CN106242534A - 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
- Publication number
- CN106242534A CN106242534A CN201610630502.1A CN201610630502A CN106242534A CN 106242534 A CN106242534 A CN 106242534A CN 201610630502 A CN201610630502 A CN 201610630502A CN 106242534 A CN106242534 A CN 106242534A
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- Prior art keywords
- ceramic monolith
- ceramic
- tail gas
- vehicle tail
- modifying
- Prior art date
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- 239000000919 ceramic Substances 0.000 title claims abstract description 73
- 238000000034 method Methods 0.000 title claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 42
- 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
- 229910001593 boehmite Inorganic materials 0.000 claims abstract description 25
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims abstract description 25
- 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
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- 239000012265 solid product Substances 0.000 claims description 8
- 239000000395 magnesium oxide Substances 0.000 claims description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 7
- 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
- 238000001914 filtration Methods 0.000 claims description 6
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 6
- 238000007670 refining Methods 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 5
- 239000011230 binding agent Substances 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
- 238000000227 grinding Methods 0.000 claims description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 239000005995 Aluminium silicate Substances 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- 235000012211 aluminium silicate Nutrition 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000007790 solid phase Substances 0.000 claims description 4
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 3
- 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
- 239000011496 polyurethane foam Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 6
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 18
- 239000000463 material Substances 0.000 description 11
- 239000002245 particle 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
- 239000002086 nanomaterial Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000004575 stone Substances 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
- 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
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000008187 granular material Substances 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
- 239000000126 substance 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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 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
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 208000006673 asthma Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 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
- 239000000446 fuel 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
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 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
- 230000004044 response Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002689 soil 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
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
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- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
- C04B38/0615—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances the burned-out substance being a monolitic element having approximately the same dimensions as the final article, e.g. a porous polyurethane sheet or a prepreg obtained by bonding together resin particles
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- 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
- C04B41/5025—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 ceramic materials
- C04B41/5045—Rare-earth oxides
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- 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
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
- F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
- F01N3/2825—Ceramics
- F01N3/2828—Ceramic multi-channel monoliths, e.g. honeycombs
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
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- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5454—Particle size related information expressed by the size of the particles or aggregates thereof nanometer sized, i.e. below 100 nm
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- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
Vehicle tail gas treater ceramic monolith surface is with nanocrystalline method of modifying, including prepare nanocrystal boehmite solid-liquid mixing step, be that deionized water mixes to obtain colloidal sol by the nanocrystal boehmite solid-liquid mixture of the cerium oxide of lanthana, 8～12%, 40～60% of 8～12%, surplus, colloidal sol is coated in ceramic monolith and dry, the step of roasting.Lanthana, cerium oxide is added in nanocrystal boehmite solid-liquid mixture, improve heat stability and the catalysis activity of the colloidal sol that impregnated in ceramic monolith surface, simultaneously, nanocrystal boehmite is prone to remove impurity and improves purity, also provide bigger specific surface area and bond strength for catalyst carrier, and improve the high-temperature stability of modified ceramic monolith.
Description
Technical field
The present invention relates to the nanocrystalline method of modifying in vehicle tail gas treater ceramic monolith surface.
Background technology
In recent years rhenium, with rapid development of economy, the haze phenomenon that PM2.5 causes happens occasionally, and one of them is important former
Cause is the pollution that transportation is brought.The tail gas of vehicle fuel burning and exhausting contains multiple chemical composition, including the completeest
Full burning hydrocarbon, nitrogen oxides and carbon monoxide, these are all the origin causes of formation causing haze.Imperfect combustion hydro carbons in atmosphere may be used
Photochemical reaction occurs, and nitrogen oxides and carbon monoxide can cause the symptoms such as the dyspnea of people, respiratory tract infection and asthma, with
Time, make decline in pulmonary function.Using vehicle tail gas treater catalytic purification method is a kind of effective ways reducing tail gas pollution, but
Existing vehicle tail gas treater is only suitable for the catalyst of part, needs badly and provides a kind of and various catalyst activity component to be respectively provided with
The vehicle tail gas treater of matched well.
Summary 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 stability and catalysis activity.
