CN109364701A - It is a kind of for handling the composite silicon carbide ceramic pipe and preparation method of high-temp waste gas - Google Patents

It is a kind of for handling the composite silicon carbide ceramic pipe and preparation method of high-temp waste gas Download PDF

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CN109364701A
CN109364701A CN201811164280.4A CN201811164280A CN109364701A CN 109364701 A CN109364701 A CN 109364701A CN 201811164280 A CN201811164280 A CN 201811164280A CN 109364701 A CN109364701 A CN 109364701A
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filter membrane
supporter
silicon carbide
preparation
powder
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CN109364701B (en
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黄宇
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Pingxiang Sanli Science And Technology Co Ltd
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Pingxiang Sanli Science And Technology Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/54—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms
    • B01D46/543—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms using membranes
    • 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
    • B01D53/22—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 by diffusion
    • B01D53/228—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 by diffusion characterised by specific membranes
    • 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
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B17/00—Details of, or accessories for, apparatus for shaping the material; Auxiliary measures taken in connection with such shaping
    • B28B17/02—Conditioning the material prior to shaping
    • B28B17/026—Conditioning ceramic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B19/00—Machines or methods for applying the material to surfaces to form a permanent layer thereon
    • B28B19/0038—Machines or methods for applying the material to surfaces to form a permanent layer thereon lining the outer wall of hollow objects, e.g. pipes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B3/00—Producing shaped articles from the material by using presses; Presses specially adapted therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B3/00—Producing shaped articles from the material by using presses; Presses specially adapted therefor
    • B28B3/006—Pressing by atmospheric pressure, as a result of vacuum generation or by gas or liquid pressure acting directly upon the material, e.g. jets of compressed air
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
    • C04B28/26—Silicates of the alkali metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/065—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on SiC
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/067—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds comprising a particular metallic binder
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00482—Coating or impregnation materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/0081—Uses not provided for elsewhere in C04B2111/00 as catalysts or catalyst carriers

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Biomedical Technology (AREA)
  • Inorganic Chemistry (AREA)
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  • Ceramic Products (AREA)
  • Filtering Materials (AREA)

Abstract

The invention discloses a kind of for handling the composite silicon carbide ceramic pipe and preparation method of high-temp waste gas, the ceramic tube includes supporter, the filter membrane being attached in supporting body surface and the catalyst being attached in ceramic tube, the preparation method comprises the following steps: by composite particles powder, sintering aid, binder, plasticizer, dispersing agent, lubricant is added deionized water ball milling mixing and is configured to plastic mud material, the composite particles powder is with silicon carbide powder, metal powder, sinter additives are main material, it is green compact through aging plastic mud material forming, dry and sinter into supporter, film drying again sinters ceramic tube into.Efficiency of dust collection is improved, in the environment of high temperature, high concentration, strong corrosive, physics interception is carried out to the inorganic and organic element in flue gas with stable performance and chemical catalysis is handled, has achieved the purpose that efficient process.

Description

It is a kind of for handling the composite silicon carbide ceramic pipe and preparation method of high-temp waste gas
Technical field
The present invention relates to high-temp waste gas processing technology fields, more particularly, to a kind of for handling the composite carbon of high-temp waste gas SiClx ceramic tube and preparation method.
Background technique
Not only temperature is high for the exhaust gas of the industries such as metallurgy, machinery, chemical industry, electric power emitted, but also containing a large amount of Dust and pernicious gas are to cause one of principal element of environmental pollution.Under hot conditions, since exhaust gas viscous force has larger change Change, humidity declines to a great extent, and fine grained coacervation is greatly lowered, so having to the separation of particle more highly difficult.Hot industry is useless The main species of gas purification techniques have: cloth bag waste gas purification, whirlwind waste gas purification, wet-process waste gas purification, electrostatic waste gas purification, mistake Filter waste gas purification etc., wherein cloth-bag type waste gas purification cannot bear the high temperature of exhaust gas, its separable partial size of whirlwind waste gas purification compared with Greatly, it is only used for the pretreatment of high-temp waste gas purification, wet-process waste gas purification be comprehensively utilized its thermal energy cannot again, but easily produce Raw secondary pollution；The problem of electrostatic waste gas purification is again high in the presence of primary investment, take up a large area and insulate etc., and and other The deduster of type is compared, and the exhaust purification efficiency of porous ceramic filter is high, can remove 5 μm or more of grit, most important It is high temperature resistant, operating temperature has under the hot environments such as oxidation, reduction good anticorrosive up to 800 DEG C or more Property, therefore porous ceramic filter plays important function in terms of high-temperature dust removal, but the ceramic tube of porous ceramic filter It is uneven that it is easy to appear finished product structure during the preparation process, compression strength and toughness is not high；Filter membrane and supporter conjugation Not enough, and filter membrane cannot effectively stop little particle dust, and various exhaust gas removal efficiencies are undesirable.
