CN105642297A - Method for coating surface of iolite with macro-porous perovskite oxide catalyst - Google Patents
Method for coating surface of iolite with macro-porous perovskite oxide catalyst Download PDFInfo
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- CN105642297A CN105642297A CN201511005821.5A CN201511005821A CN105642297A CN 105642297 A CN105642297 A CN 105642297A CN 201511005821 A CN201511005821 A CN 201511005821A CN 105642297 A CN105642297 A CN 105642297A
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- 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
- 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
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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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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- 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
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Abstract
The invention provides a method for coating the surface of iolite with a macro-porous perovskite oxide catalyst. The method comprises the following steps: 1, roasting iolite honeycomb ceramic, carrying out acid treatment, washing, and drying to obtain pretreated iolite; 2, dipping the pretreated iolite in alumina sol, carrying out vacuum drying, and roasting to obtain coating layer coated iolite; 3, dipping the coating layer coated iolite in a PMMA microsphere emulsion, and drying to obtain PMMA microspheres-iolite; and 4, dipping the PMMA microspheres-iolite in catalyst precursor sol, carrying out vacuum drying, and roasting to obtain an iolite filter with the surface coated with the macro-porous perovskite oxide catalyst.
Description
Technical field
The invention belongs to environmental protection field, it relates to a kind of by the method for macropore perovskite oxide catalyst-coated on trichroite surface.
Background technology
Improve the activity of soot particulate (PM) catalyst for clarifying of exhaust gas from diesel vehicle discharge, reduce the temperature of combustion of soot particulate, thus enable soot particulate trap long time continuous working, it is reduce the diesel emission the most direct method of soot particulate. One gas-solid (soot) due to the eliminative reaction of soot the deep oxidation reaction process of-(Gu catalyzer) three-phase complexity, the raising of catalyst activity is not only closely related with the redox property of oxide catalyst itself, simultaneously also closely related with the exposure level of solid catalyst and PM. The catalyzer of same active ingredient, more high with the engagement capacity of soot, activity is more good. But, due to the granularity relatively big (diameter of single soot particle is greater than 25nm) of soot particulate, it is difficult to enter in catalyzer or carrier micropore and reacts, even super large mesoporous molecular sieve (maximum diameter of hole is about 20nm), the diffusion of soot particulate also has certain resistance, soot particulate can only with the exterior surface of catalyzer, thus the utilization ratio making active surface area reduces greatly. Therefore macropore perovskite oxide catalyzer is prepared significant for diesel soot burning.
The effect applying macropore perovskite oxide catalyzer on the filter has two, and one is the already mentioned cyclic regeneration efficiency that can improve strainer above, thus the work making strainer long-time continuously; Another is then to play a role in filtering, the catalyzer applying macropore shape looks on strainer can form good reticulated structure at filter surfaces, as a filtering net can filtration of particulate matters well, play an effect filtered, thus improve the filtration efficiency of strainer.
Strainer applies macropore perovskite oxide catalyzer; for the temperature of combustion reducing carbon soot particles; improve cyclic regeneration ability and the filtration efficiency of strainer; reduce exhaust gas from diesel vehicle to pollute; protection of the environment is significant, is also one of this area problem demanding prompt solution, but the coating method of cordierite filters of the prior art existence coating difficulty is bigger; coating procedure is complicated, applies the problems such as the more difficult control in uniform and stable property aspect.
Summary of the invention
In view of the above problems, it is an object of the invention to provide a kind of by the method for macropore perovskite oxide catalyst-coated on trichroite surface, simultaneously, it is provided that a kind of macropore perovskite oxide catalyst filter.
In order to reach foregoing invention object, the present invention provide a kind of by macropore perovskite oxide catalyst-coated in the method on trichroite surface, comprise the following steps:
Step one: by cordierite honeycomb ceramic roasting, then carries out acid treatment, through washing, drying, obtains pretreated trichroite;
Step 2: described pretreated trichroite is put into Alumina gel dipping, then through vacuum-drying, roasting, obtains being coated with cated trichroite;
Step 3: cated for described painting trichroite is put into PMMA microsphere emulsion dipping, then through dry, obtains PMMA microsphere-trichroite;
Step 4: described PMMA microsphere-trichroite is put into catalyst precursor colloidal sol dipping, through vacuum-drying, roasting, obtains the cordierite filters that surface-coated has macropore perovskite oxide catalyzer.
