CN115254129B - Honeycomb body for purifying automobile exhaust and preparation method thereof - Google Patents
Honeycomb body for purifying automobile exhaust and preparation method thereof Download PDFInfo
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- CN115254129B CN115254129B CN202210729764.9A CN202210729764A CN115254129B CN 115254129 B CN115254129 B CN 115254129B CN 202210729764 A CN202210729764 A CN 202210729764A CN 115254129 B CN115254129 B CN 115254129B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000010410 layer Substances 0.000 claims abstract description 126
- 239000002346 layers by function Substances 0.000 claims abstract description 44
- 239000000843 powder Substances 0.000 claims abstract description 29
- 229910002187 La0.8Sr0.2CoO3 Inorganic materials 0.000 claims abstract description 15
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- 239000002002 slurry Substances 0.000 claims description 108
- 238000004321 preservation Methods 0.000 claims description 98
- 238000000576 coating method Methods 0.000 claims description 86
- 239000011248 coating agent Substances 0.000 claims description 82
- 238000010438 heat treatment Methods 0.000 claims description 73
- 238000001354 calcination Methods 0.000 claims description 69
- 238000001816 cooling Methods 0.000 claims description 49
- 238000001035 drying Methods 0.000 claims description 39
- 238000007664 blowing Methods 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 230000008569 process Effects 0.000 claims description 26
- 239000003292 glue Substances 0.000 claims description 20
- 239000011148 porous material Substances 0.000 claims description 19
- 238000007605 air drying Methods 0.000 claims description 18
- 238000003618 dip coating Methods 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 16
- 230000001105 regulatory effect Effects 0.000 claims description 14
- 238000007493 shaping process Methods 0.000 claims description 12
- 238000000746 purification Methods 0.000 claims description 9
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 7
- 229910018921 CoO 3 Inorganic materials 0.000 claims description 7
- 238000005520 cutting process Methods 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 7
- 238000004898 kneading Methods 0.000 claims description 7
- 239000005011 phenolic resin Substances 0.000 claims description 7
- 229920001568 phenolic resin Polymers 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 claims description 6
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 claims description 6
- 229940088601 alpha-terpineol Drugs 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000007849 furan resin Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 2
- 230000001070 adhesive effect Effects 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 8
- 239000007789 gas Substances 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 6
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 2
- 229930195733 hydrocarbon Natural products 0.000 abstract description 2
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 17
- 239000000919 ceramic Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 230000010355 oscillation Effects 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910010293 ceramic material Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 230000035939 shock Effects 0.000 description 7
- 229910052878 cordierite Inorganic materials 0.000 description 5
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 210000001161 mammalian embryo Anatomy 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003809 bile pigment Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- -1 cerium ions Chemical class 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000012855 volatile organic compound Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/9454—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific device
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0063—Granulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0234—Impregnation and coating simultaneously
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/65—Catalysts not containing noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
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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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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Abstract
The invention discloses a honeycomb body for purifying automobile exhaust and a preparation method thereof, the honeycomb body sequentially comprises a honeycomb body carrier, a base layer, a connecting layer and a functional layer, wherein the honeycomb body carrier consists of NiO and Y 2 O 3 /ZrO 2 And a binder; the base layer is formed by Y 2 O 3 /ZrO 2 And PVB; the connecting layer is made of Gd 2 O 3 /CeO 2 And PVB; the functional layer is made of La 0.8 Sr 0.2 CoO 3 And Gd 2 O 3 /CeO 2 And (5) preparing powder. The honeycomb body prepared by the invention has good catalytic conversion effect on tail gas, has remarkable effect on conversion of nitrogen oxides, hydrocarbon and CO at normal temperature and even low temperature, and has the characteristics of low cost and easy industrial application.
Description
Technical Field
The invention belongs to the technical field of ceramics, and particularly relates to a honeycomb body for purifying automobile exhaust and a preparation method thereof.
Background
With the increasing number of global motor vehicles in keeping, automobile exhaust pollution has become one of the main sources of air pollution. The main components of the automobile exhaust are CO and NO x 、SO x Volatile organic compounds, particulate matter, and the like. At present, honeycomb ceramic materials are widely used in automobile exhaust treatment. The surface of the honeycomb ceramic material is generally coated with an alumina or silica coating with a larger specific surface area so as to increase the specific surface area of the honeycomb ceramic material. Wherein, the catalytic coating is firstly pulped to form uniform slurry solution, then coated on the surface of the honeycomb ceramics, and then baked. Therefore, it is necessary to develop a slurry formulation and coating method that has good dispersibility, high bond strength, and good activity. Whether the catalytic coating is uniformly dispersed on the surface of the carrier directly affects the catalytic activity of the monolithic catalyst, and further directly affects the purification effect of the aftertreatment system.
CeO 2 Has good oxygen storage and release capacity, can be used as an oxygen buffer when being added into a three-way catalyst of automobile exhaust as a cocatalyst, and can pass through Ce when oxygen is rich 3+ Conversion to Ce 4+ Absorbing oxygen to ensure NO x Reduced by CO and HC, ceO when oxygen is deficient 2 Oxygen is released to oxidize CO and HC, thereby achieving effective purification of CO, HC and NO x Is a target of (a). But due to the carThe temperature of the discharged tail gas is very high>1000 c), the ceria catalyst is susceptible to aging and sintering, resulting in a decrease in oxygen storage capacity.
In the prior art, chinese patent CN112717927B discloses a preparation method and application of an automobile exhaust treatment catalyst, wherein the catalyst sequentially comprises a substrate layer, a coating layer and a load layer, and the substrate layer is honeycomb ceramics; the coating layer comprises La 2 O 3 /Al 2 O 3 And cerium zirconium composite metal oxide; the load layer is noble metal, the noble metal is one or more of Pt, rh and Pd, and the catalyst has good catalytic effect, and has the characteristics of low cost and easy industrial application. However, the thermal shock resistance and mechanical strength of the cordierite honeycomb ceramics as the catalyst carrier are not considered, which may lead to a decrease in the service performance of the catalyst. For example, the gas temperature at the outlet of the automobile engine is about 800 ℃, and the automobile engine is frequently started and flamed in use, so that the ceramic carrier repeatedly bears the thermal shock impact from room temperature to 800 ℃ for a long time; if the thermal shock resistance (DeltaT) is poor, the honeycomb ceramic carrier is quickly broken, so that the catalytic converter is disabled; the higher the Δt of a ceramic, the lower its coefficient of thermal expansion, so it is common in the art to distinguish and characterize the Δt of a honeycomb ceramic by the coefficient of thermal expansion. And the catalytic temperature of the honeycomb catalyst in the prior art is above 250 ℃, so that the application range of the honeycomb catalyst is limited.
Therefore, there is a need in the art for a honeycomb catalyst that has excellent catalytic effect, low shedding rate, low catalytic temperature, and good thermal shock resistance and mechanical strength.
Disclosure of Invention
In view of the shortcomings of the prior art, the present invention is directed to a honeycomb body for purifying automobile exhaust and a preparation method thereof, so as to solve the problems mentioned in the background art.
