CN105435859B - Vehicle tail gas treater ceramic monolith surface is with nanocrystalline method of modifying - Google Patents
Vehicle tail gas treater ceramic monolith surface is with nanocrystalline method of modifying Download PDFInfo
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- CN105435859B CN105435859B CN201610022747.6A CN201610022747A CN105435859B CN 105435859 B CN105435859 B CN 105435859B CN 201610022747 A CN201610022747 A CN 201610022747A CN 105435859 B CN105435859 B CN 105435859B
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- vehicle tail
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- 239000000919 ceramic Substances 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 28
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 28
- 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 abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 239000002159 nanocrystal Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 13
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 16
- 239000002994 raw material Substances 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 11
- 238000000227 grinding Methods 0.000 claims description 9
- 239000012265 solid product Substances 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- 239000000395 magnesium oxide Substances 0.000 claims description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000010828 elution Methods 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000003518 caustics Substances 0.000 claims description 5
- 239000001913 cellulose Substances 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000011496 polyurethane foam Substances 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 229910000329 aluminium sulfate Inorganic materials 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
- 238000007670 refining Methods 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 239000002689 soil Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 17
- 239000002245 particle Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 239000002105 nanoparticle Substances 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 4
- 239000005995 Aluminium silicate Substances 0.000 description 3
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 235000012211 aluminium silicate Nutrition 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 208000000059 Dyspnea Diseases 0.000 description 1
- 206010013975 Dyspnoeas Diseases 0.000 description 1
- 241000264877 Hippospongia communis Species 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 206010057190 Respiratory tract infections Diseases 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 208000006673 asthma Diseases 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- KYYSIVCCYWZZLR-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)molybdenum Chemical compound [Co+2].[O-][Mo]([O-])(=O)=O KYYSIVCCYWZZLR-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- -1 hydrogen Sodium hydroxide Chemical class 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002103 nanocoating Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000009325 pulmonary function Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B01J35/56—
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5072—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with oxides or hydroxides not covered by C04B41/5025
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
Vehicle tail gas treater ceramic monolith surface is with nanocrystalline method of modifying, including be made nanocrystal boehmite solid-liquid mix the step of, by 5 ~ 10% lanthana, 5 ~ 10% cerium oxide, 30 ~ 50% nanocrystal boehmite solid-liquid mixture, surplus be deionized water mix to obtain colloidal sol, by colloidal sol be coated in ceramic monolith and dry, be calcined the step of.Lanthana, cerium oxide are added in nanocrystal boehmite solid-liquid mixture, improve the heat endurance and catalytic activity for the colloidal sol for being impregnated in ceramic monolith surface, simultaneously, nanocrystal boehmite is easy to removal of impurities and improves purity, also provided for catalyst carrier than larger specific surface area and bond strength, and improve the high-temperature stability of modified ceramic monolith.
Description
Technical field
The present invention relates to vehicle tail gas treater ceramic monolith surface with nanocrystalline method of modifying.
Background technology
In recent years, with rapid development of economy, haze phenomenon happens occasionally caused by PM2.5, one of them important original
Cause is the pollution that transportation is brought.The tail gas of vehicle fuel burning and exhausting contains a variety of chemical compositions, including endless
Full burning hydrocarbon, nitrogen oxides and carbon monoxide, these are all the origin causes of formation for causing haze.Imperfect combustion hydro carbons in atmosphere may be used
Generation photochemical reaction, nitrogen oxides and carbon monoxide can cause the symptoms such as expiratory dyspnea, respiratory tract infection and the asthma of people, together
When, make decline in pulmonary function.It is a kind of effective ways for reducing tail gas pollution using vehicle tail gas treater catalytic purification method, but
The catalyst of existing vehicle tail gas treater only applicable part, needs offer badly and a kind of is respectively provided with various catalyst activity components
The vehicle tail gas treater of matched well.
The content of the invention
It is an object of the invention to provide a kind of vehicle tail gas treater ceramic monolith surface with nanocrystalline method of modifying, make
Vehicle tail gas treater has higher heat endurance and catalytic activity.