In the above-mentioned methods, it is preferable that, the temperature rise rate of described roasting is 1 DEG C/min.
In the above-mentioned methods, it is preferable that, in described step 2, described pretreated trichroite is put into after Alumina gel floods and is at the uniform velocity proposed, and at the uniform velocity blows the Alumina gel of residual in the duct of described trichroite with air-flow.
In the above-mentioned methods, it is preferable that, in described step 3, the cated trichroite of described painting is put into after PMMA microsphere emulsion is flooded and is at the uniform velocity proposed, and at the uniform velocity blows the PMMA microsphere emulsion of residual in the duct of described trichroite with air-flow.
In the above-mentioned methods, preferably, in described step 4, described PMMA microsphere-trichroite is put into after catalyst precursor colloidal sol floods and is at the uniform velocity proposed, and the catalyst precursor colloidal sol of residual in the duct of described trichroite is at the uniform velocity blown with air-flow, then natural subsidence is air-dry.
In the above-mentioned methods, it is preferable that, the preparation process of described PMMA microsphere emulsion comprises:
MMA monomer and water are mixed, is heated to 60 DEG C-80 DEG C, then leads to into nitrogen degassed, obtain the first mixed solution;
Initiator is added in described first mixed solution, stop leading to into nitrogen, react 1-3 hour, obtain PMMA microsphere emulsion.
In aforesaid method, it is preferable that, described initiator comprises Potassium Persulphate; Described initiator comprises Potassium Persulphate; And the ratio of mixture of described MMA monomer, water and initiator is (50-100) ml:(150-400) ml:(0.3-1.2) g.
In the above-mentioned methods, it is preferable that, described nitrogen degassed time is within 2h.
The preparation method of above-mentioned PMMA microsphere emulsion can also be prepared by this area ordinary method.
In the above-mentioned methods, it is preferable that, the preparation process of described catalyst precursor colloidal sol comprises:
By KNO3, lanthanum nitrate, transition metal nitrate is by (0.1-0.5): (0.1-0.9): the mol ratio of 1 is dissolved in the solution comprising ethylene glycol complexing agent, methyl alcohol or ethanol co-solvent, forms catalyst precursor mixing solutions;
By described catalyst precursor mixing solutions at 50-80 DEG C hydrothermal treatment consists 2-4 hour, add dust technology and ammoniacal liquor regulates the pH value of described catalyst precursor mixing solutions to be 3-5 simultaneously; Hydrothermal treatment consists 4-10h at 30-60 DEG C, is then cooled to room temperature again, forms the catalyst precursor colloidal sol that viscosity under 5-80 DEG C of condition is 50-500cp.
In the above-mentioned methods, it is preferable that, described transition metal nitrate comprises any one in manganous nitrate, iron nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cupric nitrate, chromium nitrate, nickelous nitrate.
In the above-mentioned methods, it is preferable that, in step one, the temperature of described roasting is 500-1200 DEG C, and the time is 4-8h;The temperature of described drying is 90-150 DEG C, and the time is 4-12h;
In step 2, the time of described dipping is 1-3min, and number of times is 2-3 time; Described vacuum drying temperature is 50-150 DEG C, and the time is 4-12h; The temperature of described roasting is 450-850 DEG C, and the time is 4-8h;
In step 3, the time of described dipping is within 2min, and number of times is 1 time; The temperature of described drying is 40-80 DEG C, and the time is 8-16h;
In step 4, the time of described dipping is within 2min, and number of times is 3-5 time; Described vacuum drying temperature is 100-150 DEG C, and the time is 8-16h; The temperature of described roasting is 450-750 DEG C, and the time is 4-10h.
