CN111138164B - Denitration catalyst module frame based on ceramic matrix and preparation method thereof - Google Patents
Denitration catalyst module frame based on ceramic matrix and preparation method thereof Download PDFInfo
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- CN111138164B CN111138164B CN201911397262.5A CN201911397262A CN111138164B CN 111138164 B CN111138164 B CN 111138164B CN 201911397262 A CN201911397262 A CN 201911397262A CN 111138164 B CN111138164 B CN 111138164B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- 239000000919 ceramic Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims description 4
- 239000011159 matrix material Substances 0.000 title description 2
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000002002 slurry Substances 0.000 claims description 42
- 238000001354 calcination Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 21
- 238000007789 sealing Methods 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 12
- 238000004898 kneading Methods 0.000 claims description 12
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 11
- 238000003825 pressing Methods 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 239000005995 Aluminium silicate Substances 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- 235000012211 aluminium silicate Nutrition 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 10
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000395 magnesium oxide Substances 0.000 claims description 10
- 238000007569 slipcasting Methods 0.000 claims description 10
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 10
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 10
- 239000000454 talc Substances 0.000 claims description 10
- 229910052623 talc Inorganic materials 0.000 claims description 10
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 9
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 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
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 20
- 239000000178 monomer Substances 0.000 abstract description 13
- 229910000831 Steel Inorganic materials 0.000 abstract description 5
- 239000010959 steel Substances 0.000 abstract description 5
- 238000009434 installation Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000000306 component Substances 0.000 description 9
- 235000012222 talc Nutrition 0.000 description 8
- 239000003566 sealing material Substances 0.000 description 7
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003546 flue gas Substances 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 239000003426 co-catalyst Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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- C04B33/00—Clay-wares
- C04B33/02—Preparing or treating the raw materials individually or as batches
- C04B33/13—Compounding ingredients
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- 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
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- 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
- B01J23/20—Vanadium, niobium or tantalum
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- 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
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- 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
- B01J23/32—Manganese, technetium or rhenium
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Abstract
The invention discloses a denitration catalyst module frame based on a ceramic base, which relates to the technical field of denitration catalysts and comprises a left side plate, a right side plate, a top plate, a bottom plate, a first supporting unit frame, a second supporting unit frame and lifting lugs; two side edges of the top plate are respectively fixed with the opposite tops of the left side plate and the right side plate; two side edges of the bottom plate are respectively fixed with the opposite bottoms of the left side plate and the right side plate; the first supporting unit frame is fixed on the lower surface of the top plate and is respectively fixed with the opposite side surfaces of the left side plate and the right side plate; the second supporting unit frame is fixed on the upper surface of the bottom plate and is respectively fixed with the opposite side surfaces of the left side plate and the right side plate. The invention also provides a method for preparing the ceramic-based denitration catalyst module frame. The invention has the beneficial effects that: the invention has simple integral structure, low density compared with a steel frame and low transportation and installation cost; the pressure difference between two ends of the module is small, the utilization rate of the active sites of the catalyst monomers is high, and the denitration activity is high.
Description
Technical Field
The invention relates to the technical field of denitration catalysts, in particular to a denitration catalyst module frame based on a ceramic base and a preparation method thereof.
Background
The SCR denitration technology means that nitrogen oxides are NH-bonded under the action of a catalyst 3 Reduction to nitrogen. The SCR denitration technology is widely applied to the field of coal-fired kilns. The current situation of energy structure in China is more coal, less oil and less gas, so the pressure of denitration treatment for coal-fired kilns is increasingly severe. The requirements of relevant standards on green development are more and more strict, and the main targets of environmental management at the present stage are tasks and targets of strengthening atmospheric pollution management, improving environmental quality and the like, and the total amount of nitrogen oxides is continuously controlled.
The core component of the SCR denitration technology is a denitration catalyst module, and the denitration catalyst module directly influences the overall effect of the SCR denitration system. The module frame is formed by generally using steel module parts and forming the module frame through rivets or screws or welding modes in the traditional SCR denitration catalyst module frame. The frame needs to be filled with ceramic fiber gaskets and ceramic fiber blankets as sealing materials in gaps between the catalyst monomers and the frame, so that smoke is prevented from passing through the gaps, and the denitration efficiency is reduced.