In order to achieve the above purpose, the present invention provides the following technical solutions:
a honeycomb body for automobile exhaust purification sequentially comprises a honeycomb body carrier, a base layer, a connecting layer and a functional layer from inside to outside, wherein the honeycomb body carrier comprises NiO and Y 2 O 3 /ZrO 2 And a binder; the base layer is formed by Y 2 O 3 /ZrO 2 And PVB; the connecting layer is made of Gd 2 O 3 /CeO 2 And PVB; the functional layer is made of La 0.8 Sr 0.2 CoO 3 And Gd 2 O 3 /CeO 2 And (5) preparing powder.
Preferably, the honeycomb carrier comprises the following raw materials in parts by weight: 25-35 parts of NiO and Y 2 O 3 /ZrO 2 15-25 parts of adhesive and 4-8 parts of binder; the Y is 2 O 3 /ZrO 2 Y in (a) 2 O 3 With ZrO 2 The molar mass ratio of (2) is 8:92; the particle size of the NiO powder is 0.5-1.5 mu m, and the Y is 2 O 3 /ZrO 2 The particle size of the powder is 0.3-0.6 mu m; the binder is one or more of alpha-terpineol, phenolic resin and furan resin.
Preferably, Y is present in the base layer in mass percent 2 O 3 /ZrO 2 25-35%, PVB 0.5-1.5%, and ethanol solvent for the rest; the Y is 2 O 3 /ZrO 2 Y in (a) 2 O 3 With ZrO 2 The molar mass ratio of (2) is 8:92; the thickness of the base layer is 20-40 mu m.
Preferably, the Gd is contained in the connecting layer in percentage by mass 2 O 3 /CeO 2 20-30%, PVB 1-2%, and ethanol solvent for the rest; the Gd 2 O 3 /CeO 2 Gd in 2 O 3 With CeO 2 The molar mass ratio of (2) is 8:2; the thickness of the connecting layer is 20-30 mu m.
Preferably, la is contained in the functional layer in percentage by mass 0.8 Sr 0.2 CoO 3 And Gd 2 O 3 /CeO 2 20-25% of powder, and the balance of solvent ethanol; the La is 0.8 Sr 0.2 CoO 3 And Gd 2 O 3 /CeO 2 La in powder 0.8 Sr 0.2 CoO 3 With Gd 2 O 3 /CeO 2 The molar mass ratio of (2) is 1:1-3; the Gd 2 O 3 /CeO 2 Gd in 2 O 3 With CeO 2 The molar mass ratio of (3): 7, preparing a base material; the thickness of the functional layer is 20-40 mu m.
The invention also provides a preparation method of the honeycomb body for purifying automobile exhaust, which comprises the following steps:
(1) Preparation of a honeycomb carrier: niO and Y 2 O 3 /ZrO 2 Ball milling, adding binder, stirring, kneading into paste, placing into extruder, regulating pressure regulating valve of extruder to 25kgf/cm 2 Extruding under air extraction, and slowly increasing pressure to 40kgf/cm 2 Slowly extruding the wet honeycomb blank, cutting off after extruding the honeycomb columns to the required length, shaping at 200 ℃, and calcining the blank after shaping to obtain a honeycomb carrier;
(2) Dip coating of a honeycomb substrate: coating and covering the part, which does not need to be coated, of the honeycomb body carrier obtained in the step (1 by using white glue, drying, immersing the honeycomb body carrier in the base layer slurry for 2-4min after the drying is finished, pulling up, throwing away the redundant slurry, blowing through honeycomb pore canals to finish primary coating, immersing the honeycomb structural body in the base layer slurry reversely for 2-4min, pulling up, throwing away the redundant slurry, blowing through the honeycomb pore canals to finish secondary coating, and then placing the honeycomb structural body in room temperature for air drying and calcining to obtain the honeycomb body coated with the base layer;
(3) Dip coating of the honeycomb connecting layer: preparing a connecting layer slurry, namely coating and covering the part, which is not required to be coated, of the honeycomb body coated with the base layer, obtained in the step (2) by using white glue, then drying, immersing the honeycomb body in the base layer slurry for 2-4min after drying, pulling up, throwing away excessive slurry, blowing through honeycomb pore canals to finish primary coating, immersing the honeycomb structure in the connecting layer slurry reversely for 2-4min, pulling up, throwing away excessive slurry, blowing through the honeycomb pore canals to finish secondary coating, and then placing the honeycomb structure at room temperature for air drying and calcining to obtain the honeycomb body coated with the connecting layer;
(4) Dip coating of honeycomb functional layers: and (3) configuring the functional layer slurry, coating and covering the part, which is not required to be coated, of the honeycomb body coated with the connecting layer, obtained in the step (3) by using white glue, then drying, immersing the honeycomb body in the basic layer slurry for 2-4min after drying, pulling up, throwing away excessive slurry, blowing through honeycomb pore channels to finish primary coating, immersing the honeycomb structure in the functional layer slurry reversely for 2-4min, pulling up, throwing away excessive slurry, blowing through the honeycomb pore channels, finishing secondary coating, and then placing the honeycomb structure in the air drying and calcining at room temperature to obtain the honeycomb body for purifying automobile exhaust.
Preferably, the shaping process in the step (1) is as follows: heating to 60 ℃ at the speed of 1-2 ℃/min under the room temperature condition, then heating to 120 ℃ at the speed of 1-2 ℃/min after heat preservation for 1-3h, heating to 200 ℃ at the speed of 1-2 ℃/min after heat preservation for 1-3h, and naturally cooling to room temperature after heat preservation for 3-5 h;
the calcination process comprises the following steps: heating to 300 ℃ at the speed of 4-6 ℃/min under the room temperature condition, then heating to 600 ℃ at the speed of 4-6 ℃/min after heat preservation for 1-3h, heating to 900 ℃ at the speed of 4-6 ℃/min after heat preservation for 1-3h, heating to 1100 ℃ at the speed of 4-6 ℃/min after heat preservation for 1-3h, and naturally cooling to room temperature after heat preservation for 3-5 h.
Preferably, the calcining process in step (2) is as follows: heating to 500 ℃ at the rate of 2-4 ℃/min under the room temperature condition, then heating to 1200 ℃ at the rate of 1-2 ℃/min after heat preservation for 1-3h, then heating to 1300-1400 ℃ at the rate of 1-2 ℃/min after heat preservation for 4-6h, then cooling to 1000 ℃ at the rate of 1-2 ℃/min after heat preservation for 6-8h, then cooling to 500 ℃ at the rate of 1-2 ℃/min after heat preservation for 1-3h, and finally naturally cooling to room temperature after heat preservation for 1-3 h.
Preferably, the calcining process in step (3) is as follows: heating to 500 ℃ at the rate of 2-4 ℃/min under the room temperature condition, then heating to 1200-1250 ℃ at the rate of 1-2 ℃/min after heat preservation for 1-3h, then cooling to 1000 ℃ at the rate of 1-2 ℃/min after heat preservation for 4-6h, then cooling to 500 ℃ at the rate of 1-2 ℃/min after heat preservation for 1-3h, and finally naturally cooling to room temperature after heat preservation for 3-5 h.
Preferably, the calcining process in step (4) is as follows: the calcination temperature is 900-1250 ℃ and the calcination time is 4-6h.
