CN111330634A - Corrugated plate type denitration catalyst and preparation method thereof - Google Patents
Corrugated plate type denitration catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 96
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 43
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims abstract description 34
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 30
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 17
- 239000002808 molecular sieve Substances 0.000 claims abstract description 16
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000010304 firing Methods 0.000 claims abstract description 11
- 238000010030 laminating Methods 0.000 claims abstract description 6
- 239000002002 slurry Substances 0.000 claims description 39
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 36
- 238000002156 mixing Methods 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 16
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 15
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 15
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 239000003365 glass fiber Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 235000006408 oxalic acid Nutrition 0.000 claims description 12
- 239000000835 fiber Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000005407 aluminoborosilicate glass Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 239000003292 glue Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 12
- 239000004408 titanium dioxide Substances 0.000 abstract description 9
- 239000002131 composite material Substances 0.000 abstract description 6
- 239000011149 active material Substances 0.000 abstract description 4
- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- 239000004480 active ingredient Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- -1 nitrogen-containing compound Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- UGNQWDWTUMJUAN-UHFFFAOYSA-N [Mo](=O)(=O)=O.[O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [Mo](=O)(=O)=O.[O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] UGNQWDWTUMJUAN-UHFFFAOYSA-N 0.000 description 1
- CLRJCOAGHQIHPD-UHFFFAOYSA-N [W](=O)(=O)=O.[O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [W](=O)(=O)=O.[O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] CLRJCOAGHQIHPD-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000010340 shenyuan Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7807—A-type
-
- 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
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
Abstract
The invention provides a corrugated plate type denitration catalyst and a preparation method thereof, and belongs to the technical field of denitration catalysts. The composite carrier of porous molecular sieve, graphene and titanium dioxide is used as an active material carrier, has high adsorbability, can actively adsorb reactants to perform active catalytic reduction reaction, can load more active components to excite the activity of the active materials and improve the activity of the corrugated plate type denitration catalyst, and is combined with the active components of molybdenum trioxide, tungsten trioxide and ammonium metavanadate, so that the obtained catalyst is slightly influenced by temperature and can adapt to wider use conditions, and the active temperature range is 120-280 ℃; in addition, the preparation method provided by the invention prepares the carrier and the active component into pug, and then obtains the corrugated plate type denitration catalyst through punch forming, laminating assembly and firing in sequence, wherein the corrugated plate type denitration catalyst has an integral structure, has the advantage of high strength and does not have the problem of falling.
Description
Technical Field
The invention relates to the technical field of denitration catalysts, and particularly relates to a corrugated plate type denitration catalyst and a preparation method thereof.
Background
The air treatment is the key point of attention of adults, the Selective Catalytic Reduction (SCR) denitration technology is the most widely applied and mature flue gas denitration technology all over the world at present, the application history has been decades, the denitration efficiency can reach more than 90%, and no secondary pollution is caused. The key point of the SCR denitration technology lies in a denitration catalyst, and the denitration catalyst commonly used in the current SCR denitration technology mainly takes titanium dioxide as a carrier and vanadium pentoxide, vanadium pentoxide-tungsten trioxide or vanadium pentoxide-molybdenum trioxide as active ingredients to be made into a honeycomb type, a plate type or a corrugated plate type.
At present, two types of corrugated plate type denitration catalysts are usually produced, one type is obtained by taking a metal plate as a framework, spraying titanium dioxide loaded with active ingredients on the framework for multiple times, drying and firing, but the catalyst obtained by the method is easy to resonate and fall off, and the activity temperature is high and is 300-400 ℃; the other method is that the ceramic fiber paper is firstly molded to be corrugated, then the ceramic fiber paper is dipped in slurry loaded with titanium dioxide of active ingredients, and then the slurry is dried and fired in sequence, the method has the advantages that the adhesive force of the titanium dioxide loaded with the active ingredients on the ceramic fiber is small, the titanium dioxide is easy to fall off, the activity is unstable, and the activity temperature is high and is 280-380 ℃. Therefore, the corrugated plate type denitration catalyst prepared by the existing preparation method has the problems of high activity temperature and easy falling.
