CN108434870B - Filter element type carrier and preparation method thereof, and supported catalyst and preparation method thereof - Google Patents
Filter element type carrier and preparation method thereof, and supported catalyst and preparation method thereof Download PDFInfo
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- CN108434870B CN108434870B CN201810258249.0A CN201810258249A CN108434870B CN 108434870 B CN108434870 B CN 108434870B CN 201810258249 A CN201810258249 A CN 201810258249A CN 108434870 B CN108434870 B CN 108434870B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims description 18
- 239000000919 ceramic Substances 0.000 claims abstract description 82
- 239000000835 fiber Substances 0.000 claims abstract description 78
- 239000011148 porous material Substances 0.000 claims abstract description 40
- 239000011230 binding agent Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000011790 ferrous sulphate Substances 0.000 claims description 7
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 7
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 239000002657 fibrous material Substances 0.000 claims 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 22
- 239000000428 dust Substances 0.000 abstract description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003546 flue gas Substances 0.000 abstract description 5
- 239000000969 carrier Substances 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Images
Classifications
-
- B01J35/58—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
- B01D39/2068—Other inorganic materials, e.g. ceramics
-
- 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
- B01D46/0027—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions
-
- 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
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
Abstract
The invention belongs to the technical field of catalyst carriers. The filter element type carrier provided by the invention comprises a single-end opening pipe made of ceramic fiber; the ceramic fiber single-end opening pipe has a pore structure, the pores are formed by ceramic fibers in a cross-laminated arrangement mode, and the inner diameter of each pore is 10-180 mu m; the total volume of the pores accounts for 80-95% of the total volume of the single-end open-ended tube made of the ceramic fibers. The invention also provides a supported catalyst which comprises an active component and a carrier, wherein the carrier is a supported carrier. When the supported catalyst prepared by using the filter element type carrier is used for denitration treatment, the denitration efficiency reaches 80-97% in a middle-low temperature region of 260-400 ℃, and the filter element type carrier provided by the invention can effectively filter dust in flue gas and reduce the influence of the dust on the catalytic performance of the catalyst.
Description
Technical Field
The invention belongs to the technical field of catalyst carriers, and particularly relates to a filter element type carrier and a preparation method thereof, a supported catalyst and a preparation method thereof.
Background
The catalyst carrier is a dispersing agent, an adhesive or a support body of the catalytic active component, is a framework for loading the catalytic active component, and can improve the catalytic performance of the catalytic active component. In order to increase the loading capacity of the catalyst carrier, researchers have continuously improved the structure of the catalyst carrier, such as flat plate type, corrugated type and honeycomb type, which are widely used catalyst carrier configurations. As shown in fig. 1, the honeycomb type carrier is named because it has a honeycomb porous structure, and compared with a flat plate type or corrugated type carrier, the honeycomb type carrier has a large specific surface area, and is beneficial to loading more catalytic active components, so that the honeycomb type carrier is widely applied to the field of industrial denitration, but the catalytic performance of a catalyst prepared from the honeycomb type carrier is easily influenced.
Disclosure of Invention
The invention aims to provide a filter element type carrier and a preparation method thereof.
In order to achieve the above purpose, the invention provides a filter element type carrier, which comprises a single-end opening pipe made of ceramic fiber; the ceramic fiber single-end opening pipe has a pore structure, the pores are formed by ceramic fibers in a cross-laminated arrangement mode, and the inner diameter of each pore is 10-180 mu m; the total volume of the pores accounts for 80-95% of the total volume of the single-end open-ended tube made of the ceramic fibers.
Preferably, the inner diameter of the ceramic fiber single-end opening pipe is 30-150 mm, and the thickness of the side wall of the ceramic fiber single-end opening pipe is 8-20 mm.
Preferably, the length of the ceramic fiber single-end open-ended pipe is 100-8000 mm.
Preferably, the open end of the ceramic fiber single-end open-ended tube is flanged or tapered.