The technical scheme that the present invention is used for achieving the above object is: vehicle tail gas treater ceramic monolith surface is with receiving
The method of modifying of meter Jing, comprises the following steps:
Step one, by caustic solution and aluminum salt solution according to [OH]-: [Al]3+=3:(1～2) mol ratio mix
Close, at normal temperatures after stirring 8～12min, proceed in the autoclave that temperature is 102～160 DEG C, after reaction 1～10h, prepare solid
Phase product, circulates solid product 1～4 time through sucking filtration, drip washing, prepares nanocrystal boehmite solid-liquid mixture, standby；
Step 2, according to percentage by weight, take successively 8～the cerium oxide of the lanthana of 12%, 8～12% and 40～
The nanocrystal boehmite solid-liquid mixture of 60%, surplus is deionized water, by lanthana, cerium oxide, nanocrystal boehmite solid-liquid
Mixture and deionized water mix to obtain colloidal sol, take out after ceramic monolith immerses in this colloidal sol 10～40min, and blow down pottery load
The intrapore colloidal sol of body passage, after drying 1～4h, roasts at a temperature of ceramic monolith is placed in 100～120 DEG C at 500～550 DEG C
Burn 0.5～5h, and drying, baking operation are circulated 0～2 time, prepare modified vehicle tail gas treater ceramic monolith.
Wherein, the caustic solution used by 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, the size 10～40nm of the nanocrystal boehmite solid-liquid mixture that step one prepares.
In the present invention, the ceramic monolith used by step 2, its raw material by percentage by weight be 90～93.5% nanocrystalline
The cellulose of nanocrystalline magnesium oxide, 1～3% of the Kaolin of aluminium oxide, 2～5%, 0.5～5% and 1～the binding agent group of 4%
Become.
One of optimal way, 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, being then added thereto to raw material
Gross weight 40～the water of 60%, grinding 2～3h, obtain ceramic size, standby；
B, ceramic size is immersed in polyurethane foam, and at 120～150 DEG C, is dried into powdery, and be processed into tool
There is the ceramic body of required shape and size, standby；
C, prepared ceramic body is calcined at 1450～1650 DEG C 3～10h, after naturally cooling to room temperature, prepare pottery
Ceramic carrier.
The two of optimal way, the preparation method of ceramic monolith includes:
A, weigh each raw material according to the ratio described in ceramic monolith raw material and mix, adding weight and account for and weigh raw material gross weight
40～the deionized water of 60%, after ball milling 2～3h, it is placed in thick refining machine thick refining 2～3 times, after old 20～24h, prepares slurry,
Standby；
B, prepared dry body is placed in incinerator, at 1300～1700 DEG C of temperature lower calcinations 3～10h, cools to the furnace
After room temperature, prepare ceramic monolith.
Owing to the granule of nano material itself is tiny, specific surface area is huge, agglomeration easily occurs.Say on conventional meaning
Nano material, be under scanning electron microscope display the particle diameter that individual particle is 1～100nm, but, this nano material is at Ma Er
But the particle diameter of tens microns it is shown as on literary composition laser particle analyzer.Trace it to its cause, be that nano material is easily reunited, in outward appearance after reunion
Upper display has reached the particle diameter of tens microns, even if so making to add in existing production nano level granular materials, actual
On remain as micron order, it is difficult to the real effect playing nano-particle.
Beneficial effect: the present invention prepares nanocrystal boehmite solid-liquid mixture by caustic solution and aluminum salt solution, receives
The brilliant boehmite of rice is in single nanoparticle dispersity, thus makes still to present Nano grade when adding formation colloidal sol,
Show the character of nano-scale particle, may be considered still in single_phase system after the addition, in mixed process dispersivity good,
Can be evenly distributed；In nanocrystal boehmite solid-liquid mixture, add lanthana, cerium oxide, improve and impregnated in ceramic monolith table
The heat stability of the colloidal sol in face and catalysis activity, meanwhile, nanocrystal boehmite is prone to remove impurity and improves purity, is also catalyst carrier
Provide bigger specific surface area and bond strength, and improve the high-temperature stability of modified ceramic monolith.
