CN116870897A - Wall-flow denitration catalyst and preparation method thereof - Google Patents
Wall-flow denitration catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims description 15
- 239000007788 liquid Substances 0.000 claims abstract description 84
- 239000002539 nanocarrier Substances 0.000 claims abstract description 75
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 42
- 239000011259 mixed solution Substances 0.000 claims abstract description 40
- 239000000243 solution Substances 0.000 claims abstract description 29
- 125000002091 cationic group Chemical group 0.000 claims abstract description 26
- 239000000084 colloidal system Substances 0.000 claims abstract description 26
- 150000001768 cations Chemical class 0.000 claims abstract description 19
- 239000002270 dispersing agent Substances 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011148 porous material Substances 0.000 claims abstract description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 33
- 238000000227 grinding Methods 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000001179 sorption measurement Methods 0.000 claims description 16
- 229920006395 saturated elastomer Polymers 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 235000006408 oxalic acid Nutrition 0.000 claims description 11
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000002808 molecular sieve Substances 0.000 claims description 8
- 239000004576 sand Substances 0.000 claims description 8
- 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 8
- 239000004408 titanium dioxide Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 229920000881 Modified starch Polymers 0.000 claims description 5
- 239000004368 Modified starch Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 235000019426 modified starch Nutrition 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 239000005995 Aluminium silicate Substances 0.000 claims description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 235000012211 aluminium silicate Nutrition 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 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 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 2
- 229920002678 cellulose Polymers 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 125000000129 anionic group Chemical group 0.000 abstract description 3
- 230000008021 deposition Effects 0.000 abstract 1
- 239000002105 nanoparticle Substances 0.000 abstract 1
- 230000032683 aging Effects 0.000 description 31
- 238000007664 blowing Methods 0.000 description 28
- 239000000306 component Substances 0.000 description 18
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 12
- 239000003546 flue gas Substances 0.000 description 12
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
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- 239000002671 adjuvant Substances 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
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- 239000002344 surface layer Substances 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003933 environmental pollution control Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
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- 230000006872 improvement Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention provides a wall-flow denitration catalyst, which comprises a nano active mixed solution, a cation auxiliary agent and a porous carrier; the nano active mixed solution comprises an active solution and a nano carrier solution; the nano-carrier liquid comprises 100 parts of deionized water, 6-18 parts of nano-carrier, 0.5-2 parts of dispersing agent and 8-15 parts of alkaline colloid auxiliary agent. According to the invention, the uniform deposition of the anionic nanoparticles in the nano active mixed solution on the surface of the internal pores of the porous carrier can be promoted by the pretreatment of the cationic auxiliary agent on the porous carrier; meanwhile, the nano carrier in the nano active mixed solution can provide a large number of active sites for the active components of the catalyst, and the alkaline colloid auxiliary agent can effectively fix the active components and the nano carrier, so that the wall flow type denitration catalyst disclosed by the invention has the characteristics of rich and uniform active sites, high denitration efficiency, good stripping resistance and long service life.
Description
Technical Field
The invention belongs to the technical field of dedusting and denitration catalysts for boiler flue gas purification, and particularly relates to a wall-flow denitration catalyst and a preparation method thereof.
Background
Along with the continuous coding of the national environmental pollution control policy, the continuous improvement of the requirements on boiler flue gas treatment forces the denitration catalyst industry to be continuously updated and improve the product quality, so that more high-quality technologies are also presented, wherein the high-temperature dedusting and denitration integrated technology is one of the most advanced boiler flue gas treatment technologies at present, and can realize dedusting and denitration integrated treatment at a higher temperature, so that the problems of energy consumption increase and high operation cost caused by the prior flue gas treatment technology that the traditional flue gas treatment technology needs to be cooled and dedusted before heating and denitration can be solved, and the two sets of independent operation equipment of the traditional dedusting and denitration can be integrated into one set of equipment, thereby reducing the occupied area and further reducing the operation cost.
