CN105435859A - Modification method of nanocrystalline for surface of ceramic carrier of vehicle exhaust processor - Google Patents
Modification method of nanocrystalline for surface of ceramic carrier of vehicle exhaust processor Download PDFInfo
- Publication number
- CN105435859A CN105435859A CN201610022747.6A CN201610022747A CN105435859A CN 105435859 A CN105435859 A CN 105435859A CN 201610022747 A CN201610022747 A CN 201610022747A CN 105435859 A CN105435859 A CN 105435859A
- Authority
- CN
- China
- Prior art keywords
- ceramic monolith
- nanocrystalline
- ceramic
- tail gas
- liquid mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000919 ceramic Substances 0.000 title claims abstract description 80
- 238000002715 modification method Methods 0.000 title abstract 2
- 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
- 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
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000000853 adhesive Substances 0.000 claims abstract description 3
- 230000001070 adhesive effect Effects 0.000 claims abstract description 3
- 239000002159 nanocrystal Substances 0.000 claims description 25
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 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
- 239000012265 solid product Substances 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000000395 magnesium oxide Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003518 caustics Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 239000012266 salt solution Substances 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000005995 Aluminium silicate Substances 0.000 claims description 5
- 235000012211 aluminium silicate Nutrition 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
- 238000007670 refining 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
- 238000000498 ball milling Methods 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000011496 polyurethane foam Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 238000005202 decontamination Methods 0.000 abstract 1
- 230000003588 decontaminative effect Effects 0.000 abstract 1
- 238000007598 dipping method Methods 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 18
- 239000002245 particle Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 239000002086 nanomaterial Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 230000000694 effects Effects 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 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
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 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
- 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
- 208000006673 asthma Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 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
- 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
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 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
- 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
- 239000000047 product 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
A modification method of nanocrystalline for the surface of a ceramic carrier of a vehicle exhaust processor comprises a step of preparing a nanocrystalline boehmite solid-liquid mixture, and a step of mixing 5-10 percent of lanthanum oxide, 5-10 percent of cerium oxide, 30-50 percent of the nanocrystalline boehmite solid-liquid mixture, and the balance of deionized water to obtain sol, coating the ceramic carrier with the sol, drying and roasting. The lanthanum oxide and the cerium oxide are added into the nanocrystalline boehmite solid-liquid mixture, so the thermal stability and catalytic activity of the sol dipping the surface of the ceramic carrier are improved; meanwhile, nanocrystalline boehmite is easy for decontamination and purity improvement, provides a relatively big specific surface area and adhesive strength for a catalyst carrier, and improves the high temperature stability of the modified ceramic carrier.
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 major reason is the pollution that transportation is brought.The tail gas of vehicle fuel burning and exhausting contains number of chemical composition, comprises imperfect combustion hydro carbons, nitrogen oxide and carbon monoxide, and these are all the origin causes of formation causing haze.Can there is photochemical reaction in imperfect combustion hydro carbons, nitrogen oxide and carbon monoxide can cause expiratory dyspnea, the symptom such as respiratory tract infection and asthma of people, meanwhile, make decline in pulmonary function in atmosphere.Vehicle tail gas treater catalytic purification method is adopted to be 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 all to have the vehicle tail gas treater of matched well.
Summary of the invention
The object of this invention is to provide a kind of vehicle tail gas treater ceramic monolith surface with nanocrystalline method of modifying, make vehicle tail gas treater have higher heat endurance and catalytic activity.
