in the step (4) is mixed solution of gamma-chloropropyl trimethoxysilane and anhydrous toluene, the concentration of the gamma-chloropropyl trimethoxysilane is 10-20 wt%, the dosage of the gamma-chloropropyl trimethoxysilane is 3-5% of the weight of the anodized aluminum material, and the vacuumizing treatment is assisted in the process of the step (4), so that the vacuum degree is 90-100Pa;
the solution used for removing the shielding layer in the step (5) is a mixed solution of NaOH, naF and ethanol, wherein the NaOH is as follows: naF: the mass ratio of the ethanol is (2-5): 1-2): 7.
2. The method for preparing a catalyst carrier according to claim 1, wherein in the step (1), the aluminum alloy substrate is a 5-series aluminum alloy, and the thickness of the aluminum alloy is less than 0.5cm.
3. The method for preparing a catalyst carrier according to claim 1, wherein in the step (2), the pretreatment comprises a step of alkaline degreasing-hot water washing-alkaline washing-hot water washing-cold water washing-acid washing-water washing.
4. The method for preparing a catalyst carrier according to claim 1, wherein the solution used for removing the aluminum substrate in the step (6) is a copper chloride-hydrochloric acid aqueous solution, the concentration of hydrochloric acid is 7-10wt.%, and the concentration of copper chloride is 0.1-0.15M.
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