The technical scheme that is used to achieve the above object of the present invention for：Vehicle tail gas treater ceramic monolith surface is with receiving
Meter Jing method of modifying, comprises the following steps：
Step 1: by caustic solution and aluminum salt solution according to [OH]—：[Al]3+=3：The mol ratio of (1 ~ 2) is mixed,
At normal temperatures after 5 ~ 10min of stirring, it is transferred in the autoclave that temperature is 102 ~ 160 DEG C, after 1 ~ 10h of reaction, solid product is made,
By solid product by suction filtration, elution circulation 1 ~ 4 time, nanocrystal boehmite solid-liquid mixture is made, it is standby；
Step 2: according to percentage by weight, 5 ~ 10% lanthana, 5 ~ 10% cerium oxide are taken successively and 30 ~ 50% is received
The brilliant boehmite solid-liquid mixture of rice, surplus is deionized water, by lanthana, cerium oxide, nanocrystal boehmite solid-liquid mixture and
Deionized water mixes to obtain colloidal sol, and ceramic monolith is immersed in the colloidal sol and taken out after 10 ~ 40min, and blows down ceramic monolith access opening
Colloidal sol in gap, ceramic monolith is placed at a temperature of 100 ~ 120oC and dried after 1 ~ 4h, 0.5 ~ 5h is calcined at 500 ~ 550 DEG C, and
It will dry, baking operation is circulated 0 ~ 2 time, and modified vehicle tail gas treater ceramic monolith is made.
Wherein, the caustic solution used in step one is sodium hydroxide or potassium hydroxide solution；Aluminum salt solution is AlCl3·
6H2O、Al(NO3)3·9H2O or Al2(SO4)3·18H2O solution.
Wherein, 10~40nm of size of nanocrystal boehmite solid-liquid mixture made from step one.
In the present invention, the ceramic monolith used in step 2, its raw material by percentage by weight be 90 ~ 93.5% nanocrystalline oxygen
Change aluminium, 2 ~ 5% kaolin, 0.5 ~ 5% nanocrystalline magnesia, 1 ~ 3% cellulose and 1 ~ 4% adhesive composition.
One of preferred embodiment, the preparation method of ceramic monolith includes：
A, weigh each raw material according to the percentage by weight described in ceramic monolith raw material and mix, raw material is then added thereto
The water of gross weight 40 ~ 60%, 2 ~ 3h of grinding obtains ceramic slurry, standby；
B, ceramic slurry is immersed in polyurethane foam, and dries at 100 ~ 130 DEG C powdering, and be processed into and have
The ceramic body of required shape and size, it is standby；
C, obtained ceramic body calcined into 2 ~ 10h at 1300 ~ 1500 DEG C, naturally cool to after room temperature, ceramics are made
Carrier.
The two of preferred embodiment, the preparation method of ceramic monolith includes：
A, weigh each raw material according to the ratio described in ceramic monolith raw material and mix, add weight and account for and weighs raw material gross weight
After 40 ~ 60% deionized water, 2 ~ 3h of ball milling, it is placed in thick mill after slightly refining 2 ~ 3 times, old 20 ~ 24h and slurry is made, it is standby；
B, obtained slurry is put into single lead screw ex truding briquetting machine moulded pottery not yet put in a kiln to bake is made, and it is 100 ~ 130 DEG C that moulded pottery not yet put in a kiln to bake is placed in into temperature
Dryness finalization is standby into dry body in far infrared stove；
C, obtained dry body is placed in incinerator, in 1300 ~ 1700 DEG C of 2 ~ 10h of temperature lower calcination, cools to room with the furnace
Wen Hou, is made ceramic monolith.
Because the particle of nano material in itself is tiny, specific surface area is huge, agglomeration easily occurs.Said on conventional meaning
Nano material, be the particle diameter that the individual particle that is shown under ESEM is 1 ~ 100nm, still, the nano material is in Ma Er
But tens microns of particle diameter is shown as on literary laser particle analyzer.To find out its cause, being that nano material is easily reunited, in outward appearance after reunion
Upper display has reached tens microns of particle diameter, so that even if adding nano level granular materials in existing production, actual
On remain as micron order, it is difficult to really play a part of nano particle.
