CN113198456A - Catalytic filtration composite element and preparation method and application thereof - Google Patents
Catalytic filtration composite element and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 78
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 65
- 238000001914 filtration Methods 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 57
- 239000000835 fiber Substances 0.000 claims abstract description 50
- 239000000919 ceramic Substances 0.000 claims abstract description 47
- 239000002002 slurry Substances 0.000 claims abstract description 31
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 238000001354 calcination Methods 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 14
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002270 dispersing agent Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 230000002195 synergetic effect Effects 0.000 claims abstract description 5
- 238000000465 moulding Methods 0.000 claims abstract description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 99
- 239000003054 catalyst Substances 0.000 claims description 86
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 61
- 239000004408 titanium dioxide Substances 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 40
- 239000000377 silicon dioxide Substances 0.000 claims description 31
- 239000002243 precursor Substances 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 24
- 239000011230 binding agent Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- 239000010936 titanium Substances 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 8
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 239000002808 molecular sieve Substances 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012684 catalyst carrier precursor Substances 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 239000013618 particulate matter Substances 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 229910052863 mullite Inorganic materials 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 22
- 238000012360 testing method Methods 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 230000008569 process Effects 0.000 description 14
- 239000000428 dust Substances 0.000 description 13
- 239000003546 flue gas Substances 0.000 description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- 230000002776 aggregation Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
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- 238000005054 agglomeration Methods 0.000 description 4
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- 238000006555 catalytic reaction Methods 0.000 description 3
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- 230000007613 environmental effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
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- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
- B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
- B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
- B01D46/2411—Filter cartridges
-
- 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
-
- B01J35/40—
-
- B01J35/61—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
Abstract
The invention provides a catalytic filtration composite element and a preparation method and application thereof. The preparation method comprises the steps of mixing ceramic fibers, silica sol and a dispersing agent to form uniform slurry, mixing the slurry, injecting the slurry into a mold, demolding after molding, drying and calcining to obtain a base material; immersing the substrate in the first solution, keeping the substrate in vacuum for a period of time, taking out the substrate, performing microwave drying, and roasting to obtain an intermediate element; and immersing the intermediate element in the second solution, keeping the intermediate element in vacuum for a period of time, taking out the intermediate element, drying the intermediate element by microwave, and roasting to obtain the catalytic filtration composite element. The invention further provides a catalytic filtration composite element obtained by the preparation method and application thereof in synergetic removal of particulate matters and NOx. The composite element has the advantages of large pores, high toughness, large specific surface area, low pressure drop, high filtration efficiency and high catalytic activity.
Description
Technical Field
The invention relates to the technical field of high-temperature flue gas integrated purification, in particular to a catalytic filtration composite element and a preparation method and application thereof.
Background
With the continuous improvement of the emission standard of the flue gas and the increasing severity of the environmental protection situation, the comprehensive treatment and purification of the combustion flue gas pollutants become the central importance of the energy and environmental fields in China. Dust particles and Nitrogen Oxides (NO) in discharged flue gas in various fields of coal-fired power generation, petrochemical industry, metallurgy, waste incineration and the likex) Is the main component of atmospheric pollutants and also is the root cause of a series of environmental problems such as haze, photochemical smog, acid rain and the like. The dust removal and the catalytic denitration in the traditional high-temperature flue gas purification process are two independent operation units, and the ammonia (NH) introduced into the flue gas is usually utilized within the temperature range of 200-3) NO is reacted under the action of catalystxReducing to nontoxic and pollution-free nitrogen (N)2) After the temperature is reduced, dust particles in the flue gas are removed through cloth bag filtration or electrostatic dust removal, and the series process has the problems of complex process, high investment and operation cost, high energy consumption, large occupied area and the like.
In recent years, the dust removal and denitration integrated synergistic technology integrates two purification units, realizes the multifunction of an operation unit, solves the problems of the traditional series purification process, and becomes a new development trend in the field of high-temperature flue gas purification. The catalytic filtering composite element can remove dust particles and NO in a synergic mannerxOf new materials ofThe high-temperature flue gas passes through the catalytic filtering composite element, dust particles are intercepted on the outer surface of the element, and NO is contained in the flue gasxThe catalyst in the element is removed by selective catalytic reduction reaction, and the method becomes a new dust removal and denitration integrated technology with great application prospect.