Disclosure of Invention
The invention aims to provide a corrugated plate type denitration catalyst and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a corrugated plate type denitration catalyst, which comprises the following steps:
mixing graphene, nano titanium dioxide, a porous molecular sieve, molybdenum trioxide, tungsten trioxide, ammonium metavanadate, oxalic acid and water to obtain a mixed solution;
adjusting the pH value of the mixed solution to 6-7 by adopting ammonia water, and then sequentially stirring, mixing, standing and dehydrating to obtain denitration catalyst slurry; the solid content of the denitration catalyst slurry is 80-90 wt%;
curing the denitration catalyst slurry, and mixing the cured denitration catalyst slurry with ethylene-vinyl acetate copolymer and glass fiber to obtain denitration catalyst slurry;
stamping and forming the denitration catalyst mud material to obtain a corrugated sheet;
spraying resin glue among a plurality of corrugated sheets, and then laminating and assembling to obtain a corrugated plate type denitration catalyst blank;
and firing the corrugated plate type denitration catalyst blank to obtain the corrugated plate type denitration catalyst.
Preferably, the amount of each raw material for preparing the corrugated plate type denitration catalyst is as follows in parts by mass: 0.3-1.4 parts of graphene, 10-20 parts of nano titanium dioxide, 18-35 parts of a porous molecular sieve, 3-6 parts of molybdenum trioxide, 1-8 parts of tungsten trioxide, 0.1-8 parts of ammonium metavanadate, 4.5-4.8 parts of oxalic acid, 0.5-1 parts of an ethylene-vinyl acetate copolymer and 16-25 parts of glass fiber.
Preferably, the graphene is added in the form of graphene aqueous slurry, and the solid content of the graphene aqueous slurry is 60-70 wt%.
Preferably, the porous molecular sieve is a 3A molecular sieve; the glass fiber is aluminoborosilicate glass fiber.
Preferably, the solid content of the mixed solution is 65-75 wt%.
Preferably, the stirring and mixing temperature is 55-65 ℃, the rotating speed is 300-500 rpm, and the time is 2.8-3.2 h; and standing is carried out at room temperature, and the standing time is 1.8-2.2 h.
Preferably, the curing is carried out at room temperature, and the curing time is 40 min-2 h.
Preferably, the firing temperature is 600-800 ℃, and the time is 2.5-3.5 h.
Preferably, the thickness of the corrugated sheet is 0.2-0.4 mm, the height of the corrugated sheet is 6-9 mm, and the distance between peaks and valleys is 4-9 mm.
The invention also provides the corrugated plate type denitration catalyst obtained by the preparation method of the technical scheme.
The composite carrier of porous molecular sieve, graphene and titanium dioxide is used as an active material carrier, the composite carrier has high adsorbability, can adsorb reactants, and performs catalytic reduction reaction, namely active reaction, a conventional denitration catalyst performs collision reduction with the catalyst through a nitrogen-containing compound, namely passive reaction, the carrier can be loaded with more active components to excite the activity of the active materials and improve the activity of the corrugated plate type denitration catalyst, the carrier is combined with the active components of molybdenum trioxide, tungsten trioxide and ammonium metavanadate, the obtained catalyst is slightly influenced by temperature and can adapt to wider use conditions, and the active temperature range is 120-280 ℃; in addition, the preparation method provided by the invention prepares the carrier and the active component into pug, and then obtains the corrugated plate type denitration catalyst through punch forming, laminating assembly and firing in sequence, wherein the corrugated plate type denitration catalyst has an integral structure, has the advantage of high strength and cannot fall off; in addition, the preparation method provided by the invention is simple and high in production efficiency, a batch of catalysts can be produced within 24 hours, and compared with the production period of 15-30 days in the traditional forming process (framework surface dipping forming), the production period is greatly shortened.
Detailed Description
The invention provides a preparation method of a corrugated plate type denitration catalyst, which comprises the following steps:
mixing graphene, nano titanium dioxide, a porous molecular sieve, molybdenum trioxide, tungsten trioxide, ammonium metavanadate, oxalic acid and water to obtain a mixed solution;
adjusting the pH value of the mixed solution to 6-7 by adopting ammonia water, and then sequentially stirring, mixing, standing and dehydrating to obtain denitration catalyst slurry; the solid content of the denitration catalyst slurry is 80-90 wt%;
curing the denitration catalyst slurry, and mixing the cured denitration catalyst slurry with ethylene-vinyl acetate copolymer and glass fiber to obtain denitration catalyst slurry;
stamping and forming the denitration catalyst mud material to obtain a corrugated sheet;
spraying resin glue on the surfaces of a plurality of corrugated sheets, and then laminating and assembling to obtain a corrugated plate type denitration catalyst blank;
and firing the corrugated plate type denitration catalyst blank to obtain the corrugated plate type denitration catalyst.