Detailed description of the invention
Below in conjunction with 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 with nanocrystalline method of modifying, comprises the following steps: step one, by severe
Property aqueous slkali and aluminum salt solution are according to [OH]-: [Al]3+=3:(1～2) mol ratio mix, at normal temperatures stirring 8～
After 12min, proceed in the autoclave that temperature is 102～160 DEG C, after reaction 1～10h, prepare solid product, by solid product warp
Cross sucking filtration, drip washing circulates 1～4 time, prepares nanocrystal boehmite solid-liquid mixture, standby；
Step 2, according to percentage by weight, take successively 8～the cerium oxide of the lanthana of 12%, 8～12% and 40～
The nanocrystal boehmite solid-liquid mixture of 60%, surplus is deionized water, by lanthana, cerium oxide, nanocrystal boehmite solid-liquid
Mixture and deionized water mix to obtain colloidal sol, take out after ceramic monolith immerses in this colloidal sol 10～40min, and blow down pottery load
The intrapore colloidal sol of body passage, after drying 1～4h, roasts at a temperature of ceramic monolith is placed in 100～120 DEG C at 500～550 DEG C
Burn 0.5～5h, and drying, baking operation are circulated 0～2 time, prepare modified vehicle tail gas treater ceramic monolith.
Embodiment 1
Vehicle tail gas treater ceramic monolith surface with nanocrystalline method of modifying, comprises the following steps: step one, by hydrogen
Sodium hydroxide solution and Al2(SO4)3·18H2O solution is according to [OH]-: [Al]3+=3:(1～2) mol ratio mix, and adjust
Joint mixed solution Ph is 7, at normal temperatures after stirring 10min, proceeds in the autoclave that temperature is 105 DEG C ± 3 DEG C, after reaction 3h,
Prepare solid product, solid product is circulated 4 times through sucking filtration, drip washing, prepared a size of 10～the nanocrystal boehmite of 40nm
Solid-liquid mixture, standby；
Step 2, according to percentage by weight, take successively 93.5% nanocrystalline aluminium oxide, the Kaolin of 2%, 0.5%
Nanocrystalline magnesium oxide, the cellulose of 1% and the binder materials of 3% also mix, and are then added thereto to raw material gross weight 60%
Water, grinding 2.5h, obtain ceramic size, standby；
Step 3, ceramic size is immersed in polyurethane foam, and at 130 DEG C, is dried into powdery, and be processed into tool
There is the ceramic body of required shape and size, standby；
Step 4, prepared ceramic body is calcined at 1350 DEG C 8h, after naturally cooling to room temperature, prepare pottery and carry
Body；
Step 5, according to percentage by weight, take successively 10% lanthana, the cerium oxide of 10%, 30% nanocrystalline suddenly
Nurse stone solid-liquid mixture and 50% deionized water, mix to obtain colloidal sol, is immersed in this colloidal sol by the ceramic monolith that step 4 prepares
Take out after 20min, and blow down the intrapore colloidal sol of ceramic monolith passage, after drying 2h at a temperature of ceramic monolith is placed in 100 DEG C,
Roasting 1h at 550 DEG C；After drying 2h at a temperature of repeating ceramic monolith is placed in 100 DEG C, roasting 1h at 550 DEG C, prepare and change
The vehicle tail gas treater ceramic monolith of property.