Can remove particulate matter and NO synergisticallyxThe catalytic filtration composite element has become a research hotspot at home and abroad, wherein the ceramic membrane filtration element with the functions of dust removal and catalytic denitration and the preparation method thereof (patent number: ZL201611078604.3) disclose a ceramic membrane filtration element with the functions of dust removal and denitration and the preparation method thereof. The element includes a support, a separation membrane, and a denitration catalyst. The method comprises the steps of firstly spraying a separation membrane layer on the surface of a support to obtain a coated pipe, then pretreating the coated pipe, loading a denitration catalyst on the pretreated coated pipe, and finally carrying out heat treatment to obtain the ceramic membrane filtering element. However, the catalytic composite filter element of this type has the problems of large pressure drop, poor catalytic performance, short service life and high price, which are mainly attributed to the low porosity of the prepared filter element (<40%) and brittleness, easy agglomeration and uneven distribution of the supported catalyst, etc.
Disclosure of Invention
In order to solve the above problems, the present invention provides a catalytic filtration composite element, a method for preparing the same, and applications of the same. The composite element has the characteristics of low pressure drop, high filtering efficiency and high catalytic activity, and can be used for removing particulate matters and nitrogen oxides in a synergistic manner.
In order to achieve the above object, the present invention provides a method for preparing a catalytic filtration composite element, comprising:
s1, mixing the ceramic fiber, the silica sol and the dispersing agent to form uniform slurry, mixing the slurry and injecting the slurry into a mold, demolding after molding, and calcining to obtain a base material;
s2, immersing the filter element into the first solution, keeping the filter element in vacuum for a period of time, taking out the filter element, drying the filter element by microwave until the weight is constant, and roasting to obtain an intermediate element;
s3, immersing the intermediate element into the second solution, keeping the intermediate element in vacuum for a period of time, taking out the intermediate element, drying the intermediate element by microwave until the weight of the intermediate element is constant, and roasting the intermediate element to obtain the catalytic filtration composite element;
the first solution contains a catalyst carrier precursor, and the second solution contains a precursor of a catalyst active component and a precursor of a catalyst promoter.
In the specific embodiment of the present invention, in S1, the ceramic fiber has higher toughness, which can improve the mechanical properties and prolong the service life of the composite element. In some embodiments, the ceramic fibers may include one or a combination of two or more of aluminosilicate fibers, mullite fibers, alumina fibers, soluble ceramic fibers. The diameter of the ceramic fiber is generally controlled to be 0.5 μm to 15 μm.
In a specific embodiment of the present invention, in S1, the dispersant generally includes polyacrylamide and/or sodium carboxymethyl cellulose.
In the specific embodiment of the present invention, the mass ratio of the ceramic fiber, the silica sol and the dispersant is generally controlled to (1-5): (5-98): (0.05-4) in S1.
In the specific embodiment of the present invention, in S1, after the slurry is formed, most of the silica sol is uniformly distributed at the crossing positions between the ceramic fibers for bonding the cross-stacked ceramic fibers, and a small portion of the silica sol is also distributed on the surfaces of the ceramic fibers. After the formed slurry is dried, the silica sol is completely dried and cured and converted into a silica binder (the ceramic fiber itself also has a small amount of silica components, and the silica binder is used to refer to silica additionally added in the preparation process of the base material in order to avoid confusion). The generated silica binder can be used for bonding and fixing the ceramic fibers which are stacked in a crossed way to form a rigid framework of the composite element; on the other hand, the catalyst can replace titanium dioxide and the like to a certain extent to play a role of a catalyst carrier, so that the using amount of the catalyst carrier such as titanium dioxide and the like is saved, and the pressure drop of the composite element is reduced.
In the present embodiment, in S1, the slurry is formed by vacuum suction. During the vacuum pumping process, the ceramic fibers in the slurry are continuously accumulated in the mold to form a cross-stacked structure, and the silica sol is distributed at the cross of the ceramic fibers in a large quantity to bond the stacked ceramic fibers into a rigid skeleton.
In the embodiment of the present invention, in S1, the operation of drying to constant weight is generally further included after the slurry is demolded and before the calcination. The drying method is not limited, for example, microwave drying or the like can be adopted, and the drying process can make the silica binder uniformly distributed in the matrix forming process. Specifically, when the drying mode of microwave drying is adopted in S1, the power of microwave drying may be controlled to 70W-1000W.