Compared with the prior art, the invention has the following beneficial effects:
(1) The honeycomb body for purifying automobile exhaust prepared by the invention is prepared by NiO and Y 2 O 3 /ZrO 2 And binder to form honeycomb support, niO and Y are bonded together with binder 2 O 3 /ZrO 2 The ceramic material is bridged together, the carrier is extruded and molded through a porous die by an extrusion molding method, the pore shape and the size are controllable, the continuous production is easy, the ceramic material is used for replacing cordierite honeycomb ceramics, and the YSZ ceramic material has the advantages of high melting point, high hardness, good thermal shock resistance, low density, low heat conductivity, linear expansion coefficient approaching to metal materials, high strength and toughness, chemical corrosion resistance and the like, and can improve the thermal shock resistance of the honeycomb body; simultaneously coating a layer of Y on the surface of the carrier 2 O 3 /ZrO 2 The base layer has high bonding strength with the carrier and similar thermal expansion coefficient, and the coating is not easy to fall off.
(2) The honeycomb body for purifying automobile exhaust is prepared by introducing Gd into a connecting layer 2 O 3 /CeO 2 The cerium ions and zirconium crystals in the base layer form cerium-zirconium solid solution, so that the temperature resistance can be improved, and meanwhile, the cerium-zirconium solid solution is used as a cocatalyst, so that the catalytic performance of the honeycomb body can be improved; and the coating of the connecting layer is uniformly dispersed and closely paved on the surface of the base layer, particles in the connecting layer are closely and fully contacted with the base layer after calcination, the combination is firm, and the falling rate is low.
(3) The honeycomb body for purifying automobile exhaust prepared by the invention has the functional layer of La 0.8 Sr 0.2 CoO 3 And Gd 2 O 3 /CeO 2 Powder of Gd 2 O 3 /CeO 2 The powder and the connecting layer have good compatibility, and the bonding strength of the functional layer and the connecting layer is improved, so that the functional layer and the connecting layer are not easy to fall off; the prepared honeycomb body has good tail gas catalytic conversion effect, the existing honeycomb body catalyst is used at the temperature of more than 250 ℃, the honeycomb body can be used at normal temperature or even at low temperature, has obvious effect on conversion of nitrogen oxides, hydrocarbon and CO, expands the application range of the honeycomb body, has low cost and is easy to workAnd the characteristics of industrialized application.
(4) According to the preparation method of the honeycomb body for purifying the automobile exhaust, when different coatings are prepared, the coatings have good bonding strength through different calcining processes, the surfaces of particles react with each other under the reasonable heating and cooling speeds and the reasonable heat preservation time, the sintering temperature is improved, the activity of atoms is enhanced, the number of atoms which can be overcome to be blocked is increased, the surface energy of a system is reduced, a sample is densified, the particles are combined into a whole, the compressive strength of the honeycomb is improved, meanwhile, the proper heat preservation time ensures that the inner crystal phase and the outer crystal phase of the coating are uniform, and proper grain size can be obtained, so that the catalytic performance of the honeycomb body is improved.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The Y is 2 O 3 /ZrO 2 The powder is purchased from Guangzhou Hongwu materials science and technology Co., ltd, and has a particle size of 0.3-0.6 μm; the Gd 2 O 3 /CeO 2 According to literature (preparation and research of LSM-LSC composite cathode of solid oxide fuel cell, hou Zhifang, university of Dai-Lian traffic university, published article 2005); la (La) 0.8 Sr 0.2 CoO 3 According to the literature (mullite fiber ceramic supported La 0.8 Sr 0.2 CoO 3 Is prepared by the preparation and the catalytic performance of the traditional Chinese medicine, such as Bilin, etc., university of North China university (natural science edition), 9 months in 2006; the phenolic resin is purchased from Henan Huanshan Utility Co., ltd, and the product number is 9100; the furan resin is purchased from Shandong denuo new material science and technology Co., ltd, and the brand is DN1432; the PVB is manufactured by DuPont company of the United states, and the model is 9850; the cordierite powder was purchased from the epitaxial mineral processing plant, programming, chart No. F-568.
Example 1
The preparation method of the honeycomb body for purifying automobile exhaust comprises the following steps:
(1) Preparation of a honeycomb carrier: 250g of NiO (particle size of 0.5 μm) and 150. 150g Y 2 O 3 /ZrO 2 (Y 2 O 3 With ZrO 2 The molar mass ratio of (2) is 8:92, particle size of 0.3 μm), followed by adding 10g of alpha-terpineol and 30g of phenolic resin, stirring uniformly and kneading into paste, placing into an extruder, regulating the pressure regulating valve of the extruder to 25kgf/cm 2 Extruding under air extraction, and slowly increasing pressure to 40kgf/cm 2 Slowly extruding the honeycomb wet blank, cutting off after the honeycomb column is extruded to the required length, heating to 60 ℃ at the speed of 1 ℃/min under the condition of room temperature, then heating to 120 ℃ at the speed of 1 ℃/min after heat preservation for 1h, heating to 200 ℃ at the speed of 1 ℃/min after heat preservation for 1h, naturally cooling to room temperature after heat preservation for 3h, and calcining the blank after shaping is finished, wherein the calcining process comprises the following steps: heating to 300 ℃ at the speed of 4 ℃/min under the room temperature condition, then heating to 600 ℃ at the speed of 4 ℃/min after heat preservation for 1h, then heating to 900 ℃ at the speed of 4 ℃/min after heat preservation for 1h, heating to 1100 ℃ at the speed of 4 ℃/min after heat preservation for 1h, and finally naturally cooling to room temperature after heat preservation for 3h to obtain the honeycomb carrier;
(2) Dip coating of a honeycomb substrate: and (3) performing base layer slurry configuration: will be 250g Y 2 O 3 /ZrO 2 Powder (Y) 2 O 3 With ZrO 2 The molar mass ratio of (2) is 8:92, the grain diameter is 0.3 mu m), 5g PVB is added into 745g absolute ethyl alcohol, ultrasonic oscillation is carried out for 1h, then standing is carried out for 24h, ultrasonic oscillation is carried out for 15min again before coating, and base layer slurry preparation is completed; coating and covering the part of the honeycomb carrier which does not need to be coated, which is obtained in the step (1), with white glue, then drying, immersing in the basic layer slurry for 2min after drying, pulling up, throwing away the redundant slurry, blowing through the honeycomb duct to finish one-time coating, immersing the honeycomb structure body in the basic layer slurry reversely, immersing for 2min, pulling up, throwing away the redundant slurry, blowing through the honeycomb duct to finish secondary coating, and thenThen the honeycomb structure is placed at room temperature for air drying and calcination, and the calcination process is as follows: heating to 500 ℃ at the speed of 2 ℃/min under the room temperature condition, then heating to 1200 ℃ at the speed of 1 ℃/min after heat preservation for 1h, heating to 1300 ℃ at the speed of 1 ℃/min after heat preservation for 4h, then cooling to 1000 ℃ at the speed of 1 ℃/min after heat preservation for 8h, then cooling to 500 ℃ at the speed of 1 ℃/min after heat preservation for 1h, and finally naturally cooling to room temperature after heat preservation for 1h to obtain the honeycomb body coated with the base layer; the thickness of the base layer is 20 mu m;