Beneficial effect：Nanocrystal boehmite solid-liquid mixture is made by caustic solution and aluminum salt solution in the present invention, receives
The brilliant boehmite of rice is in single nanoparticle dispersity, so allows for still showing Nano grade when addition forms colloidal sol,
Show the property of nano-scale particle, may be considered after the addition still in single_phase system, in mixed process dispersivity it is good,
It can be evenly distributed；Lanthana, cerium oxide are added in nanocrystal boehmite solid-liquid mixture, raising is impregnated in ceramic monolith table
The heat endurance and catalytic activity of the colloidal sol in face, meanwhile, nanocrystal boehmite is easy to removal of impurities and improves purity, is also catalyst carrier
There is provided than larger specific surface area and bond strength, and improve the high-temperature stability of modified ceramic monolith.
Embodiment
With reference to specific embodiment to the vehicle tail gas treater ceramic monolith surface of the present invention with nanocrystalline modification
Method is described further, so that those skilled in the art can be better understood from the present invention and can be practiced, but is lifted
Embodiment is not as a limitation of the invention.
Vehicle tail gas treater ceramic monolith surface is comprised the following steps with nanocrystalline method of modifying：Step 1: will be severe
Property aqueous slkali and aluminum salt solution are according to [OH]—：[Al]3+=3：The mol ratio of (1 ~ 2) is mixed, and 5 ~ 10min is stirred at normal temperatures
Afterwards, be transferred to during temperature is 102 ~ 160 DEG C of autoclave, after 1 ~ 10h of reaction, solid product be made, by solid product by suction filtration,
Elution circulation 1 ~ 4 time, is made nanocrystal boehmite solid-liquid mixture, standby；
Step 2: according to percentage by weight, 5 ~ 10% lanthana, 5 ~ 10% cerium oxide are taken successively and 30 ~ 50% is received
The brilliant boehmite solid-liquid mixture of rice, surplus is deionized water, by lanthana, cerium oxide, nanocrystal boehmite solid-liquid mixture and
Deionized water mixes to obtain colloidal sol, and ceramic monolith is immersed in the colloidal sol and taken out after 10 ~ 40min, and blows down ceramic monolith access opening
Colloidal sol in gap, ceramic monolith is placed at a temperature of 100 ~ 120oC and dried after 1 ~ 4h, 0.5 ~ 5h is calcined at 500 ~ 550 DEG C, and
It will dry, baking operation is circulated 0 ~ 2 time, and modified vehicle tail gas treater ceramic monolith is made.
Embodiment 1
Vehicle tail gas treater ceramic monolith surface is comprised the following steps with nanocrystalline method of modifying：Step 1: by hydrogen
Sodium hydroxide solution and Al2(SO4)3·18H2O solution is according to [OH]—：[Al]3+=3：The mol ratio of (1 ~ 2) is mixed, and is adjusted
Mixed solution Ph is 7, is stirred at normal temperatures after 10min, is transferred in the autoclave that temperature is 105 DEG C ± 3 DEG C, after reaction 3h, system
Solid product is obtained, by solid product by suction filtration, elution circulation 4 times, nanocrystal boehmite solid-liquid of the size for 10 ~ 40nm is made
Mixture, it is standby；
Step 2: according to percentage by weight, 93.5% nanometer crystal alumina, 2% kaolin, 0.5% nanometer is taken successively
Brilliant magnesia, 1% cellulose and 3% binder materials and mixing, then add the water of raw material gross weight 60%, grinding thereto
2.5h, obtains ceramic slurry, standby；
Step 3: ceramic slurry is immersed in polyurethane foam, and powdering is dried at 130 DEG C, and be processed into tool
There is the ceramic body of required shape and size, it is standby；
Step 4: obtained ceramic body is calcined into 8h at 1350 DEG C, naturally cool to after room temperature, ceramics are made and carry
Body；
Step 5: according to percentage by weight, 10% lanthana, 10% cerium oxide, 30% nanocrystal boehmite is taken successively
Solid-liquid mixture and 50% deionized water, mix to obtain colloidal sol, and ceramic monolith made from step 4 is immersed into 20min in the colloidal sol
After take out, and blow down the intrapore colloidal sol of ceramic monolith passage, ceramic monolith be placed at a temperature of 100oC after drying 2h, 550
1h is calcined at DEG C；Repeat ceramic monolith being placed at a temperature of 100oC and dry after 2h, be calcined 1h at 550 DEG C, modified vapour is made
Tailstock treatment apparatus ceramic monolith.