Chinese patent CN 109985515 a discloses a standardized granule SCR denitration catalyst module, and the top of catalyst frame is provided with first sealing strip and second sealing strip respectively, and is vertical arrangement between first sealing strip and the second sealing strip, and first sealing strip and second sealing strip all adopt refractory material to make. Four sides of catalyst frame are provided with and are used for fixed baffle, and the baffle is provided with four altogether, and connects through connecting the plate between four baffles two liang, and the connecting plate is "L" type structure, and the inside of connecting the plate is seted up flutedly for connecting the baffle, the bolt mouth that is used for fixed stop is still seted up in the outside of connecting the plate. The drawbacks of this technique are as follows: the sealing material can improve the pressure difference between two ends of the catalyst and reduce the fluidity of flue gas, thereby reducing the denitration activity of the catalyst; and because SCR honeycomb denitration catalyst monomer is that the whole is extruded the production, the monomer is close to the side of module frame and is active, and the packing sealing material can make the flue gas can't contact with this side, leads to the waste of catalyst active site.
Disclosure of Invention
One of the technical problems to be solved by the present invention is to provide a denitration catalyst module frame based on a ceramic substrate, which has a simple structure and can improve the activity of a catalyst monomer.
The invention solves the technical problems through the following technical means:
a denitration catalyst module frame based on a ceramic base comprises a left side plate, a right side plate, a top plate, a bottom plate, a first supporting unit frame, a second supporting unit frame and lifting lugs; the left side plate, the right side plate, the top plate, the bottom plate, the first supporting unit frame, the second supporting unit frame and the lifting lugs are all made of ceramic pug; the module frame is formed by high-pressure slip casting, drying and calcining the ceramic pug among the left side plate, the right side plate, the top plate, the bottom plate, the first supporting unit frame, the second supporting unit frame and the lifting lug;
the left side edge and the right side edge of the top plate are respectively connected with the tops of the opposite side surfaces of the left side plate and the right side plate; the left side edge and the right side edge of the bottom plate are respectively connected with the bottom of the opposite side surfaces of the left side plate and the right side plate; the first supporting unit frame is fixed on the lower surface of the top plate, and the left end and the right end of the first supporting unit frame are respectively connected with the opposite side surfaces of the left side plate and the right side plate; the second supporting unit frame is fixed on the upper surface of the bottom plate, and the left end and the right end of the second supporting unit frame are respectively connected with the opposite side surfaces of the left side plate and the right side plate; the lifting lugs are fixed on the upper surface of the top plate in an array.
Has the advantages that: according to the invention, the module frame is prepared by high-pressure slip casting, drying and calcining the ceramic pug with denitration activity, the whole structure is simple, and compared with the steel frame in the prior art, the module frame has low density and low transportation and installation cost; and the contact surface of the catalyst monomer and the frame does not need to be filled with a sealing material, the pressure difference between two ends of the module is small, the fluidity of the flue gas can be improved, and the high utilization rate of the active sites of the catalyst monomer and the denitration activity can be further improved.
Preferably, the first support unit frame includes a plurality of first lateral supports and a plurality of first vertical supports; the first transverse support pieces are fixed on the lower surface of the top plate in an array mode, and the left end and the right end of each first transverse support piece are connected with the opposite side faces of the left side plate and the right side plate; the first vertical supporting pieces are fixed on the lower surface of the top plate in an array manner, and the first vertical supporting pieces and the first transverse supporting pieces are mutually crossed;
the second support unit frame includes a plurality of second lateral supports and a plurality of second vertical supports; the plurality of second transverse supporting pieces are fixed on the upper surface of the bottom plate in an array mode, and the left end and the right end of each second transverse supporting piece are connected with the opposite side faces of the left side plate and the right side plate; the second vertical support pieces are fixed on the upper surface of the bottom plate in an array mode, and the second vertical support pieces and the second transverse support pieces are mutually crossed.
Preferably, a plurality of the first vertical supports and a plurality of the first transverse supports are mutually perpendicularly crossed; the plurality of second vertical supports and the plurality of second transverse supports are mutually and perpendicularly crossed.