The technical scheme that the present invention is adopted for achieving the above object is: the nanocrystalline method of modifying in vehicle tail gas treater ceramic monolith surface, comprises 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 5 ~ 10min at normal temperatures, proceeding to temperature is in the autoclave of 102 ~ 160 DEG C, after reaction 1 ~ 10h, obtained solid product, by solid product through suction filtration, drip washing circulation 1 ~ 4 time, obtained nanocrystal boehmite solid-liquid mixture, for subsequent use;
Step 2, according to percentage by weight, get the lanthana of 5 ~ 10% successively, the cerium oxide of 5 ~ 10% and the nanocrystal boehmite solid-liquid mixture of 30 ~ 50%, surplus is deionized water, by lanthana, cerium oxide, nanocrystal boehmite solid-liquid mixture and deionized water are mixed to get colloidal sol, ceramic monolith is immersed in this colloidal sol and take out after 10 ~ 40min, and blow down the intrapore colloidal sol of ceramic monolith passage, after drying 1 ~ 4h under ceramic monolith being placed in 100 ~ 120oC temperature, roasting 0.5 ~ 5h at 500 ~ 550 DEG C, and will dry, baking operation circulation 0 ~ 2 time, the vehicle tail gas treater ceramic monolith of obtained modification.
Wherein, the caustic solution that step one is used is NaOH or potassium hydroxide solution; Aluminum salt solution is AlCl
36H
2o, Al (NO
3)
39H
2o or Al
2(SO
4)
318H
2o solution.
Wherein, the size 10 ~ 40nm of the nanocrystal boehmite solid-liquid mixture that step one is obtained.
In the present invention, the ceramic monolith that step 2 is used, nanocrystalline aluminium oxide, the kaolin of 2 ~ 5%, nanocrystalline magnesia, the cellulose of 1 ~ 3% and the adhesive of 1 ~ 4% of 0.5 ~ 5% that its raw material is 90 ~ 93.5% by percentage by weight form.
One of preferred embodiment, the preparation method of ceramic monolith comprises:
A, take each raw material according to the percentage by weight described in ceramic monolith raw material and mix, then add the water of raw material gross weight 40 ~ 60% wherein, grinding 2 ~ 3h, obtains ceramic size, for subsequent use;
B, ceramic size to be immersed in polyurethane foam, and to be dried into powdery at 100 ~ 130 DEG C, and be processed into the ceramic body with required shape and size, for subsequent use;
C, obtained ceramic body calcine 2 ~ 10h at 1300 ~ 1500 DEG C, after naturally cooling to room temperature, obtain ceramic monolith.
Preferred embodiment two, the preparation method of ceramic monolith comprises:
A, take each raw material according to the ratio described in ceramic monolith raw material and mix, adding weight and account for the deionized water taking raw material gross weight 40 ~ 60%, after ball milling 2 ~ 3h, be placed in the slightly refining 2 ~ 3 times of thick refining machine, after old 20 ~ 24h, obtained slurry, for subsequent use;
B, obtained slurry is put into single lead screw ex truding briquetting machine make moulded pottery not yet put in a kiln to bake, and moulded pottery not yet put in a kiln to bake to be placed in temperature be that the far infrared stove dryness finalization of 100 ~ 130 DEG C becomes dry body, for subsequent use;
C, obtained dry body is placed in incinerator, at 1300 ~ 1700 DEG C of temperature lower calcination 2 ~ 10h, after cooling to room temperature with the furnace, obtained ceramic monolith.
Because the particle of nano material itself is tiny, specific area is huge, very easily occurs agglomeration.The nano material that conventional meaning is said is the individual particle shown under ESEM is the particle diameter of 1 ~ 100nm, but this nano material is but shown as the particle diameter of tens microns on Malvern laser particle analyzer.Trace it to its cause, be that nano material is very easily reunited, after reunion, show the particle diameter having reached tens microns in appearance, even if make like this to add nano level granular materials in existing production, in fact be still micron order, be difficult to the real effect playing nano particle.
Beneficial effect: the present invention obtains nanocrystal boehmite solid-liquid mixture by caustic solution and aluminum salt solution, nanocrystal boehmite is in single nanoparticle dispersity, so just make to add when forming colloidal sol and still present Nano grade, show the character of nano-scale particle, can think after the addition to be still in single_phase system, in mixed process dispersivity good, can be evenly distributed; Lanthana, cerium oxide is added in nanocrystal boehmite solid-liquid mixture, improve the heat endurance and the catalytic activity that impregnated in the colloidal sol on ceramic monolith surface, simultaneously, nanocrystal boehmite is easy to removal of impurities and improves purity, also for catalyst carrier provides larger specific area and bond strength, and the high-temperature stability of modified ceramic monolith is improved.