In the above-mentioned methods, it is preferable that, described acid-treated method is that described cordierite honeycomb ceramic is put into the dust technology that concentration is 5-20wt%, normal temperature closed processes 6-48h after baking.
In the above-mentioned methods, it is preferable that, the solid content of described Alumina gel is 10-50%, and pH value is 3-4, and when 5-80 DEG C, its viscosity is 50-500cp.
In the above-mentioned methods, it is preferable that, the measurement of described viscosity carries out all at ambient pressure.
In the above-mentioned methods, it is preferable that, the solid content of described PMMA microsphere emulsion is 5%-10%, PMMA microsphere single dispersing, and microsphere diameter is 100nm-1000nm.
In the above-mentioned methods, preferably, described PMMA microsphere emulsion can by regulating the consumption of the consumption of MMA monomer, Potassium Persulphate, stir time the rotating speed of stirring rod, temperature of reaction by the size controlling of PMMA microsphere within the scope of 100nm-1000nm, and the uniform particle diameter of PMMA microsphere.
In the above-mentioned methods, it is preferable that, described cordierite honeycomb ceramic be of a size of 5.66 inches �� 6 inches, porosity be 65%, BODY WITH SQUARE APERTURE 1mm �� 1mm.
In the above-mentioned methods, it is preferable that, described catalyzer is the catalyzer for diesel car tail gas refining.
The present invention also provides by above-mentioned arbitrary item by integral filters obtained for the method for macropore perovskite oxide catalyst-coated on trichroite surface, and wherein, described catalyzer is the perovskite oxide catalyzer of macroporous structure.
In addition, the present invention also provides the application of a kind of above-mentioned cordierite filters in diesel soot purification processes, and wherein, described diesel soot purification is treated to catalysis carbon-smoke combustion.
The method that macropore perovskite catalyst is coated in trichroite surface provided by the invention is simple, well macropore perovskite oxide catalyzer can be coated in cordierite filters surface by sol-gel-dip method, thus form regular macropore perovskite oxide catalyst filter, and this catalyzer is connected tight with this strainer. Owing to the activity of macropore perovskite oxide catalyzer is higher, soot catalyticcombustion temperature can be reduced very well, therefore the monoblock type cordierite filters of the macropore perovskite oxide catalyzer of the present invention has good diesel soot purification effect and good researching value. In addition, all solution in coating procedure can reuse, and effectively reduces production cost.
Accompanying drawing explanation
Figure 1A is LaFeO in embodiment 13The front scan Electronic Speculum figure that macropore shape looks perovskite oxide catalyzer applies on cordierite.
Figure 1B-Fig. 1 D is LaFeO in embodiment 13Cross-sectional scans Electronic Speculum figure under the different scales that macropore shape looks perovskite oxide catalyzer applies on cordierite.
Fig. 2 A is LaMnO in embodiment 23The front scan Electronic Speculum figure that macropore shape looks perovskite oxide catalyzer applies on cordierite.
Fig. 2 B-Fig. 2 D is LaMnO in embodiment 23Cross-sectional scans Electronic Speculum figure under the different scales that macropore shape looks perovskite oxide catalyzer applies on cordierite.
Fig. 3 A is LaKCoO in embodiment 33The front scan Electronic Speculum figure that macropore shape looks perovskite oxide catalyzer applies on cordierite.
Fig. 3 B-Fig. 3 D is LaKCoO in embodiment 33Cross-sectional scans Electronic Speculum figure under the different scales that macropore shape looks perovskite oxide catalyzer applies on cordierite.
Embodiment
In order to the technology feature to the present invention, object and useful effect have understanding clearly, the existing technical scheme to the present invention carries out following detailed explanation, but can not be interpreted as can the restriction of practical range to the present invention.