Graphene, nano titanium dioxide, a porous molecular sieve, molybdenum trioxide, tungsten trioxide, ammonium metavanadate, oxalic acid and water are mixed to obtain a mixed solution.
In the present invention, the amount of each raw material for preparing the corrugated plate-type denitration catalyst is preferably as follows in parts by mass: 0.3-1.4 parts of graphene, 10-20 parts of nano titanium dioxide, 18-35 parts of a porous molecular sieve, 3-6 parts of molybdenum trioxide, 1-8 parts of tungsten trioxide, 0.1-8 parts of ammonium metavanadate, 4.5-4.8 parts of oxalic acid, 0.5-1 parts of an ethylene-vinyl acetate copolymer and 16-25 parts of glass fiber.
In the invention, the raw materials for preparing the corrugated plate type denitration catalyst preferably comprise 0.3-1.4 parts of graphene, more preferably 0.7-1.4 parts, and most preferably 1.0-1.4 parts by mass; the graphene is preferably added in the form of graphene aqueous slurry, and the solid content (namely the mass percentage content of the graphene) of the graphene aqueous slurry is preferably 60-70 wt%, and more preferably 66 wt%; the amount of the graphene is 0.5 to 2 parts by weight in terms of the amount of the graphene aqueous slurry. The source of the graphene aqueous slurry is not particularly limited, and any commercially available graphene aqueous slurry can be used, and in the embodiment of the present invention, the graphene aqueous slurry is preferably a graphene aqueous slurry of suzhou carbofeng graphene technologies, wherein the purity of graphene is 99.9%, and the particle size is preferably 0.5 to 5 μm. In the invention, the graphene is used as one of carriers, has the characteristics of large specific surface area and strong adsorption performance, and is used with titanium dioxide and a porous molecular sieve as composite carriers.
In the invention, based on the mass parts of graphene, the raw materials for preparing the corrugated plate type denitration catalyst preferably comprise 10-20 parts of nano titanium dioxide, more preferably 12-20 parts, and most preferably 16-20 parts; the source of the nano titanium dioxide is not particularly limited, the nano titanium dioxide can be commercially available, and in the embodiment of the invention, the nano titanium dioxide is preferably analytically pure nano titanium dioxide of Tianjin Shenyuan chemical reagent company. In the invention, the nano titanium dioxide is used as a carrier, and forms a composite carrier with graphene and a porous molecular sieve.
In the invention, based on the mass parts of graphene, the raw material for preparing the corrugated plate type denitration catalyst preferably comprises 18-35 parts of porous molecular sieve, more preferably 20-30 parts, and most preferably 20-25 parts; the porous molecular sieve is preferably a 3A molecular sieve; the source of the 3A molecular sieve is not particularly limited in the present invention, and any commercially available 3A molecular sieve may be used, and in the examples of the present invention, the 3A molecular sieve is preferably a 3A molecular sieve of MR-102 model of beijing rui and xiangyuan environmental protection materials ltd. In the invention, the porous molecular sieve has larger specific surface area, is combined with graphene and titanium dioxide to be used as a composite carrier, and has higher adsorbability on reactants, so that active catalytic reduction reaction can be carried out, and the activity of the corrugated plate type denitration catalyst is improved.
In the invention, the raw material for preparing the corrugated plate type denitration catalyst preferably comprises 3-6 parts of molybdenum trioxide based on the mass part of graphene, more preferably 4-6 parts, and most preferably 5-6 parts. In the invention, the molybdenum trioxide is used as an active ingredient and can catalyze and reduce nitrogen oxide.
In the invention, the raw material for preparing the corrugated plate type denitration catalyst preferably comprises 1-8 parts of tungsten trioxide based on the mass part of graphene, more preferably 4-7 parts of tungsten trioxide, and most preferably 6-7 parts of tungsten trioxide. In the present invention, the tungsten trioxide is used as an active ingredient to catalytically reduce nitrogen oxide.