The invention provides a preparation method of the filter element type carrier in the technical scheme, which comprises the following steps:
(1) mixing ceramic fiber, a binder and water to obtain a mixed solution; the mass ratio of the ceramic fibers to the binder to the water is 1: 0.1-0.3: 100;
(2) immersing a filter element type carrier mould into the mixed liquid obtained in the step (1), and then obtaining a filter element type carrier primary blank through negative pressure forming and demoulding; drying the primary blank of the filter element type carrier to obtain the filter element type carrier;
the filter element type die is provided with micropores, the diameter of each micropore is 40-80 meshes, and the density of each micropore is 60000-120000/m2。
Preferably, the binder in step (1) is silica sol, polyacrylamide or starch.
The invention also provides a supported catalyst, which comprises a carrier and an active component; the carrier is the filter element type carrier in the technical scheme or the filter element type carrier prepared by the preparation method in the technical scheme, and the active components are distributed in the pores of the single-end open-ended pipe made of ceramic fibers of the filter element type carrier.
Preferably, the mass of the active component is 8-80% of the mass of the filter element type carrier.
Preferably, the active component comprises ferrous sulphate.
The invention provides a preparation method of the supported catalyst in the technical scheme, which comprises the following steps:
(a) mixing a compound corresponding to the active component with water to obtain an active component aqueous solution;
(b) and (b) dipping the filter element type carrier into the active component aqueous solution obtained in the step (a), and drying the dipped filter element type carrier to obtain the supported catalyst.
The filter element type carrier comprises a ceramic fiber single-end opening pipe, wherein the ceramic fiber single-end opening pipe is of a pore structure, pores are formed by ceramic fibers in a crossed and laminated arrangement mode, and the inner diameter of each pore is 10-180 mu m; the total volume of the pores accounts for 80-95% of the total volume of the single-end open-ended tube made of the ceramic fibers. The carrier provided by the invention is of a filter element type structure, can filter dust in flue gas, reduces the coverage of the dust on the catalyst, avoids the poisoning of the catalyst by heavy metal in the dust, and further improves the stability of the catalytic performance of the catalyst. The results of the embodiments of the invention show that when the supported catalyst obtained by loading ferrous sulfate on the filter element type carrier is used for denitration treatment, the denitration efficiency reaches 80-97% in a middle and low temperature region of 260-400 ℃, which indicates that the filter element type carrier provided by the invention can effectively filter dust in flue gas and reduce the influence of the dust on the catalytic performance of the catalyst.
Drawings
FIG. 1 is a schematic diagram of a honeycomb carrier of the prior art;
FIG. 2 is a schematic view of the primary blank negative pressure forming of the filter element carrier of the present invention;
FIG. 3 is an external view of a cartridge type carrier according to example 1;
FIG. 4 is an external view of a supported catalyst obtained in example 1;
FIG. 5 is a microscopic view of a cartridge carrier of example 1;
FIG. 6 is a statistical chart of pore size distribution of pores of a filter element type carrier in example 1;
FIG. 7 is an SEM image of the supported catalyst obtained in example 1 at different magnification.
Detailed Description
The invention provides a filter element type carrier, which comprises a single-end open tubular product made of ceramic fibers; the ceramic fiber single-end opening pipe has a pore structure, the pores are formed by ceramic fibers in a cross-laminated arrangement mode, and the inner diameter of each pore is 10-180 mu m; the total volume of the pores accounts for 80-95% of the total volume of the single-end open-ended tube made of the ceramic fibers.