Embodiment 1
The present embodiment provides a kind of LaFeO3The method that macropore shape looks perovskite oxide catalyzer applies on cordierite, it comprises the following steps:
Step one: Vehicle element
To be of a size of 5.66 inches �� 6 inches, porosity be 65%, the lumpy cordierite honeycomb substrate of BODY WITH SQUARE APERTURE 1mm �� 1mm pottery 700-900 DEG C of roasting 8h, then it is the dust technology supersound process 20-120min of 5% by mass concentration, and carry out 24h closed processes at normal temperatures, it is washed with distilled water to neutrality subsequently, put into the dry 5h of thermostatic drying chamber of 120 DEG C again, obtain pretreated trichroite for subsequent use;
Step 2: the coating of Alumina gel coating
The Alumina gel dust technology that solid content is 20% is adjusted to pH value is 3-4, and controlling its viscosity under normal pressure 50 DEG C of conditions is 200cp, and it airtight is deposited; Above-mentioned pretreated trichroite is put into this Alumina gel and floods 1-3min, and at the uniform velocity propose under lift state with lifting instrument, it is proposed to after blow the residual aluminum colloidal sol in hole, trichroite road with blower, then use N2Uniform speed slow blows dry, repeats 2-3 time, then the vacuum drying oven putting into 120 DEG C dry 5h, subsequently 550 DEG C of constant temperature calcining 6h in retort furnace, obtains being coated with cated trichroite aluminium, and the temperature rise rate of this retort furnace is 1 DEG C/min;
Step 3: the preparation of PMMA microsphere emulsion
It is added in flask by the deionized water of 100gMMA monomer and 850ml distillation to stir, this flask is heated to 70 DEG C, then leads to into N2Carry out degassed, and this flask is heated to 75 DEG C, maintain 30min, obtain the first mixed solution;
2g Potassium Persulphate is dissolved in 50ml water, is then added in above-mentioned flask, stop logical N2, sustained reaction 1h at 75 DEG C, obtains the PMMA microsphere emulsion of single dispersing that solid content is 5%-10% and microspherulite diameter equal, and this PMMA microsphere particle size range is 100-1000nm;
Step 4: the coating of PMMA microsphere emulsion
The cated trichroite of painting obtained for step 2 is put into the homemade PMMA microsphere emulsion of step 3 flood 10s and at the uniform velocity propose under lift state with lifting instrument, blow the residual PMMA microsphere emulsion in hole, trichroite road with blower after proposition, put into 50 DEG C of thermostatic drying chamber dried overnight again, repeat 2-3 time, obtain PMMA microsphere-trichroite;
Step 5: the preparation of catalyst precursor colloidal sol
Lanthanum nitrate, iron nitrate are dissolved in the solution of ethylene glycol complexing agent, methyl alcohol or ethanol co-solvent by the mol ratio of 1:1, then solution glass stick are evenly stirred, be configured to catalyst precursor mixing solutions;
By this catalyst precursor solution 80 DEG C of heating in water bath, and continuously stirring 2-4h, in the process by dust technology and ammoniacal liquor adjust ph to 3, be then cooled to room temperature, form catalyst precursor colloidal sol, then at 60 DEG C hydrothermal treatment consists 4-6h;The viscosity regulating this catalyst precursor colloidal sol under normal pressure 50 DEG C of conditions is 235cp;
Step 6: the preparation of macropore perovskite oxide catalyzer
PMMA microsphere-cordierite carrier obtained for step 4 is put into the obtained catalyst precursor colloidal sol of step 5 flood 10s and at the uniform velocity propose under lift state with lifting instrument, it is proposed to after blow the colloidal sol of residual in hole, trichroite road with blower, then use N2Uniform speed slow blows dry, then places it in natural subsidence in semienclosed container air-dry, repeats 3-5 time, then puts into the vacuum drying oven dried overnight of 120 DEG C, subsequently 600 DEG C of constant temperature calcining 5h in retort furnace, and obtaining surface-coated has LaFeO3The perovskite oxide integral filters of macropore shape looks, the temperature rise rate of this retort furnace is 1 DEG C/min.
In the present embodiment, above-mentioned PMMA microsphere emulsion can by suitably regulating the consumption of the consumption of MMA monomer, Potassium Persulphate, stir time the rotating speed of stirring rod, temperature of reaction by the size controlling of PMMA microsphere within the scope of 100-1000nm.