In order to realize popularization and application of the high-temperature dust removal and denitration integrated technology in various fields, a catalyst which is more efficient, stable and long in service life is required to be used as a core component. At present, a catalyst capable of meeting the integration of high-temperature dust removal and denitration is mainly a wall-flow catalyst, dust in flue gas is separated through a surface layer of a catalyst carrier, and the remaining dust-free flue gas reacts with a denitration catalyst when passing through a thick layer and an inner surface layer of the catalyst carrier wall, so that nitrogen oxides in the flue gas are removed, and flue gas purification is realized.
The existing wall-flow type high-temperature flue gas dedusting and denitration integrated catalyst is represented by a ceramic fiber filter cylinder, and can meet the existing dedusting and denitration requirements, but the catalyst has uneven distribution of active components, low combination degree with a carrier and fewer active sites, so that the effective contact time of nitrogen oxides and the catalyst is influenced, the nitrogen oxides are easily peeled off from the carrier, and the denitration efficiency and the service life are influenced.
Disclosure of Invention
In view of the above, the invention provides a wall-flow denitration catalyst and a preparation method thereof, which aim to solve the problems of uneven distribution of active components, low combination degree with a carrier, fewer active sites and influence on denitration efficiency and service life of the existing wall-flow denitration catalyst.
The invention provides a wall-flow denitration catalyst which consists of nano active mixed liquid, a cation auxiliary agent and a porous carrier.
The nano active mixed solution of the wall-flow denitration catalyst is formed by mixing an active solution and a nano carrier solution.
The active liquid is according to V 2 O 5 And WO 3 The molar ratio of (2) is 1: (0.5-1.5) consists of mixed oxalic acid solution of ammonium metavanadate and ammonium metatungstate.
The nano-carrier liquid consists of 100 parts of deionized water, 6-18 parts of nano-carrier, 0.5-2 parts of dispersing agent and 8-15 parts of alkaline colloid auxiliary agent.
The nano carrier of the nano carrier liquid can be composed of one or more of titanium dioxide, molecular sieve, diatomite and kaolin.
Preferably, the grain diameter D50 of the nano-carrier is less than or equal to 300nm, and D90 is less than or equal to 600nm.
Preferably, the nano-carrier is prepared from titanium dioxide, molecular sieve and diatomite according to the following ratio of 1: (0.2-0.8): (0.1-0.5).
The dispersing agent of the nano-carrier liquid can be one or more of polyethylene glycol, polyvinyl alcohol, dodecyl polyoxyethylene ether and diethanolamine.
The alkaline colloid auxiliary agent of the nano-carrier liquid can be one or more of silica sol, aluminum sol and titanium sol.
Preferably, the alkaline colloid auxiliary agent is silica sol, aluminum sol and titanium sol, and the mass ratio of the silica sol to the aluminum sol to the titanium sol is 1: (0.05-0.5): (0.1-1.5).
Preferably, in the alkaline colloid auxiliary agent, the solid content of the adopted silica sol is 30%, the particle size D50 is 10nm, and the pH value is 9.0-10.2.
Preferably, in the alkaline colloid auxiliary agent, the solid content of the adopted aluminum sol is 20%, the particle size D50 is 10nm, and the pH value is 7.0-9.0.
Preferably, in the alkaline colloid auxiliary agent, the solid content of the adopted titanium sol is 8%, the particle size D50 is 3nm, and the pH value is 8.7-10.0.
The cationic auxiliary agent of the wall-flow denitration catalyst can be composed of one or more aqueous solutions of cationic modified starch, cationic polyacrylamide and cationic cellulose, and is preferably cationic modified starch.
Preferably, the cationic modified starch has a molar substitution of 0.028 to 0.036 and a viscosity of 80 to 140 mPas (25 ℃ C., 4.0% strength).
Preferably, the concentration of the aqueous solution of the cationic assistant is 0.5 to 4.0wt%, and more preferably 0.5 to 3.0wt%.
The porous carrier of the wall-flow denitration catalyst can be a filter cylinder type, a plate type or a plugged honeycomb type porous material.
Preferably, the porous support has an open porosity of 75-90%.
The invention provides a preparation method of a wall-flow denitration catalyst, which comprises the following steps:
a, preparing an active liquid: according to V 2 O 5 And WO 3 The molar ratio of (2) is 1: (0.5-1.5), and dissolving ammonium metavanadate and ammonium metatungstate in an oxalic acid solution.
