CN101913912A - Method for coating cordierite honeycomb - Google Patents
Method for coating cordierite honeycomb Download PDFInfo
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- CN101913912A CN101913912A CN2010102192991A CN201010219299A CN101913912A CN 101913912 A CN101913912 A CN 101913912A CN 2010102192991 A CN2010102192991 A CN 2010102192991A CN 201010219299 A CN201010219299 A CN 201010219299A CN 101913912 A CN101913912 A CN 101913912A
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- CN
- China
- Prior art keywords
- coating
- cordierite honeycomb
- active
- honeycomb
- cordierite
- Prior art date
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- Granted
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 107
- 229910052878 cordierite Inorganic materials 0.000 title claims abstract description 102
- 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 title claims abstract description 102
- 239000011248 coating agent Substances 0.000 title claims abstract description 80
- 238000000034 method Methods 0.000 title claims abstract description 33
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000002134 carbon nanofiber Substances 0.000 claims abstract description 50
- 239000002002 slurry Substances 0.000 claims abstract description 33
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- 238000002791 soaking Methods 0.000 claims abstract description 3
- 239000011148 porous material Substances 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 17
- 238000009826 distribution Methods 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000012266 salt solution Substances 0.000 claims description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 4
- 238000004134 energy conservation Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910001679 gibbsite Inorganic materials 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 241000264877 Hippospongia communis Species 0.000 claims 15
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000919 ceramic Substances 0.000 description 20
- 239000007789 gas Substances 0.000 description 19
- 238000002360 preparation method Methods 0.000 description 16
- 238000004458 analytical method Methods 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000011268 mixed slurry Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000037396 body weight Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000004050 hot filament vapor deposition Methods 0.000 description 3
- 229910021392 nanocarbon Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000007613 slurry method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000007084 catalytic combustion reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- OHBTULDTCSOWOY-UHFFFAOYSA-N [C].C=C Chemical compound [C].C=C OHBTULDTCSOWOY-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910001648 diaspore Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010433 feldspar Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention discloses a method for coating a cordierite honeycomb. The method comprises the following steps of: (1) contacting the cordierite honeycomb stained with metal salt with a carbonic gas source at the temperature of between 400 and 800 DEG C for 0.5 to 12 hours to obtain the cordierite honeycomb on which carbon nanofiber is grown; (2) soaking the cordierite honeycomb on which the carbon nanofiber is grown and which is obtained in the step (1) into active aluminum oxide (Al2O3)-containing slurry for 10 to 60 minutes to obtain the cordierite honeycomb on which the carbon nanofiber is grown and the Al2O3-containing slurry is coated; and (3) baking the cordierite honeycomb on which the carbon nanofiber is grown and the Al2O3-containing slurry is coated and which is obtained in the step (2) at the temperature of between 400 and 800 DEG C for 2 to 10 hours to obtain the cordierite honeycomb with an active Al2O3 coating.
Description
Technical field
The invention belongs to material and make the field, be specifically related to a kind of coating process and technology of cordierite honeycomb.
Background technology
Trichroite (2MgO2Al
2O
35SiO
2) be a kind of stupalith, be that the honeycomb of matrix preparation has physical strength height, pressure and falls that little (fluid is little through out-of-date honeycomb two ends pressure reduction with the trichroite, mean that power waste is little), characteristics such as low, the Heat stability is good of thermal expansivity, be widely used in filtering, the chemical industry and the environmental protection fields such as catalytic purification of heat exchange, energy-conservation, vehicle exhaust and plant gas.The very little (＜1m of its specific surface area but
2/ g), and generally need be in the coating of honeycomb channel surface-coated one deck bigger serface, to increase itself and effective contact area of the medium of being handled.Active A l
2O
3Enrich and stable performance in, source big because of specific surface area, becomes the first-selection of ceramic honeycomb body coating.Pickling process and slurry method are two kinds and are commonly used in coating active A l on the ceramic honeycomb
2O
3Method: the former is immersed in ceramic honeycomb in aluminum soluble salt or the aluminium colloidal sol, changes active A l into through aftertreatment
2O
3Coating; The latter will contain active A l
2O
3The slurry of powder directly soaks or sprays on the honeycomb channel wall, promptly forms coating after the thermal treatment.According to the application requiring of cordierite honeycomb bodies, need to select different preparation technology of coating in different field.An Qin etc. are at " ceramic honeycomb carrier γ-Al
2O
3The coating progress " in (chemistry circular, the 3rd phase of calendar year 2001 135-140 page or leaf) literary composition, commented ceramic honeycomb carrier active A l
2O
3The progress of coating is thought when ceramic honeycomb carrier is used as the structural support of catalyzer active A l
2O
3The Surface Physical Chemistry property effect of coating the dispersion state of active ingredient on coating, and the carrying out smoothly of catalyzed reaction, so the preparation technology of coating is very crucial.