Detailed description of the invention
Below in conjunction with specific embodiment, vehicle tail gas treater ceramic monolith surface of the present invention is described further with nanocrystalline method of modifying, can better understand the present invention to make those skilled in the art and can be implemented, but illustrated 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 caustic solution and aluminum salt solution according to [OH]
-: [Al]
3+=3:(1 ~ 2) mol ratio mix, after stirring 5 ~ 10min at normal temperatures, proceeding to temperature is in the autoclave of 102 ~ 160 DEG C, after reaction 1 ~ 10h, obtained solid product, by solid product through suction filtration, drip washing circulation 1 ~ 4 time, obtained nanocrystal boehmite solid-liquid mixture, for subsequent use;
Step 2, according to percentage by weight, get the lanthana of 5 ~ 10% successively, the cerium oxide of 5 ~ 10% and the nanocrystal boehmite solid-liquid mixture of 30 ~ 50%, surplus is deionized water, by lanthana, cerium oxide, nanocrystal boehmite solid-liquid mixture and deionized water are mixed to get colloidal sol, ceramic monolith is immersed in this colloidal sol and take out after 10 ~ 40min, and blow down the intrapore colloidal sol of ceramic monolith passage, after drying 1 ~ 4h under ceramic monolith being placed in 100 ~ 120oC temperature, roasting 0.5 ~ 5h at 500 ~ 550 DEG C, and will dry, baking operation circulation 0 ~ 2 time, the vehicle tail gas treater ceramic monolith of obtained modification.
Embodiment 1
Vehicle tail gas treater ceramic monolith surface with nanocrystalline method of modifying, comprises the following steps: step one, by sodium hydroxide solution and Al
2(SO
4)
318H
2o solution is according to [OH]
-: [Al]
3+=3:(1 ~ 2) mol ratio mix, and regulate mixed solution Ph to be 7, after stirring 10min at normal temperatures, proceeding to temperature is in the autoclave of 105 DEG C ± 3 DEG C, after reaction 3h, obtained solid product, circulates solid product 4 times through suction filtration, drip washing, the obtained nanocrystal boehmite solid-liquid mixture being of a size of 10 ~ 40nm, for subsequent use;
Step 2, according to percentage by weight, get successively the nanocrystalline aluminium oxide of 93.5%, 2% kaolin, 0.5% nanocrystalline magnesia, the cellulose of 1% and the binder materials of 3% mix, then add the water of raw material gross weight 60% wherein, grinding 2.5h, obtain ceramic size, for subsequent use;
Step 3, ceramic size to be immersed in polyurethane foam, and to be dried into powdery at 130 DEG C, and be processed into the ceramic body with required shape and size, for subsequent use;
Step 4, obtained ceramic body is calcined 8h at 1350 DEG C, after naturally cooling to room temperature, obtained ceramic monolith;
Step 5, according to percentage by weight, get the lanthana of 10%, the cerium oxide of 10%, the nanocrystal boehmite solid-liquid mixture of 30% and 50% deionized water successively, be mixed to get colloidal sol, the ceramic monolith that step 4 is obtained is immersed in this colloidal sol and takes out after 20min, and blow down the intrapore colloidal sol of ceramic monolith passage, after drying 2h under ceramic monolith being placed in 100oC temperature, roasting 1h at 550 DEG C; After drying 2h under repeating ceramic monolith to be placed in 100oC temperature, roasting 1h at 550 DEG C, the vehicle tail gas treater ceramic monolith of obtained modification.