(3) Dip coating of the honeycomb connecting layer: and (3) preparing a connecting layer slurry: 200g Gd 2 O 3 /CeO 2 Powder (Gd) 2 O 3 With CeO 2 The molar mass ratio is 3: 7) Adding 10g of PVB into 790 absolute ethyl alcohol, carrying out ultrasonic vibration for 1h, standing for 24h, carrying out ultrasonic vibration for 15min again before coating, and completing the preparation of the slurry of the connecting layer; coating and covering the part, which is not required to be coated, of the honeycomb body coated with the base layer, obtained in the step (2) by using white glue, drying, immersing the honeycomb body in the slurry of the connecting layer for 2 minutes after drying, pulling up, throwing away the redundant slurry, blowing through the honeycomb duct to finish primary coating, immersing the honeycomb structure in the slurry of the connecting layer reversely, immersing the honeycomb body for 2 minutes, pulling up, throwing away the redundant slurry, blowing through the honeycomb duct to finish secondary coating, and then placing the honeycomb structure in the air drying and calcining at room temperature, wherein the calcining process comprises the following steps: heating to 500 ℃ at the speed of 2 ℃/min under the room temperature condition, then heating to 1200 ℃ at the speed of 1 ℃/min after heat preservation for 1h, then cooling to 1000 ℃ at the speed of 1 ℃/min after heat preservation for 6h, then cooling to 500 ℃ at the speed of 1 ℃/min after heat preservation for 1h, and finally naturally cooling to room temperature after heat preservation for 3h to obtain the honeycomb body coated with the connecting layer; the thickness of the connecting layer is 20 mu m;
(4) Dip coating of honeycomb functional layers: functional layer slurry configuration: 200g of La 0.8 Sr 0.2 CoO 3 And Gd 2 O 3 /CeO 2 Powder (wherein La 0.8 Sr 0.2 CoO 3 85g of Gd 2 O 3 /CeO 2 115g of Gd 2 O 3 With CeO 2 The molar mass ratio is 3: 7) Adding the mixture into 800g of absolute ethyl alcohol,performing ultrasonic vibration for 1h, standing for 24h, performing ultrasonic vibration for 15min again before coating, and completing the configuration of the slurry of the connecting layer; coating and covering the part, which is not required to be coated, of the honeycomb body coated with the connecting layer, obtained in the step (3) by using white glue, drying, immersing the part in the functional layer slurry for 2 minutes after the drying is finished, pulling up, throwing away excessive slurry, blowing through honeycomb pore channels to finish primary coating, immersing the honeycomb structure in the functional layer slurry reversely, immersing the part for 2 minutes, pulling up, throwing away excessive slurry, blowing through the honeycomb pore channels to finish secondary coating, and then placing the honeycomb structure in the air drying and calcining at room temperature, wherein the calcining process comprises the following steps: the calcination temperature is 900 ℃, the calcination time is 6 hours, and the thickness of the functional layer is 20 mu m, so that the honeycomb body for purifying the automobile exhaust is obtained.
Example 2
The preparation method of the honeycomb body for purifying automobile exhaust comprises the following steps:
(1) Preparation of a honeycomb carrier: 300g of NiO (particle size 1 μm) and 200. 200g Y 2 O 3 /ZrO 2 (Y 2 O 3 With ZrO 2 The molar mass ratio of (2) is 8:92, particle size of 0.5 μm), followed by adding 15g of alpha-terpineol and 45g of phenolic resin, stirring uniformly and kneading into paste, placing into an extruder, regulating the pressure regulating valve of the extruder to 25kgf/cm 2 Extruding under air extraction, and slowly increasing pressure to 40kgf/cm 2 Slowly extruding the honeycomb wet blank, cutting off after the honeycomb column is extruded to the required length, heating to 60 ℃ at the speed of 1 ℃/min under the condition of room temperature, then heating to 120 ℃ at the speed of 1 ℃/min after heat preservation for 2 hours, heating to 200 ℃ at the speed of 1 ℃/min after heat preservation for 2 hours, naturally cooling to room temperature after heat preservation for 4 hours, and calcining the blank after shaping is finished, wherein the calcining process comprises the following steps: heating to 300 ℃ at a rate of 5 ℃/min under the condition of room temperature, then heating to 600 ℃ at a rate of 5 ℃/min after heat preservation for 2 hours, then heating to 900 ℃ at a rate of 5 ℃/min after heat preservation for 2 hours, heating to 1100 ℃ at a rate of 5 ℃/min after heat preservation for 2 hours, and finally naturally cooling to room temperature after heat preservation for 4 hours to obtain a honeycomb carrier;
(2) Honeycomb base layer soakingAnd (3) coating: and (3) performing base layer slurry configuration: will 300g Y 2 O 3 /ZrO 2 Powder (Y) 2 O 3 With ZrO 2 The molar mass ratio of (2) is 8:92, the grain diameter is 0.5 mu m), 10g PVB is added into 690g absolute ethyl alcohol, ultrasonic oscillation is carried out for 1h, then standing is carried out for 24h, ultrasonic oscillation is carried out for 15min again before coating, and base layer slurry preparation is completed; coating and covering the part, which does not need to be coated, of the honeycomb carrier obtained in the step (1) by using white glue, drying, immersing the honeycomb carrier in base layer slurry for 3min after drying, pulling up, throwing away excessive slurry, blowing through honeycomb channels to finish primary coating, immersing the honeycomb structure in the base layer slurry reversely, immersing the honeycomb structure for 3min, pulling up, throwing away excessive slurry, blowing through the honeycomb channels to finish secondary coating, and then placing the honeycomb structure in the air drying and calcining at room temperature, wherein the calcining process comprises the following steps: heating to 500 ℃ at a speed of 3 ℃/min under the room temperature condition, then heating to 1200 ℃ at a speed of 1 ℃/min after heat preservation for 2 hours, heating to 1400 ℃ at a speed of 1 ℃/min after heat preservation for 5 hours, cooling to 1000 ℃ at a speed of 1 ℃/min after heat preservation for 7 hours, cooling to 500 ℃ at a speed of 1 ℃/min after heat preservation for 2 hours, and naturally cooling to room temperature after heat preservation for 2 hours to obtain a honeycomb body coated with a base layer; the thickness of the base layer is 30 mu m;
(3) Dip coating of the honeycomb connecting layer: and (3) preparing a connecting layer slurry: 250g Gd 2 O 3 /CeO 2 Powder (Gd) 2 O 3 With CeO 2 The molar mass ratio is 3: 7) Adding 15g of PVB into 735g of absolute ethyl alcohol, carrying out ultrasonic vibration for 1h, standing for 24h, carrying out ultrasonic vibration for 15min again before coating, and completing the preparation of the slurry of the connecting layer; coating and covering the part, which is not required to be coated, of the honeycomb body coated with the base layer, obtained in the step (2) by using white glue, drying, immersing the honeycomb body in the slurry of the connecting layer for 3min after drying, pulling up, throwing away the redundant slurry, blowing through the honeycomb duct to finish primary coating, immersing the honeycomb structure in the slurry of the connecting layer reversely, immersing the honeycomb body for 3min, pulling up, throwing away the redundant slurry, blowing through the honeycomb duct to finish secondary coating, and then placing the honeycomb structure in the air drying and calcining at room temperature, wherein the calcining process comprises the following steps: heating to 500 at a rate of 3 ℃/min under room temperature conditionsHeating to 1250 ℃ at a speed of 1 ℃/min after heat preservation for 2 hours, cooling to 1000 ℃ at a speed of 1 ℃/min after heat preservation for 5 hours, cooling to 500 ℃ at a speed of 1 ℃/min after heat preservation for 2 hours, and naturally cooling to room temperature after heat preservation for 4 hours to obtain a honeycomb body coated with a connecting layer; the thickness of the connecting layer is 25 mu m;
(4) Dip coating of honeycomb functional layers: functional layer slurry configuration: 230g La 0.8 Sr 0.2 CoO 3 And Gd 2 O 3 /CeO 2 Powder (wherein La 0.8 Sr 0.2 CoO 3 62g of Gd 2 O 3 /CeO 2 Has a mass of 168g, gd 2 O 3 With CeO 2 The molar mass ratio is 3: 7) Adding 770g of absolute ethyl alcohol, carrying out ultrasonic vibration for 1h, standing for 24h, carrying out ultrasonic vibration for 15min again before coating, and completing the preparation of the slurry of the connecting layer; coating and covering the part, which is not required to be coated, of the honeycomb body coated with the connecting layer, obtained in the step (3) by using white glue, drying, immersing the part in the functional layer slurry for 3min after drying, pulling up, throwing away excessive slurry, blowing through honeycomb pore channels to finish primary coating, immersing the honeycomb structure in the functional layer slurry reversely, immersing the part for 3min, pulling up, throwing away excessive slurry, blowing through the honeycomb pore channels to finish secondary coating, and then placing the honeycomb structure at room temperature for air drying and calcining, wherein the calcining process comprises the following steps: the calcination temperature is 1100 ℃, the calcination time is 5 hours, and the thickness of the functional layer is 30 mu m, so that the honeycomb body for purifying the automobile exhaust is obtained.