No matter the coating process of traditional ceramic honeycomb carrier is pickling process or slurry method, all is that ceramic honeycomb carrier directly is immersed in the coating precursor of colloidal sol shape or pulp-like, and what obtain at last all is the closely knit coating of structure.Disclosing a kind of as Chinese patent CN101653730 is the preparation method of the three-way catalyst of carrier with the cordierite honeycomb, and its floating coat slurries are direct impregnation or disposable being coated on the cordierite honeycomb substrate.Chinese patent CN1814568 discloses a kind of preparation of NZP family coating-honeycomb cordierite ceramic composite carrier, coating colloidal sol also be at normal temperatures directly dip-coating on honeycomb cordierite ceramic, formed complex carrier at last.The coating particles that these coating processes obtain at last irregularly is deposited on the channel surface of ceramic honeycomb carrier usually, the fluid channel of larger aperture is less and irregular in the coating, be unfavorable for the fluidic rapid diffusion, also be unfavorable for making full use of of coating inner surface.
Therefore, this area presses for the coating process that a kind of new cordierite honeycomb carrier is provided.
Summary of the invention
The present invention aims to provide a kind of coating process of new cordierite honeycomb carrier.
In a first aspect of the present invention, a kind of coating process of cordierite honeycomb is provided, described method comprises step:
(1) cordierite honeycomb that will speckle with metal-salt contacts 0.5-12 hour at 400-800 ℃ with the carbon containing source of the gas, and obtaining growing has the cordierite honeycomb of carbon nano fiber;
(2) growth that step (1) is obtained has the cordierite honeycomb of carbon nano fiber to be immersed in to contain active A l
2O
3Slurry in 10-60 minute, obtain the growth carbon nano fiber is arranged and is coated with active A l
2O
3The cordierite honeycomb of slurry; With
(3) growth that step (2) is obtained has carbon nano fiber and is coated with active A l
2O
3The cordierite honeycomb of slurry obtained active A l at 400-800 ℃ of roasting 2-10 hour
2O
3The cordierite honeycomb of coating.
Metal-salt described in the step (1) is selected from nitrate, halogeno salt or vitriol, and described metal is selected from nickel, iron, cobalt or copper; Carbon containing source of the gas described in the step (1) is selected from ethene, ethane, methane or carbon monoxide.
Contain active A l described in the step (2)
2O
3Slurry in active A l
2O
3Solid content is 25-45wt%; Described active A l
2O
3Presoma be selected from the mixing of following one or more: pseudo-boehmite powder, gibbsite powder and Virahol aluminium powder.
The cordierite honeycomb that speckles with metal-salt described in the step (1) is by soaking acquisition in 0.5-24 hour with cordierite honeycomb in metal salt solution, in the gross weight of described metal salt solution, metal salt concentrations wherein is 0.1-5wt%.
In a second aspect of the present invention, provide a kind of active A l that has
2O
3The cordierite honeycomb of coating, in the gross weight of described coating honeycomb, active A l wherein
2O
3The weight percent of coating is 5-30wt%; Described active A l
2O
3The aperture of coating is 2-100nm; Described active A l
2O
3The pore size distribution of coating is two peak structure, and major bore is 2-10nm, and inferior aperture is 10-100nm.
In another preference, the active A l in the cordierite honeycomb provided by the invention
2O
3Coating is by obtaining as above-mentioned coating process provided by the invention.
In a third aspect of the present invention, provide a kind of aforesaid active A l that has provided by the invention
2O
3The purposes of the cordierite honeycomb of coating is as the carrier of catalyzer; The carrier of described catalyzer is used for heat exchange, energy-conservation, vehicle exhaust is handled or plant gas is handled.