In the specific embodiment of the present invention, in S1, the stacking density of the ceramic fibers and the distribution density of the silica binder at the intersections of the ceramic fibers may be adjusted by adjusting the vacuum suction conditions. Specifically, the parameters of the vacuum suction are generally controlled to be more than 0m/min and less than or equal to 20m/min, and specifically, after most of the liquid in the slurry is pumped away, the speed of the gas in the vacuum suction process is generally 10m/min-12 m/min.
In the specific embodiment of the invention, in S1, the calcination temperature is 400-1000 ℃, the calcination time is 2-5 h, and the temperature rise rate of the calcination is 1-10 ℃/min.
In a specific embodiment of the present invention, in S2, the catalyst support precursor includes a titanium source, such as a titanium sol, etc., and the titanium sol generally has a solid content of 5 to 20%. In some embodiments, the support precursor can further include a cerium source, a precursor of a molecular sieve, and the like.
In a specific embodiment of the present invention, in S2, the microwave drying manner is a drying manner with rapid heating and uniform heat distribution, which can effectively inhibit the carrier precursor such as titanium sol from forming agglomerates during the migration process to the surface of the substrate, so that the carrier such as titanium dioxide is uniformly distributed in the thickness direction of the substrate and the surface of the ceramic fiber, and the substrate maintains high porosity and specific surface area in the vicinity of the surface after loading the carrier such as titanium dioxide; meanwhile, the microwave drying method can change the grain size and the grain diameter of the titanium dioxide and increase the specific surface area of the titanium dioxide in a rapid drying mode. In some embodiments, the microwave drying power in S2 is generally 100W to 900W.
In the specific embodiment of the present invention, in S2, the temperature of the calcination is generally controlled to be 300-500 ℃, the time of the calcination is generally controlled to be 2-5 h, and the temperature rise rate of the calcination is generally controlled to be 1-10 ℃/min.
In the specific embodiment of the present invention, the degree of vacuum at which the substrate is immersed in the first solution in S2 is generally controlled to be 0.09MPa or more, and the time for keeping the immersion is generally controlled to be 20min to 60 min.
In a specific embodiment of the present invention, in S3, the precursor of the catalyst active component includes a vanadium source, and the precursor of the catalyst promoter includes a tungsten source, and the second solution may be obtained by heating a mixed solution including an acid, the precursor of the catalyst active component, the precursor of the catalyst promoter, and water. The heating is generally carried out at a temperature of 60-80 deg.C, and is terminated when the solution turns dark blue, and the heating time at 60-80 deg.C is usually controlled to be 10min-20min, such as 15min-20 min. The mass ratio of the acid, the catalyst active component precursor, the catalyst promoter precursor and the water is generally controlled to be (0.05-5): (0.05-5):100, the acid may be oxalic acid or the like, the vanadium source may include ammonium metavanadate or the like, and the tungsten source may include ammonium metatungstate or the like.
In a specific embodiment of the present invention, in S3, the second solution containing the catalyst active component precursor and the catalyst promoter precursor is reacted to generate the catalyst active component and the catalyst promoter. In the process, the generated catalyst active component and the catalyst auxiliary agent can be uniformly distributed on the surfaces of the silicon dioxide binder and the titanium dioxide by adopting a microwave drying mode, so that the exposed catalytic reaction active sites in the composite element are increased. In some embodiments, the microwave drying power in S3 is generally 100W to 900W.
In the specific embodiment of the present invention, in S3, the temperature of the calcination is generally controlled to be 300-500 ℃, the time of the calcination is generally controlled to be 2-5 h, and the temperature rise rate of the calcination is generally controlled to be 1-10 ℃/min.
In the specific embodiment of the present invention, the degree of vacuum at which the intermediate member is immersed in the second solution in S3 is generally controlled to be 0.09MPa or more, and the time for keeping the immersion is generally controlled to be 20min to 60 min.