In the invention, the raw material for preparing the corrugated plate type denitration catalyst preferably comprises 0.1-8 parts of ammonium metavanadate, more preferably 2-4.5 parts of ammonium metavanadate, and most preferably 3-4.5 parts of ammonium metavanadate based on the mass parts of graphene. In the present invention, ammonium metavanadate as an active ingredient can catalytically reduce nitrogen oxide, and molybdenum trioxide, tungsten trioxide and ammonium metavanadate as active ingredients are combined to generate strong oxidizing property to react NO in a denitration processxAnd NH3By oxidation to N2And H2O。
In the invention, the raw material for preparing the corrugated plate type denitration catalyst preferably comprises 4.5-4.8 parts of oxalic acid, more preferably 4.6-4.8 parts of oxalic acid, and most preferably 4.7-4.8 parts of graphene by mass. In the present invention, the oxalic acid is used as a dissolving agent to dissolve molybdenum trioxide, tungsten trioxide and ammonium metavanadate.
In the invention, the raw material for preparing the corrugated plate type denitration catalyst preferably comprises 0.5-1 part of ethylene-vinyl acetate copolymer, more preferably 0.5-0.8 part, and most preferably 0.5-0.6 part by mass of graphene. In the present invention, the source of the ethylene-vinyl acetate copolymer is not particularly limited, and a commercially available ethylene-vinyl acetate copolymer may be used, and in the present embodiment, the ethylene-vinyl acetate copolymer is preferably an ethylene-vinyl acetate copolymer of the CH1401-1H type, which is a product of the higher co-pending co-company of hong kong. In the present invention, the ethylene-vinyl acetate copolymer is used as a setting agent for forming a pug.
In the invention, based on the mass parts of graphene, the raw materials for preparing the corrugated plate type denitration catalyst preferably comprise 16-25 parts of glass fiber, more preferably 16-20 parts, and most preferably 16-18 parts; the glass fiber is preferably aluminoborosilicate glass fiber; the average length of the glass fiber is preferably 5-7 cm, more preferably 6cm, and the average diameter is preferably 0.06 cm. The source of the aluminoborosilicate glass fiber is not particularly limited and can be a commercially available product, and in the embodiment of the invention, the aluminoborosilicate glass fiber is preferably an LPGY-5 type aluminoborosilicate glass fiber of Gallery DekKai thermal insulation material Co. According to the invention, the glass fiber can enhance the strength of the corrugated plate type denitration catalyst and avoid falling off.
In the invention, the solid content of the mixed solution is preferably 65-75 wt%, and more preferably 70 wt%.
After a mixed solution is obtained, ammonia water is adopted to adjust the pH value of the mixed solution to 6-7, and then the mixed solution is stirred, mixed, stood and dehydrated in sequence to obtain the denitration catalyst slurry.
In the present invention, the mass concentration of the ammonia water is preferably 4 to 6%, and more preferably 5%. In the invention, the pH value of the mixed solution is adjusted to 6-7, so that the corrosivity of the raw material can be reduced to the minimum, the raw material does not have corrosivity, and the corrosion to stamping equipment is reduced.
In the invention, the stirring and mixing temperature is preferably 55-65 ℃, more preferably 60 ℃, the rotating speed is preferably 300-500 rpm, more preferably 400rpm, and the time is preferably 2.8-3.2 h, more preferably 3 h; the standing is preferably carried out at room temperature (i.e. without additional heating or cooling), and the standing time is preferably 1.8-2.2 hours, more preferably 2 hours. In the invention, the stirring and mixing can mix all the raw materials more uniformly; stirring and mixing under the preferable conditions to achieve more than 95% of complete mixing uniformity; the standing can further ensure the uniform mixing of the materials.
In the invention, the solid content (i.e. the mass percentage of the solid) of the denitration catalyst slurry is 80-90 wt%, and preferably 85 wt%.
The conditions for the dehydration are not particularly limited in the present invention, and the desired solid content can be obtained, and in the embodiment of the present invention, the temperature for the dehydration is preferably 60 ℃.
After the denitration catalyst slurry is obtained, the denitration catalyst slurry is solidified and then mixed with the ethylene-vinyl acetate copolymer and the glass fiber to obtain the denitration catalyst slurry.
In the present invention, the curing is performed at room temperature (i.e., without additional heating or cooling), and the curing time is preferably 40min to 2h, and more preferably 60 min. In the invention, the whole water content of the raw materials is moderate and the raw materials have certain viscosity in the curing process.