Embodiment 2
Step one, by potassium hydroxide solution and Al (NO3)3·9H2O solution is according to [OH]-: [Al]3+=3:1.6 mole
Ratio mixes, and at normal temperatures after stirring 8min, proceeds in the autoclave that temperature is 157 DEG C ± 3 DEG C, after reaction 1h, prepares solid
Phase product, circulates solid product 2 times through sucking filtration, drip washing, prepares a size of 10～40nm nanocrystal boehmite solid-liquid mixing
Body, standby；
Step 2, according to percentage by weight, take successively 90% the nanocrystalline aluminium oxide that particle diameter is 10～100nm, 5%
Kaolin, the particle diameter of 1% are nanocrystalline magnesium oxide, the cellulose of 3% and the binder materials of 1% of 20～100nm and mix,
Then it is added thereto to the water of raw material gross weight 55%, after ball milling 3h, is placed in thick refining machine thick refining 3 times, after old 24h, prepares slurry
Material, standby；
Step 3, prepared slurry is put into single lead screw ex truding briquetting machine is made moulded pottery not yet put in a kiln to bake, and moulded pottery not yet put in a kiln to bake is placed in temperature is 130 DEG C
In far infrared stove, dryness finalization becomes dry body, standby；
Step 4, prepared dry body is placed in incinerator, at 1500 DEG C of temperature lower calcination 10h, cools to room temperature with the furnace
After, prepare ceramic monolith；
Step 5, according to percentage by weight, take successively 8% lanthana, the cerium oxide of 7%, the nanocrystalline vigorous nurse of 50%
Stone solid-liquid mixture and 35% deionized water, mix to obtain colloidal sol, is immersed in this colloidal sol by the ceramic monolith that step 4 prepares
Take out after 40min, and blow down the intrapore colloidal sol of ceramic monolith passage, after drying 1h at a temperature of ceramic monolith is placed in 120 DEG C,
Roasting 5h at 500 DEG C, and drying, baking operation are circulated 2 times, prepare modified vehicle tail gas treater ceramic monolith.
Embodiment 3
Step one, by potassium hydroxide solution and AlCl3·6H2O solution is according to [OH]-: [Al]3+The mol ratio of=3:1 is carried out
Mixing, at normal temperatures after stirring 5min, proceeds in the autoclave that temperature is 130 DEG C, after reaction 5h, prepares solid product, will be solid
Phase product circulates 1 time through sucking filtration, drip washing, prepares a size of 10～40nm nanocrystal boehmite solid-liquid mixtures, standby；
Step 2, according to percentage by weight, the particle diameter taking 91% successively is the nanocrystalline aluminium oxide of 10nm, the kaolinite of 2%
Soil, the particle diameter of 2.5% are the nanocrystalline magnesium oxide of 50nm, the cellulose of 2% and the binder materials of 2.5% and mix, then
It is added thereto to the water of raw material gross weight 40%, grinding 2h, obtains ceramic size, standby；
Step 3, prepared ceramic body is calcined at 1500 DEG C 10h, after naturally cooling to room temperature, prepare pottery and carry
Body, standby；
Step 5, according to percentage by weight, take successively 5% lanthana, the cerium oxide of 10%, the nanocrystalline vigorous nurse of 45%
Stone solid-liquid mixture and the deionized water of 40%, mix to obtain colloidal sol, is immersed in this colloidal sol by the ceramic monolith that step 4 prepares
Take out after 10min, and blow down the intrapore colloidal sol of ceramic monolith passage, after drying 4h at a temperature of ceramic monolith is placed in 115 DEG C,
Roasting 0.5h at 535 DEG C, prepares modified vehicle tail gas treater ceramic monolith.
Nanocrystalline magnesium oxide used by the embodiment of the present invention 1～3, is by the Application No. of earlier application
Based on the preparation method of a kind of highly-pure magnesium hydroxide nanometer disclosed in CN2009100651656, and by prepared hydroxide
Magnesium is nanocrystalline be placed in 400 DEG C of calcining 20min after, be cooled to room temperature with the rate of temperature fall of 8～12 DEG C/h, prepare nanocrystalline oxidation
Magnesium.The MgO formed after sintering is in single nanoparticle dispersity, so mixes to add and fashionable still presents Nano grade, table
Reveal the character of nano-scale particle, may be considered after the addition still in single_phase system, disperse in ball milling or grinding process
Property is good, can be evenly distributed, and makes the combination of each material in the powder of formation the tightst.
Ceramic monolith obtained by the embodiment of the present invention 1～3, the spy that specific surface area is big, aeration resistance is little, regularity is strong
Point, through modified, ceramic monolith can be with noble metal catalyst, Raney nickel, cobaltmolybdate catalyst, palladium catalyst, titanium catalysis
The catalyst activity components such as agent are respectively provided with matched well.Ceramic honey comb owing to making has nanostructured so that product is high
Temperature excellent in mechanical performance, thermal shock resistance and anti-wear performance are excellent.And by lanthana, cerium oxide, the mixing of nanocrystal boehmite solid-liquid
Body and deionized water mix colloidal sol is coated in ceramic monolith, dry, roasting, obtain the nano coating in dispersity, not only
Enhance the high temperature hardness of material after sintering, simultaneously because its special size range, in the material Dispersed precipitate, moreover it is possible to make material
Material keeps higher toughness, and can substantially suppress the brittle fracture of material, significantly improve the thermal shock resistance of material.