In the invention, the filter element type carrier comprises a single-end open tubular product made of ceramic fiber; as shown in fig. 2, the open end of the single-end open tubular product made of ceramic fibers is preferably a flange or a cone, so as to avoid the cracking or breaking of the filter element carrier due to weight during the use of the filter element carrier, and further improve the service life of the filter element carrier. In the invention, the inner diameter of the ceramic fiber single-end opening pipe is preferably 30-150 mm, and more preferably 45-120 mm; the side wall thickness of the ceramic fiber single-end opening pipe is preferably 8-20 mm, and more preferably 10-15 mm. The length of the single-end opening pipe made of the ceramic fiber is not particularly required, and the length of the single-end opening pipe made of the ceramic fiber preferably comprises, but is not limited to, 100-8000 mm, and further preferably 150-4500 mm. In the invention, the thickness of the bottom of the closed end of the ceramic fiber single-end open-ended tube is preferably 10-20 mm, and more preferably 12-15 mm. The invention has no special requirements on the cross section shape of the single-end open pipe made of the ceramic fiber, including but not limited to round or rectangle.
In the invention, the ceramic fiber single-end opening pipe has pores, and the pore diameter of the pores is 10-180 μm, preferably 20-100 μm, and more preferably 40-80 μm. In the invention, the total volume of the pores accounts for 80-95% of the total volume of the single-end open-ended tube made of the ceramic fibers, more preferably 85-92%, and even more preferably 88-90%. In the present invention, the pores are formed by cross-ply arrangement of ceramic fibers. In the invention, the pores are distributed on the surface and inside of the single-end open-ended tube made of the ceramic fiber. According to the invention, the active component is loaded by utilizing the pores of the single-end-opening pipe made of the ceramic fiber, so that the loading capacity of the active component can be improved, the direct contact between the active component and dust can be avoided, and the influence of the dust on the catalytic performance of the active component is reduced.
In the invention, the ceramic fiber single end opening pipe further comprises residual binder. In the invention, the mass ratio of the binder to the ceramic fiber in the single-end open-ended tube made of the ceramic fiber is preferably 0.1-3: 97-99.9, and more preferably 1-2.5: 97.5-99. The invention has no special requirements on the chemical composition of the ceramic fiber; in the present invention, the kinds of the ceramic fiber include, but are not limited to, alumina and silica-made ceramic fiber, calcium oxide, magnesium oxide and silica-made soluble ceramic fiber. In the present invention, the binder is preferably silica, polyacrylamide, or starch, and more preferably silica. The present invention does not require a particular source of the ceramic fibers and binder, and may be accomplished using commercially available products well known to those skilled in the art.
In the invention, the density of the filter element type carrier is preferably 270-330 kg/m3More preferably 280 to 320kg/m3(ii) a The air permeability of the filter element type carrier is preferably 50-250 m3/m20.5 KPa.h, more preferably 70 to 180m3/m2·0.5KPa·h。
The invention provides a preparation method of the filter element type carrier in the technical scheme, which comprises the following steps:
(1) mixing ceramic fiber, a binder and water to obtain a mixed solution; the mass ratio of the ceramic fibers to the binder to the water is 1: 0.1-0.3: 100;
(2) immersing a filter element type carrier mould into the mixed liquid obtained in the step (1), and then obtaining a filter element type carrier primary blank through negative pressure forming and demoulding; drying the primary blank of the filter element type carrier to obtain the filter element type carrier;
the filter element type die is provided with micropores, the diameter of each micropore is 40-80 meshes, and the density of each micropore is 60000-120000/m2。
According to the invention, ceramic fiber, a binder and water are mixed to obtain a mixed solution. In the present invention, the chemical composition of the ceramic fibers is consistent with the ceramic in the single end open tube made of ceramic fibers and is not repeated here. The present invention does not require a particular source of the ceramic fibers and may be accomplished using commercially available products well known to those skilled in the art.
In the present invention, the binder is identical to the binder in the single end open tubular product made of ceramic fibers and is not repeated here. In the present invention, the binder is preferably provided in the form of an aqueous dispersion. The mass concentration of the aqueous binder dispersion is not particularly critical in the present invention, and those skilled in the art will appreciate. In the present invention, when the binder is silica, the silica is preferably provided in the form of a silica sol. In the present invention, the mass concentration of silica in the silica sol is preferably 25 to 35%, and more preferably 27 to 32%. The invention does not require a particular manner of forming the silica sol, and may be carried out in a manner known to those skilled in the art. The present invention does not require a particular source of the binder and may employ commercially available products well known to those skilled in the art.