In a specific embodiment of the present invention, the above preparation method may comprise:
1. stirring 1-5 parts of ceramic fiber, 5-98 parts of silica sol and 0.05-4 parts of dispersant by mass to form uniform slurry, injecting the slurry into a mold, pumping most of liquid out of the mold by adopting a vacuum pumping method, taking out the slurry when the slurry is formed and no liquid leaks, drying the formed slurry, calcining at the temperature of 400 ℃ for 2-5 h, wherein the heating rate in the roasting process is 1-10 ℃/min, and taking out the slurry after the room temperature is recovered to obtain a base material;
2. immersing the substrate in the step 1 in a first solution containing a carrier precursor (such as a titanium source and the like) to enable the liquid level of the solution to exceed the element, then placing the solution in a vacuum apparatus, vacuumizing to more than 0.09MPa, and keeping the vacuum apparatus for 20-60 min; taking out the filter element from the first solution, placing the filter element in a microwave dryer for drying to constant weight at the power of 100-;
3. mixing acid, a catalyst active component precursor and a catalyst auxiliary agent precursor with the mass ratio of (0.05-5):100 with water, stirring and heating to 60-80 ℃, keeping the temperature constant, continuing to heat for 10-30 min after the temperature reaches 60-80 ℃, stopping heating when the solution turns into dark blue to obtain a second solution, and standing for later use; immersing the intermediate element in the step 2 in a second solution, wherein the liquid level of the solution is higher than that of the intermediate element, putting the second solution and the intermediate element into a vacuum apparatus together, vacuumizing to more than 0.09MPa, and keeping for 20-60 min continuously; and then taking out the intermediate element from the second solution, drying the intermediate element by 100-900W microwaves to constant weight, roasting the intermediate element for 2-5 h at the temperature of 500 ℃ and the temperature rise rate of 1-10 ℃/min in the roasting process, and taking out the intermediate element after the temperature is restored to the room temperature to obtain the catalytic filtration composite element.
The invention also provides a catalytic filtration composite element, which is obtained by the preparation method.
In a specific embodiment of the invention, the catalytic filtration composite element generally comprises a substrate, a catalyst support (e.g., titania, etc.), a catalyst active component, and a catalyst adjunct, wherein the substrate comprises ceramic fibers and a silica binder.
In a specific embodiment of the invention, the structural framework of the substrate is ceramic fibers stacked in a crossed manner and a silica binder located at the crossed position of the ceramic fibers, the surface of the ceramic fibers in the substrate is loaded with a catalyst carrier, and the catalyst active component and the catalyst auxiliary agent are distributed on the surfaces of the catalyst carrier and the silica binder. In some embodiments, there is a small amount of silica binder distributed on the surface of the ceramic fibers in addition to a large amount of silica binder distributed at the intersections of the ceramic fibers.
In a specific embodiment of the present invention, the above-described substrate having a framework of a cross-stacked structure exhibits high porosity and specific surface area. The specific surface of the substrate is generally 50m2More than g, preferably up to 60m2Above/g, the porosity of the substrate is generally above 80%, preferably above 85%. The specific surface area of the composite member supporting titanium dioxide or the like is generally 55m2More than g, preferably up to 62m2The porosity is usually 75% or more (preferably 85% or more, more preferably 95% or more).
In a particular embodiment of the invention, the silica binder has a similar catalyst support effect as titania, e.g., a catalytic filtration composite element that is not loaded with titania (only silica, catalyst active component and catalyst promoter loaded) still has a catalytic efficiency of 30% or more at 300 ℃ (see fig. 5). In the composite element provided by the invention, the silica binder and the titanium dioxide can form a double-carrier structure, so that the catalytic activity of the composite element is improved. In this case, the amount of titanium dioxide loaded in the composite element can be appropriately reduced, thereby reducing the manufacturing cost of the element and reducing the operating voltage. In particular embodiments, the mass of the catalyst support (titania, etc.) is generally from 0.5 to 15% of the mass of the substrate. The titanium dioxide is typically anatase titanium dioxide, and the particle size of the titanium dioxide is typically 0.02 μm to 5 μm.
In the specific embodiment of the invention, the catalyst active component generally comprises vanadium pentoxide and the like, and the mass of the catalyst active component is generally controlled to be 0.5-10% of the mass of titanium dioxide.
In a specific embodiment of the present invention, the catalyst aid generally comprises tungsten trioxide or the like, and the mass of the catalyst aid is generally controlled to be 1 to 15% of the mass of titanium dioxide.
In a particular embodiment of the invention, the catalyst active component may also be used in other conventional active components, such as CeO2、Fe2O3The catalyst auxiliaries can also be the customary auxiliary components, for example MoO3Etc., the composition of the second solution may be adjusted according to the specific catalyst active component and catalyst promoter used.
In a specific embodiment of the present invention, the above-mentioned catalytic filtering composite element may further comprise other commonly used catalyst carriers, such as molecular sieve, CeO, etc., in addition to titanium dioxide2And the like.