Summary of the invention
For the problems of above-mentioned high-temp waste gas in the prior art processing, the present invention provides a kind of compression strength and Toughness enhancing, filter membrane and supporter conjugation are good, the raising of exhaust gas removal efficiency for handling the compound carbonizing of high-temp waste gas Silicon ceramic tube and preparation method.
The invention is realized by the following technical scheme: a kind of for handling the composite silicon carbide ceramic pipe and system of high-temp waste gas Preparation Method, the ceramic tube include supporter, the filter membrane being attached in supporting body surface and are attached to urging in ceramic tube Agent, the preparation method comprises the following steps:
A, the preparation of supporter
(1), deionization water polo is added in following composite particles powder, sintering aid, binder, plasticizer, dispersing agent, lubricant Mill is hybridly prepared into plastic mud material, and the composite particles powder is former based on silicon carbide powder, metal powder, sinter additives To expect, it is 240-250 μm that silicon carbide powder, which accounts for 80~90wt% average grain diameter, in the main material, and metal powder accounts for 5~12wt%, Sinter additives account for 2~10wt%, and the binder accounts for 1~10wt%, and the plasticizer accounts for 0.5~15wt%, the dispersion Agent accounts for 0.1~2wt%, and the lubricant accounts for 1~15wt%, and the metal powder includes at least one of titaniferous, manganese, zinc；
(2), plastic mud material manufactured in step A is set it is aging under sealing, then use dry-pressing formed or isostatic pressing method Plastic mud material forming after will be aging is green compact, and green compact after molding are dried moisture, heat preservation；Finally it is with temperature in kiln 1420-1600 DEG C, soaking time be 2-3h under conditions of by green sintering at supporter；
B, the preparation of filter membrane slurry
The weight proportion of the material component of filter membrane are as follows: silicon carbide powder 85~88wt% average grain diameter is 20-50 μm, reinforcing agent 7~10 wt%, 2~4wt% of carbonate, above-mentioned component weight are 100 wt%, are subject on the basis of the raw material of filter membrane outside 1~2wt% of sodium carboxymethylcellulose, distilled water 150-180wt%, each raw material uniformly mix according to the ratio, and filter membrane slurry is made Material, the reinforcing agent be weight ratio be 7:1:2 pyrophillite, south hole mud, silica flour, the carbonate be barium carbonate or calcium carbonate At least one；
C, supporter plated film
Filter membrane slurry obtained in step B is sprayed into supporting body surface obtained in step A, through drying at room temperature, then is placed on Dry 2~3h at 60 DEG C~70 DEG C of constant temperature in drying box, then 120~130 DEG C of dry 1h~2h are warming up to, it is re-fed into electric furnace and rises Then temperature keeps the temperature 1-3h cooling, the supporter for being coated with filter membrane is made to 550~600 DEG C of 2~3h；
D, the coating of catalyst
Catalyst pulp each component ball milling mixing according to the ratio, the weight proportion of the catalyst pulp component are as follows: V2O5 is accounted for 0.3~0.5 wt %, CuO account for 0.5~0.8 wt%, SiO2 and account for 5~10 wt%, remaining is TiO2, and above-mentioned component weight is 100 Wt%, it is additional to account on the basis of catalyst pulp weight: 0.1~0.5 wt% of industrial-grade sodium silicate, 50~300 wt% of water； The supporter obtained in step C for being coated with filter membrane is immersed in catalyst pulp and is coated, is put into microwave after taking-up It is dried under conditions of 20-25min, power 200-220W, temperature are at 480-520 DEG C, recycles above-mentioned coating and drying course, directly Weight to catalyst is the 10-15wt% of supporter, obtains the ceramic tube with the efficient process exhaust gas.