In view of the above, the invention provides a kind of coating process of new cordierite honeycomb carrier.
Description of drawings
Fig. 1 has shown that cordierite honeycomb, growth have the cordierite honeycomb of carbon nano fiber and active A l is arranged
2O
3The outward appearance of the cordierite honeycomb of coating; Wherein
A is a cordierite honeycomb, and B is the cordierite honeycomb that growth has carbon nano fiber, and C has active A l
2O
3The cordierite honeycomb of coating.
Fig. 2 has shown the pore size distribution situation of the coating honeycomb that embodiment 1,2,3 obtains respectively; Wherein X-coordinate is aperture d (nm of unit), and ordinate zou is dV/dlog (the d) (cm of unit
3/ (gnm)), physics meaning is: gas adsorption amount (pore volume) increases Δ V when the aperture increases Δ d, and d maps to d with Δ V/ Δ, is pore distribution curve.
Embodiment
The research prompting that the contriver is extensive and deep, by the catalytic chemical vapor deposition technique growing nano carbon fiber, coating contains active A l then on cordierite honeycomb
2O
3Slurry, remove carbon nano fiber again, thereby obtain a kind of active A l that has
2O
3The cordierite honeycomb of coating, Al wherein
2O
3The aperture of coating is in the mesopore scope, distributing is two peak structure, and this technology makes pore size controlled, is a kind of brand-new preparation thinking.
As used herein, " cordierite honeycomb " or " cordierite honeycomb carrier " all is meant a kind of with trichroite (2MgO2Al
2O
35SiO
2) be the ceramic structure of principal crystalline phase, the cellular passage of tool, the structure shape has right cylinder, spheroid, cubes, and that channel architecture has is square, trilateral, circle etc., and the quantity of unit cross section upper channel is defined as hole density, is generally 200-600 hole number/inch
2(cpsi), can use the ceramic process manufacturing of this area routine, such as but not limited to, be that main raw material makes with general ceramic process with talcum, clay, aluminum oxide, feldspar etc.Also can obtain by the commercial channel, such as but not limited to, the product of the loyal brightness pottery in Suzhou company limited.The preferred cordierite honeycomb of the present invention (or claim cordierite honeycomb carrier) is meant the structure that forms with the cordierite ceramic sintering with integral honeycomb shape passage well known in the art, is right cylinder, and channel architecture is square, and hole density is 300cpsi.
As used herein, " carrier " is meant the structure that is used for supporting, disperseing other material, support of the catalyst as known in the art.In the present invention, " coating honeycomb " is meant and supports and be dispersed with active A l
2O
3The cordierite honeycomb of coating.
As used herein, " carbon nano fiber " is meant that a kind of diameter is 5-350nm, and length is the nano-carbon material with filamentary structure that 1 μ m-1mm does not wait.Can adopt method well known in the art preparation, be the catalytic chemical vapor deposition technique preparation in the Chinese patent of CN1793451 such as but not limited to, publication number, and catalyzer can adopt monometallic or alloys such as Fe, Co, Ni; The carbon containing source of the gas can adopt CO, CH
4, C
2H
4Deng, carbon nano fiber catalytic growth temperature is 500-800 ℃.Adopt different metal catalysts, be used different carbon containing sources of the gas, can obtain the carbon nano fiber of different structure size, as carbon nanofibers, tubular type carbon nano fiber or fish-bone carbon nano fiber.
As used herein, " active A l
2O
3Slurry " and " contain active A l
2O
3The slurry of powder " all be meant active A l
2O
3The mixing solutions that powder and water form.Described active A l
2O
3Powder is with following one or more blended active As l
2O
3Form after the presoma dehydration of powder or the hydrolysis: pseudo-boehmite powder (diaspore powder), gibbsite powder and Virahol aluminium powder; More preferably, dehydration or hydrolysis are after form active A l after 400-800 ℃ of roasting
2O
3Powder.