Embodiment 2
Step one, by potassium hydroxide solution and Al (NO
3)
39H
2o solution is according to [OH]
-: [Al]
3+the mol ratio of=3:1.6 mixes, and after stirring 8min at normal temperatures, proceeding to temperature is in the autoclave of 157 DEG C ± 3 DEG C, after reaction 1h, obtained solid product, circulates solid product 2 times through suction filtration, drip washing, obtain and be of a size of 10 ~ 40nm nanocrystal boehmite solid-liquid mixture, for subsequent use;
Step 2, according to percentage by weight, the particle diameter getting 90% is successively the nanocrystalline aluminium oxide of 10 ~ 100nm, the kaolin of 5%, the particle diameter of 1% are 20 ~ 100nm nanocrystalline magnesia, the cellulose of 3% and the binder materials of 1% also mix, then the water of raw material gross weight 55% is added wherein, after ball milling 3h, be placed in thick refining machine slightly to refine 3 times, after old 24h, obtained slurry, for subsequent use;
Step 3, obtained slurry is put into single lead screw ex truding briquetting machine make moulded pottery not yet put in a kiln to bake, and moulded pottery not yet put in a kiln to bake to be placed in temperature be that the far infrared stove dryness finalization of 130 DEG C becomes dry body, for subsequent use;
Step 4, obtained dry body is placed in incinerator, at 1500 DEG C of temperature lower calcination 10h, after cooling to room temperature with the furnace, obtained ceramic monolith;
Step 5, according to percentage by weight, get the lanthana of 8%, the cerium oxide of 7%, the nanocrystal boehmite solid-liquid mixture of 50% and 35% deionized water successively, be mixed to get colloidal sol, the ceramic monolith that step 4 is obtained is immersed in this colloidal sol and takes out after 40min, and blow down the intrapore colloidal sol of ceramic monolith passage, and after drying 1h under ceramic monolith being placed in 120oC temperature, roasting 5h at 500 DEG C, and oven dry, baking operation are circulated 2 times, the vehicle tail gas treater ceramic monolith of obtained modification.
Embodiment 3
Step one, by potassium hydroxide solution and AlCl
36H
2o solution is according to [OH]
-: [Al]
3+the mol ratio of=3:1 mixes, and after stirring 5min at normal temperatures, proceeding to temperature is in the autoclave of 130 DEG C, after reaction 5h, obtained solid product, circulates solid product 1 time through suction filtration, drip washing, obtain and be of a size of 10 ~ 40nm nanocrystal boehmite solid-liquid mixture, for subsequent use;
Step 2, according to percentage by weight, the particle diameter getting 91% is successively the nanocrystalline aluminium oxide of 10nm, the kaolin of 2%, the particle diameter of 2.5% are 50nm nanocrystalline magnesia, the cellulose of 2% and the binder materials of 2.5% also mix, then the water of raw material gross weight 40% is added wherein, grinding 2h, obtain ceramic size, for subsequent use;
Step 3, ceramic size to be immersed in polyurethane foam, and to be dried into powdery at 125 DEG C, and be processed into the ceramic body with required shape and size, for subsequent use;
Step 4, obtained ceramic body is calcined 10h at 1500 DEG C, after naturally cooling to room temperature, obtained ceramic monolith, for subsequent use;
Step 5, according to percentage by weight, get successively the lanthana of 5%, the cerium oxide of 10%, the nanocrystal boehmite solid-liquid mixture of 45% and 40% deionized water, be mixed to get colloidal sol, the ceramic monolith that step 4 is obtained is immersed in this colloidal sol and takes out after 10min, and blow down the intrapore colloidal sol of ceramic monolith passage, after drying 4h under ceramic monolith being placed in 115oC temperature, roasting 0.5h at 535 DEG C, the vehicle tail gas treater ceramic monolith of obtained modification.