The second technical problem to be solved by the present invention is to provide a method for preparing a denitration catalyst module frame based on a ceramic base, comprising the following steps:
(1) preparing ceramic pug, and stirring and kneading the ceramic pug;
(2) sealing the slurry kneaded in the step (1), and preserving;
(3) pressing the aged slurry in the step (2) into a water permeable mold by using a high pressure valve, closing the high pressure valve after the slurry is completely hardened in the mold, discharging the redundant slurry, and forming a blank;
(4) and (4) drying and calcining the blank formed in the step (3) to obtain the ceramic-based denitration catalyst module frame.
Further, the ceramic pug is prepared from the following raw materials in parts by weight: 17 parts of alumina, 4 parts of magnesia, 21 parts of silica, 27 parts of talc, 33 parts of kaolin, 4 parts of sodium carboxymethyl cellulose, 1 part of catalyst, 3 parts of a cocatalyst component and 40 parts of 20 wt% ammonia water.
Further, in the step (1), the kneading is carried out at 750rpm for 1 to 4 hours.
Further, the catalyst in the step (1) comprises ammonium metavanadate or manganese nitrate; the cocatalyst comprises ammonium metatungstate or cerium nitrate.
Further, the step (2) is aged for 12-24 h.
Further, in the step (3), the pressure in the die is maintained to be 0.1-1MPa for 0.5-2 h.
Further, the drying step (4) is performed at 180 ℃ for 10h, and the calcination step is performed at 1380 ℃ and 1420 ℃ for 8-12 h.
Has the advantages that: according to the invention, the module frame is prepared by high-pressure slip casting, drying and calcining the ceramic mud material, the ceramic mud material has denitration activity, the contact surface of the catalyst monomer and the frame does not need to be filled with a sealing material, the pressure difference between two ends of the module is small, the fluidity of flue gas can be improved, and the high utilization rate of the active sites of the catalyst monomer and the denitration activity can be further improved.
The invention has the advantages that:
(1) according to the invention, the module frame is prepared by high-pressure slip casting, drying and calcining the ceramic pug with denitration activity, the overall structure is simple, and compared with the steel frame in the prior art, the module frame has the advantages of low density and low transportation and installation cost.
(2) According to the invention, the module frame is prepared by high-pressure slip casting, drying and calcining the ceramic mud material, the ceramic mud material has denitration activity, the contact surface of the catalyst monomer and the frame does not need to be filled with a sealing material, the pressure difference between two ends of the module is small, the fluidity of flue gas can be improved, and the high utilization rate of the active sites of the catalyst monomer and the denitration activity can be further improved.
Drawings
FIG. 1 is a schematic structural diagram of a ceramic based denitration catalyst module frame according to an embodiment of the present invention;
fig. 2 is a schematic front structural view of a frame of a denitration catalyst module according to an embodiment of the present invention.
The reference numbers indicate:
the support comprises a left side plate 1, a right side plate 2, a top plate 3, a bottom plate 4, a first support unit frame 5, a first transverse support 51, a first vertical support 52, a second support unit frame 6, a second transverse support 61, a second vertical support 62 and a lifting lug 7.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Test materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The specific techniques or conditions not specified in the examples can be performed according to the techniques or conditions described in the literature in the field or according to the product specification.
Example 1
As shown in fig. 1, the present embodiment discloses a denitration catalyst module frame based on ceramic base, specifically, with reference to the orientation of fig. 1, comprising a left side plate 1, a right side plate 2, a top plate 3, a bottom plate 4, a first support unit frame 5, a second support unit frame 6 and a lifting lug 7; the left side plate 1, the right side plate 2, the top plate 3, the bottom plate 4, the first supporting unit frame 5, the second supporting unit frame 6 and the lifting lugs 7 are all made of ceramic pug; the module frame is formed by high-pressure slip casting, drying and calcining a left side plate 1, a right side plate 2, a top plate 3, a bottom plate 4, a first supporting unit frame 5, a second supporting unit frame 6 and a lifting lug 7 through ceramic pug.