In the present invention, the mass ratio of the ceramic fiber, the binder and water is 1:0.1 to 0.3:100, and more preferably 1:0.2: 100. The invention has no special requirement on the mixing mode of the ceramic fiber, the binder and the water, and the mixing mode which is well known by the technicians in the field can be adopted.
After the mixed solution is obtained, the filter element type carrier mould is immersed into the mixed solution, and then the primary blank of the filter element type carrier is obtained through negative pressure forming and demoulding. The negative pressure forming is a process of attaching ceramic fibers in a mixed solution to the surface of a filter element type mould by using negative pressure so as to form a primary blank of a filter element type carrier. As shown in fig. 7, 1 is a mixed liquid, 2 is a negative pressure connection port, 3 is a filter element type mold, 4 is ceramic fiber, wherein the filter element type mold is a single end opening pipe, the opening end of the pipe is communicated with the negative pressure connection port and is used for discharging water in the mixed liquid(ii) a And the pipe body of the filter element type mould is provided with micropores. After the negative pressure is communicated, water in the mixed liquid is discharged through the micropores on the filter element type mould tube body, the binder is adsorbed on the surface of the ceramic fiber and is retained on the outer surface of the mould tube body together with the ceramic fiber to form a filter element type carrier primary blank. In the invention, the diameter of the micropores is preferably 40-80 meshes, and is further preferably 50-60 meshes; the density of the micropores is 60000-120000/m2More preferably 80000 to 100000 pieces/m2. In the present invention, the negative pressure is preferably-0.6 to-0.4 MPa, and more preferably-0.5 to-0.45 MPa. The invention has no special requirement on the pressure maintaining time of the negative pressure, so that the thickness of the ceramic fiber retained on the outer surface of the filter element type mould can be stopped as required. The present invention does not require any particular embodiment of the negative pressure, and may be implemented as is known to those skilled in the art. In the present invention, the material of the filter element type mold is preferably stainless steel.
And after the mixed solution is injected into the filter element type mould, the ceramic fiber in the mixed solution is solidified and molded under the action of the binder. The present invention has no special requirement on the specific implementation conditions of the curing molding, and the conditions are well known to those skilled in the art. After the ceramic fiber is solidified and formed, the filter element type mould is removed, and a filter element type carrier primary blank is obtained. The removal mode of the filter element type mould is not particularly required by the invention, and the mode known by the technical personnel in the field can be adopted.
After the primary blank of the filter element type carrier is obtained, the primary blank of the filter element type carrier is dried to obtain the filter element type carrier. In the present invention, the water content of the filter element type carrier is not more than 13%. In the invention, the drying temperature is preferably 100-230 ℃, and more preferably 120-200 ℃. The invention has no special requirement on the drying time, and the filter element type carrier with the water content in the range can be obtained. The present invention has no special requirements for the specific implementation of the drying, and in the embodiment of the present invention, the drying is preferably performed in an oven.
The invention also provides a supported catalyst, which comprises a carrier and an active component; the carrier is the filter element type carrier in the technical scheme or the filter element type carrier prepared by the preparation method in the technical scheme, and the active components are distributed in the pores of the single-end open-ended pipe made of ceramic fibers of the filter element type carrier.
In the invention, the supported catalyst comprises a carrier, and the carrier is a carrier of the filter element in the technical scheme or a filter element type carrier prepared by the preparation method in the technical scheme, and the process is not repeated.