The nanocrystalline magnesia that the embodiment of the present invention 1 ~ 3 is used, by based on the preparation method of the application number of earlier application a kind of highly-pure magnesium hydroxide nanometer disclosed in CN2009100651656, and after obtained magnesium hydroxide nanocrystal being placed in 400 DEG C of calcining 20min, room temperature is cooled to, obtained nanocrystalline magnesia with the rate of temperature fall of 5 ~ 10 DEG C/h.The MgO formed after sintering is in single nanoparticle dispersity, such mixing adds and fashionablely still presents Nano grade, show the character of nano-scale particle, can think after the addition to be still in single_phase system, in ball milling or grinding process dispersivity good, can be evenly distributed, make the combination of each material in the powder of formation also tightr.
Ceramic monolith obtained by the embodiment of the present invention 1 ~ 3, the feature that specific area is large, aeration resistance is little, regularity is strong, through modified, ceramic monolith all can have matched well with catalyst activity components such as noble metal catalyst, Raney nickel, cobaltmolybdate catalyst, palladium catalyst, titanium catalysts.Because the ceramic honey comb made has nanostructured, make product mechanical behavior under high temperature excellence, thermal shock resistance and anti-wear performance excellent.And lanthana, cerium oxide, nanocrystal boehmite solid-liquid mixture and deionized water are mixed to get colloidal sol and are coated in ceramic monolith, oven dry, roasting, obtain the nano coating in dispersity, not only increase the high temperature hardness of the rear material of sintering, simultaneously due to its special size range, Dispersed precipitate in the material, can also make material keep higher toughness, and obviously can suppress the brittle fracture of material, significantly improves the thermal shock resistance of material.
The nanocrystal boehmite that the present invention obtains or nanocrystal boehmite solid-liquid mixture, have nano-scale particle size (being less than 100 nanometers) in Malvern laser particle analyzer meaning with higher than 99% purity, it is huge that nano-scale dimension determines its specific area, is particularly conducive to and adds fast response as catalyst; High-purity, determine it and the unnecessary side reaction of generation may be caused few as catalyst, and fabulous for high-temperature behavior during ceramic material.The present invention produces without any noxious material, avoids the pollution to environment, and 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 characterized in that, comprises 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 5 ~ 10min at normal temperatures, proceeding to temperature is in the autoclave of 102 ~ 160 DEG C, after reaction 1 ~ 10h, obtained solid product, by solid product through suction filtration, drip washing circulation 1 ~ 4 time, obtained nanocrystal boehmite solid-liquid mixture, for subsequent use;
Step 2, according to percentage by weight, get the lanthana of 5 ~ 10% successively, the cerium oxide of 5 ~ 10% and the nanocrystal boehmite solid-liquid mixture of 30 ~ 50%, surplus is deionized water, by lanthana, cerium oxide, nanocrystal boehmite solid-liquid mixture and deionized water are mixed to get colloidal sol, ceramic monolith is immersed in this colloidal sol and take out after 10 ~ 40min, and blow down the intrapore colloidal sol of ceramic monolith passage, after drying 1 ~ 4h under ceramic monolith being placed in 100 ~ 120oC temperature, roasting 0.5 ~ 5h at 500 ~ 550 DEG C, and will dry, baking operation circulation 0 ~ 2 time, the vehicle tail gas treater ceramic monolith of obtained modification.
2. vehicle tail gas treater ceramic monolith surface according to claim 1 is with nanocrystalline method of modifying, it is characterized in that: described caustic solution is NaOH or potassium hydroxide solution; Described aluminum salt solution is AlCl
36H
2o, Al (NO
3)
39H
2o or Al
2(SO
4)
318H
2o solution.
3. the nanocrystalline method of modifying in vehicle tail gas treater ceramic monolith surface according to claim 1, is characterized in that: the size 10 ~ 40nm of the nanocrystal boehmite solid-liquid mixture that step one is obtained.