In the present embodiment, surface-coated has LaFeO3The LaFeO that provided by the present embodiment of macropore shape looks perovskite oxide integral filters3Obtained by the method that macropore shape looks perovskite oxide catalyzer applies on cordierite. As shown in Figure 1A, LaFeO3After catalyzer applies on cordierite, form macropore shape looks cordierite filters regular, aperture equal. This LaFeO3Catalyzer is macropore perovskite oxide catalyzer. Please refer to Figure 1B-Fig. 1 D, LaFeO simultaneously3After catalyzer applies on cordierite, with this trichroite surface close adhesion, and surface regular equal.
Embodiment 2
The present embodiment provides a kind of LaMnO3The method that macropore shape looks perovskite oxide catalyzer applies on cordierite, it comprises the following steps:
Step one: Vehicle element
To be of a size of 5.66 inches �� 6 inches, porosity be 65%, the lumpy cordierite honeycomb substrate of BODY WITH SQUARE APERTURE 1mm �� 1mm pottery 700-900 DEG C of roasting 4-8h, then it is the dust technology supersound process 20-120min of 5% by mass concentration, and carry out 24h closed processes at normal temperatures, it is washed with distilled water to neutrality subsequently, put into the dry 5h of thermostatic drying chamber of 120 DEG C again, obtain pretreated trichroite for subsequent use;
Step 2: the coating of Alumina gel coating
The Alumina gel dust technology that solid content is 25% is adjusted to pH value is 3-4, and controlling its viscosity under normal pressure 10 DEG C of conditions is 50cp, and it airtight is deposited; Above-mentioned pretreated trichroite is put into this Alumina gel and floods 1-3min, and at the uniform velocity propose under lift state with lifting instrument, it is proposed to after blow the residual aluminum colloidal sol in hole, trichroite road with blower, then use N2Uniform speed slow blows dry, repeats 2-3 time, then the vacuum drying oven putting into 120 DEG C dry 5h, subsequently 550 DEG C of constant temperature calcining 6h in retort furnace, obtains being coated with cated trichroite aluminium, and the temperature rise rate of this retort furnace is 1 DEG C/min;
Step 3: the preparation of PMMA microsphere emulsion
It is added in flask by the deionized water of 100gMMA monomer and 850ml distillation to stir, this flask is heated to 70 DEG C, then leads to into N2Carry out degassed, and this flask is heated to 75 DEG C, maintain 30min, obtain the first mixed solution;
2g Potassium Persulphate is dissolved in 50ml water, is then added in above-mentioned flask, stop logical N2, sustained reaction 1h at 75 DEG C, obtains the PMMA microsphere emulsion of single dispersing that solid content is 5%-10% and microspherulite diameter equal, and this PMMA microsphere particle size range is 100-1000nm;
Step 4: the coating of PMMA microsphere emulsion
The cated trichroite of painting obtained for step 2 is put into the homemade PMMA microsphere emulsion of step 3 flood 10s and at the uniform velocity propose under lift state with lifting instrument, blow the residual PMMA microsphere emulsion in hole, trichroite road with blower after proposition, put into 50 DEG C of thermostatic drying chamber dried overnight again, repeat 2-3 time, obtain PMMA microsphere-trichroite;
Step 5: the preparation of catalyst precursor colloidal sol
Lanthanum nitrate, manganous nitrate are dissolved in the solution of ethylene glycol complexing agent, methyl alcohol or ethanol co-solvent by the mol ratio of 1:1, then solution glass stick are evenly stirred, be configured to catalyst precursor mixing solutions;
By this catalyst precursor solution 80 DEG C of heating in water bath, and continuously stirring 2-4h, in the process by dust technology and ammoniacal liquor adjust ph to 3-4, be then cooled to room temperature, form catalyst precursor colloidal sol, then at 60 DEG C hydrothermal treatment consists 4-6h; The viscosity regulating this catalyst precursor colloidal sol under normal pressure 10 DEG C of conditions is 400cp;
Step 6: the preparation of macropore perovskite oxide catalyzer
PMMA microsphere-cordierite carrier obtained for step 4 is put into the obtained catalyst precursor colloidal sol of step 5 flood 10s and at the uniform velocity propose under lift state with lifting instrument, it is proposed to after blow the colloidal sol of residual in hole, trichroite road with blower, then use N2Uniform speed slow blows dry, then places it in natural subsidence in semienclosed container air-dry, repeats 3-5 time, then puts into the vacuum drying oven dried overnight of 120 DEG C, subsequently 600 DEG C of constant temperature calcining 5h in retort furnace, and obtaining surface-coated has LaMnO3The perovskite oxide integral filters of macropore shape looks, the temperature rise rate of this retort furnace is 1 DEG C/min.