The left side and the right side of the top plate 3 are respectively connected with the tops of the opposite sides of the left side plate 1 and the right side plate 2; the left side and the right side of the bottom plate 4 are respectively connected with the bottom of the opposite side surfaces of the left side plate 1 and the right side plate 2; the first supporting unit frame 5 is fixed on the lower surface of the top plate 3, and the left and right ends of the first supporting unit frame 5 are respectively connected with the opposite side surfaces of the left side plate 1 and the right side plate 2; the second supporting unit frame 6 is fixed on the upper surface of the bottom plate 4, and the left end and the right end of the second supporting unit frame 6 are respectively connected with the opposite side surfaces of the left side plate 1 and the right side plate 2; a plurality of lifting lugs 7 are fixed on the upper surface of the top plate 4 in an array.
As shown in fig. 2, the first supporting unit frame 5 includes a plurality of first transverse supports 51 and a plurality of first vertical supports 52; a plurality of first transverse supporting pieces 51 are fixed on the lower surface of the top plate 3 in an array manner, and the left and right ends of the plurality of first transverse supporting pieces 51 are connected with the opposite side surfaces of the left side plate 1 and the right side plate 2; the plurality of first vertical supporting pieces 52 are fixed on the lower surface of the top plate 3 in an array manner, and the plurality of first vertical supporting pieces 52 and the plurality of first transverse supporting pieces 51 are mutually crossed; the second support unit frame 6 includes a plurality of second lateral supports 61 and a plurality of second vertical supports 62; the plurality of second transverse supporting pieces 61 are fixed on the upper surface of the bottom plate 4 in an array mode, and the left end and the right end of each second transverse supporting piece 61 are connected with the opposite side surfaces of the left side plate 1 and the right side plate 2; the second vertical supports 62 are fixed on the upper surface of the bottom plate 4 in an array, and the second vertical supports 62 and the second transverse supports 61 are crossed.
According to the invention, the module frame is prepared by high-pressure slip casting, drying and calcining the ceramic pug with denitration activity, the whole structure is simple, and compared with the steel frame in the prior art, the module frame has low density and low transportation and installation cost; and the contact surface of the catalyst monomer and the frame does not need to be filled with a sealing material, the pressure difference between two ends of the module is small, the fluidity of the flue gas can be improved, and the high utilization rate of the active sites of the catalyst monomer and the denitration activity can be further improved.
Preferably, the plurality of first vertical supports and the plurality of first transverse supports are mutually and perpendicularly crossed; the plurality of second vertical supports and the plurality of second transverse supports are mutually perpendicularly crossed.
Example 2
(1) Mixing 17 parts of aluminum oxide, 4 parts of magnesium oxide, 21 parts of silicon oxide, 27 parts of talc, 33 parts of kaolin, 4 parts of sodium carboxymethylcellulose, 1 part of ammonium metavanadate, 3 parts of ammonium metatungstate and 40 parts of 20 wt% ammonia water in parts by weight, and stirring and kneading for 1 hour at 750 rpm;
(2) sealing and storing the kneaded slurry, and aging for 12 h;
(3) pressing the aged slurry obtained in the step (2) into a water permeable mold fixed in advance through a high pressure valve, maintaining the pressure in the mold to be 0.5MPa, keeping the pressure for 0.5h, closing the high pressure valve after the slurry is completely hardened in the mold, and removing redundant slurry to obtain a molded blank;
(4) and (4) drying the blank formed in the step (3) at 180 ℃ for 10 hours, and calcining at 1380 ℃ for 8 hours to obtain the ceramic-based denitration catalyst module frame.
Example 3
(1) Mixing 17 parts of aluminum oxide, 4 parts of magnesium oxide, 21 parts of silicon oxide, 27 parts of talcum, 33 parts of kaolin, 4 parts of sodium carboxymethylcellulose, 1 part of ammonium metavanadate, 3 parts of ammonium metatungstate and 40 parts of 20 wt% ammonia water according to parts by weight, and stirring and kneading for 2 hours at 750 rpm;
(2) sealing and storing the kneaded slurry for aging for 18 hours;
(3) pressing the aged slurry in the step (2) into a water-permeable mold fixed in advance through a high-pressure valve, maintaining the pressure in the mold to be 0.75MPa, keeping for 1h, closing the high-pressure valve after the slurry is completely hardened in the mold, and removing redundant slurry to obtain a formed blank;
(4) and (4) drying the blank formed in the step (3) at 180 ℃ for 10h, and calcining at 1400 ℃ for 10h to obtain the ceramic-based denitration catalyst module frame.