Further, the sinter additives are graphite, boron carbide or bamboo charcoal；The binder is polyvinyl butyral Or polyvinyl alcohol water solution, the plasticizer are glycerol or ethyl-methyl sulfuric acid, the dispersing agent is polyacrylic acid or tetramethyl Ammonium hydroxide, the lubricant are oleic acid, paraffin or fish oil.
Further, described dry-pressing formed or isostatic pressing pressure is 100~250MPa, when the dwell time is pressure maintaining Between be 10~60s.
Among the above: although the bulky grain silicon carbide in the raw material of supporter can be such that porosity improves, intensity and toughness It is insufficient, therefore be added in the raw material of supporter and form composite granule compared with metal powders such as the titanium of low melting point, manganese, zinc in right amount It is the carbide or silicide of the titanium for generation, manganese, zinc, is filled in around bulky grain silicon-carbide particle powder, so that big There is stronger binding ability between grain silicon-carbide particle powder, improve flexural strength between compound carbofrax material and tough Property, it should be noted that it is obtained through overtesting, the content of metal powder is no more than 12%, otherwise between compound carbofrax material Flexural strength and toughness downward trend will occur.
South hole mud, originates in the Jiangxi Province Pingxiang City Luxi County town Nan Keng, chemical component: aluminium oxide: 32.70%, silica 52.30%, di-iron trioxide 1.12%, magnesia 0.20%, calcium oxide 0.15%, titanium dioxide 0.14% and a small amount of other impurities, south Hole mud can increase the high temperature cohesive strength, thermal shock resistance and creep resistance of filter membrane in filter membrane；
Pyrophillite, silicic acid aluminum feedstock, chemical structural formula are Al2 [Si4O10] (OH) 2, monoclinic system, usually at compact massive, piece Shape or radiated aggregation.White, micro-strip is pale yellow or light green color, translucent.Glassy lustre, pearl shape iridescence；Hardness 1~2；Than 2.66~2.90 are weighed, has grease sense, pyrophillite can reduce the contraction and deformation of filter membrane in filter membrane, improve the strong of filter membrane Degree, while can effectively reduce sintering temperature, improve compactness；
Sillimanite, also known as silimanite, ingredient is Al2O3 SiO2 or Al2SiO5, wherein containing Al2O3 63.11%, SiO2 36.89%, belong to orthorhombic system.Crystal is in sheet-pile shape, needle column, and usually radial and fibrous agrregate has white, greyish white Color, celadon, brown, hardness larger 6 ~ 7.3.23 ~ 3.25g/cm3 of density.Mullite and dioxy can be converted into heating process SiClx mixture, conversion temperature is higher, is 1550 ~ 1750 DEG C, and volume expansion is 6% ~ 7.2%, volume change when temperature reduces Very little, quartz play adjustment in the plasticity of filter membrane, and liquid phase viscosity is high in high temperature, can reduce and shrink when dry, shorten Drying time prevents filter membrane is heavy from collapsing；
The effect of carbonate is can to increase the wear resistance and corrosion resistance of filter membrane, and sodium carboxymethylcellulose is to increase The viscosity of slurry combines little particle silicon carbide, reinforcing agent and carbonate in filter membrane more effectively.
Compared with prior art, the present invention beneficial effect is: mainly using bulky grain silicon carbide as main material and adulterate Composite material ceramic tube supporter is made in metal powder, improves supporter compression strength and toughness；And using small in filter membrane Grained silicon carbide powder is main material, effectively stops the tiny dust particles in high-temperature gas, and be added in filter membrane slurry Composite fortifier, so that not needing transition zone between supporter and filter membrane can combine well, little particle silicon carbide is not yet It can enter in the hole of bulky grain silicon carbide and result in blockage, improve the properties of filter membrane；And it is used in V205、TiO2Catalysis CuO, SiO2, which is added, in agent reduces noble metal cost, improves efficiency of dust collection, in the environment of high temperature, high concentration, strong corrosive, Physics interception is carried out to the inorganic and organic element in flue gas with stable performance and chemical catalysis is handled, has reached efficient process Purpose.