The mixing mode is not particularly limited, and the uniformly mixed materials can be obtained.
After the denitration catalyst mud is obtained, the denitration catalyst mud is subjected to punch forming to obtain the corrugated sheet.
The specific mode of the punch forming is not specially limited, and the conventional punch forming method is adopted, for example, the punch forming is carried out by adopting a Shandong Lunan machine tool YL22-50T hydraulic press.
The specification of the corrugated sheet is not particularly limited, and a person skilled in the art can form the corrugated sheet with the required specification according to the requirement. In the embodiment of the invention, the thickness of the corrugated sheet is preferably 0.2-0.4 mm, the height is preferably 6-9 mm, and the peak-valley distance is preferably 4-9 mm.
After the corrugated sheets are obtained, resin glue is sprayed among the plurality of corrugated sheets and then the sheets are stacked and assembled to obtain the corrugated plate type denitration catalyst blank.
In the present invention, the resin glue is preferably a 150 epoxy resin glue. In the invention, the resin adhesive is used for adhering corrugated plates to form a corrugated plate type denitration catalyst blank. The amount of the resin adhesive is not particularly limited in the present invention, and may be any amount that can bond the corrugated sheets, and in the embodiment of the present invention, the amount of the resin adhesive is preferably 0.2mm in terms of coating thickness.
The number of the stacked and assembled corrugated sheets is not particularly limited in the present invention, and one skilled in the art can select the number of the corrugated sheets according to needs, and in the embodiment of the present invention, the number of the stacked and assembled corrugated sheets is preferably 10.
After the corrugated plate type denitration catalyst blank is obtained, the corrugated plate type denitration catalyst blank is fired to obtain the corrugated plate type denitration catalyst.
In the invention, the firing temperature is preferably 600-800 ℃, more preferably 720-760 ℃, most preferably 750 ℃, and the time is preferably 2.5-3.5 h, more preferably 3 h. In the invention, in the firing process, organic components are decomposed and volatilized, and simultaneously, moisture is removed, so that the corrugated plate type denitration catalyst is more stable.
The invention also provides the corrugated plate type denitration catalyst obtained by the preparation method of the technical scheme.
The following will explain in detail a corrugated plate type denitration catalyst and a preparation method thereof provided by the present invention with reference to examples, but they should not be construed as limiting the scope of the present invention.
Examples 1 to 3
Mixing graphene water-based slurry (with the solid content of 66 wt%, wherein the purity of graphene is 99.9%, and the particle size is 0.5-5 mu m), nano titanium dioxide, a 3A molecular sieve, molybdenum trioxide, tungsten trioxide, ammonium metavanadate, oxalic acid and water to obtain a mixed solution with the solid content of 70 wt%;
adjusting the pH value of the mixed solution to 7 by adopting ammonia water with the mass concentration of 5%, stirring at the rotation speed of 400rpm at 60 ℃ for 3h, standing at room temperature for 2h, and dehydrating in a drying chamber at 60 ℃ until the solid content is 85 wt% to obtain denitration catalyst slurry;
standing and curing the denitration catalyst slurry at room temperature for 1h, and uniformly mixing the denitration catalyst slurry with an ethylene-vinyl acetate copolymer and aluminoborosilicate glass fibers (the average length is 6cm, and the average diameter is 0.06cm) to obtain denitration catalyst slurry;
stamping and forming the denitration catalyst mud material to obtain corrugated sheets with the thickness of 1.2mm, the height of 360mm and the peak-valley interval of 420 mm;
spraying 150 epoxy resin glue with the thickness of 0.2mm between 10 corrugated sheets, and then laminating and assembling to obtain a corrugated plate type denitration catalyst blank;
and firing the corrugated plate type denitration catalyst blank at 750 ℃ for 3h to obtain the corrugated plate type denitration catalyst.
The time length of the whole process is less than 24 h.