Example 3
The preparation method of the honeycomb body for purifying automobile exhaust comprises the following steps:
(1) Preparation of a honeycomb carrier: 350g of NiO (particle size 1.5 μm) and 250. 250g Y were mixed 2 O 3 /ZrO 2 (Y 2 O 3 With ZrO 2 The molar mass ratio of (2) is 8:92, particle size of 0.6 μm), followed by adding 30g of alpha-terpineol and 50g of furan resin, stirring uniformly and kneading into paste, placing into an extruder, regulating the pressure regulating valve of the extruder to 25kgf/cm 2 Extruding under air extraction, and slowly increasing pressure to 40kgf/cm 2 Make the followingSlowly extruding the honeycomb wet blank, cutting off after extruding the honeycomb column to the required length, heating to 60 ℃ at the speed of 2 ℃/min under the condition of room temperature, then heating to 120 ℃ at the speed of 2 ℃/min after heat preservation for 3 hours, heating to 200 ℃ at the speed of 2 ℃/min after heat preservation for 3 hours, naturally cooling to room temperature after heat preservation for 5 hours, and calcining the blank after shaping, wherein the calcining process is as follows: heating to 300 ℃ at the rate of 6 ℃/min under the room temperature condition, then heating to 600 ℃ at the rate of 6 ℃/min after heat preservation for 3 hours, then heating to 900 ℃ at the rate of 6 ℃/min after heat preservation for 3 hours, heating to 1100 ℃ at the rate of 6 ℃/min after heat preservation for 3 hours, and finally naturally cooling to room temperature after heat preservation for 5 hours to obtain the honeycomb carrier;
(2) Dip coating of a honeycomb substrate: and (3) performing base layer slurry configuration: will be 350g Y 2 O 3 /ZrO 2 Powder (Y) 2 O 3 With ZrO 2 The molar mass ratio of (2) is 8:92, the grain diameter is 0.6 mu m), 15g PVB is added into 635g absolute ethyl alcohol, ultrasonic oscillation is carried out for 1h, then standing is carried out for 24h, ultrasonic oscillation is carried out for 15min again before coating, and base layer slurry preparation is completed; coating and covering the part, which does not need to be coated, of the honeycomb carrier obtained in the step (1) by using white glue, drying, immersing the honeycomb carrier in base layer slurry for 4min after drying, pulling up, throwing away excessive slurry, blowing through honeycomb channels to finish primary coating, immersing the honeycomb structure in the base layer slurry reversely, immersing the honeycomb structure for 4min, pulling up, throwing away excessive slurry, blowing through the honeycomb channels to finish secondary coating, and then placing the honeycomb structure in the air drying and calcining at room temperature, wherein the calcining process comprises the following steps: heating to 500 ℃ at a speed of 4 ℃/min under the room temperature condition, then heating to 1200 ℃ at a speed of 2 ℃/min after heat preservation for 3 hours, heating to 1400 ℃ at a speed of 2 ℃/min after heat preservation for 6 hours, cooling to 1000 ℃ at a speed of 2 ℃/min after heat preservation for 6 hours, cooling to 500 ℃ at a speed of 2 ℃/min after heat preservation for 3 hours, and naturally cooling to room temperature after heat preservation for 3 hours to obtain a honeycomb body coated with a base layer; the thickness of the base layer is 40 mu m;
(3) Dip coating of the honeycomb connecting layer: and (3) preparing a connecting layer slurry: 300g Gd 2 O 3 /CeO 2 Powder (Gd) 2 O 3 With CeO 2 The molar mass ratio is 3: 7) Adding 20g of PVB into 680g of absolute ethyl alcohol, carrying out ultrasonic vibration for 1h, standing for 24h, carrying out ultrasonic vibration for 15min again before coating, and completing the preparation of the slurry of the connecting layer; coating and covering the part, which is not required to be coated, of the honeycomb body coated with the base layer, obtained in the step (2) by using white glue, drying, immersing the honeycomb body in the slurry of the connecting layer for 4min after drying, pulling up, throwing away the redundant slurry, blowing through the honeycomb duct to finish primary coating, immersing the honeycomb structure in the slurry of the connecting layer reversely, immersing the honeycomb body for 4min, pulling up, throwing away the redundant slurry, blowing through the honeycomb duct to finish secondary coating, and then placing the honeycomb structure in the air drying and calcining at room temperature, wherein the calcining process comprises the following steps: heating to 500 ℃ at the speed of 4 ℃/min under the room temperature condition, then heating to 1250 ℃ at the speed of 2 ℃/min after heat preservation for 3 hours, then cooling to 1000 ℃ at the speed of 2 ℃/min after heat preservation for 4 hours, then cooling to 500 ℃ at the speed of 2 ℃/min after heat preservation for 3 hours, and finally naturally cooling to room temperature after heat preservation for 5 hours to obtain the honeycomb body coated with the connecting layer; the thickness of the connecting layer is 30 mu m;
(4) Dip coating of honeycomb functional layers: functional layer slurry configuration: 250g of La 0.8 Sr 0.2 CoO 3 And Gd 2 O 3 /CeO 2 Powder (wherein La 0.8 Sr 0.2 CoO 3 50g of Gd 2 O 3 /CeO 2 The mass is 200g, gd 2 O 3 With CeO 2 The molar mass ratio is 3: 7) Adding 750g of absolute ethyl alcohol, carrying out ultrasonic vibration for 1h, standing for 24h, carrying out ultrasonic vibration for 15min again before coating, and completing the preparation of the slurry of the connecting layer; coating and covering the part, which is not required to be coated, of the honeycomb body coated with the connecting layer, obtained in the step (3) by using white glue, drying, immersing the part in the functional layer slurry for 4min after the drying is finished, pulling up, throwing away excessive slurry, blowing through honeycomb pore channels to finish primary coating, immersing the honeycomb structure in the functional layer slurry reversely, immersing the part for 4min, pulling up, throwing away excessive slurry, blowing through the honeycomb pore channels to finish secondary coating, and then placing the honeycomb structure in the air drying and calcining at room temperature, wherein the calcining process comprises the following steps: the calcination temperature is 1250 ℃, the calcination time is 4 hours, and the function is thatThe thickness of the layer is 40 mu m, and the honeycomb body for purifying the automobile exhaust is obtained.