Specific embodiment
In order to make those skilled in the art more fully understand technical solution of the present invention, come combined with specific embodiments below into One step the present invention is described in detail.
Embodiment one
The composite silicon carbide ceramic pipe and preparation method of the processing high-temp waste gas, the ceramic tube include supporter, are attached to Filter membrane in supporting body surface and the catalyst being attached in ceramic tube, the preparation method comprises the following steps:
A, the preparation of supporter
(1), deionization water polo is added in following composite particles powder, sintering aid, binder, plasticizer, dispersing agent, lubricant Mill is hybridly prepared into plastic mud material, and the composite particles powder is former based on silicon carbide powder, metal powder, sinter additives Expect, it is 240 μm that silicon carbide powder, which accounts for 80wt% average grain diameter, in the main material, and metal powder accounts for 12wt%, and (manganese, zinc respectively account for one Half), sinter additives account for 4wt%, and the binder accounts for 1.3wt%, and the plasticizer accounts for 0.5wt%, and the dispersing agent accounts for 0.2wt%, the lubricant account for 2wt%, and the sinter additives are boron carbide；The binder is polyvinyl alcohol water solution, The plasticizer is ethyl-methyl sulfuric acid, and the dispersing agent is tetramethylammonium hydroxide, and the lubricant is paraffin；
(2), plastic mud material manufactured in step A is set to aging under sealing modeling after then using dry pressing will be aging Property mud material forming be green compact, by green compact after molding dry moisture, heat preservation；It is finally 1420 DEG C with temperature in kiln, heat preservation The condition that time is 3h is by green sintering at supporter, and the dry-pressing formed pressure is 100MPa, when the dwell time is pressure maintaining Between be 10s；
B, the preparation of filter membrane slurry
The weight proportion of the material component of filter membrane are as follows: silicon carbide powder 86wt% average grain diameter is 30 μm, reinforcing agent 10 Wt%, carbonate 4wt%, above-mentioned component weight are 100 wt%, the carboxymethyl cellulose being subject on the basis of the raw material of filter membrane outside Plain 2 wt% of sodium, distilled water 180wt%, each raw material uniformly mix according to the ratio, and filter membrane slurry is made, and the reinforcing agent is attached most importance to For amount than pyrophillite, south hole mud, silica flour for 7:1:2, the carbonate is barium carbonate；
C, supporter plated film
Filter membrane slurry obtained in step B is sprayed into supporting body surface obtained in step A, through drying at room temperature, then is placed on Dry 2h at 60 DEG C of constant temperature in drying box, then 120 DEG C of dry 1h are warming up to, it is re-fed into electric furnace and is warming up to 600 DEG C of 2h, then protect Warm 1h is cooling, and the supporter for being coated with filter membrane is made；
D, the coating of catalyst
Catalyst pulp each component ball milling mixing according to the ratio, the weight proportion of the catalyst pulp component are as follows: V2O5 is accounted for 0.3wt %, CuO account for 0.5 wt%, SiO2 and account for 5 wt%, remaining is TiO2, and above-mentioned component weight is 100 wt%, and additional account for is urged On the basis of agent slurry weight: 0.1 wt% of industrial-grade sodium silicate, 50 wt% of water；Filtering is coated with by obtained in step C The supporter of film, which is immersed in catalyst pulp, to be coated, and is put into after taking-up in microwave and is existed in 20min, power 200W, temperature It is dried under conditions of 480 DEG C, recycles above-mentioned coating and drying course, until the weight of catalyst is the 10wt% of supporter, obtained To the ceramic tube with the efficient process exhaust gas.
Through detecting, the density of the ceramic tube of efficient process exhaust gas prepared by embodiment one is 1 .8g/cm3, the heat-resisting sudden turn of events Property: >=650 DEG C, acid resistance >=98%, fastness to alkali >=92%, porosity 58%, bending strength 7MPa；Fracture toughness is 280Pa·m1/2, ceramic tube of the invention is assembled in hot precipitator, in 480 DEG C of reaction temperature, SO2 content 2100mg/ m3, NO content 469mg/m3, air speed 4300h-1Under conditions of, NO removal rate 96.4%, sulfur oxidation rate 22.8%.