Embodiment 2
Step 1: by potassium hydroxide solution and Al (NO3)3·9H2O solution is according to [OH]—：[Al]3+=3：1.6 mol ratio
Mixed, stirred at normal temperatures after 8min, is transferred in the autoclave that temperature is 157 DEG C ± 3 DEG C, after reaction 1h, solid phase is made
Product, by solid product by suction filtration, elution circulation 2 times, it is 10 ~ 40nm nanocrystal boehmite solid-liquid mixtures that size, which is made,
It is standby；
Step 2: according to percentage by weight, nanometer crystal alumina, 5% height that the particle diameter that 90% is taken successively is 10 ~ 100nm
Ridge soil, 1% particle diameter are 20 ~ 100nm nanocrystalline magnesia, 3% cellulose and 1% binder materials and mixing, Ran Houxiang
Wherein add after the water of raw material gross weight 55%, ball milling 3h, be placed in thick mill after slightly refining 3 times, old 24h and slurry is made, it is standby；
Moulded pottery not yet put in a kiln to bake is made Step 3: obtained slurry is put into single lead screw ex truding briquetting machine, and it is 130 DEG C that moulded pottery not yet put in a kiln to bake is placed in into temperature
Dryness finalization is standby into dry body in far infrared stove；
Step 4: obtained dry body is placed in incinerator, in 1500 DEG C of temperature lower calcination 10h, room temperature is cooled to the furnace
Afterwards, ceramic monolith is made；
Step 5: according to percentage by weight, taking 8% lanthana, 7% cerium oxide, 50% nanocrystal boehmite to consolidate successively
Liquid mixture and 35% deionized water, mix to obtain colloidal sol, and ceramic monolith made from step 4 is immersed in the colloidal sol after 40min
Take out, and blow down the intrapore colloidal sol of ceramic monolith passage, ceramic monolith is placed at a temperature of 120oC and dried after 1h, at 500 DEG C
Lower roasting 5h, and drying, baking operation are circulated 2 times, modified vehicle tail gas treater ceramic monolith is made.
Embodiment 3
Step 1: by potassium hydroxide solution and AlCl3·6H2O solution is according to [OH]—：[Al]3+=3：1 mol ratio is carried out
Mixing, is stirred after 5min at normal temperatures, is transferred in the autoclave that temperature is 130 DEG C, and after reaction 5h, solid product is made, will be solid
Phase product is by suction filtration, elution circulation 1 time, and it is 10 ~ 40nm nanocrystal boehmite solid-liquid mixtures that size, which is made, standby；
Step 2: according to percentage by weight, take successively 91% particle diameter for 10nm nanometer crystal alumina, 2% kaolin,
Nanocrystalline magnesia, 2% cellulose and 2.5% binder materials and mixing that 2.5% particle diameter is 50nm, then thereto
The water of raw material gross weight 40% is added, grinding 2h obtains ceramic slurry, standby；
Step 3: ceramic slurry is immersed in polyurethane foam, and powdering is dried at 125 DEG C, and be processed into tool
There is the ceramic body of required shape and size, it is standby；
Step 4: obtained ceramic body is calcined into 10h at 1500 DEG C, naturally cool to after room temperature, ceramics are made and carry
Body, it is standby；
Step 5: according to percentage by weight, 5% lanthana, 10% cerium oxide, 45% nanocrystal boehmite is taken successively
Solid-liquid mixture and 40% deionized water, mix to obtain colloidal sol, and ceramic monolith made from step 4 is immersed in the colloidal sol
Taken out after 10min, and blow down the intrapore colloidal sol of ceramic monolith passage, ceramic monolith is placed at a temperature of 115oC and dried after 4h,
0.5h is calcined at 535 DEG C, modified vehicle tail gas treater ceramic monolith is made.