4. the nanocrystalline method of modifying in vehicle tail gas treater ceramic monolith surface according to claim 1, it is characterized in that: the ceramic monolith that step 2 is used, nanocrystalline aluminium oxide, the kaolin of 2 ~ 5%, nanocrystalline magnesia, the cellulose of 1 ~ 3% and the adhesive of 1 ~ 4% of 0.5 ~ 5% that its raw material is 90 ~ 93.5% by percentage by weight form.
5. the nanocrystalline method of modifying in vehicle tail gas treater ceramic monolith surface according to claim 4, is characterized in that: the preparation method of ceramic monolith comprises:
A, take each raw material and mix according to percentage by weight according to claim 4, then add the water of raw material gross weight 40 ~ 60% wherein, grinding 2 ~ 3h, obtains ceramic size, for subsequent use;
B, ceramic size to be immersed in polyurethane foam, and to be dried into powdery at 100 ~ 130 DEG C, and be processed into the ceramic body with required shape and size, for subsequent use;
C, obtained ceramic body calcine 2 ~ 10h at 1300 ~ 1500 DEG C, after naturally cooling to room temperature, obtain ceramic monolith.
6. the nanocrystalline method of modifying in vehicle tail gas treater ceramic monolith surface according to claim 4, is characterized in that: the preparation method of ceramic monolith comprises:
A, take each raw material and mix according to ratio according to claim 4, adding weight and account for the deionized water taking raw material gross weight 40 ~ 60%, after ball milling 2 ~ 3h, be placed in the slightly refining 2 ~ 3 times of thick refining machine, after old 20 ~ 24h, obtained slurry, for subsequent use;
B, obtained slurry is put into single lead screw ex truding briquetting machine make moulded pottery not yet put in a kiln to bake, and moulded pottery not yet put in a kiln to bake to be placed in temperature be that the far infrared stove dryness finalization of 100 ~ 130 DEG C becomes dry body, for subsequent use;
C, obtained dry body is placed in incinerator, at 1300 ~ 1700 DEG C of temperature lower calcination 2 ~ 10h, after cooling to room temperature with the furnace, obtained ceramic monolith.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610022747.6A CN105435859B (en) | 2016-01-14 | 2016-01-14 | Vehicle tail gas treater ceramic monolith surface is with nanocrystalline method of modifying |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610022747.6A CN105435859B (en) | 2016-01-14 | 2016-01-14 | Vehicle tail gas treater ceramic monolith surface is with nanocrystalline method of modifying |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105435859A true CN105435859A (en) | 2016-03-30 |
| CN105435859B CN105435859B (en) | 2017-10-17 |
Family
ID=55546751
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610022747.6A Active CN105435859B (en) | 2016-01-14 | 2016-01-14 | Vehicle tail gas treater ceramic monolith surface is with nanocrystalline method of modifying |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105435859B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20060211569A1 (en) * | 2005-03-16 | 2006-09-21 | Sud-Chemie Inc. | Oxidation catalyst on a substrate utilized for the purification of exhaust gases |
| US20110044874A1 (en) * | 2009-08-21 | 2011-02-24 | Sud-Chemie Inc. | Oxidation Catalyst and Method for Destruction of CO, VOC and Halogenated VOC |
| 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 |
-
2016
- 2016-01-14 CN CN201610022747.6A patent/CN105435859B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20060211569A1 (en) * | 2005-03-16 | 2006-09-21 | Sud-Chemie Inc. | Oxidation catalyst on a substrate utilized for the purification of exhaust gases |
| US20110044874A1 (en) * | 2009-08-21 | 2011-02-24 | Sud-Chemie Inc. | Oxidation Catalyst and Method for Destruction of CO, VOC and Halogenated VOC |
| 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 |
Non-Patent Citations (1)
| Title |
|---|