Example 4
(1) Mixing 17 parts of aluminum oxide, 4 parts of magnesium oxide, 21 parts of silicon oxide, 27 parts of talc, 33 parts of kaolin, 4 parts of sodium carboxymethylcellulose, 1 part of ammonium metavanadate, 3 parts of ammonium metatungstate and 40 parts of 20 wt% ammonia water in parts by weight, and stirring and kneading for 4 hours at 750 rpm;
(2) sealing and storing the kneaded slurry for 24 h;
(3) pressing the aged slurry in the step (2) into a water-permeable mold fixed in advance through a high-pressure valve, maintaining the pressure in the mold to be 1MPa, keeping for 2 hours, closing the high-pressure valve after the slurry is completely hardened in the mold, and removing redundant slurry to obtain a formed blank;
(4) and (4) drying the blank formed in the step (3) at 180 ℃ for 10h, and calcining at 1420 ℃ for 12h to obtain the module frame based on the ceramic-based denitration catalyst.
Example 5
(1) Stirring 17 parts of aluminum oxide, 4 parts of magnesium oxide, 21 parts of silicon oxide, 27 parts of talcum, 33 parts of kaolin, 4 parts of sodium carboxymethylcellulose, 10 parts of manganese nitrate, 2 parts of cerium nitrate and 40 parts of 20 wt% ammonia water according to parts by weight, and kneading for 1h at 750 rpm;
(2) sealing and storing the kneaded slurry, and aging for 12 h;
(3) pressing the aged slurry obtained in the step (2) into a water permeable mold fixed in advance through a high pressure valve, maintaining the pressure in the mold to be 0.5MPa, keeping the pressure for 0.5h, closing the high pressure valve after the slurry is completely hardened in the mold, and removing redundant slurry to obtain a molded blank;
(4) and (4) drying the blank formed in the step (3) at 180 ℃ for 10 hours, and calcining at 1380 ℃ for 8 hours to obtain the ceramic-based denitration catalyst module frame.
Comparative example 1
(1) Stirring and kneading 17 parts of aluminum oxide, 4 parts of magnesium oxide, 21 parts of silicon oxide, 27 parts of talcum, 33 parts of kaolin, 4 parts of sodium carboxymethylcellulose and 40 parts of 20 wt% ammonia water for 1 hour according to parts by weight;
(2) sealing and storing the kneaded slurry for 12 h;
(3) pressing the aged slurry in the step (2) into a water permeable mold fixed in advance through a high pressure valve, maintaining the pressure in the mold to be 0.5MPa, keeping for 0.5h, closing the high pressure valve after the slurry is completely hardened in the mold, and discharging redundant slurry;
(4) and drying the formed blank at 180 ℃ for 10 hours, and calcining at 1380 ℃ for 8 hours to obtain the denitration catalyst module frame.
Comparative example 2
(1) Stirring and kneading 17 parts of aluminum oxide, 4 parts of magnesium oxide, 21 parts of silicon oxide, 27 parts of talc, 33 parts of kaolin, 4 parts of sodium carboxymethylcellulose, 0.5 part of ammonium metavanadate, 3 parts of ammonium metatungstate and 40 parts of 20 wt% ammonia water for 1 hour;
(2) sealing and storing the kneaded slurry, and aging for 12 h;
(3) pressing the aged slurry in the step (2) into a water-permeable mold fixed in advance through a high-pressure valve, maintaining the pressure in the mold to be 0.5MPa, keeping the pressure for 0.5h, and closing the high-pressure valve to remove redundant slurry after the slurry is completely hardened in the mold;
(4) and drying the formed blank body at 180 ℃ for 10 hours, and calcining at 1380 ℃ for 8 hours to obtain the denitration catalyst module frame.