The invention further provides a catalytic filter element for synergistically removing particulate matters and NOx, which comprises the catalytic filter composite element. For example, the catalytic efficiency of the catalytic reaction of the catalytic filter composite element at the temperature of 250 ℃ and 350 ℃ can reach 100%.
The invention has the beneficial effects that:
1. the preparation method of the invention obtains the base material with higher porosity and specific surface area by utilizing a microwave drying mode, is beneficial to uniform dispersion and loading of the catalyst carrier, the catalyst active component and the catalyst auxiliary agent on the base material, and can reduce the pressure drop of the composite element, prolong the retention time of gas and ensure that the catalytic reaction is more sufficient; meanwhile, the microwave drying mode can avoid the agglomeration of the source solution of the silicon dioxide binder, the titanium dioxide, the catalyst active component and the catalyst auxiliary agent when the source solution migrates to the surface of the base material, the components can be uniformly distributed in the thickness direction of the element and the surface of the base material, the reaction activity in the composite element is increased, and the catalytic efficiency is improved; in addition, the microwave drying mode can limit the crystal grain and the grain size of the catalyst carrier, improve the specific surface area and further improve the catalytic activity of the catalytic filter element.
2. The silicon dioxide binder in the composite element provided by the invention has the function of a catalyst carrier, and can form a double-carrier structure with the catalyst carrier (titanium dioxide and the like), so that the catalytic performance of the composite element is greatly improved, the loading capacity of the font of the catalyst is saved, and the manufacturing cost and the operation pressure drop of the composite element are reduced.
3. The composite element provided by the invention has the advantages of high porosity, large specific surface area, uniform structure and the like, has more excellent catalytic performance after being loaded with the catalyst compared with the traditional ceramic powder type composite element, has certain toughness, is not easy to damage in the processes of transportation, installation and use, and has longer service life.
4. The preparation method provided by the invention has the advantages of simple and efficient process, short preparation period and low manufacturing cost, and avoids the problem of non-ideal catalytic performance of the composite element caused by improper preparation process.
Drawings
FIG. 1 is a schematic structural view of a catalytic filtration composite element of example 1.
FIG. 2 is an SEM photograph of titania formed by different drying methods in test example 1.
FIG. 3 is an XRD spectrum of titanium dioxide formed by different drying modes in test example 1.
Fig. 4 is a physical photograph and an SEM photograph of the catalytic filtration composite member prepared in example 1 and comparative example 2.
Fig. 5 is a denitration performance test chart of the catalytic filtration composite members prepared in example 1, comparative example 1 and comparative example 2.
Fig. 6 is a denitration performance test chart of the catalytic filtration composite member prepared in examples 1 to 3.
Description of the symbols: 10-ceramic fibers; 20-silicon dioxide; 30-titanium dioxide.
Detailed Description
The technical solutions of the present invention will be described in detail below in order to clearly understand the technical features, objects, and advantages of the present invention, but the present invention is not limited to the practical scope of the present invention.
The following examples and comparative examples employ the following reagent specifications: the diameter of the aluminum silicate fiber is 3-8 μm; sodium carboxymethylcellulose, 300-800 mpa.s; the solid content of the silica sol is 30 wt%, and the average particle size of the silica is 13 nm; the titanium sol had a solid content of 8 wt% and the titanium dioxide had an average particle diameter of 15 nm.
Example 1
The embodiment provides a catalytic filtration composite element, and a preparation method thereof comprises the following steps:
1. based on the total mass of the slurry as 100 percent, 2 percent of aluminum silicate fiber, 0.5 percent of sodium carboxymethyl cellulose and 97.5 percent (based on the mass of silicon dioxide) of silica sol are stirred in a high-speed disperser for 90min to form uniform slurry. Injecting the slurry into a mold, and pumping most of liquid out of the mold by adopting a vacuum pumping method, wherein after most of the liquid in the slurry is pumped out, the speed of vacuum pumped gas is 10-12 m/min; taking out the slurry when the slurry is formed and no liquid leaks out, putting the formed slurry into a microwave dryer, drying the slurry at 700W until the power is constant, and completely drying and curing the silica sol in the slurry to form a rigid structure; then calcining for 3h at 600 ℃, wherein the heating rate in the calcining process is 10 ℃/min, and taking out after the room temperature is recovered to obtain the base material.