In the present embodiment, above-mentioned PMMA microsphere emulsion can by suitably regulating the consumption of the consumption of MMA monomer, Potassium Persulphate, stir time the rotating speed of stirring rod, temperature of reaction by the size controlling of PMMA microsphere within the scope of 100-1000nm.
In the present embodiment, surface-coated has LaMnO3The LaMnO that provided by the present embodiment of the perovskite oxide integral filters of macropore shape looks3Obtained by the method that macropore shape looks perovskite oxide catalyzer applies on cordierite. As shown in Figure 2 A, LaMnO3After catalyzer applies on cordierite, form macropore shape looks perovskite oxide integral filter device regular, aperture equal. This LaMnO3Catalyzer is macropore perovskite oxide catalyzer. Please refer to Fig. 2 B-Fig. 2 D, LaMnO simultaneously3After catalyzer applies on cordierite, with this trichroite surface close adhesion, and surface regular equal.
Embodiment 3
The present embodiment provides a kind of LaKCoO3The method that macropore shape looks perovskite oxide catalyzer applies on cordierite, it comprises the following steps:
Step one: Vehicle element
To be of a size of 5.66 inches �� 6 inches, porosity be 65%, the lumpy cordierite honeycomb substrate of BODY WITH SQUARE APERTURE 1mm �� 1mm pottery 700-900 DEG C of roasting 4-8h, then it is the dust technology supersound process 20-120min of 5% by mass concentration, and carry out 24h closed processes at normal temperatures, it is washed with distilled water to neutrality subsequently, put into the dry 5h of thermostatic drying chamber of 120 DEG C again, obtain pretreated trichroite for subsequent use;
Step 2: the coating of Alumina gel coating
The Alumina gel dust technology that solid content is 20% is adjusted to pH value is 3-4, and controlling its viscosity under normal pressure 60 DEG C of conditions is 400cp, it airtight is deposited;Above-mentioned pretreated trichroite is put into this Alumina gel and floods 1-3min, and at the uniform velocity propose under lift state with lifting instrument, it is proposed to after blow the residual aluminum colloidal sol in hole, trichroite road with blower, then use N2Uniform speed slow blows dry, repeats 2-3 time, then the vacuum drying oven putting into 120 DEG C dry 5h, subsequently 550 DEG C of constant temperature calcining 6h in retort furnace, obtains being coated with cated trichroite aluminium, and the temperature rise rate of this retort furnace is 1 DEG C/min;
Step 3: the preparation of PMMA microsphere emulsion
It is added in flask by the deionized water of 100gMMA monomer and 850ml distillation to stir, this flask is heated to 70 DEG C, then leads to into N2Carry out degassed, and this flask is heated to 75 DEG C, maintain 30min, obtain the first mixed solution;
2g Potassium Persulphate is dissolved in 50ml water, is then added in above-mentioned flask, stop logical N2, sustained reaction 1h at 75 DEG C, obtains the PMMA microsphere emulsion of single dispersing that solid content is 5%-10% and microspherulite diameter equal, and this PMMA microsphere particle size range is 100-1000nm;
Step 4: the coating of PMMA microsphere emulsion
The cated trichroite of painting obtained for step 2 is put into the homemade PMMA microsphere emulsion of step 3 flood 10s and at the uniform velocity propose under lift state with lifting instrument, blow the residual PMMA microsphere emulsion in hole, trichroite road with blower after proposition, put into 50 DEG C of thermostatic drying chamber dried overnight again, repeat 2-3 time, obtain PMMA microsphere-trichroite;
Step 5: the preparation of catalyst precursor colloidal sol