As used herein, " pore size distribution analysis " is meant the process of using pore size distribution determinator (for example, the ASAP-2010 type pore size distribution determinator of Micromeritics Instrument Corp. U.S.A's production) that pore size distribution is measured." pore size distribution " is meant the different apertures at different levels of pore volume increasing degree under the unit aperture that exists in the material.As promptly having shown the pore size distribution curve of the coating honeycomb that is obtained among the embodiment in the accompanying drawing 2, its ordinate zou has promptly been expressed the variation of pore volume under the unit aperture." major bore " is meant the pairing aperture of peak-peak in the pore size distribution curve, i.e. the aperture of the pore volume increasing degree maximum under the unit aperture.Volume increasing degree under " inferior aperture " unit of being meant aperture time big aperture.
The coating process of cordierite honeycomb
The invention provides a kind of coating process of cordierite honeycomb, described method comprises step:
(1) cordierite honeycomb that will speckle with metal-salt contacts 0.5-12 hour at 400-800 ℃ with the carbon containing source of the gas, and obtaining growing has the cordierite honeycomb of carbon nano fiber;
(2) growth that step (1) is obtained has the cordierite honeycomb of carbon nano fiber to be immersed in to contain active A l
2O
3Slurry in 10-60 minute, obtain the growth carbon nano fiber is arranged and is coated with active A l
2O
3The cordierite honeycomb of slurry; With
(3) growth that step (2) is obtained has carbon nano fiber and is coated with active A l
2O
3The cordierite honeycomb of slurry obtained active A l at 400-800 ℃ of roasting 2-10 hour
2O
3The cordierite honeycomb of coating.
The cordierite honeycomb that speckles with metal-salt in the described coating process obtains by cordierite honeycomb is soaked 0.5-24 hour (preferred 3-6 hour) in metal salt solution, and in the gross weight of described metal salt solution, metal salt concentrations wherein is 0.1-5wt%.Preferably, the cordierite ceramic that speckles with metal-salt in the described coating process is the cordierite ceramic that exsiccant speckles with metal-salt, is to take out to dry, dry (100-140 ℃ preferably is 120 ℃) and obtain after immersion.
Preferably, in the step (1), the cordierite ceramic that exsiccant is speckled with metal-salt contacts 0.5-12 hour with the carbon containing source of the gas at 400-800 ℃ (more preferably being 1-4 hour) in a process furnace, carry out catalytic growth, at N
2Or be cooled to room temperature in the rare gas element (being selected from He or Ar), obtaining growing has the cordierite ceramic of carbon nano fiber.
The growth that step (1) can be obtained in the step (2) has the cordierite honeycomb of carbon nano fiber to be immersed in to contain active A l
2O
3Slurry in 10-60 minute (preferred 15-45 minute), take out remove unnecessary slurry after, in baking oven dry 12 hours, oven temperature was 120 ℃.
The temperature rise rate that roasting in the step (3) can 0.5-5 ℃/minute (preferred 1-3 ℃/minute) rises to 400-800 ℃ (preferred 500-700 ℃) with temperature and stablize 2-10 hour (preferably 4-8 hour), thereby removes carbon nano fiber, only retentive activity Al
2O
3Be coated on the cordierite honeycomb passage.Described roasting can be carried out in retort furnace.