Nanocrystalline magnesia used in the embodiment of the present invention 1 ~ 3, is the Application No. by earlier application
Based on a kind of preparation method of highly-pure magnesium hydroxide nanometer disclosed in CN2009100651656, and by obtained hydroxide
Magnesium is nanocrystalline to be placed in after 400 DEG C of calcining 20min, is cooled to room temperature with 5 ~ 10 DEG C/h rate of temperature fall, nanocrystalline magnesia is made.
The MgO formed after sintering is in single nanoparticle dispersity, still shows Nano grade when so mixing is added, shows
The property of nano-scale particle, may be considered still in single_phase system after the addition, in ball milling or grinding process dispersivity it is good,
It can be evenly distributed, make the combination of each material in the powder to be formed also even closer.
Ceramic monolith obtained by the embodiment of the present invention 1 ~ 3, the characteristics of specific surface area is big, aeration resistance is small, regularity is strong,
By modified, ceramic monolith can be with noble metal catalyst, Raney nickel, cobaltmolybdate catalyst, palladium catalyst, titanium catalyst etc.
Catalyst activity component is respectively provided with matched well.Because the ceramic honey comb being made has nanostructured so that product high temperature power
Learn excellent performance, thermal shock resistance and excellent wear-resisting property.And by lanthana, cerium oxide, nanocrystal boehmite solid-liquid mixture and
Deionized water mix colloidal sol is coated in ceramic monolith, drying, roasting obtain the nano coating in dispersity, not only strengthened
The high temperature hardness of material after sintering, simultaneously because its special size range, Dispersed precipitate in the material, moreover it is possible to protect material
Higher toughness is held, and can substantially suppress the brittle fracture of material, significantly improve the thermal shock resistance of material.
Nanocrystal boehmite or nanocrystal boehmite solid-liquid mixture produced by the present invention, with Malvern laser particle analyzer
Nano-scale particle size in meaning（Less than 100 nanometers）With the purity higher than 99%, nano-scale dimension determines that its specific surface area is huge
Greatly, accelerate to react particular benefit as catalyst；High-purity, the unnecessary of generation may be caused by determining it as catalyst
Side reaction it is few, and for ceramic material when high-temperature behavior it is fabulous.The present invention is produced without any noxious material, it is to avoid to environment
Pollution, therefore, the present invention have environmental protection characteristic.
Claims (6)
1. vehicle tail gas treater ceramic monolith surface is with nanocrystalline method of modifying, it is characterised in that comprise the following steps：
Step 1: by caustic solution and aluminum salt solution according to [OH]—：[Al]3+=3：The mol ratio of (1 ~ 2) is mixed, normal
After 5 ~ 10min of the lower stirring of temperature, it is transferred in the autoclave that temperature is 102 ~ 160 DEG C, after 1 ~ 10h of reaction, solid product is made, will be solid
Nanocrystal boehmite solid-liquid mixture is made by suction filtration, elution circulation 1 ~ 4 time in phase product, standby；
Step 2: according to percentage by weight, take successively 5 ~ 10% lanthana, 5 ~ 10% cerium oxide and 30 ~ 50% it is nanocrystalline
Boehmite solid-liquid mixture, surplus is deionized water, by lanthana, cerium oxide, nanocrystal boehmite solid-liquid mixture and go from
Sub- water mixes to obtain colloidal sol, and ceramic monolith is immersed in the colloidal sol and taken out after 10 ~ 40min, and is blown down in ceramic monolith passage hole
Colloidal sol, ceramic monolith is placed at a temperature of 100 ~ 120oC after 1 ~ 4h of drying, 0.5 ~ 5h is calcined at 500 ~ 550 DEG C, and will dry
Dry, baking operation is circulated 0 ~ 2 time, and modified vehicle tail gas treater ceramic monolith is made.
2. vehicle tail gas treater ceramic monolith surface according to claim 1 nanocrystalline method of modifying, its feature
It is：Described caustic solution is sodium hydroxide or potassium hydroxide solution；Described aluminum salt solution is AlCl3·6H2O、Al
(NO3)3·9H2O or Al2(SO4)3·18H2O solution.