B, preparation of nano carrier liquid: preparing mixed solution by 100 parts of deionized water, 6-18 parts of nano carrier, 0.5-2 parts of dispersing agent and 8-15 parts of alkaline colloid auxiliary agent, and grinding and dispersing the mixed solution to obtain nano carrier solution.
C, preparing a nano active mixed solution: and uniformly mixing the active liquid and the nano-carrier liquid to obtain a nano-active mixed liquid.
D, preparing a cation auxiliary solution: the cationic assistant is prepared into aqueous solution with concentration of 0.5-4.0 wt%.
E, pretreatment of a porous carrier: and (3) immersing the porous carrier in a cationic auxiliary agent, taking out the porous carrier after saturated adsorption, draining surface liquid, and placing the porous carrier in a blast drying oven for primary drying.
F porous carrier supports active components: and (3) immersing the pretreated porous carrier in the nano active mixed solution, taking out the porous carrier after saturated adsorption, draining surface liquid, placing the porous carrier in a blast drying oven, and drying the porous carrier for the second time to obtain a wall-flow denitration catalyst finished product.
Preferably, in the step B, the grinding and dispersing may be performed by any one of a roller ball mill, a planetary ball mill, and a sand mill, and more preferably, the grinding and dispersing may be performed by a sand mill.
Preferably, in step E, the primary drying temperature of the porous carrier pretreatment is 60 to 90 ℃, and more preferably 60 to 80 ℃.
Preferably, in step F, the secondary drying temperature of the porous carrier-supported active ingredient is 100 to 150 ℃, more preferably 100 to 120 ℃.
The invention has the beneficial effects that the anion and cation electric neutralization mechanism is adopted, the porous carrier is firstly subjected to cation auxiliary agent modification pretreatment, and then the active components and the catalyst carrier are firmly and uniformly adhered to the porous carrier through the anion colloid auxiliary agent in the nano active mixed solution, so that the problems of uneven distribution and low adhesive force of the active components of the catalyst can be effectively solved; meanwhile, the high specific surface area characteristic of the uniformly distributed nano carrier provides a large number of active sites for the active components of the catalyst, so that the catalytic efficiency and the service life of the wall-flow denitration catalyst can be effectively improved.
Drawings
FIG. 1 is a flow chart of a process for preparing a wall-flow denitration catalyst according to the present invention.
Fig. 2 is a graph showing denitration efficiency before and after aging blowing in example 1 of the present invention.
FIG. 3 is a graph showing denitration efficiency before and after aging blowing in example 2 of the present invention.
FIG. 4 is a graph showing denitration efficiency before and after aging blowing in example 3 of the present invention.
FIG. 5 is a graph showing denitration efficiency before and after aging blowing in example 4 of the present invention.
FIG. 6 is a graph showing denitration efficiency before and after aging blowing in a comparative example of the present invention.
Detailed Description
For a further understanding of the present invention, reference will now be made in detail to the preferred embodiments of the present invention in conjunction with the following specific examples, which are intended to illustrate some, but not all, of the examples of the present invention and other embodiments of the present invention which may be made by one of ordinary skill in the art without undue burden and are within the scope of the present invention.
The invention provides a wall-flow denitration catalyst which consists of nano active mixed liquid, a cation auxiliary agent and a porous carrier.
The nano active mixed solution of the wall-flow denitration catalyst is formed by mixing an active solution and a nano carrier solution.
In the invention, the active liquid consists of main active components of the denitration catalyst according to V 2 O 5 And WO 3 The molar ratio of (2) is 1: (0.5-1.5) is prepared from mixed oxalic acid solution of ammonium metavanadate and ammonium metatungstate. In order to facilitate comparative evaluation of denitration efficiency of the catalyst before and after aging blowing, in the embodiment of the present invention, it is preferable to use V to be low 2 O 5 And WO 3 The molar ratio of (2) is 1: 1.2.