Embodiment two
The composite silicon carbide ceramic pipe and preparation method of the processing high-temp waste gas, the ceramic tube include supporter, are attached to Filter membrane in supporting body surface and the catalyst being attached in ceramic tube, the preparation method comprises the following steps:
A, the preparation of supporter
(1), deionization water polo is added in following composite particles powder, sintering aid, binder, plasticizer, dispersing agent, lubricant Mill is hybridly prepared into plastic mud material, and the composite particles powder is former based on silicon carbide powder, metal powder, sinter additives Expect, it is 250 μm that silicon carbide powder, which accounts for 88wt% average grain diameter, in the main material, and metal powder accounts for 5wt%(titanium), sintering addition Agent accounts for 2wt%, and the binder accounts for 1wt%, and the plasticizer accounts for 0.6wt%, and the dispersing agent accounts for 0.4wt%, the lubrication Agent accounts for 3wt%, and the sinter additives are graphite；The binder is polyvinyl butyral, and the plasticizer is glycerol, institute Stating dispersing agent is polyacrylic acid, and the lubricant is oleic acid；
(2), plastic mud material manufactured in step A is set it is aging under sealing, then using isostatic pressing method will be aging after Plastic mud material forming is green compact, and green compact after molding are dried moisture, heat preservation；It is finally 1600 DEG C with temperature in kiln, protects For the condition that the warm time is 3h by green sintering at supporter, the pressure of the isostatic pressing is 250MPa, and the dwell time is to protect The pressure time is 60s；
B, the preparation of filter membrane slurry
The weight proportion of the material component of filter membrane are as follows: 90 wt% average grain diameter of silicon carbide powder be 50 μm, reinforcing agent 7wt%, Carbonate 3wt%, above-mentioned component weight are 100 wt%, the sodium carboxymethylcellulose 1 being subject on the basis of the raw material of filter membrane outside Wt%, distilled water 150wt%, each raw material uniformly mix according to the ratio, filter membrane slurry are made, the reinforcing agent is that weight ratio is Pyrophillite, south the hole mud, silica flour of 7:1:2, the carbonate is calcium carbonate；
C, supporter plated film
Filter membrane slurry obtained in step B is sprayed into supporting body surface obtained in step A, through drying at room temperature, then is placed on Dry 3h at 70 DEG C of constant temperature in drying box, then 130 DEG C of dry 2h are warming up to, it is re-fed into electric furnace and is warming up to 600 DEG C of 3h, then protect Warm 3h is cooling, and the supporter for being coated with filter membrane is made；
D, the coating of catalyst
Catalyst pulp each component ball milling mixing according to the ratio, the weight proportion of the catalyst pulp component are as follows: V2O5 is accounted for 0.5 wt %, CuO account for 0.8 wt%, SiO2 and account for 10 wt%, remaining is TiO2, and above-mentioned component weight is 100 wt%, additional to account for On the basis of catalyst pulp weight: 0.5 wt% of industrial-grade sodium silicate, 300 wt% of water；It is coated with obtained in step C The supporter of filter membrane, which is immersed in catalyst pulp, to be coated, and is put into microwave after taking-up in 25min, power 220W, temperature Degree is dried under conditions of 520 DEG C, recycles above-mentioned coating and drying course, until the weight of catalyst is supporter 15wt% obtains the ceramic tube with the efficient process exhaust gas.
Through detecting, the density of the ceramic tube of efficient process exhaust gas prepared by embodiment two is 2 .1g/cm3, the heat-resisting sudden turn of events Property: >=650 DEG C, acid resistance >=98%, fastness to alkali >=92%, porosity 65%, bending strength 9MPa；Fracture toughness is 420Pa·m1/2, ceramic tube of the invention is assembled in hot precipitator, in 520 DEG C of reaction temperature, SO2 content 2200mg/ m3, NO content 480mg/m3, air speed 4200h-1Under conditions of, NO removal rate 98.4%, sulfur oxidation rate 20.1%.
Embodiment of above is only used to illustrate the technical scheme of the present invention and not to limit it, although referring to specific embodiment to this Invention is described in detail, those skilled in the art should understand that, technical solution of the present invention can be repaired Change or equivalent replacement should all cover and want in right of the invention without departing from the spirit and scope of the technical solution of the present invention It asks in the range of protection.