In a preference of the present invention, the coating process following steps of described cordierite honeycomb:
(1) on the cordierite ceramic honeycomb carrier, by the catalytic chemical vapor deposition technique growing nano carbon fiber: the concentration that commercially available cordierite honeycomb is immersed in 2000ml is 0.5-24 hour (preferred 3-6 hour) in the metal salt solution of 0.1wt%-5wt%, dry after the taking-up, 120 ℃ of oven dry; In the carbon nano fiber growth furnace of packing into then, feed the carbon containing source of the gas, carry out catalytic growth at 600 ℃, the time is 0.5-12 hour (preferred 1-4 hour); Behind the growth ending at N
2Or cool off in the inert atmosphere such as Ar;
(2) contain active A l according to the disclosed mixed slurry method preparation of document (Chen Chunbo etc., the preparation of the high firmness cordierite honeycomb of large specific surface coating, Industrial Catalysis, 2010 the 3rd phase 40-45 pages or leaves)
2O
3Slurry, active A l in the slurry
2O
3Solid content is 25-45wt%; The growth that step (1) is obtained has the cordierite honeycomb carrier of carbon nano fiber, is immersed in the above-mentioned slurry, and the time is 10-60 minute (preferred 15-45 minute), takes out the back and blows down growth with air cannon and carbon nano fiber is arranged and be coated with active A l
2O
3Unnecessary slurry in the cordierite honeycomb of slurry, in 120 ℃ of baking ovens dry 12 hours then;
(3) growth that the follow procedure intensification obtains step (2) in the retort furnace air atmosphere has carbon nano fiber and is coated with active A l
2O
3The cordierite honeycomb of slurry carries out roasting, temperature rise rate is 0.5-5 ℃/minute (preferred 1-3 a ℃/minute), stablize 2-10 hour (preferred 4-8 hour) to 400-800 ℃ (preferred 500-700 ℃), in this stage, carbon nano fiber is oxidized to carbonic acid gas gradually and removes, stay more regular pore, the duct undersized is in intermediate pore size scope (2-100nm) in the scantlings of the structure of carbon nano fiber; Promptly obtained active A l after the cooling
2O
3The cordierite honeycomb of coating, Al
2O
3It is 5-30% that coating wt accounts for the cordierite honeycomb gross weight.
In method provided by the invention, described metal-salt includes but not limited to nitrate, halogeno salt and vitriol; Described metal includes but not limited to nickel, iron, cobalt and copper; Described metal salt solution includes but not limited to the aqueous solution, ethanolic soln and ethylene glycol solution.
In method provided by the invention, described metal salt solution concentration, the gross weight in described metal salt solution is 0.1-5wt%, preferred 0.5-2.5wt%.
Described carbon containing source of the gas is such as but not limited to ethene, ethane, methane and carbon monoxide.
The cordierite honeycomb coating process
The coating process of cordierite honeycomb provided by the invention also is simultaneously a kind of coating process of new cordierite honeycomb.
The coating honeycomb
The coating honeycomb for preparing by coating process provided by the invention, in its gross weight, active A l wherein
2O
3The weight percent of coating is 5-30wt%; Described active A l
2O
3The aperture of coating is in mesopore scope (2-100nm).
The via hole diameter distributional analysis, active A l in the coating honeycomb provided by the invention
2O
3The duct of coating is two peak structure, and major bore is 2-10nm, and inferior aperture is 10-100nm.
The purposes of coating honeycomb
The carrier of the coating honeycomb useful as catalysts for preparing by coating process provided by the invention.During the described coating honeycomb that contains catalyzer can be used for heat exchange, energy-conservation, vehicle exhaust is handled or plant gas handles.
The above-mentioned feature that the present invention mentions, or the feature that embodiment mentions can arbitrary combination.All features that this case specification sheets is disclosed can with any composition forms and usefulness, each feature that is disclosed in the specification sheets can anyly provide the alternative characteristics of identical, impartial or similar purpose to replace.Therefore removing has special instruction, and the feature that is disclosed only is the general example of equalization or similar features.
Major advantage of the present invention is:
1, adopts coating process method of the present invention, Al
2O
3Exist in the middle of the coating pore that two peak structure distributes and aperture in the mesopore scope, help fluidic and transmit fast, help making full use of of coating inner surface, also help improving application process efficient.
2, coating process method provided by the invention, process is simple, operation, and the size adjustable of pore easily.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example is usually according to the normal condition or the condition of advising according to manufacturer.Unless otherwise indicated, otherwise all percentage ratio, ratio, ratio or umber by weight.
Unit in the percent weight in volume among the present invention is well-known to those skilled in the art, for example is meant the weight of solute in 100 milliliters solution.
Unless otherwise defined, the same meaning that employed all specialties and scientific words and one skilled in the art are familiar with in the literary composition.In addition, any method similar or impartial to described content and material all can be applicable in the inventive method.The usefulness that preferable implementation method described in the literary composition and material only present a demonstration.
The aperture distributional analysis is to use the pore size distribution determining instrument available from the ASAP2010 type of U.S. Merck ﹠ Co., Inc to carry out in the embodiment of the invention, and measuring method is the cryogenic nitrogen physical adsorption.
Cordierite honeycomb bodies in the embodiment of the invention is available from the loyal brightness pottery in Suzhou company limited.