In the invention, the nano-carrier liquid can provide a large number of active sites for the active components of the denitration catalyst, and colloid auxiliaries in the nano-carrier liquid can effectively fix the nano-carrier and the active components of the catalyst, realize secondary loading of the catalyst and the nano-carrier on the porous carrier and solve the problem of stripping of the catalyst, so the nano-carrier liquid is a key of the implementation of the technical scheme of the invention, and in the embodiment of the invention, the nano-carrier liquid consists of 100 parts of deionized water, 6-18 parts of the nano-carrier, 0.5-2 parts of the dispersing agent and 8-15 parts of the alkaline colloid auxiliaries.
In the present invention, the nano-carrier may be composed of one or more of titanium dioxide, molecular sieve, diatomite and kaolin, more preferably titanium dioxide, molecular sieve and diatomite, wherein the mass ratio of titanium dioxide, molecular sieve and diatomite is 1: (0.2-0.8): (0.1-0.5), most preferably 1: (0.2-0.5): (0.1-0.3), in embodiments of the present invention, may be 1:0.2:0.1, 1:0.3:0.2, 1:0.4:0.3 or 1:0.5:0.3.
In the present invention, the weight part of the nano-carrier is 6-18 parts, preferably 8-15 parts, most preferably 10-13 parts, and in the embodiment of the present invention, 8 parts, 10 parts, 12 parts or 15 parts;
in the present invention, the dispersant may be composed of one or more of polyethylene glycol, polyvinyl alcohol, dodecyl polyoxyethylene ether, and diethanolamine, and the dispersant may be 0.5 to 2 parts by weight, preferably 0.5 to 1.8 parts by weight, more preferably 0.8 to 1.4 parts by weight, and in the embodiment of the present invention, the dispersant may be 0.8 parts by weight, 1.2 parts by weight, 1.4 parts by weight, or 1.8 parts by weight.
In the invention, the alkaline colloid auxiliary agent can be composed of one or more of silica sol, alumina sol and titanium sol, preferably silica sol, alumina sol and titanium sol, wherein the mass ratio of the silica sol to the alumina sol to the titanium sol is 1: (0.05-0.5): (0.1 to 1.5), more preferably 1: (0.05-0.3): (0.1 to 1.2), most preferably 1: (0.08-0.2): (0.1-1.0), in embodiments of the present invention, may be 1:0.08:0.2, 1:0.1:0.4, 1:0.15:0.6, or 1:0.18:1.0.
In the present invention, the porous carrier of the wall-flow denitration catalyst may be a filter cartridge type, a plate type or a plugged honeycomb type porous material, and the open porosity is 75 to 90%, preferably 75 to 85%, and in the embodiment of the present invention, the porous carrier is preferably a plate type porous carrier, and the open porosity is 82 to 85%.
The invention also provides a preparation method of the wall-flow denitration catalyst, which comprises the following steps:
a, preparing an active liquid: according to V 2 O 5 And WO 3 The molar ratio of (2) is 1: (0.5-1.5), and dissolving ammonium metavanadate and ammonium metatungstate in an oxalic acid solution.
B, preparation of nano carrier liquid: preparing mixed solution by 100 parts of deionized water, 6-18 parts of nano carrier, 0.5-2 parts of dispersing agent and 8-15 parts of alkaline colloid auxiliary agent, and grinding and dispersing the mixed solution to obtain nano carrier solution.
C, preparing a nano active mixed solution: and uniformly mixing the active liquid and the nano-carrier liquid to obtain a nano-active mixed liquid.
D, preparing a cation auxiliary solution: the cationic assistant is prepared into aqueous solution with concentration of 0.5-4.0 wt%.
E, pretreatment of a porous carrier: and (3) immersing the porous carrier in a cationic auxiliary agent, taking out the porous carrier after saturated adsorption, draining surface liquid, and placing the porous carrier in a blast drying oven for primary drying.
F porous carrier supports active components: and (3) immersing the pretreated porous carrier in the nano active mixed solution, taking out the porous carrier after saturated adsorption, draining surface liquid, placing the porous carrier in a blast drying oven, and drying the porous carrier for the second time to obtain a wall-flow denitration catalyst finished product.