3. vehicle tail gas treater ceramic monolith surface according to claim 1 nanocrystalline method of modifying, its feature
It is：10~40nm of size of nanocrystal boehmite solid-liquid mixture made from step one.
4. vehicle tail gas treater ceramic monolith surface according to claim 1 nanocrystalline method of modifying, its feature
It is：Ceramic monolith used in step 2, nanometer crystal alumina, 2 ~ 5% height of its raw material by percentage by weight for 90 ~ 93.5%
Ridge soil, 0.5 ~ 5% nanocrystalline magnesia, 1 ~ 3% cellulose and 1 ~ 4% adhesive composition.
5. vehicle tail gas treater ceramic monolith surface according to claim 4 nanocrystalline method of modifying, its feature
It is：The preparation method of ceramic monolith includes：
A, weigh each raw material according to the percentage by weight described in claim 4 and mix, then add thereto raw material gross weight 40 ~
60% water, 2 ~ 3h of grinding obtains ceramic slurry, standby；
B, ceramic slurry is immersed in polyurethane foam, and dries at 100 ~ 130 DEG C powdering, and be processed into required
The ceramic body of shape and size is wanted, it is standby；
C, obtained ceramic body calcined into 2 ~ 10h at 1300 ~ 1500 DEG C, naturally cool to after room temperature, ceramic monolith is made.
6. vehicle tail gas treater ceramic monolith surface according to claim 4 nanocrystalline method of modifying, its feature
It is：The preparation method of ceramic monolith includes：
A, weigh each raw material according to the percentage by weight described in claim 4 and mix, add weight and account for and weighs raw material gross weight
After 40 ~ 60% deionized water, 2 ~ 3h of ball milling, it is placed in thick mill after slightly refining 2 ~ 3 times, old 20 ~ 24h and slurry is made, it is standby；
B, obtained slurry is put into single lead screw ex truding briquetting machine moulded pottery not yet put in a kiln to bake is made, and it is remote red for 100 ~ 130 DEG C that moulded pottery not yet put in a kiln to bake is placed in into temperature
Dryness finalization is standby into dry body in outer line oven；
C, obtained dry body is placed in incinerator, in 1300 ~ 1700 DEG C of 2 ~ 10h of temperature lower calcination, cooled to the furnace after room temperature,
Ceramic monolith is made.
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| CN1272403A (en) * | 1999-04-30 | 2000-11-08 | 山西净土实业有限公司 | Modified catalyst active carrier and its preparation method |
| US6677261B1 (en) * | 2002-07-31 | 2004-01-13 | Corning Incorporated | Alumina-bound high strength ceramic honeycombs |
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| CN103127959A (en) * | 2011-11-24 | 2013-06-05 | 福州大学 | Carbon monoxide transformation catalyst carrier, preparation method of the carbon monoxide transformation catalyst carrier, and catalyst based on the carbon monoxide transformation catalyst carrier |
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| US7332454B2 (en) * | 2005-03-16 | 2008-02-19 | Sud-Chemie Inc. | Oxidation catalyst on a substrate utilized for the purification of exhaust gases |
| US8475755B2 (en) * | 2009-08-21 | 2013-07-02 | Sub-Chemie Inc. | Oxidation catalyst and method for destruction of CO, VOC and halogenated VOC |
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|---|---|---|---|---|
| CN1272403A (en) * | 1999-04-30 | 2000-11-08 | 山西净土实业有限公司 | Modified catalyst active carrier and its preparation method |
| US6677261B1 (en) * | 2002-07-31 | 2004-01-13 | Corning Incorporated | Alumina-bound high strength ceramic honeycombs |
| CN102764651A (en) * | 2011-05-06 | 2012-11-07 | 中国石油化工股份有限公司 | Method for preparing shell-layer catalyst and shell-layer catalyst |
| CN103127959A (en) * | 2011-11-24 | 2013-06-05 | 福州大学 | Carbon monoxide transformation catalyst carrier, preparation method of the carbon monoxide transformation catalyst carrier, and catalyst based on the carbon monoxide transformation catalyst carrier |
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