The proportions of the main raw materials used in examples 1 to 3 in parts by mass are shown in Table 1,
TABLE 1 compounding ratio of main raw materials used in examples 1 to 3
| Proportioning | Example 1 | Example 2 | Example 3 |
| Graphene water-based slurry (in terms of graphene) | 0.7 | 1.0 | 1.4 |
| Nano titanium dioxide | 12 | 16 | 20 |
| 3A molecular sieve | 30 | 25 | 20 |
| Molybdenum trioxide | 4 | 5 | 6 |
| Tungsten trioxide | 4 | 6 | 7 |
| Ammonium metavanadate | 2 | 3 | 4.5 |
| Aluminoborosilicate glass fiber | 20 | 18 | 16 |
| Ethylene-vinyl acetate copolymer | 0.8 | 0.6 | 0.5 |
| Oxalic acid | 4.6 | 4.7 | 4.8 |
| Water (W) | 11.4 | 10.7 | 10.3 |
The flue gas denitration catalyst detection technical specification (GB/T38219-2019) is adopted to detect the activity temperature and the basic denitration efficiency (namely the lowest denitration efficiency in the activity temperature range) in the activity temperature range of the corrugated plate type denitration catalyst obtained in the examples 1-3, and the results are shown in Table 2. Wherein the test conditions are as follows: the reaction space velocity: 6000h-1The composition of the gas used in the test was: NO 1000ppm, NH3：1000ppm，SO2：100ppm，O2：6％，H2O: 10 percent. As can be seen from Table 2, the corrugated plate type denitration catalysts obtained in examples 1 to 3 all had an activation temperature of less than 300 ℃ and a basic denitration efficiency of 90% or more.
Table 2 results of performance test of corrugated plate type denitration catalysts obtained in examples 1 to 3
| Item | Example 1 | Example 2 | Example 3 |
| Activation temperature (. degree.C.) | 220～280 | 150～220 | 120～150 |
| Basic denitration efficiency (%) | 90 | 92 | 93 |
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a corrugated plate type denitration catalyst is characterized by comprising the following steps:
mixing graphene, nano titanium dioxide, a porous molecular sieve, molybdenum trioxide, tungsten trioxide, ammonium metavanadate, oxalic acid and water to obtain a mixed solution;
adjusting the pH value of the mixed solution to 6-7 by adopting ammonia water, and then sequentially stirring, mixing, standing and dehydrating to obtain denitration catalyst slurry; the solid content of the denitration catalyst slurry is 80-90 wt%;
curing the denitration catalyst slurry, and mixing the cured denitration catalyst slurry with ethylene-vinyl acetate copolymer and glass fiber to obtain denitration catalyst slurry;
stamping and forming the denitration catalyst mud material to obtain a corrugated sheet;
spraying resin glue among a plurality of corrugated sheets, and then laminating and assembling to obtain a corrugated plate type denitration catalyst blank;
and firing the corrugated plate type denitration catalyst blank to obtain the corrugated plate type denitration catalyst.
2. The production method according to claim 1, wherein the amount of each raw material for producing the corrugated plate-type denitration catalyst is as follows in parts by mass: 0.3-1.4 parts of graphene, 10-20 parts of nano titanium dioxide, 18-35 parts of a porous molecular sieve, 3-6 parts of molybdenum trioxide, 1-8 parts of tungsten trioxide, 0.1-8 parts of ammonium metavanadate, 4.5-4.8 parts of oxalic acid, 0.5-1 parts of an ethylene-vinyl acetate copolymer and 16-25 parts of glass fiber.
3. The preparation method according to claim 1 or 2, wherein the graphene is added in the form of graphene aqueous slurry, and the solid content of the graphene aqueous slurry is 60-70 wt%.
4. The production method according to claim 1 or 2, characterized in that the porous molecular sieve is a 3A molecular sieve; the glass fiber is aluminoborosilicate glass fiber.
5. The method according to claim 1, wherein the mixed solution has a solid content of 65 to 75 wt%.
6. The preparation method according to claim 1, wherein the stirring and mixing temperature is 55-65 ℃, the rotation speed is 300-500 rpm, and the time is 2.8-3.2 h; and standing is carried out at room temperature, and the standing time is 1.8-2.2 h.
7. The method according to claim 1, wherein the curing is performed at room temperature, and the curing time is 40min to 2 hours.
8. The method according to claim 1, wherein the firing is carried out at 600 to 800 ℃ for 2.5 to 3.5 hours.
9. The method of claim 1, wherein the corrugated sheet has a thickness of 0.2 to 0.4mm, a height of 6 to 9mm, and a peak-to-valley pitch of 4 to 9 mm.
10. The corrugated plate type denitration catalyst obtained by the preparation method of any one of claims 1 to 9.
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