In the present invention, in the step B, the grinding and dispersing may be performed by using any one of a roller ball mill, a planetary ball mill or a sand mill, and more preferably, the grinding and dispersing are performed by a sand mill, and in the embodiment of the present invention, the magnitude of the linear speed of the sand mill affects the kinetic energy intensity applied to the material particles by the grinding medium, and is preferably 10m/s; the smaller the diameter of the grinding media of the sand mill, the more the media loading number and the contact points of the grinding balls are, so that the grinding is more sufficient, but the too small grinding media tend to easily cause the blockage of an outlet separator of the sand mill, and the grinding media are preferably zirconia beads with the diameter of 0.8mm according to the target granularity of the nano carrier, and the media loading rate is 85%.
Preferably, in step E, the primary drying temperature of the porous support pretreatment is 60 to 90 ℃, more preferably 60 to 80 ℃, and in the embodiment of the present invention, most preferably 75 ℃.
Preferably, in step F, the porous support is subjected to secondary drying of the active ingredient at a temperature of 100 to 150 ℃, more preferably 100 to 120 ℃, and in the embodiment of the present invention, most preferably 115 ℃.
In the specific embodiment of the invention, 10000 times of aging spraying treatment are carried out on the wall-flow type denitration catalyst by adopting a filter material dynamic filtering performance test method, and the stripping resistance and the service life of the wall-flow type denitration catalyst are evaluated by comparing the denitration efficiency of the catalyst before and after aging spraying.
In the present invention, N is used 2 、O 2 、NO、NH 3 Mixing the gases to simulate the flue gas and denitrateEfficiency evaluation, wherein the denitration efficiency test conditions are no=400 ppm, nh3=400 ppm, h2o=5%, ghsv=2000 h-1, a=1.0.
Compared with the prior art, the invention has the following advantages:
1. the wall-flow denitration catalyst provided by the invention has the characteristics of uniform catalyst distribution, high denitration efficiency, good stripping resistance and long service life.
2. The nano carrier of the wall-flow denitration catalyst provided by the invention can provide a large number of active sites for the catalyst, improve the denitration efficiency and solve the problem of few active sites of the catalyst.
3. The alkaline colloid auxiliary agent in the nano carrier of the wall-flow denitration catalyst provided by the invention can effectively fix active ingredients and the nano carrier, improve the stripping resistance of the catalyst, and solve the problems of poor stripping resistance and short service life of the catalyst.
4. The pretreatment method of the porous carrier provided by the invention can uniformly distribute cation sites in the porous carrier, and uniformly adsorb anion components in the nano active carrier liquid on the surface of pores in the porous carrier through an anion-cation neutralization adsorption mechanism, so that the problem of uneven catalyst distribution is solved.
For further explanation of the present invention, the wall-flow denitration catalyst provided by the present invention is described in detail with reference to specific examples, but it should not be construed as limiting the scope of the present invention.
Example 1
A, preparing an active liquid: according to V 2 O 5 And WO 3 The molar ratio of (2) is 1:1.2, ammonium metavanadate and ammonium metatungstate are dissolved in oxalic acid solution.
B, preparation of nano carrier liquid: preparing mixed solution by 100 parts of deionized water, 9 parts of nano carrier, 0.8 part of dispersing agent and 8 parts of alkaline colloid auxiliary agent, and grinding and dispersing the mixed solution to obtain nano carrier liquid.
C, preparing a nano active mixed solution: and uniformly mixing the active liquid and the nano-carrier liquid to obtain a nano-active mixed liquid.
D, preparing a cation auxiliary solution: the cationic adjuvant was formulated as an aqueous solution with a concentration of 1.8 wt%.
E, pretreatment of a porous carrier: the porous carrier is immersed in the cation auxiliary agent, taken out after saturated adsorption, drained of surface liquid, placed in a blast drying box and dried at 75 ℃.
F porous carrier supports active components: and (3) immersing the pretreated porous carrier in the nano active mixed solution, taking out the porous carrier after saturated adsorption, draining surface liquid, placing the porous carrier in a blast drying oven, and performing secondary drying at 115 ℃ to obtain a wall-flow denitration catalyst finished product.