Comparative example 3
(1) Stirring and kneading 17 parts of aluminum oxide, 4 parts of magnesium oxide, 21 parts of silicon oxide, 27 parts of talc, 33 parts of kaolin, 4 parts of sodium carboxymethylcellulose, 6 parts of manganese nitrate, 2 parts of cerium nitrate and 40 parts of 20 wt% ammonia water for 1 hour;
(2) sealing and storing the kneaded slurry for 12 h;
(3) pressing the aged slurry in the step (2) into a water permeable mold fixed in advance through a high pressure valve, maintaining the pressure in the mold to be 0.5MPa, keeping for 0.5h, closing the high pressure valve after the slurry is completely hardened in the mold, and discharging redundant slurry;
(4) and drying the formed blank body at 180 ℃ for 10 hours, and calcining at 1380 ℃ for 8 hours to obtain the denitration catalyst module frame.
Example 9
Catalyst Activity test
The ceramic-based catalyst module frames prepared in examples 2 to 5 and comparative examples 1 to 3 were cut into 50mm × 50mm pieces, the 3 pieces were placed in a quartz tube performance evaluation reaction apparatus with the inner diameter of the quartz tube being 100mm, a simulated gas was introduced, and activity evaluation was performed by changing the catalytic reaction temperature by adjusting the temperature of the fixed bed. The composition of the simulated gas was: NO (1000ppm), NH 3 (1000ppm)、O 2 (6vol％)、N 2 As a carrier gas, the total flow rate of the gas was 2000 mL/min. The catalytic efficiency is shown in table 1.
Table 1 shows denitration efficiency tables of the ceramic-based catalyst module frames obtained in examples 2 to 5 and comparative examples 1 to 3
As shown in table 1, the module frame prepared by subjecting the ceramic slip mixed with the denitration catalyst component to high pressure slip casting, drying, and calcining has SCR denitration activity. As can be seen from the results of table 1, when 1 part of ammonium metavanadate as a catalyst component and 3 parts of ammonium metatungstate as a co-catalyst component, the SCR denitration activity of the module frame was around 77%; when 10 parts of manganese nitrate as a catalyst component and 2 parts of cerium nitrate as a co-catalyst component, the module frame SCR denitration activity was 74%.
As can be seen from the results of comparative examples 1 to 3, when any catalyst component and co-catalyst component were not added to the ceramic sludge, the module frame did not have SCR denitration activity; when the content of the main catalyst component in the ceramic slurry is reduced, the SCR denitration activity of the denitration frame is obviously reduced.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A denitration catalyst module frame based on a ceramic base comprises a left side plate, a right side plate, a top plate, a bottom plate, a first supporting unit frame, a second supporting unit frame and lifting lugs; the left side edge and the right side edge of the top plate are respectively connected with the tops of the opposite side surfaces of the left side plate and the right side plate; the left side edge and the right side edge of the bottom plate are respectively connected with the bottom of the side surface opposite to the left side plate and the right side plate; the first supporting unit frame is fixed on the lower surface of the top plate, and the left end and the right end of the first supporting unit frame are respectively connected with the opposite side surfaces of the left side plate and the right side plate; the second supporting unit frame is fixed on the upper surface of the bottom plate, and the left end and the right end of the second supporting unit frame are respectively connected with the opposite side surfaces of the left side plate and the right side plate; a plurality of the lug is fixed in the array the roof upper surface, its characterized in that: the left side plate, the right side plate, the top plate, the bottom plate, the first supporting unit frame, the second supporting unit frame and the lifting lugs are all made of ceramic pug; the module frame is formed by high-pressure slip casting, drying and calcining the ceramic pug among the left side plate, the right side plate, the top plate, the bottom plate, the first supporting unit frame, the second supporting unit frame and the lifting lug;
the high-pressure slip casting specifically comprises the following steps: pressing the aged ceramic mud into a water permeable mold by using a high pressure valve, closing the high pressure valve after the mud is completely hardened in the mold, discharging redundant slurry, and forming a blank;
the ceramic pug is prepared from the following raw materials in parts by weight: 17 parts of aluminum oxide, 4 parts of magnesium oxide, 21 parts of silicon oxide, 27 parts of talc, 33 parts of kaolin, 4 parts of sodium carboxymethylcellulose, 1 part of catalyst, 3 parts of cocatalyst and 40 parts of ammonia water with the concentration of 20 wt% of aqueous solution, wherein the catalyst comprises ammonium metavanadate or manganese nitrate, and the cocatalyst comprises ammonium metatungstate or cerium nitrate;
the preparation method of the denitration catalyst module frame comprises the following steps:
(1) preparing ceramic pug, and stirring and kneading the ceramic pug;
(2) sealing the slurry kneaded in the step (1), and preserving;
(3) pressing the aged slurry in the step (2) into a water permeable mold by using a high pressure valve, closing the high pressure valve after the slurry is completely hardened in the mold, discharging the redundant slurry, and forming a blank;
(4) and (4) drying and calcining the green body formed in the step (3) to obtain the ceramic-based denitration catalyst module frame.