2. Immersing the substrate in the step 1 in titanium sol (as a first solution) with solid content of 8 wt% to make the solution level exceed the element, and then placing the substrate in a vacuum apparatus, and vacuumizing to 0.098MPa for 40 min. And taking out the filter element from the first solution, placing the filter element in a microwave dryer for 385W power drying to constant weight, placing the filter element in a high-temperature furnace for roasting at 300 ℃ for 3h, wherein the heating rate in the roasting process is 5 ℃/min, and taking out the filter element after the room temperature is recovered to obtain an intermediate element, wherein the intermediate element is loaded with titanium dioxide.
3. Mixing oxalic acid, ammonium metavanadate, ammonium metatungstate and water in a mass ratio of 0.8:0.4:0.8:100, heating to 70 ℃ while stirring, keeping the temperature constant, stopping heating after the solution turns to dark blue after 10min to obtain a second solution, and standing for later use. Immersing the intermediate element in the step 2 in a second solution, wherein the liquid level of the solution is higher than that of the intermediate element, putting the second solution and the intermediate element into a vacuum apparatus, vacuumizing to 0.098MPa, and keeping for 40 min. And then taking out the intermediate element from the second solution, placing the intermediate element in a microwave dryer for 385W power drying to constant weight, finally placing the intermediate element in a high-temperature furnace for roasting at 300 ℃ for 3h, wherein the heating rate in the roasting process is 5 ℃/min, and taking out the intermediate element after the room temperature is recovered to obtain the catalytic filtration composite element.
The structure of the catalytic filtering composite element is schematically shown in figure 1. As can be seen from fig. 1, the main skeleton of the composite element is formed by the ceramic fibers 10 arranged in a cross-stacked manner, and the ceramic fibers 10 are bonded and fixed by the silica 20 to form a rigid structure. Titanium dioxide 30 and a small amount of silicon dioxide are uniformly distributed on the surface of the ceramic fiber 10, and both have the function of a catalyst carrier. Vanadium pentoxide (not shown in fig. 1) as an active component of the catalyst and tungsten trioxide (not shown in fig. 1) as a catalyst assistant are uniformly distributed on the surfaces of the silicon dioxide 20 and the titanium dioxide 30.
Through tests, the porosity of the catalytic filtration composite element prepared in the embodiment is 84%, and the specific surface area is 68m2/g。
The composite element is subjected to dust removal and denitration performance tests, the initial pressure drop of the composite element is 180Pa at the gas velocity of 1m/min, the dust removal efficiency exceeds 99.9 percent, and the concentration of downstream dust particles is lower than 5mg/m3The catalytic denitration efficiency reaches 100% in the temperature range of 250-375 ℃.
Example 2
This example provides a method for preparing a catalytic filtration composite element, which differs from example 1 only in that: the power of microwave drying in step 2 was 231W, and other experimental steps and experimental parameters were the same as those in example 1.
Example 3
This example provides a method for preparing a catalytic filtration composite element, which differs from example 1 only in that: the power of microwave drying in step 2 was 700W, and other experimental steps and experimental parameters were the same as those in example 1.
Comparative example 1
The comparative example provides a preparation method of a catalytic filtration composite member not loaded with titanium dioxide, which is different from the preparation method of example 1 only in that step 2 is not included, and other experimental steps and experimental parameters are the same as those of example 1; namely, the substrate prepared in the step 1 is directly immersed in a second solution formed by oxalic acid, ammonium metavanadate, ammonium metatungstate and water, and microwave drying and roasting are carried out according to the same experimental parameters as those of the embodiment 1, so as to obtain the catalytic filtration composite element.
Comparative example 2
This comparative example provides a method for preparing a catalytic filtration composite member, which is different from example 1 only in that air-blast drying is used instead of microwave drying in step 2, the air-blast drying condition is 120 ℃ for 12h, and other experimental steps and experimental parameters are the same as those in example 1.
Test example 1
The test example tests the structural influence of different drying modes on the titanium dioxide formed by the titanium sol. Specifically, a titanium sol having a solid content of 8 wt% was dried in a microwave drying mode of drying at 385W to a constant weight and a blast drying mode of drying at 120 ℃ for 12 hours, respectively, and firing conditions were the same as in step 2 of example 1.
Fig. 2 is SEM photographs of the two titanium dioxide samples, wherein a is a titanium dioxide formed by air-blast drying and b is a titanium dioxide formed by microwave drying. As can be seen from fig. 2, the titanium dioxide particles formed by the forced air drying are spherical as a whole, and the particle size is larger as a whole; the titanium dioxide formed by microwave drying is mainly irregular particles, and the particle size is smaller as a whole.