In the invention, the supported catalyst comprises active components which are distributed in the pores of the single-end open-ended pipe made of ceramic fibers of the filter element type carrier. According to the invention, the loading amount of the supported catalyst is preferably 8-80%, and more preferably 15-40%, based on the mass percentage of the active component in the filter element type carrier. In the present invention, the active component preferably comprises ferrous sulfate.
When the supported catalyst is used for denitration catalysis, the catalytic efficiency of the supported catalyst at 260 ℃ or higher is preferably 80% or higher, and more preferably 80.1-97%. In the invention, the catalytic efficiency of the supported catalyst is more than 95% at the temperature of 320-380 ℃.
The invention provides a preparation method of the supported catalyst in the technical scheme, which comprises the following steps:
(a) mixing a compound corresponding to the active component with water to obtain an active component aqueous solution;
(b) and (b) dipping the filter element type carrier into the active component aqueous solution obtained in the step (a), and drying the dipped filter element type carrier to obtain the supported catalyst.
According to the invention, a compound corresponding to an active component is mixed with water to obtain an active component aqueous solution. In the present invention, the mass ratio of the compound to water is preferably 20 to 80:100, and more preferably 40 to 60: 100. In the present invention, the compound corresponding to the active component is preferably ferrous sulfate. The present invention does not require a particular source of the compound, and may employ commercially available products well known to those skilled in the art.
After the active component aqueous solution is obtained, the filter element type carrier is soaked into the active component aqueous solution. The invention has no special requirement on the specific dosage of the active component aqueous solution, so that the filter element type carrier can be submerged by the active component aqueous solution. The present invention does not require special embodiments of the impregnation, as will be familiar to the skilled person.
After impregnation, the impregnated filter element type carrier is dried to remove moisture, so that the supported catalyst is obtained. In the invention, the drying temperature is preferably less than or equal to 500 ℃, more preferably 80-480 ℃, and even more preferably 120-200 ℃. The present invention has no special requirements for the specific implementation mode of the drying, and the method is well known to those skilled in the art.
For further illustration of the present invention, the filter element type carrier and the preparation method thereof, the supported catalyst and the preparation method thereof provided by the present invention will be described in detail below with reference to the drawings and examples, but they should not be construed as limiting the scope of the present invention.
Example 1:
mixing ceramic fiber with aluminosilicate as a chemical component, silica sol with the mass concentration of 30% and water according to the mass ratio of 1:0.2:100 to obtain a mixed solution; according to the figure 2, a stainless steel filter element type mould is placed in the mixed liquid, negative pressure is connected to the opening end of the mould, the negative pressure is controlled to be-0.6 MPa, after 1min, the mould is moved out of the mixed liquid, demoulding and drying are carried out at 120 ℃, the drying time is 480min, the filter element type carrier with the length of 1000mm and the thickness of 8.5mm and the appearance as shown in the figure 3 is obtained, and the filter element type carrier is a filter element ceramic fiber single-end opening pipe material which is known from the figure 3.
Mixing and dissolving ferrous sulfate heptahydrate and water according to the mass ratio of 60:100 to obtain a ferrous sulfate solution; soaking the filter element type carrier in ferrous sulfate solution for 2min, and drying the soaked filter element type carrier at 120 ℃ for 6h to obtain the supported catalyst shown in the figure 4, wherein the loading capacity is 15%.
The structure of the filter element carrier obtained in this example was characterized by a scanning electron microscope, and the characterization results are shown in fig. 5. As shown in fig. 5, the ceramic fibers in the filter element type carrier are arranged in a cross-layered manner to form a dense pore structure.
The microscopic morphology parameters of the filter element carrier obtained in this example were counted by using Image Pro Plus software, and a pore size distribution diagram of the filter element carrier was obtained, as shown in fig. 6. In fig. 6, B is the outer surface of the cartridge carrier; c is a section which is one half of the distance from the outer surface of the filter element type carrier; d is a section half of the distance from the inner surface of the filter element type carrier; e is the central section of the filter element type carrier; f is the inner surface of the filter element type carrier. As can be seen from fig. 6: the pore diameter of the sample is 10-180 μm, wherein pores with the pore diameter of 20-80 μm are abundant.