And (3) carrying out aging blowing treatment on the obtained wall-flow denitration catalyst finished product, and respectively testing denitration performance of the denitration catalyst before and after aging blowing, wherein the obtained result is shown in a figure 2, the catalytic efficiency difference of the wall-flow denitration catalyst before and after aging blowing is smaller, the wall-flow denitration catalyst and the wall-flow denitration catalyst have higher denitration efficiency, and the denitration efficiency before and after aging blowing is 98.2% and 96.7% respectively at 350 ℃.
Example 2
A, preparing an active liquid: according to V 2 O 5 And WO 3 The molar ratio of (2) is 1:1.2, ammonium metavanadate and ammonium metatungstate are dissolved in oxalic acid solution.
B, preparation of nano carrier liquid: preparing mixed solution by 100 parts of deionized water, 12 parts of nano-carrier, 1.2 parts of dispersing agent and 10 parts of alkaline colloid auxiliary agent, and grinding and dispersing the mixed solution to obtain nano-carrier liquid.
C, preparing a nano active mixed solution: and uniformly mixing the active liquid and the nano-carrier liquid to obtain a nano-active mixed liquid.
D, preparing a cation auxiliary solution: the cationic adjuvant was formulated as an aqueous solution with a concentration of 1.8 wt%.
E, pretreatment of a porous carrier: the porous carrier is immersed in the cation auxiliary agent, taken out after saturated adsorption, drained of surface liquid, placed in a blast drying box and dried at 75 ℃.
F porous carrier supports active components: and (3) immersing the pretreated porous carrier in the nano active mixed solution, taking out the porous carrier after saturated adsorption, draining surface liquid, placing the porous carrier in a blast drying oven, and performing secondary drying at 115 ℃ to obtain a wall-flow denitration catalyst finished product.
And (3) carrying out aging blowing treatment on the obtained wall-flow denitration catalyst finished product, and respectively testing denitration performance of the denitration catalyst before and after aging blowing, wherein the obtained result is shown in a figure 3, the catalytic efficiency difference of the wall-flow denitration catalyst before and after aging blowing is smaller, the wall-flow denitration catalyst and the wall-flow denitration catalyst have higher denitration efficiency, and the denitration efficiency before and after aging blowing is 97.7% and 96.3% respectively at 350 ℃.
Example 3
A, preparing an active liquid: according to V 2 O 5 And WO 3 The molar ratio of (2) is 1:1.2, ammonium metavanadate and ammonium metatungstate are dissolved in oxalic acid solution.
B, preparation of nano carrier liquid: preparing mixed solution by 100 parts of deionized water, 15 parts of nano carrier, 1.8 parts of dispersing agent and 12 parts of alkaline colloid auxiliary agent, and grinding and dispersing the mixed solution to obtain nano carrier liquid.
C, preparing a nano active mixed solution: and uniformly mixing the active liquid and the nano-carrier liquid to obtain a nano-active mixed liquid.
D, preparing a cation auxiliary solution: the cationic adjuvant was formulated as an aqueous solution with a concentration of 1.8 wt%.
E, pretreatment of a porous carrier: the porous carrier is immersed in the cation auxiliary agent, taken out after saturated adsorption, drained of surface liquid, placed in a blast drying box and dried at 75 ℃.
F porous carrier supports active components: and (3) immersing the pretreated porous carrier in the nano active mixed solution, taking out the porous carrier after saturated adsorption, draining surface liquid, placing the porous carrier in a blast drying oven, and performing secondary drying at 115 ℃ to obtain a wall-flow denitration catalyst finished product.
And (3) carrying out aging blowing treatment on the obtained wall-flow denitration catalyst finished product, and respectively testing denitration performance of the denitration catalyst before and after aging blowing, wherein the obtained result is shown in a figure 4, the catalytic efficiency difference of the wall-flow denitration catalyst before and after aging blowing is smaller, the wall-flow denitration catalyst and the wall-flow denitration catalyst have higher denitration efficiency, and the denitration efficiency before and after aging blowing is 98.2% and 97.1% respectively at 350 ℃.
Example 4
A, preparing an active liquid: according to V 2 O 5 And WO 3 The molar ratio of (2) is 1:1.2, ammonium metavanadate and ammonium metatungstate are dissolved in oxalic acid solution.
