CN113209960A - Honeycomb type denitration catalyst and preparation method and application thereof - Google Patents
Honeycomb type denitration catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 194
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 44
- 239000002994 raw material Substances 0.000 claims abstract description 42
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 37
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000003112 inhibitor Substances 0.000 claims abstract description 36
- 239000003546 flue gas Substances 0.000 claims abstract description 35
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 35
- 239000011593 sulfur Substances 0.000 claims abstract description 35
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 33
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 21
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 15
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000005520 cutting process Methods 0.000 claims abstract description 13
- 238000001125 extrusion Methods 0.000 claims abstract description 12
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 10
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 10
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 9
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 9
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 9
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 9
- 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 abstract description 9
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000008117 stearic acid Substances 0.000 claims abstract description 9
- 230000032683 aging Effects 0.000 claims abstract description 8
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 8
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 8
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 8
- 239000003365 glass fiber Substances 0.000 claims abstract description 8
- 239000004310 lactic acid Substances 0.000 claims abstract description 7
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 42
- 239000011248 coating agent Substances 0.000 claims description 35
- 238000000576 coating method Methods 0.000 claims description 35
- 239000000463 material Substances 0.000 claims description 28
- 230000008569 process Effects 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 19
- 229920001131 Pulp (paper) Polymers 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 18
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 16
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 15
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 15
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 15
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 229920001973 fluoroelastomer Polymers 0.000 claims description 12
- 239000004743 Polypropylene Substances 0.000 claims description 10
- -1 polypropylene Polymers 0.000 claims description 10
- 229920001155 polypropylene Polymers 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 9
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 8
- 239000004115 Sodium Silicate Substances 0.000 claims description 8
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 8
- 238000005299 abrasion Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 5
- 239000000835 fiber Substances 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 230000000052 comparative effect Effects 0.000 description 33
- 239000011148 porous material Substances 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 27
- 230000000694 effects Effects 0.000 description 16
- 239000010881 fly ash Substances 0.000 description 7
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 108010081750 Reticulin Proteins 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 5
- 235000011130 ammonium sulphate Nutrition 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 238000003483 aging Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical group N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/28—Molybdenum
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
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Abstract
The application relates to the field of flue gas treatment, and particularly discloses a honeycomb type denitration catalyst, and a preparation method and application thereof. The honeycomb denitration catalyst comprises a honeycomb catalyst body, wherein the catalyst body is made and molded by the following raw materials in parts by weight: 600-620 parts of titanium dioxide, 12-29 parts of ammonium metavanadate, 18-42 parts of ammonium molybdate, 16-45 parts of glass fiber, 12-34 parts of kaolin, 1-3 parts of stearic acid, 3.6-9.5 parts of polyethylene oxide, 4.2-8.4 parts of lactic acid and 10-50 parts of sulfur inhibitor, wherein the sulfur inhibitor comprises one or a combination of two of silica sol and alumina sol; the preparation method comprises the following steps: preparing raw materials; preparing an ammonium metavanadate solution; mixing; filtration-pre-extrusion; aging; extruding; drying; roasting; and (6) cutting. The honeycomb type denitration catalyst has the advantage of improving the denitration efficiency of the denitration catalyst.
Description
Technical Field
The application relates to the field of flue gas treatment, in particular to a honeycomb type denitration catalyst and a preparation method and application thereof.
Background
Selective Catalytic Reduction (SCR) is the most critical technology for controlling nitrogen oxide (NOx) emission and is widely applied toDenitration of industrial flue gas in thermal power plants, incineration plants and the like, and purification of tail gas of diesel motor vehicles. The technology uses NH generated by urea, ammonia water or liquid ammonia3The core is a denitration catalyst which is a reducing agent.
In the related technology, the Chinese patent with the publication number of CN102974340B discloses a preparation method of a honeycomb V-Ti low-temperature flue gas denitration catalyst, the catalyst is prepared by a material mixing process and a forming process, and in the catalyst, nano-TiO accounting for 70-90% of the mass of the catalyst is used2V is used as a carrier and accounts for 5-15% of the mass of the catalyst2O5The catalyst is an active component, and the metal oxide auxiliary agent is one or more of oxides of Cr, Mn, Cu, Ce, W and Mo, and accounts for 4-16% of the mass of the catalyst.
The inventors consider that the following drawbacks exist in the related art: when the denitration catalyst prepared by the method is used, the pore channel blockage condition of the denitration catalyst is serious, so that the denitration efficiency of the denitration catalyst is reduced.