The density, air permeability and porosity of the sample obtained in this example were measured by using a Shimadzu AUY120 balance density tester according to the method for testing porosity and volume weight of porous ceramics (GB/T1966-1996), and the results are shown in Table 1.
According to the porous ceramic compression strength test method (GB/T1964-.
The microstructure of the supported catalyst obtained in this example was characterized by scanning electron microscopy, as shown in fig. 7. Fig. 7 is a microscopic view of the supported catalyst under different magnifications, and it can be seen from fig. 7 that the active component is supported on the surface of the ceramic fiber and distributed in the pores formed by the cross-laminated ceramic fibers in the filter element type carrier.
The test conditions of the catalytic performance of the supported catalyst are as follows: the flue gas flow rate is 6m/min, and the test results are shown in Table 2.
Example 2:
a filter element type carrier and a supported catalyst were prepared according to the method of example 1, except that high-temperature resistant ceramic fibers, silica sol having a mass concentration of 25%, and water were mixed in a ratio of 1:0.3: 100; the negative pressure is-0.5 MPa; the loading of the resulting supported catalyst was 20%.
The structure and performance of the filter element type carrier and the supported catalyst were tested according to the method of example 1, and the test results are shown in tables 1 and 2.
Example 3:
a filter element type carrier and a supported catalyst were prepared according to the method of example 1, except that the loading amount of the active component was 40%. The results of the catalytic performance tests of the supported catalysts are shown in table 2.
Example 4:
a filter element type carrier and a supported catalyst were prepared in the same manner as in example 1, except that the supported amount of the catalytically active component in the supported catalyst was 8%. The results of the catalytic performance tests of the supported catalysts are shown in table 2.
TABLE 1 test results of filter element type carrier structures of examples 1 to 4
As can be seen from the data in Table 1, the porosity of the filter element type carrier provided by the invention is higher, and the filter element type carrier is favorable for improving the loading capacity of the active component; in addition, the air permeability of the filter element type carrier is high, the permeability of the nitrogen-containing flue gas is improved, and the catalytic efficiency of the supported catalyst is further improved. The impact strength of the filter element type carrier provided by the invention reaches more than 0.6MPa, the compressive strength reaches 90MPa, and the supported catalyst with excellent strength performance is favorably obtained.
Table 2 results of testing catalytic performance of Supported catalysts in examples 1 to 4
As can be seen from the data in table 2, when the supported catalyst provided by the present invention is used for denitration treatment, 80% of denitration efficiency can be obtained in a low temperature region at 260 ℃, and when the temperature is 350 ℃, the denitration efficiency reaches 99.7%, which indicates that the supported catalyst provided by the present invention has excellent catalytic efficiency in the low temperature region.
Comparative example 1
The iron-based denitration catalyst powder is used as a catalyst, the catalytic efficiency is tested under the same conditions, and the test results are shown in table 3.
Table 3 results of testing catalytic performance of comparative example 1 catalyst
| Temperature of | NOx(ppm) | Denitration efficiency% |
| Inlet port | 906 | ---- |
| 200 | 895 | 1.2 |
| 250 | 854 | 5.7 |
| 300 | 449 | 50.4 |
| 350 | 59 | 93.5 |
| 400 | 14 | 98.5 |
As can be seen from the data in Table 3, the iron-based denitration catalyst powder has a denitration efficiency of 93.5% at 350 ℃, but has a low denitration efficiency in a temperature range of 200-300 ℃.
From examples 1 to 4, it can be seen that the supported catalyst prepared by using the filter element type carrier provided by the invention has a large loading capacity, and the catalytic performance of the supported catalyst is good. In a denitration catalysis experiment, the supported catalyst provided by the invention can have the denitration efficiency higher than 80% under the condition of being lower than 350 ℃.