Lanthanum nitrate, saltpetre, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES are dissolved in the solution of ethylene glycol complexing agent, methyl alcohol or ethanol co-solvent by the mol ratio of 0.9:0.1:1, then solution glass stick are evenly stirred, be configured to catalyst precursor mixing solutions;
By this catalyst precursor solution 80 DEG C of heating in water bath, and continuously stirring 2-4h, in the process by dust technology and ammoniacal liquor adjust ph to 3-5, be then cooled to room temperature, form catalyst precursor colloidal sol, then at 60 DEG C hydrothermal treatment consists 4-8h; The viscosity regulating this catalyst precursor colloidal sol under normal pressure 30 DEG C of conditions is 200cp;
Step 6: the preparation of macropore perovskite oxide catalyzer
PMMA microsphere-cordierite carrier obtained for step 4 is put into the obtained catalyst precursor colloidal sol of step 5 flood 10s and at the uniform velocity propose under lift state with lifting instrument, it is proposed to after blow the colloidal sol of residual in hole, trichroite road with blower, then use N2Uniform speed slow blows dry, then places it in natural subsidence in semienclosed container air-dry, repeats 3-5 time, then puts into the vacuum drying oven dried overnight of 120 DEG C, subsequently 600 DEG C of constant temperature calcining 5h in retort furnace, and obtaining surface-coated has LaKCoO3The perovskite oxide integral filters of macropore shape looks, the temperature rise rate of this retort furnace is 1 DEG C/min.
In the present embodiment, above-mentioned PMMA microsphere emulsion can by suitably regulating the consumption of the consumption of MMA monomer, Potassium Persulphate, stir time the rotating speed of stirring rod, temperature of reaction by the size controlling of PMMA microsphere within the scope of 100-1000nm.
Surface-coated in the present embodiment has LaKCoO3The LaKCoO that provided by the present embodiment of the perovskite oxide catalyzer integral filters of macropore shape looks3Obtained by the method that macropore shape looks perovskite oxide catalyzer applies on cordierite. As shown in Figure 3A, LaKCoO3After catalyzer applies on cordierite, form macropore shape looks cordierite filters regular, aperture equal.This LaKCoO3Catalyzer is the perovskite oxide catalyzer of macroporous structure. Please refer to Fig. 3 B-Fig. 3 D, LaKCoO simultaneously3After catalyzer applies on cordierite, with this trichroite surface close adhesion, and surface regular equal.
In sum, embodiment 1-3 is first by cordierite honeycomb ceramic carrier high-temperature roasting and dilute nitric acid solution pre-treatment, and uses ultrasonic oscillation instrument to carry out ultrasonic oscillation certain time, after distilled water wash is clean, is placed on thermostatic drying chamber inner drying; Then pretreated trichroite is put into the Alumina gel dipping good with pre-treatment, dipping final vacuum loft drier inner drying, high-temperature roasting in retort furnace; Next is impregnated into by the trichroite scribbling Alumina gel in the good microballoon emulsion of pre-treatment, cryodrying; Finally the trichroite scribbling microballoon emulsion is immersed in catalyst precursor colloidal sol and floods completely, dry in vacuum drying oven after dipping, and high-temperature roasting in retort furnace, finally obtain and it is supported with macropore perovskite oxide catalyzer integral filters, and all solution used in preparation process can reuse. It thus is seen that the method that the present invention adopts is simple, effectively reduce use cost.