Claims (3)

1. a kind of for handling the composite silicon carbide ceramic pipe and preparation method of high-temp waste gas, it is characterised in that: the ceramic tube Including supporter, the filter membrane being attached in supporting body surface and the catalyst being attached in ceramic tube, the preparation method The following steps are included:
A, the preparation of supporter
(1), deionization water polo is added in following composite particles powder, sintering aid, binder, plasticizer, dispersing agent, lubricant Mill is hybridly prepared into plastic mud material, and the composite particles powder is former based on silicon carbide powder, metal powder, sinter additives Material, it is 240-250 μm that silicon carbide powder, which accounts for 80~90wt% average grain diameter, in the main material, metal powder accounts for 5~ 12wt%, sinter additives account for 2~10wt%, and the binder accounts for 1~10wt%, and the plasticizer accounts for 0.5~15wt%, institute State dispersing agent and account for 0.1~2wt%, the lubricant accounts for 1~15wt%, the metal powder include titanium, manganese, zinc at least one Kind；
(2), plastic mud material manufactured in step A is set it is aging under sealing, then use dry-pressing formed or isostatic pressing method Plastic mud material forming after will be aging is green compact, and green compact after molding are dried moisture, heat preservation；Finally it is with temperature in kiln 1420-1600 DEG C, soaking time be 2-3h under conditions of by green sintering at supporter；
B, the preparation of filter membrane slurry
The weight proportion of the material component of filter membrane are as follows: 85~88 wt% average grain diameter of silicon carbide powder is 20-50 μm, enhances 7~10 wt% of agent, 2~4wt% of carbonate, above-mentioned component weight are 100 wt%, are subject on the basis of the raw material of filter membrane outside 1~2 wt% of sodium carboxymethylcellulose, distilled water 150-180wt%, each raw material uniformly mixes according to the ratio, and filter membrane is made Slurry, the reinforcing agent be weight ratio be 7:1:2 pyrophillite, south hole mud, silica flour, the carbonate be barium carbonate or carbonic acid At least one of calcium；
C, supporter plated film
Filter membrane slurry obtained in step B is sprayed into supporting body surface obtained in step A, through drying at room temperature, then is placed on Dry 2~3h at 60 DEG C~70 DEG C of constant temperature in drying box, then 120~130 DEG C of dry 1h~2h are warming up to, it is re-fed into electric furnace and rises Then temperature keeps the temperature 1-3h cooling, the supporter for being coated with filter membrane is made to 550~600 DEG C of 2~3h；
D, the coating of catalyst
Catalyst pulp each component ball milling mixing according to the ratio, the weight proportion of the catalyst pulp component are as follows: V2O5 is accounted for 0.3~0.5 wt %, CuO account for 0.5~0.8 wt%, SiO2 and account for 5~10 wt%, remaining is TiO2, and above-mentioned component weight is 100 Wt%, it is additional to account on the basis of catalyst pulp weight: 0.1~0.5 wt% of industrial-grade sodium silicate, 50~300 wt% of water； The supporter obtained in step C for being coated with filter membrane is immersed in catalyst pulp and is coated, is put into microwave after taking-up It is dried under conditions of 20-25min, power 200-220W, temperature are at 480-520 DEG C, recycles above-mentioned coating and drying course, directly Weight to catalyst is the 10-15wt% of supporter, obtains the ceramic tube with the efficient process exhaust gas.
2. it is according to claim 1 a kind of for handling the composite silicon carbide ceramic pipe and preparation method of high-temp waste gas, Be characterized in that: the sinter additives are graphite, boron carbide or bamboo charcoal；The binder is polyvinyl butyral or polyethylene Alcohol solution, the plasticizer be glycerol or ethyl-methyl sulfuric acid, the dispersing agent be polyacrylic acid or tetramethylammonium hydroxide, The lubricant is oleic acid, paraffin or fish oil.
3. it is according to claim 1 a kind of for handling the composite silicon carbide ceramic pipe and preparation method of high-temp waste gas, Be characterized in that: described dry-pressing formed or isostatic pressing pressure is 100~250MPa, the dwell time be 10 the dwell time~ 60s。
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