B, preparation of nano carrier liquid: preparing mixed solution by 100 parts of deionized water, 18 parts of nano-carrier, 2.0 parts of dispersing agent and 15 parts of alkaline colloid auxiliary agent, and grinding and dispersing the mixed solution to obtain nano-carrier liquid.
C, preparing a nano active mixed solution: and uniformly mixing the active liquid and the nano-carrier liquid to obtain a nano-active mixed liquid.
D, preparing a cation auxiliary solution: the cationic adjuvant was formulated as an aqueous solution with a concentration of 1.8 wt%.
E, pretreatment of a porous carrier: the porous carrier is immersed in the cation auxiliary agent, taken out after saturated adsorption, drained of surface liquid, placed in a blast drying box and dried at 75 ℃.
F porous carrier supports active components: and (3) immersing the pretreated porous carrier in the nano active mixed solution, taking out the porous carrier after saturated adsorption, draining surface liquid, placing the porous carrier in a blast drying oven, and performing secondary drying at 115 ℃ to obtain a wall-flow denitration catalyst finished product.
And (3) carrying out aging blowing treatment on the obtained wall-flow denitration catalyst finished product, and respectively testing denitration performance of the denitration catalyst before and after aging blowing, wherein the obtained results are shown in a figure 5, the catalytic efficiency of the wall-flow denitration catalyst is almost unchanged before and after aging blowing, the two are kept to be higher denitration efficiency, and the denitration efficiency before and after aging blowing is respectively 98.5% and 98.1% at 350 ℃.
Comparative example
In order to further embody the technical advantages of the invention, the comparative example removes the pretreatment steps of the anionic colloid auxiliary agent and the porous carrier cationic auxiliary agent in the nano carrier liquid, and the specific implementation steps are as follows:
a, preparing an active liquid: according to V 2 O 5 And WO 3 The molar ratio of (2) is 1:1.2, ammonium metavanadate and ammonium metatungstate are dissolved in oxalic acid solution.
B, preparation of nano carrier liquid: according to 100 parts of deionized water, 18 parts of nano-carrier and 2.0 parts of dispersing agent, the mixed solution is ground and dispersed to obtain nano-carrier liquid.
C, preparing a nano active mixed solution: and uniformly mixing the active liquid and the nano-carrier liquid to obtain a nano-active mixed liquid.
D porous carrier loaded with active component: and (3) immersing the porous carrier in the nano active mixed solution, taking out the porous carrier after saturated adsorption, draining off surface liquid, placing the porous carrier in a blast drying box, and performing secondary drying at 115 ℃ to obtain the wall-flow denitration catalyst comparative example product.
The obtained wall-flow denitration catalyst proportional product is subjected to ageing blowing treatment, denitration performances of the denitration catalyst before and after ageing blowing are respectively tested, the obtained results are shown in a figure 6, the catalytic efficiency of the wall-flow denitration catalyst is greatly different before and after ageing blowing, the denitration efficiency before ageing blowing can reach 90.7% at 350 ℃, remarkable attenuation occurs after ageing blowing, and the denitration efficiency is only 76.2% at the same temperature.
In the comparative example, the denitration efficiency of the wall-flow denitration catalyst has a certain difference from that of the embodiment of the invention before aging and blowing, because the pretreatment steps of the anionic colloid auxiliary agent and the porous carrier cationic auxiliary agent are not missing, on one hand, the catalyst active components are not uniformly distributed in the porous carrier, so that the active components are enriched on the inner surface and the outer surface, and when the flue gas passes through the catalyst layer, the effective contact time with the catalyst is shortened, and the overall catalytic efficiency is affected to a certain extent; on the other hand, the anchoring effect of the bonding auxiliary agent on the nano-carrier and the active ingredient is absent, so that the active ingredient of the catalyst is easily influenced by high-speed air flow of injection in the aging injection process and falls off from the porous carrier, thereby influencing the service life of the denitration catalyst.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. A wall-flow denitration catalyst comprising: nano active mixed solution, cation auxiliary agent and porous carrier;
the nano active mixed solution comprises an active solution and a nano carrier solution;
the active liquid is according to V 2 O 5 And WO 3 The molar ratio of (2) is 1: (0.5-1.5) consisting of a mixed oxalic acid solution of ammonium metavanadate and ammonium metatungstate;
the nano-carrier liquid comprises 100 parts of deionized water, 6-18 parts of nano-carrier, 0.5-2 parts of dispersing agent and 8-15 parts of alkaline colloid auxiliary agent.