Active A l in the embodiment of the invention
2O
3Powder raw material is available from Shandong Aluminum company limited.
Embodiment 1
Preparation coating honeycomb 1
Getting commercially available hole density is the cordierite honeycomb bodies of 300cpsi, is of a size of φ 100mm * 150mm, and density is 0.6g/ml, is immersed in the 1.0wt% nickel nitrate aqueous solution of 2000ml 2 hours, dries after the taking-up, 120 ℃ of oven dry.In the carbon nano fiber growth furnace of then the honeycomb sample that obtains being packed into, feed ethene carbon containing source of the gas, carry out catalytic growth at 600 ℃, the time is 1h.In inert atmosphere, cool off behind the growth ending.Analysis obtains, 1.5% of the white cordierite honeycomb body weight of weight duty of the carbon nano fiber that grows, and the mean diameter of carbon nano fiber is 30nm.Next prepare solid content and be 35% contain active A l
2O
3Mixed slurry, again growth is had the cordierite honeycomb carrier of carbon nano fiber to be immersed in the above-mentioned slurry, the time is 30min, takes out the back and blows down unnecessary slurry in the honeycomb sample, dry 12h in 120 ℃ of baking ovens then with air cannon.The honeycomb sample that obtains is placed in the air atmosphere of retort furnace, and follow procedure heats up and carries out roasting, and temperature rise rate is 2 ℃/min, to 600 ℃ of stable 8h.Promptly obtain being covered with active A l after the cooling
2O
3The cordierite honeycomb 1 of coating, active A l
2O
3The weight of coating accounts for 25.1% of cordierite honeycomb bodies gross weight.The distributional analysis of sample aperture shows, is two peak structure, and major bore is 7.5nm, and inferior aperture is 24.3nm (seeing accompanying drawing 2).
Embodiment 2
Preparation coating honeycomb 2
Carbon nano fiber growing and preparing step is 0.5wt% with embodiment 1 but adjust nickel nitrate aqueous solution concentration, and adjusting the carbon nano fiber growth time simultaneously is 3h, and other condition is constant.2.5% of the white cordierite honeycomb body weight of weight duty of the carbon nano fiber that obtains growing, the mean diameter of carbon nano fiber is 15nm.Then there is the cordierite honeycomb carrier of carbon nano fiber to be immersed in growth and contains active A l
2O
3Solid content is that the time is 10min in 25% the mixed slurry, takes out the back and blows down unnecessary slurry in the honeycomb sample, dry 12h in 120 ℃ of baking ovens then with air cannon.The honeycomb sample that obtains is placed in the air atmosphere of retort furnace, and follow procedure heats up and carries out roasting, and temperature rise rate is 5 ℃/min, to 400 ℃ of stable 10h.Obtain being covered with active A l after the roasting
2O
3The cordierite honeycomb 2 of coating, Al
2O
3The weight of coating accounts for 5% of cordierite honeycomb bodies gross weight.The distributional analysis of sample aperture shows, is two peak structure, and major bore is 7.5nm, and inferior aperture is 16.1nm (seeing accompanying drawing 2).
Embodiment 3
Preparation coating honeycomb 3
Carbon nano fiber growing and preparing step is with embodiment 1, but metal salt solution is adjusted into the iron nitrate ethanolic soln, and concentration is 2.0wt%, soak time is 0.5h, adjusting the carbon nano fiber used carbon containing source of the gas of growing simultaneously is carbon monoxide, and growth time is 1h, and other condition is constant.3.5% of the white cordierite honeycomb body weight of weight duty of the carbon nano fiber that obtains growing, the mean diameter of carbon nano fiber is 55nm.Then there is the cordierite honeycomb carrier of carbon nano fiber to be immersed in growth and contains active A l
2O
3Solid content is that the time is 60min in 45% the mixed slurry, takes out the back and blows down unnecessary slurry in the honeycomb sample, dry 12h in 120 ℃ of baking ovens then with air cannon.The honeycomb sample that obtains is placed in the air atmosphere of retort furnace, and follow procedure heats up and carries out roasting, and temperature rise rate is 3 ℃/min, to 550 ℃ of stable 5h.Obtain being covered with active A l after the roasting
2O
3The cordierite honeycomb 3 of coating, Al
2O
3The weight of coating accounts for 30% of cordierite honeycomb bodies gross weight.The distributional analysis of sample aperture shows, is two peak structure, and major bore is 6.3nm, and inferior aperture is 35.8nm (seeing accompanying drawing 2).