From comparative example 1 and example 1, it can be seen that, when the active components are the same, the efficiency of the catalyst can be effectively improved by loading the active components on the filter element type carrier provided by the invention.
In the invention, the active component is homogeneously distributed in the pores of the filter element carrier, and the waste gas passes through the filter element carrier in a filtering mode, so that the contact surface area of the active component and the waste gas is increased, and the catalytic efficiency of the active component is greatly improved.
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 (9)
1. A filter element type carrier comprises a single-end open tubular product made of ceramic fiber; the ceramic fiber single-end opening pipe has a pore structure, the pores are formed by ceramic fibers in a cross-laminated arrangement mode, and the inner diameter of each pore is 10-180 mu m; the total volume of the pores accounts for 80-95% of the total volume of the single-end open-ended tube made of the ceramic fibers; the inner diameter of the ceramic fiber single-end open-ended pipe is 30-150 mm, and the thickness of the side wall of the ceramic fiber single-end open-ended pipe is 8-20 mm; the filter element type carrier is used for a denitration treatment catalyst.
2. The filter element carrier according to claim 1, wherein the length of the ceramic fiber single-end open-ended tube is 100 to 8000 mm.
3. The filter element carrier according to claim 1, wherein the open end of the single end open tubular ceramic fiber material is flanged or tapered.
4. A method for preparing the filter element type carrier according to any one of claims 1 to 3, comprising the steps of:
(1) mixing ceramic fiber, a binder and water to obtain a mixed solution; the mass ratio of the ceramic fibers to the binder to the water is 1: 0.1-0.3: 100;
(2) immersing a filter element type carrier mould into the mixed liquid obtained in the step (1), and then obtaining a filter element type carrier primary blank through negative pressure forming and demoulding; drying the primary blank of the filter element type carrier to obtain the filter element type carrier;
the filter element type die is provided with micropores, the diameter of each micropore is 40-80 meshes, and the density of each micropore is 60000-120000/m2。
5. The method according to claim 4, wherein the binder in the step (1) is silica sol, polyacrylamide or starch.
6. A supported catalyst comprising a support and an active component; the preparation method is characterized in that the carrier is the filter element carrier as claimed in any one of claims 1 to 3 or the filter element carrier prepared by the preparation method as claimed in any one of claims 4 to 5, and the active components are distributed in the pores of the single-end open-ended pipe made of ceramic fibers of the filter element carrier.
7. The supported catalyst according to claim 6, wherein the mass of the active component is 8 to 80% of the mass of the filter element carrier.
8. The supported catalyst of claim 7, wherein the active component comprises ferrous sulfate.
9. A process for preparing a supported catalyst according to claim 7 or 8, comprising:
(a) mixing a compound corresponding to the active component with water to obtain an active component aqueous solution;
(b) and (b) dipping the filter element type carrier into the active component aqueous solution obtained in the step (a), and drying the dipped filter element type carrier to obtain the supported catalyst.
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| CN109091956B (en) * | 2018-10-15 | 2020-12-08 | 安徽元琛环保科技股份有限公司 | Preparation method of dedusting and denitration integrated filter material based on ceramic fibers |
| CN110201541B (en) * | 2019-07-11 | 2021-10-12 | 江苏天雅环保科技有限公司 | Method and device for loading catalyst on ceramic fiber filter element |
| CN110922201B (en) * | 2019-12-05 | 2021-11-30 | 新乡市天诚航空净化设备有限公司 | Preparation method of ceramic fiber filter element, filter element and preparation system |
| CN111450900A (en) * | 2020-05-08 | 2020-07-28 | 山东爱亿普环保科技股份有限公司 | Cylindrical porous carrier, preparation method thereof, catalyst and application thereof |
| CN113426438B (en) * | 2021-06-25 | 2022-09-09 | 清华大学 | Coated catalyst composition, catalytic filter tube and preparation method thereof |
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