| 石涛 等: "水热辅助溶胶-凝胶法制备纳米晶γ-Al2O3及表征", 《无机化学学报》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105435859B (en) | 2017-10-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4660135B2 (en) | Zirconia-based porous body and method for producing the same | |
| CN103962087B (en) | A kind of nano calcium oxide base CO of surface coating modification 2adsorbent and preparation method thereof | |
| JPH0513702B2 (en) | ||
| CN109364905A (en) | A kind of aluminium oxide containing auxiliary agent, preparation method and the catalyst containing the aluminium oxide | |
| CN102531015A (en) | Method for preparing porous aluminum oxide superfine powder | |
| CN101134586A (en) | Method for preparing nano alumina hollow ball | |
| CN110540222B (en) | Preparation method of high-temperature-resistant activated alumina | |
| WO2020113958A1 (en) | Method for preparing high-performance iron oxide red/clay mineral hybrid pigment by mechanochemistry | |
| EP4052788A1 (en) | Support and ft synthetic catalyst, and preparation methods therefor and applications thereof | |
| CN109174077A (en) | A kind of vehicle maintenance service catalyst and preparation method thereof | |
| CN104437458B (en) | Cerium-zirconium-based composite oxide catalytic material and preparation method thereof | |
| CN101597078A (en) | A kind of sheet α-Al 2O 3The preparation method of granular powder | |
| CN108285162A (en) | A kind of Si modification aluminium oxide and the preparation method and application thereof | |
| CN114105177A (en) | Preparation method of sphere-like nano gamma-alumina | |
| CN105732085A (en) | Nanostructural corundum honeycomb ceramic body and preparation method thereof | |
| JP3531299B2 (en) | Method for producing heat-resistant transition alumina | |
| CN105435859A (en) | Modification method of nanocrystalline for surface of ceramic carrier of vehicle exhaust processor | |
| CN108525668B (en) | Preparation method of sepiolite nanofiber loaded cobalt-aluminum composite oxide | |
| CN112742397B (en) | Synthetic alcohol catalyst, preparation method and application thereof | |
| CN106242534A (en) | Vehicle tail gas treater ceramic monolith surface is with nanocrystalline method of modifying | |
| CN112744851B (en) | Raspberry type oxide microsphere and preparation method and application thereof | |
| CN106966442A (en) | It is a kind of directly to thermally decompose the method for preparing high specific surface area and mesoporous composite oxide of metal | |
| CN106745169A (en) | A kind of bigger serface mesoporous cerium oxide zirconium solid solution and preparation method thereof | |
| CN108101086B (en) | Method for preparing alumina | |
| CN112742373B (en) | Low-temperature sulfur-tolerant methanation catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: No. 6 Silver Star Science and Technology Park 471000 Henan city of Luoyang province Luoyang high tech Development Zone Fenghua Road No. 1 building four layer 401-23 Applicant after: LUOYANG SANRUIBAO NANO TECHNOLOGY CO., LTD. Address before: 471000, Henan, Jianxi province Luoyang Li Chun Road East Petrochemical booming living area 11 3-502 Applicant before: LUOYANG SANRUIBAO NANO TECHNOLOGY CO., LTD. |
|
| COR | Change of bibliographic data | ||
| CB02 | Change of applicant information |
Address after: 471000 Henan city of Luoyang province Luoyang high tech Development Zone Fenghua Road No. 6 silver Kunming Science and Technology Park 1# building four floor 401-23 Applicant after: LUOYANG SANRUIBAO NANO TECHNOLOGY CO., LTD. Address before: No. 6 Silver Star Science and Technology Park 471000 Henan city of Luoyang province Luoyang high tech Development Zone Fenghua Road No. 1 building four layer 401-23 Applicant before: LUOYANG SANRUIBAO NANO TECHNOLOGY CO., LTD. |
|
| COR | Change of bibliographic data | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CB03 | Change of inventor or designer information |
Inventor after: Gao Zhensheng Inventor after: Xu Ronghui Inventor after: Li Luoli Inventor after: Xiao Minle Inventor before: Xu Ronghui Inventor before: Li Luoli Inventor before: Xiao Minle |
|
| CB03 | Change of inventor or designer information |