Claims (10)
1., by macropore perovskite oxide catalyst-coated in the method on trichroite surface, comprise the following steps:
Step one: by cordierite honeycomb ceramic roasting, then carries out acid treatment, through washing, drying, obtains pretreated trichroite;
Step 2: described pretreated trichroite is put into Alumina gel dipping, then through vacuum-drying, roasting, obtains being coated with cated trichroite;
Step 3: cated for described painting trichroite is put into PMMA microsphere emulsion dipping, then through dry, obtains PMMA microsphere-trichroite;
Step 4: described PMMA microsphere-trichroite is put into catalyst precursor colloidal sol dipping, through vacuum-drying, roasting, obtains the cordierite filters that surface-coated has macropore perovskite oxide catalyzer.
2. method according to claim 1, it is characterised in that, the preparation process of described PMMA microsphere emulsion comprises:
MMA monomer and water are mixed, is heated to 60 DEG C-80 DEG C, then leads to into nitrogen degassed, obtain the first mixed solution;
Initiator is added in described first mixed solution, stop leading to into nitrogen, react 1-3 hour, obtain PMMA microsphere emulsion.
3. method according to claim 2, it is characterised in that, described initiator comprises Potassium Persulphate; And the ratio of mixture of described MMA monomer, water and initiator is (50-100) ml:(150-400) ml:(0.3-1.2) g.
4. method according to the arbitrary item of claim 1-3, it is characterised in that, the preparation process of described catalyst precursor colloidal sol comprises:
By KNO3, lanthanum nitrate, transition metal nitrate is by (0.1-0.5): (0.1-0.9): the mol ratio of 1 is dissolved in the solution comprising ethylene glycol complexing agent, methyl alcohol or ethanol co-solvent, forms catalyst precursor mixing solutions;
By described catalyst precursor mixing solutions at 50-80 DEG C hydrothermal treatment consists 2-4 hour, add dust technology and ammoniacal liquor regulates the pH value of described catalyst precursor mixing solutions to be 3-5 simultaneously; Hydrothermal treatment consists 4-10h at 30-60 DEG C, is then cooled to room temperature again, forms the catalyst precursor colloidal sol that viscosity under 5-80 DEG C of condition is 50-500cp.
5. the method stated according to claim 4, it is characterised in that, described transition metal nitrate comprises any one in manganous nitrate, iron nitrate, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cupric nitrate, chromium nitrate, nickelous nitrate.
6. method according to the arbitrary item of claim 1-5, it is characterised in that,
In step one, the temperature of described roasting is 500-1200 DEG C, and the time is 4-8h;The temperature of described drying is 90-150 DEG C, and the time is 4-12h;
In step 2, the time of described dipping is 1-3min, and number of times is 2-3 time; Described vacuum drying temperature is 50-150 DEG C, and the time is 4-12h; The temperature of described roasting is 450-850 DEG C, and the time is 4-8h;
In step 3, the time of described dipping is within 2min, and number of times is 1 time; The temperature of described drying is 40-80 DEG C, and the time is 8-16h;
In step 4, the time of described dipping is within 2min, and number of times is 3-5 time; Described vacuum drying temperature is 100-150 DEG C, and the time is 8-16h; The temperature of described roasting is 450-750 DEG C, and the time is 4-10h.
7. method according to the arbitrary item of claim 1-6, it is characterised in that, described acid-treated method is that described cordierite honeycomb ceramic is put into the dust technology that concentration is 5-20wt%, normal temperature closed processes 6-48h after baking.
8. method according to the arbitrary item of claim 1-7, it is characterised in that, the solid content of described Alumina gel is 10-50%, and pH value is 3-4, and when 5-80 DEG C, its viscosity is 50-500cp.
9. method according to claim 1 and 2, it is characterised in that, the solid content of described PMMA microsphere emulsion is 5%-10%, PMMA microsphere single dispersing, and microsphere diameter is 100nm-1000nm.
10. one kind by the integral filters that the method for macropore perovskite oxide catalyst-coated on trichroite surface is obtained described in the arbitrary item of claim 1-9, it is characterised in that, described catalyzer is the perovskite oxide catalyzer of macroporous structure.
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