Comparative example 1
The preparation method of the honeycomb body for purifying automobile exhaust comprises the following steps:
(1) Preparation of a honeycomb carrier: adding 400g of cordierite powder into 40g of phenolic resin, uniformly stirring and kneading to form paste, putting into an extruder, regulating the pressure regulating valve of the extruder to 25kgf/cm 2 Extruding under air extraction, and slowly increasing pressure to 40kgf/cm 2 Slowly extruding the wet honeycomb embryo, cutting off after extruding the honeycomb column to a required length, shaping at 200 ℃, taking the embryo for calcining after shaping is finished, wherein the calcining temperature is 1400 ℃, and the calcining time is 4 hours, so as to obtain a honeycomb carrier;
(2) Dip coating of a honeycomb substrate: and (3) performing base layer slurry configuration: will be 250g Y 2 O 3 /ZrO 2 Powder (Y) 2 O 3 With ZrO 2 The molar mass ratio of (2) is 8:92, the grain diameter is 0.3 mu m), 5g PVB is added into 745g absolute ethyl alcohol, ultrasonic oscillation is carried out for 1h, then standing is carried out for 24h, ultrasonic oscillation is carried out for 15min again before coating, and base layer slurry preparation is completed; coating and covering the part, which does not need to be coated, of the honeycomb carrier obtained in the step (1) by using white glue, drying, immersing the honeycomb carrier in base layer slurry for 2min after drying, pulling up, throwing away excessive slurry, blowing through honeycomb channels to finish primary coating, immersing the honeycomb structure in the base layer slurry reversely, immersing the honeycomb structure for 2min, pulling up, throwing away excessive slurry, blowing through the honeycomb channels to finish secondary coating, and then placing the honeycomb structure in the air drying and calcining at room temperature, wherein the calcining process comprises the following steps: heating to 500 ℃ at the speed of 2 ℃/min under the room temperature condition, then heating to 1200 ℃ at the speed of 1 ℃/min after heat preservation for 1h, heating to 1300 ℃ at the speed of 1 ℃/min after heat preservation for 4h, then cooling to 1000 ℃ at the speed of 1 ℃/min after heat preservation for 8h, then cooling to 500 ℃ at the speed of 1 ℃/min after heat preservation for 1h, and finally naturally cooling to room temperature after heat preservation for 1h to obtain the honeycomb body coated with the base layer; the thickness of the base layer is 20 mu m;
(3) Dip coating of the honeycomb connecting layer: connection layer slurry configuration: 200g Gd 2 O 3 /CeO 2 Powder (Gd) 2 O 3 With CeO 2 The molar mass ratio is 3: 7) Adding 10g of PVB into 790 absolute ethyl alcohol, carrying out ultrasonic vibration for 1h, standing for 24h, carrying out ultrasonic vibration for 15min again before coating, and completing the preparation of the slurry of the connecting layer; coating and covering the part, which is not required to be coated, of the honeycomb body coated with the base layer, obtained in the step (2) by using white glue, drying, immersing the honeycomb body in the slurry of the connecting layer for 2 minutes after drying, pulling up, throwing away the redundant slurry, blowing through the honeycomb duct to finish primary coating, immersing the honeycomb structure in the slurry of the connecting layer reversely, immersing the honeycomb body for 2 minutes, pulling up, throwing away the redundant slurry, blowing through the honeycomb duct to finish secondary coating, and then placing the honeycomb structure in the air drying and calcining at room temperature, wherein the calcining process comprises the following steps: heating to 500 ℃ at the speed of 2 ℃/min under the room temperature condition, then heating to 1200 ℃ at the speed of 1 ℃/min after heat preservation for 1h, then cooling to 1000 ℃ at the speed of 1 ℃/min after heat preservation for 6h, then cooling to 500 ℃ at the speed of 1 ℃/min after heat preservation for 1h, and finally naturally cooling to room temperature after heat preservation for 3h to obtain the honeycomb body coated with the connecting layer; the thickness of the connecting layer is 20 mu m;
(4) Dip coating of honeycomb functional layers: functional layer slurry configuration: 200g of La 0.8 Sr 0.2 CoO 3 And Gd 2 O 3 /CeO 2 Powder (wherein La 0.8 Sr 0.2 CoO 3 85g of Gd 2 O 3 /CeO 2 115g of Gd 2 O 3 With CeO 2 The molar mass ratio is 3: 7) Adding the mixture into 800g of absolute ethyl alcohol, carrying out ultrasonic vibration for 1h, standing for 24h, carrying out ultrasonic vibration for 15min again before coating, and completing the preparation of the slurry of the connecting layer; coating and covering the part, which is not required to be coated, of the honeycomb body coated with the connecting layer, obtained in the step (3) by using white glue, drying, immersing the part in the functional layer slurry for 2 minutes after the drying is finished, pulling up, throwing away the redundant slurry, blowing through the honeycomb duct to finish primary coating, immersing the honeycomb structure in the functional layer slurry reversely, immersing the part for 2 minutes, pulling up, throwing away the redundant slurry, blowing through the honeycomb duct to finish secondary coating, and then placing the honeycomb structure at room temperatureAir-drying and calcining, wherein the calcining process comprises the following steps: the calcination temperature is 900 ℃, the calcination time is 6 hours, and the thickness of the functional layer is 20 mu m, so that the honeycomb body for purifying the automobile exhaust is obtained.