FIG. 3 is an XRD spectrum of the two titanium dioxide samples, and from the results of FIG. 3, it can be calculated that the grain size of the air-dried titanium dioxide is 11.2nm and the grain size of the microwave-dried titanium dioxide is 10.0nm, indicating that the microwave-dried titanium dioxide has smaller grains than the air-dried titanium dioxide. Together with the results of fig. 3, fig. 2 shows that the microwave drying method is more advantageous for forming titanium dioxide particles having a small particle size, a small crystal grain size, and a large specific surface area than the air-blast drying method.
Test example 2
The present test example provides a morphological characterization of the catalytic filtration composite elements prepared in example 1 and comparative example 2, and the results are summarized in fig. 4, wherein a1 is a photograph of a sample of comparative example 2, and a2 is a surface cross-cut SEM photograph of the sample of comparative example 2; b1 is a photograph of the sample of example 1, and b2 is a surface-slit SEM photograph of the sample of example 3. As can be seen by comparing the a1 plot with the a2 plot, the composite member of comparative example 2 exhibited significant agglomeration at the surface, whereas the composite member of example 1 exhibited no agglomeration at the surface. As can be seen by comparing the b1 graph with the b2 graph, there is significant aggregation of particles between the ceramic fibers at the locations near the surface of the composite member of comparative example 2, while the aggregation of particles at the same locations in example 1 is less significant. From the above results, it can be seen that the microwave drying method is advantageous in that the inorganic particles (titanium dioxide, etc.) are uniformly distributed in the thickness direction of the substrate and on the surface of the ceramic fiber.
Test example 3
The test example performed a denitration performance test on the samples of the catalytic filtration composite members prepared in example 1, comparative example 1, and comparative example 2. The test condition is that the gas velocity is 1m/min, and the denitration performance test result is shown in FIG. 5.
As can be seen from fig. 5: (1) in the case of no supporting titanium dioxide, only supporting vanadium pentoxide and tungsten trioxide, the substrate comprising only ceramic fibers and silica (sample of comparative example 1) had a certain catalytic performance, indicating that silica in the composite member not only served as a binder between the frameworks but also had a certain catalyst carrier function. Therefore, the preparation method provided by the invention can replace a part of titanium dioxide by silicon dioxide, and achieve the aims of saving titanium dioxide, reducing cost and reducing operation pressure drop. (2) The NO conversion efficiency of the composite element obtained by microwave drying at the temperature of 150-400 ℃ is higher than that of the composite element obtained by blast drying.
As can be seen from the results of fig. 5 and test example 1, compared with forced air drying, the microwave drying method can uniformly distribute the ceramic fiber-supported catalyst carrier, the catalyst active component and the catalyst auxiliary, and can also effectively reduce the particle size of titanium dioxide, increase the specific surface area of titanium dioxide, and further effectively increase the catalytic activity of the composite element.
In the above test, the initial pressure drop of the Catalytic composite filter element of example 1 was measured to be 180Pa, which is significantly lower than the initial pressure drop of 500-600Pa of the existing Catalytic composite filter element (for example, the initial pressure drop of the filter element at a gas velocity of 1m/min is 560Pa as described in hydrotherma Synthesis of a Pt/SAPO-34@ SiC Catalytic Membrane for the filtration and Removal of NO and Particulate Matter).
Test example 4
In this test example, the denitration performance test was performed on the samples of the catalytic filtration composite elements prepared in examples 1 to 3 under the same test conditions as in test example 3, and the test results are shown in fig. 6.
As can be seen from FIG. 6, the catalytic filtration composite element formed by the 200W-700W microwave drying method has high denitration efficiency, and the NO conversion rate can reach more than 90%.
Claims (10)
1. A method of making a catalytic filtration composite element comprising:
s1, mixing the ceramic fiber, the silica sol and the dispersing agent to form uniform slurry, mixing the slurry and injecting the slurry into a mold, demolding after molding, drying and calcining to obtain a base material;
s2, immersing the substrate in the first solution, keeping the substrate in vacuum for a period of time, taking out the substrate, drying the substrate by microwave until the weight is constant, and roasting the substrate to obtain an intermediate element;
s3, immersing the intermediate element in the second solution, keeping the intermediate element in vacuum for a period of time, taking out the intermediate element, drying the intermediate element by microwave until the weight of the intermediate element is constant, and roasting the intermediate element to obtain the catalytic filtration composite element;
the first solution contains a catalyst carrier precursor, and the second solution contains a precursor of a catalyst active component and a precursor of a catalyst promoter.