Preparation process is with embodiment 1, but has the soak time of honeycomb sample in mixed slurry of carbon nano fiber to be adjusted into 20min growth, and the roasting temperature rise rate of carbon nano fiber is 0.5 ℃/min, and maturing temperature is 800 ℃, stablizes 2h, and other condition is constant.Obtain being covered with active A l after the roasting
2O
3The cordierite honeycomb 4 of coating, Al
2O
3The weight of coating accounts for 18% of cordierite honeycomb bodies gross weight.。The distributional analysis of sample aperture shows, is two peak structure, and major bore is 5.4nm, and inferior aperture is 20.6nm.
Comparative Examples 1
Earlier the preparation solid content be 35% contain active A l
2O
3Mixed slurry, get the blank cordierite honeycomb substrate and be immersed in the above-mentioned slurry, the time is 30min, takes out the back and blows down unnecessary slurry in the honeycomb sample, dry 12h in 120 ℃ of baking ovens then with air cannon.The honeycomb sample that obtains is placed in the air atmosphere of retort furnace, and follow procedure heats up and carries out roasting, and temperature rise rate is 2 ℃/min, to 600 ℃ of stable 8h.Promptly obtain being coated with active A l after the cooling
2O
3The honeycomb sample of coating, active A l
2O
3The weight of coating accounts for 25.4% of cordierite honeycomb bodies gross weight.The distributional analysis of sample aperture shows, is unimodal structure, and major bore is 7.0nm.
Application examples 1
With the coating honeycomb that obtains among the embodiment 1 carrier as palladium catalyst, palladium accounts for 0.2% of coating honeycomb gross weight, make the honeycomb sample that contains catalyzer, the catalyticcombustion that is used for plant gas is administered, waste gas consists of carbon monoxide (0.1v%), oxygen (5v%), nitrogen (94.9v%), and gas space velocity is 20000h
-1The result obtains, and the temperature when carbon monoxide 99% transforms is 205 ℃.
Use Comparative Examples 1
With the coating honeycomb that obtains in the Comparative Examples 1 carrier as palladium catalyst, palladium accounts for 0.2% of coating honeycomb gross weight, make the honeycomb sample that contains catalyzer, the catalyticcombustion that is used for plant gas is administered, waste gas consists of carbon monoxide (0.1v%), oxygen (5v%), nitrogen (94.9v%), and gas space velocity is 20000h
-1The result obtains, and temperature required when carbon monoxide 99% transforms is 228 ℃, is higher than the relevant temperature in the application examples 1.Illustrate that the catalyst performance in the application examples 1 is relatively good.
The above only is preferred embodiment of the present invention, be not in order to limit essence technology contents scope of the present invention, essence technology contents of the present invention is broadly to be defined in the claim scope of application, any technology entity or method that other people finish, if it is defined identical with the claim scope of application, also or a kind of change of equivalence, all will be regarded as being covered by among this claim scope.
Claims (10)
1. the coating process of a cordierite honeycomb is characterized in that, described method comprises step:
(1) cordierite honeycomb that will speckle with metal-salt contacts 0.5-12 hour at 400-800 ℃ with the carbon containing source of the gas, and obtaining growing has the cordierite honeycomb of carbon nano fiber;
(2) growth that step (1) is obtained has the cordierite honeycomb of carbon nano fiber to be immersed in to contain active A l
2O
3Slurry in 10-60 minute, obtain the growth carbon nano fiber is arranged and is coated with active A l
2O
3The cordierite honeycomb of slurry; With
(3) growth that step (2) is obtained has carbon nano fiber and is coated with active A l
2O
3The cordierite honeycomb of slurry obtained active A l at 400-800 ℃ of roasting 2-10 hour
2O
3The cordierite honeycomb of coating.
2. coating process as claimed in claim 1 is characterized in that, the metal-salt described in the step (1) is selected from nitrate, halogeno salt or vitriol, and described metal is selected from nickel, iron, cobalt or copper.