Comparative example 2
The preparation method of the honeycomb body for purifying automobile exhaust comprises the following steps:
(1) Preparation of a honeycomb carrier: 250g of NiO (particle size of 0.5 μm) and 150. 150g Y 2 O 3 /ZrO 2 (Y 2 O 3 With ZrO 2 The molar mass ratio of (2) is 8:92, particle size of 0.3 μm), followed by adding 10g of alpha-terpineol and 30g of phenolic resin, stirring uniformly and kneading into paste, placing into an extruder, regulating the pressure regulating valve of the extruder to 25kgf/cm 2 Extruding under air extraction, and slowly increasing pressure to 40kgf/cm 2 Slowly extruding the honeycomb wet blank, cutting off after the honeycomb column is extruded to the required length, heating to 60 ℃ at the speed of 1 ℃/min under the condition of room temperature, then heating to 120 ℃ at the speed of 1 ℃/min after heat preservation for 1h, heating to 200 ℃ at the speed of 1 ℃/min after heat preservation for 1h, naturally cooling to room temperature after heat preservation for 3h, and calcining the blank after shaping is finished, wherein the calcining process comprises the following steps: heating to 300 ℃ at the speed of 4 ℃/min under the room temperature condition, then heating to 600 ℃ at the speed of 4 ℃/min after heat preservation for 1h, then heating to 900 ℃ at the speed of 4 ℃/min after heat preservation for 1h, heating to 1100 ℃ at the speed of 4 ℃/min after heat preservation for 1h, and finally naturally cooling to room temperature after heat preservation for 3h to obtain the honeycomb carrier;
(2) Dip coating of honeycomb functional layers: functional layer slurry configuration: 200g of La 0.8 Sr 0.2 CoO 3 And Gd 2 O 3 /CeO 2 Powder (wherein La 0.8 Sr 0.2 CoO 3 85g of Gd 2 O 3 /CeO 2 115g of Gd 2 O 3 With CeO 2 The molar mass ratio is 3: 7) Adding the mixture into 800g of absolute ethyl alcohol, carrying out ultrasonic vibration for 1h, standing for 24h, carrying out ultrasonic vibration for 15min again before coating, and completing the preparation of the slurry of the connecting layer; the part of the honeycomb carrier obtained in the step (1) which is not required to be coated is whitenedCoating and covering glue, drying, immersing the glue into the functional layer slurry for 2min after drying, pulling up, throwing away excessive slurry, blowing through honeycomb channels to finish primary coating, immersing the honeycomb structure reversely into the functional layer slurry for 2min, pulling up, throwing away excessive slurry, blowing through the honeycomb channels to finish secondary coating, and then placing the honeycomb structure at room temperature for air drying and calcining, wherein the calcining process is as follows: the calcination temperature is 900 ℃, the calcination time is 6 hours, and the thickness of the functional layer is 20 mu m, so that the honeycomb body for purifying the automobile exhaust is obtained.
The honeycomb bodies obtained in examples 1-3 and comparative examples 1-2 were subjected to performance tests, specifically as follows:
and (3) falling rate test: the catalyst was uniformly purged with 10bar of compressed air at a distance of 1.5cm from the honeycomb cross section for 120s per unit cross section, and the catalyst falling rate was calculated according to the calculation formula. Shedding = (weight of honeycomb catalyst before purging-weight of honeycomb catalyst after purging)/coating loading before purging x 100%.
Coefficient of thermal expansion test: the test is carried out according to the standard QB/T1321-2012 of the method for measuring the average linear thermal expansion coefficient of ceramic materials. The test results are shown in Table 1 below:
TABLE 1 Fall Rate of Honeycomb coating and coefficient of thermal expansion Performance
| Shedding rate/% | Coefficient of thermal expansion/x 10 -6 ℃(25-800℃) | |
| Example 1 | 1.82 | 0.81 |
| Example 2 | 1.37 | 0.72 |
| Example 3 | 1.69 | 0.75 |
| Comparative example 1 | 8.41 | 1.57 |
| Comparative example 2 | 5.27 | 1.39 |
As can be seen from table 1, the coating falling rate of examples 1 to 3 was low, and the overall coating falling rate was reduced by the interaction between the coatings; at the same time, the thermal expansion coefficient of the honeycomb body is low and is smaller than 1x10 -6 The temperature is high, and the thermal shock resistance is good. While the cordierite carrier used in comparative example 1 has lower bonding strength with the coating, resulting in a significant improvement in the falling-off rate and a larger thermal expansion coefficient; in comparative example 2, the base layer and the connecting layer were not added, but only one functional layer, and the bonding strength with the support was limited, so that the falling rate was improved.
The honeycomb body prepared in example 1 was subjected to catalytic effect evaluation by the following method:
the specification of the honeycomb body: 15mm in diameter and 40mm in length;
airspeed: 30000h -1 ；
Total flow rate: 600mL/min;
simulated gas composition: o (O) 2 7000ppm,NO 1000ppm,CO 5000ppm,Ar is equilibrium gas, and under simulated atmosphere, the temperature is programmed to 50 ℃ from room temperature 2 ℃/min, and the steady state is recordedAnd (3) continuously heating to 150 ℃ in sequence, and recording the gas conversion at each temperature point. The results are shown in Table 2 below:
table 2 catalytic properties of the honeycomb of example 1 and comparative example 2
As can be seen from the above table 2, the honeycomb body prepared by the invention has good catalytic conversion effect on tail gas, has good catalytic effect at 50 ℃ and 150 ℃, and has a greatly reduced catalytic temperature compared with the existing honeycomb body catalyst, thereby having good application prospect.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. A honeycomb body for purifying automobile exhaust sequentially comprises a honeycomb body carrier, a base layer, a connecting layer and a functional layer from inside to outside, and is characterized in that the honeycomb body carrier comprises NiO and Y 2 O 3 /ZrO 2 Composite material; the base layer is formed by Y 2 O 3 /ZrO 2 And PVB; the connecting layer is made of Gd 2 O 3 /CeO 2 And PVB; the functional layer is made of La 0.8 Sr 0.2 CoO 3 And Gd 2 O 3 /CeO 2 And (5) preparing powder.
2. The honeycomb body for purifying automobile exhaust according to claim 1, wherein the honeycomb body carrier comprises the following raw materials in parts by weight: 25-35 parts of NiO and Y 2 O 3 /ZrO 2 15-25 parts of adhesive and 4-8 parts of binder; the Y is 2 O 3 /ZrO 2 Y in (a) 2 O 3 With ZrO 2 The molar ratio of (2) is 8:92;the particle size of the NiO powder is 0.5-1.5 mu m, and the Y is 2 O 3 /ZrO 2 The particle size of the powder is 0.3-0.6 mu m; the binder is one or more of alpha-terpineol, phenolic resin and furan resin.
3. The honeycomb body for automobile exhaust gas purification according to claim 1, wherein Y is in mass percent in the base layer 2 O 3 /ZrO 2 25-35%, PVB 0.5-1.5%, and ethanol solvent for the rest; the Y is 2 O 3 /ZrO 2 Y in (a) 2 O 3 With ZrO 2 The molar ratio of (2) is 8:92; the thickness of the base layer is 20-40 mu m.
4. The honeycomb body for automobile exhaust purification according to claim 1, wherein Gd in the connection layer is in mass percent 2 O 3 /CeO 2 20-30%, PVB 1-2%, and ethanol solvent for the rest; the Gd 2 O 3 /CeO 2 Gd in 2 O 3 With CeO 2 The molar ratio of (2) is 8:2; the thickness of the connecting layer is 20-30 mu m.
5. The honeycomb body for purifying automobile exhaust according to claim 1, wherein La in the functional layer is represented by mass percent 0.8 Sr 0.2 CoO 3 And Gd 2 O 3 /CeO 2 20-25% of powder, and the balance of solvent ethanol; the La is 0.8 Sr 0.2 CoO 3 And Gd 2 O 3 /CeO 2 La in powder 0.8 Sr 0.2 CoO 3 With Gd 2 O 3 /CeO 2 The molar ratio of (2) is 1:1-3; the Gd 2 O 3 /CeO 2 Gd in 2 O 3 With CeO 2 The molar ratio of (3): 7, preparing a base material; the thickness of the functional layer is 20-40 mu m.