2. The preparation method according to claim 1, wherein in S1, the ceramic fibers include one or a combination of two or more of aluminosilicate fibers, mullite fibers, alumina fibers, soluble ceramic fibers; preferably, the ceramic fibers have a diameter of 0.5 to 15 μm;
in S1, the dispersant includes polyacrylamide and/or sodium carboxymethyl cellulose;
in S1, the mass ratio of the ceramic fiber to the silica sol to the dispersant is (1-5) to (5-98) to (0.05-4);
in S2, the catalyst carrier precursor comprises a titanium source, the titanium source preferably comprises titanium sol, and the solid content of the titanium sol is preferably 5-20%; preferably, the catalyst support precursor further comprises a cerium source and/or a molecular sieve precursor;
in S3, the precursor of the active component of the catalyst comprises a vanadium source, and the precursor of the catalyst promoter comprises a tungsten source; preferably, the second solution is obtained by heating a mixed solution comprising an acid, a precursor of the catalyst active component, a precursor of the catalyst promoter and water; more preferably, the heating is carried out at 60-80 ℃ for 10min-20min, and the heating time is preferably 15min-20 min; more preferably, the mass ratio of the acid, the catalyst active component precursor, the catalyst auxiliary precursor and the water is (0.05-5): (0.05-5): 100; more preferably, the acid comprises oxalic acid, the source of vanadium comprises ammonium metavanadate, and the source of tungsten comprises ammonium metatungstate.
3. The preparation method according to claim 1, wherein in S2, the power of the microwave drying is 100W-900W; in S3, the power of the microwave drying is 100W-900W.
4. The method according to claim 1, wherein in S1, the slurry is formed by vacuum suction; preferably, the air speed of the vacuum suction is more than 0m/min and less than or equal to 20 m/min.
5. The preparation method as claimed in claim 1, wherein in S1, the calcination temperature is 400-1000 ℃, the calcination time is 2-5 h, and the temperature rise rate of the calcination is 1-10 ℃/min;
in S2, the roasting temperature is 300-500 ℃, the roasting time is 2-5 h, and the roasting temperature rise rate is 1-10 ℃/min;
in S3, the roasting temperature is 300-500 ℃, the roasting time is 2-5 h, and the roasting temperature rise rate is 1-10 ℃/min;
in S2, the vacuum degree is more than 0.09MPa, and the time for immersing the base material in the first solution is 20min-60 min;
and in S3, the vacuum degree is more than 0.09MPa, and the immersion time of the intermediate element in the second solution is 20min-60 min.
6. A catalytic filtration composite element obtained by the production method according to any one of claims 1 to 5.
7. The composite element of claim 6, wherein the catalytic filtration composite element comprises a substrate comprising ceramic fibers and a silica binder, a catalyst support, a catalytically active component, and a catalyst promoter;
preferably, the catalyst support comprises titanium dioxide, the porosity of the composite member is 75% or more, and the specific surface area of the composite member is 55m2More than g; the specific surface area of the base material is 50m2(ii) a porosity of 80% or more per g of the base material.
8. The composite member of claim 7, wherein the structural skeleton of the substrate is a cross-stacked ceramic fiber and a silica binder at the cross of the ceramic fiber, the surface of the ceramic fiber is loaded with a catalyst carrier, and the catalyst active component and the catalyst auxiliary agent are distributed on the surfaces of the catalyst carrier and the silica binder; preferably, the silica is also distributed on the surface of the ceramic fiber.
9. The composite element according to claim 7 or 8, wherein the mass of the catalyst support is 0.5-15% of the mass of the substrate; the titanium dioxide preferably comprises anatase titanium dioxide, and the particle size of the titanium dioxide is preferably 0.02-5 μm;
the catalyst active component comprises vanadium pentoxide, and the mass of the catalyst active component is preferably 0.5-10% of that of the catalyst carrier;
the catalyst auxiliary agent comprises tungsten trioxide, and the mass of the catalyst auxiliary agent is preferably 1-15% of that of the catalyst carrier;
preferably, the catalytic filtration composite element further comprises molecular sieves and/or CeO2As a catalyst support.
10. A catalytic filter element for the synergistic removal of particulate matter and NOx comprising the catalytic filter composite of any of claims 6-9.
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