3. coating process as claimed in claim 1 is characterized in that, the carbon containing source of the gas described in the step (1) is selected from ethene, ethane, methane or carbon monoxide.
4. coating process as claimed in claim 1 is characterized in that, contains active A l described in the step (2)
2O
3Slurry in active A l
2O
3Solid content is 25-45wt%; Described active A l
2O
3Presoma be selected from the mixing of following one or more: pseudo-boehmite powder, gibbsite powder and Virahol aluminium powder.
5. as the arbitrary described coating process of claim 1-4, it is characterized in that, the cordierite honeycomb that speckles with metal-salt described in the step (1) is by soaking acquisition in 0.5-24 hour with cordierite honeycomb in metal salt solution, in the gross weight of described metal salt solution, metal salt concentrations wherein is 0.1-5wt%.
6. one kind has active A l
2O
3The cordierite honeycomb of coating is characterized in that, in the gross weight of described coating honeycomb, and active A l wherein
2O
3The weight percent of coating is 5-30wt%; Described active A l
2O
3The aperture of coating is 2-100nm.
7. coating honeycomb as claimed in claim 6 is characterized in that, wherein active A l
2O
3The pore size distribution of coating is two peak structure, and major bore is 2-10nm, and inferior aperture is 10-100nm.
8. as claim 6 or 7 described coating honeycombs, it is characterized in that the coating in the described cordierite honeycomb is by arbitrary described coating process obtains as claim 1-5.
9. one kind as the arbitrary described active A l that has of claim 6-8
2O
3The purposes of the cordierite honeycomb of coating is characterized in that, as the carrier of catalyzer.
10. purposes as claimed in claim 9 is characterized in that, the carrier of described catalyzer is used for heat exchange, energy-conservation, vehicle exhaust is handled or plant gas is handled.
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| CN2010102192991A CN101913912B (en) | 2010-07-02 | 2010-07-02 | Method for coating cordierite honeycomb |
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| CN104998645A (en) * | 2015-06-30 | 2015-10-28 | 大同煤矿集团有限责任公司 | Preparation method of nickel-based methanation catalyst taking cordierite honeycomb ceramic as carrier |
| CN105457500A (en) * | 2015-12-28 | 2016-04-06 | 中国科学院城市环境研究所 | Carbon nano tube/porous ceramic hollow fiber composite ultrafiltration membrane as well as preparation method and application thereof |
| CN106116629A (en) * | 2016-06-24 | 2016-11-16 | 安庆市花蕾纺织材料有限公司 | A kind of lamellar ceramic honey comb loading CNT and preparation method thereof |
| CN107497499A (en) * | 2017-08-23 | 2017-12-22 | 华东理工大学 | A kind of monoblock type tufted alumina load catalyst and its application |
| CN114671704A (en) * | 2022-04-22 | 2022-06-28 | 广州粤瓷新材料有限公司 | Low-expansion porous cordierite and preparation method thereof |
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| CN104998645A (en) * | 2015-06-30 | 2015-10-28 | 大同煤矿集团有限责任公司 | Preparation method of nickel-based methanation catalyst taking cordierite honeycomb ceramic as carrier |
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| CN105457500A (en) * | 2015-12-28 | 2016-04-06 | 中国科学院城市环境研究所 | Carbon nano tube/porous ceramic hollow fiber composite ultrafiltration membrane as well as preparation method and application thereof |
| CN106116629A (en) * | 2016-06-24 | 2016-11-16 | 安庆市花蕾纺织材料有限公司 | A kind of lamellar ceramic honey comb loading CNT and preparation method thereof |
| CN107497499A (en) * | 2017-08-23 | 2017-12-22 | 华东理工大学 | A kind of monoblock type tufted alumina load catalyst and its application |
| CN107497499B (en) * | 2017-08-23 | 2020-05-05 | 华东理工大学 | Integral cluster-shaped alumina supported catalyst and application thereof |
| CN114671704A (en) * | 2022-04-22 | 2022-06-28 | 广州粤瓷新材料有限公司 | Low-expansion porous cordierite and preparation method thereof |
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| CN101913912B (en) | 2012-12-19 |
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