6. A method for producing a honeycomb body for automobile exhaust purification according to any one of claims 1 to 5, comprising the steps of:
(1) Preparation of a honeycomb carrier: niO and Y 2 O 3 /ZrO 2 Ball milling, adding binder, stirring, kneading into paste, placing into extruder, regulating pressure regulating valve of extruder to 25kgf/cm 2 Extruding under air extraction, and slowly increasing pressure to 40kgf/cm 2 Slowly extruding the wet honeycomb blank, cutting off after extruding the honeycomb columns to the required length, shaping at 200 ℃, and calcining the blank after shaping to obtain a honeycomb carrier;
(2) Dip coating of a honeycomb substrate: coating and covering the part, which does not need to be coated, of the honeycomb body carrier obtained in the step (1 by using white glue, drying, immersing the honeycomb body carrier in the base layer slurry for 2-4min after the drying is finished, pulling up, throwing away the redundant slurry, blowing through honeycomb pore canals to finish primary coating, immersing the honeycomb structural body in the base layer slurry reversely for 2-4min, pulling up, throwing away the redundant slurry, blowing through the honeycomb pore canals to finish secondary coating, and then placing the honeycomb structural body in room temperature for air drying and calcining to obtain the honeycomb body coated with the base layer;
(3) Dip coating of the honeycomb connecting layer: preparing a connecting layer slurry, namely coating and covering the part, which is not required to be coated, of the honeycomb body coated with the base layer, obtained in the step (2) by using white glue, then drying, immersing the honeycomb body in the base layer slurry for 2-4min after drying, pulling up, throwing away excessive slurry, blowing through honeycomb pore canals to finish primary coating, immersing the honeycomb structure in the connecting layer slurry reversely for 2-4min, pulling up, throwing away excessive slurry, blowing through the honeycomb pore canals to finish secondary coating, and then placing the honeycomb structure at room temperature for air drying and calcining to obtain the honeycomb body coated with the connecting layer;
(4) Dip coating of honeycomb functional layers: and (3) configuring the functional layer slurry, coating and covering the part, which is not required to be coated, of the honeycomb body coated with the connecting layer, obtained in the step (3) by using white glue, then drying, immersing the honeycomb body in the basic layer slurry for 2-4min after drying, pulling up, throwing away excessive slurry, blowing through honeycomb pore channels to finish primary coating, immersing the honeycomb structure in the functional layer slurry reversely for 2-4min, pulling up, throwing away excessive slurry, blowing through the honeycomb pore channels, finishing secondary coating, and then placing the honeycomb structure in the air drying and calcining at room temperature to obtain the honeycomb body for purifying automobile exhaust.
7. The method for preparing a honeycomb body for purifying automobile exhaust according to claim 6, wherein the shaping process in the step (1) is as follows: heating to 60 ℃ at the speed of 1-2 ℃/min under the room temperature condition, then heating to 120 ℃ at the speed of 1-2 ℃/min after heat preservation for 1-3h, heating to 200 ℃ at the speed of 1-2 ℃/min after heat preservation for 1-3h, and naturally cooling to room temperature after heat preservation for 3-5 h;
the calcination process comprises the following steps: heating to 300 ℃ at the speed of 4-6 ℃/min under the room temperature condition, then heating to 600 ℃ at the speed of 4-6 ℃/min after heat preservation for 1-3h, heating to 900 ℃ at the speed of 4-6 ℃/min after heat preservation for 1-3h, heating to 1100 ℃ at the speed of 4-6 ℃/min after heat preservation for 1-3h, and naturally cooling to room temperature after heat preservation for 3-5 h.
8. The method for preparing a honeycomb body for automobile exhaust purification according to claim 6, wherein the calcination process in step (2) is: heating to 500 ℃ at the rate of 2-4 ℃/min under the room temperature condition, then heating to 1200 ℃ at the rate of 1-2 ℃/min after heat preservation for 1-3h, then heating to 1300-1400 ℃ at the rate of 1-2 ℃/min after heat preservation for 4-6h, then cooling to 1000 ℃ at the rate of 1-2 ℃/min after heat preservation for 6-8h, then cooling to 500 ℃ at the rate of 1-2 ℃/min after heat preservation for 1-3h, and finally naturally cooling to room temperature after heat preservation for 1-3 h.
9. The method for preparing a honeycomb body for automobile exhaust purification according to claim 6, wherein the calcination process in step (3) is as follows: heating to 500 ℃ at the rate of 2-4 ℃/min under the room temperature condition, then heating to 1200-1250 ℃ at the rate of 1-2 ℃/min after heat preservation for 1-3h, then cooling to 1000 ℃ at the rate of 1-2 ℃/min after heat preservation for 4-6h, then cooling to 500 ℃ at the rate of 1-2 ℃/min after heat preservation for 1-3h, and finally naturally cooling to room temperature after heat preservation for 3-5 h.
10. The method for preparing a honeycomb body for automobile exhaust purification according to claim 6, wherein the calcination process in step (4) is as follows: the calcination temperature is 900-1250 ℃ and the calcination time is 4-6h.
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|---|---|---|---|---|
| CN101745375A (en) * | 2008-12-15 | 2010-06-23 | 比亚迪股份有限公司 | Cerium zirconium aluminum based multiple oxide material and preparing method thereof |
| WO2019088302A1 (en) * | 2017-11-06 | 2019-05-09 | 新日本電工株式会社 | Oxygen absorbing and releasing material, catalyst, exhaust gas purifying system, and exhaust gas treatment method |
| CN109772165A (en) * | 2018-12-14 | 2019-05-21 | 深圳大学 | A kind of tail gas clean-up reactor and preparation method thereof reacts pile with tail gas clean-up |
| CN111962098A (en) * | 2020-08-17 | 2020-11-20 | 广东电网有限责任公司广州供电局 | Oxygen electrode slurry of solid oxide electrolytic cell, preparation method of oxygen electrode slurry and solid oxide electrolytic cell |
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| BR112020017344A2 (en) * | 2018-02-26 | 2020-12-15 | Basf Corporation | CATALYSTS, BACKGROUND TREATMENT CATALYST, CATALYST PREPARATION PROCESS, TREATMENT METHODS AND PURIFICATION SYSTEM |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101745375A (en) * | 2008-12-15 | 2010-06-23 | 比亚迪股份有限公司 | Cerium zirconium aluminum based multiple oxide material and preparing method thereof |
| WO2019088302A1 (en) * | 2017-11-06 | 2019-05-09 | 新日本電工株式会社 | Oxygen absorbing and releasing material, catalyst, exhaust gas purifying system, and exhaust gas treatment method |
| CN109772165A (en) * | 2018-12-14 | 2019-05-21 | 深圳大学 | A kind of tail gas clean-up reactor and preparation method thereof reacts pile with tail gas clean-up |
| CN111962098A (en) * | 2020-08-17 | 2020-11-20 | 广东电网有限责任公司广州供电局 | Oxygen electrode slurry of solid oxide electrolytic cell, preparation method of oxygen electrode slurry and solid oxide electrolytic cell |
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