The nano carrier of the nano carrier liquid is one or more of titanium dioxide, molecular sieve, diatomite and kaolin.
The dispersing agent of the nano-carrier liquid is one or more of polyethylene glycol, polyvinyl alcohol, dodecyl polyoxyethylene ether and diethanolamine
The alkaline colloid auxiliary agent of the nano carrier liquid is one or more of silica sol, aluminum sol and titanium sol.
The cationic auxiliary agent is composed of one or more aqueous solutions of cationic modified starch, cationic polyacrylamide and cationic cellulose.
The porous carrier is a filter cylinder type, plate type or plugged honeycomb type porous material.
2. The nano-carrier liquid according to claim 1, wherein the nano-carrier is titanium dioxide, a molecular sieve and diatomite, and the mass ratio of the titanium dioxide to the molecular sieve to the diatomite is 1: (0.2-0.8): (0.1-0.5).
3. The nano-carrier liquid according to claim 1, wherein the alkaline colloid auxiliary agent is silica sol, alumina sol and titanium sol, and the mass ratio of the silica sol, the alumina sol and the titanium sol is 1: (0.05-0.5): (0.1-1.5).
4. The nano-carrier liquid according to claim 1, wherein the solid content of the silica sol used in the alkaline colloid auxiliary agent is 30%, the particle diameter D50 is 10nm, and the ph value is 9.0 to 10.2; the solid content of the aluminum sol is 20%, the particle diameter D50 is 10nm, and the pH value is 7.0-9.0. The solid content of the titanium sol is 8%, the particle diameter D50 is 3nm, and the pH value is 8.7-10.0.
5. The cationic assistant of the wall-flow denitration catalyst according to claim 1, wherein the cationic assistant is cation modified starch, the molar substitution degree is 0.028-0.036, and the viscosity is 80-140 mPa.s (25 ℃,4.0% concentration).
6. The porous carrier of the wall-flow denitration catalyst according to claim 1, wherein the porous carrier is a filter cartridge type, a plate type or a plugged honeycomb type porous material, and the open porosity is 75-90%.
7. A preparation method of a wall-flow denitration catalyst comprises the following steps:
a, preparing an active liquid: the molar ratio of V2O5 to WO3 is 1: (0.5-1.5), and dissolving ammonium metavanadate and ammonium metatungstate in an oxalic acid solution.
B, preparation of nano carrier liquid: preparing mixed solution by 100 parts of deionized water, 6-18 parts of nano carrier, 0.5-2 parts of dispersing agent and 8-15 parts of alkaline colloid auxiliary agent, and grinding and dispersing the mixed solution to obtain nano carrier solution.
C, preparing a nano active mixed solution: and uniformly mixing the active liquid and the nano-carrier liquid to obtain a nano-active mixed liquid.
D, preparing a cation auxiliary solution: the cationic assistant is prepared into aqueous solution with concentration of 0.5-4.0 wt%.
E, pretreatment of a porous carrier: and (3) immersing the porous carrier in a cationic auxiliary agent, taking out the porous carrier after saturated adsorption, draining surface liquid, and placing the porous carrier in a blast drying oven for primary drying.
F porous carrier supports active components: and (3) immersing the pretreated porous carrier in the nano active mixed solution, taking out the porous carrier after saturated adsorption, draining surface liquid, placing the porous carrier in a blast drying oven, and drying the porous carrier for the second time to obtain a wall-flow denitration catalyst finished product.
8. The method of grinding and dispersing a nano-carrier liquid according to claim 7, wherein the method of grinding and dispersing is any one of a roller ball mill, a planetary ball mill and a sand mill.
9. The primary drying of the porous support pretreatment according to claim 7, wherein the porous support pretreatment primary drying temperature is 60 to 90 ℃.
10. The porous carrier-supported active component according to claim 7, wherein the secondary drying temperature of the porous carrier-supported active component is 100 to 150 ℃.
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