Nanocrystal boehmite that the present invention prepares or nanocrystal boehmite solid-liquid mixture, have Malvern laser particle analyzer
Nano-scale particle size (less than 100 nanometers) in meaning and the purity higher than 99%, it is huge that nano-scale dimension determines its specific surface area
Greatly, fast response is added particular benefit as catalyst；High-purity, determine it and may cause the unnecessary of generation as catalyst
Side reaction few, and for ceramic material time high-temperature behavior fabulous.The present invention produces without any noxious substance, it is to avoid to environment
Pollution, therefore, the present invention has 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 one, by caustic solution and aluminum salt solution according to [OH]—: [Al]3+=3:(1～2) mol ratio mix,
After stirring 8～12min under room temperature, proceed in the autoclave that temperature is 102～160 DEG C, after reaction 1～10h, prepare solid phase and produce
Thing, circulates solid product 1～4 time through sucking filtration, drip washing, prepares nanocrystal boehmite solid-liquid mixture, standby；
Step 2, according to percentage by weight, take 8～the cerium oxide of the lanthana of 12%, 8～12% and 40～60% successively
Nanocrystal boehmite solid-liquid mixture, surplus is deionized water, by lanthana, cerium oxide, nanocrystal boehmite solid-liquid mixture
Mix to obtain colloidal sol with deionized water, take out after ceramic monolith is immersed in this colloidal sol 10～40min, and blow down ceramic monolith passage
Intrapore colloidal sol, after drying 1～4h at a temperature of ceramic monolith is placed in 100～120 DEG C, roasting 0.5 at 500～550 DEG C
～5h, and drying, baking operation are circulated 0～2 time, prepare modified vehicle tail gas treater ceramic monolith.
Vehicle tail gas treater ceramic monolith surface the most 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.
Vehicle tail gas treater ceramic monolith surface the most according to claim 1 nanocrystalline method of modifying, its feature
It is: the size 10～40nm of the nanocrystal boehmite solid-liquid mixture that step one prepares.
Vehicle tail gas treater ceramic monolith surface the most according to claim 1 nanocrystalline method of modifying, its feature
Being: the ceramic monolith used by step 2, its raw material is by nanocrystalline aluminium oxide, 2～5% that percentage by weight is 90～93.5%
The cellulose of nanocrystalline magnesium oxide, 1～3% of Kaolin, 0.5～5% and 1～the binding agent composition of 4%.
Vehicle tail gas treater ceramic monolith surface the most 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, being then added thereto to raw material gross weight 40
～the water of 60%, grinding 2～3h, obtain ceramic size, standby；
B, ceramic size is immersed in polyurethane foam, and at 120～150 DEG C, is dried into powdery, and be processed into there is institute
Need the ceramic body of shape and size, standby；
C, prepared ceramic body is calcined at 1450～1650 DEG C 3～10h, after naturally cooling to room temperature, prepare pottery and carry
Body.
Vehicle tail gas treater ceramic monolith surface the most 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 ratio described in claim 4 and mix, add weight account for weigh raw material gross weight 40～
The deionized water of 60%, after ball milling 2～3h, is placed in thick refining machine thick refining 2～3 times, prepares slurry after old 20～24h, standby；
B, prepared slurry is put into single lead screw ex truding briquetting machine is made moulded pottery not yet put in a kiln to bake, and moulded pottery not yet put in a kiln to bake is placed in temperature is 120～150 DEG C the reddest
In outer line oven, dryness finalization becomes dry body, standby；
C, prepared dry body is placed in incinerator, at 1300～1700 DEG C of temperature lower calcinations 3～10h, cools to room temperature with the furnace
After, prepare ceramic monolith.
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| CN201610630502.1A CN106242534A (en) | 2016-08-03 | 2016-08-03 | Vehicle tail gas treater ceramic monolith surface is with nanocrystalline method of modifying |
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