2. The ceramic based denitration catalyst module frame of claim 1, wherein: the first support unit frame includes a plurality of first lateral supports and a plurality of first vertical supports; the first transverse support pieces are fixed on the lower surface of the top plate in an array mode, and the left end and the right end of each first transverse support piece are connected with the opposite side faces of the left side plate and the right side plate; the first vertical support pieces are fixed on the lower surface of the top plate in an array mode, and the first vertical support pieces and the first transverse support pieces are crossed with each other;
the second support unit frame includes a plurality of second lateral supports and a plurality of second vertical supports; the plurality of second transverse supporting pieces are fixed on the upper surface of the bottom plate in an array mode, and the left end and the right end of each second transverse supporting piece are connected with the opposite side faces of the left side plate and the right side plate; the second vertical support pieces are fixed on the upper surface of the bottom plate in an array mode, and the second vertical support pieces and the second transverse support pieces are mutually crossed.
3. The ceramic based denitration catalyst module frame of claim 2, wherein: the plurality of first vertical supports and the plurality of first transverse supports are mutually and perpendicularly crossed; the plurality of second vertical supports and the plurality of second transverse supports are mutually perpendicularly crossed.
4. A method of making a ceramic based denitration catalyst module frame according to any of claims 1-3, comprising the steps of:
(1) preparing ceramic pug, and stirring and kneading the ceramic pug;
(2) sealing the slurry kneaded in the step (1), and preserving;
(3) pressing the aged slurry in the step (2) into a water-permeable mold by using a high-pressure valve, closing the high-pressure valve after the slurry is completely hardened in the mold, removing the redundant slurry, and forming a blank;
(4) and (4) drying and calcining the green body formed in the step (3) to obtain the ceramic-based denitration catalyst module frame.
5. The method of preparing a ceramic based denitration catalyst module frame of claim 4, wherein: the ceramic pug in the step (1) is prepared from the following raw materials in parts by weight: 17 parts of alumina, 4 parts of magnesium oxide, 21 parts of silicon oxide, 27 parts of talc, 33 parts of kaolin, 4 parts of sodium carboxymethylcellulose, 1 part of catalyst, 3 parts of cocatalyst and 40 parts of ammonia water with an aqueous solution concentration of 20%.
6. The method of preparing a ceramic based denitration catalyst module frame of claim 4, wherein: stirring and kneading for 1-4h at 750 rpm.
7. The method of preparing a ceramic based denitration catalyst module frame of claim 4, wherein: the catalyst in the step (1) comprises ammonium metavanadate or manganese nitrate; the cocatalyst comprises ammonium metatungstate or cerium nitrate.
8. The method of preparing a denitration catalyst module frame assembly according to claim 4, wherein: and (3) ageing for 12-24h in the step (2).
9. The method of preparing a denitration catalyst module frame assembly according to claim 4, wherein: and (4) in the step (3), maintaining the pressure in the die to be 0.1-1MPa for 0.5-2 h.
10. The method of preparing a denitration catalyst module frame assembly according to claim 4, wherein: in the step (4), drying is carried out at 180 ℃ for 10h, and calcining is carried out at 1380 ℃ and 1420 ℃ for 8-12 h.
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