Disclosure of Invention
In order to improve the denitration efficiency of the denitration catalyst, the application provides a honeycomb type denitration catalyst and a preparation method and application thereof.
In a first aspect, the present application provides a honeycomb denitration catalyst, which adopts the following technical scheme:
the honeycomb denitration catalyst comprises a honeycomb catalyst body, wherein the catalyst body is made and molded by the following raw materials in parts by weight: 600-620 parts of titanium dioxide, 12-29 parts of ammonium metavanadate, 18-42 parts of ammonium molybdate, 16-45 parts of glass fiber, 12-34 parts of kaolin, 1-3 parts of stearic acid, 3.6-9.5 parts of polyethylene oxide, 4.2-8.4 parts of lactic acid and 10-50 parts of sulfur inhibitor, wherein the sulfur inhibitor comprises one or a combination of two of silica sol and alumina sol.
By adopting the technical scheme, as the sulfur inhibitor is adopted and comprises one or the combination of two of silica sol and alumina sol, the SO in the flue gas or tail gas to be treated is reduced2To SO3Conversion rate of conversion, thereby reducing SO3And NH3Ammonium sulfate generated by the reaction is used as a catalystThe clogging of the cell channels of the body can be prevented, and thus the denitration efficiency of the denitration catalyst can be improved.
Optionally, the catalyst body is made and molded from the following raw materials in parts by weight: 600-620 parts of titanium dioxide, 20.4-26.5 parts of ammonium metavanadate, 28.4-38.7 parts of ammonium molybdate, 26.4-41 parts of glass fiber, 17.5-28.3 parts of kaolin, 1.7-2.5 parts of stearic acid, 5.2-8 parts of polyethylene oxide, 5.8-7 parts of lactic acid and 15-45 parts of sulfur inhibitor, wherein the sulfur inhibitor comprises silica sol and alumina sol, and the weight ratio of the silica sol to the alumina sol is (2-5): 1.
by adopting the technical scheme, the raw materials in the weight portion range are adopted, and particularly when the sulfur inhibitor is compounded and used by adopting silica sol and alumina sol, the sulfur inhibitor has excellent effect of reducing SO in flue gas or tail gas to be treated2To SO3The effect of the conversion rate of the conversion is that the clogging of the cell channels of the denitration catalyst is reduced, and therefore, the effect of improving the denitration efficiency of the denitration catalyst is obtained.
Optionally, the catalyst body further comprises 3-3.5 parts by weight of wood pulp powder.
Through adopting above-mentioned technical scheme, wood pulp powder can volatilize through the calcination after with other raw materials mixing of catalyst body, forms the hole in catalyst body inside to increased catalyst body's pore volume and specific surface area, reduced SO at the sulphur inhibitor2After the conversion of (3), the successful SO is still converted3And NH3The ammonium sulfate generated after combination can enter the pores communicated with the pore channels through the pore channels on the catalyst body, so that the blocking condition of the pore channels is further reduced, and the effect of improving the denitration efficiency of the denitration catalyst is obtained.
Optionally, the catalyst body further comprises 1-7 parts by weight of carboxymethyl cellulose.
By adopting the technical scheme, when the wood pulp powder and the carboxymethyl cellulose are compounded for use, the catalyst has more excellent effects of improving the pore volume and the specific surface area of the catalyst, so that the pore channel blockage condition of the denitration catalyst is reduced, and the effect of improving the denitration efficiency of the denitration catalyst is obtained.
Optionally, the denitration catalyst further comprises a wear-resistant coating, the wear-resistant coating is formed by coating a wear-resistant coating mixed solution on the windward side of the catalyst body and then curing, and the wear-resistant coating mixed solution comprises liquid sodium silicate, polypropylene reticular fiber and 26-41 type fluororubber particles in a weight ratio of 7:2: 1.
In the process of using the denitration catalyst, under the condition of higher gas flow speed of flue gas, larger fly ash particles carried in the flue gas easily wear the windward side of the catalyst body, and cause the loss of active ingredients on the catalyst body under the long-term wearing state, by adopting the technical scheme, the windward side of the catalyst body is provided with the wear-resistant coating, liquid sodium silicate is firstly used as a binder, polypropylene mesh fibers and 26-41 type fluororubber particles are adhered together and then adhered to the windward side of the catalyst body, the polypropylene mesh fibers and the 26-41 type fluororubber particles are firmly adhered to the windward side of the catalyst body along with the solidification of the liquid sodium silicate, the polypropylene mesh fibers form a mesh structure, the 26-41 type fluororubber particles form a plurality of protruding points on the mesh structure, when the flue gas carries the larger fly ash particles to pass through the denitration catalyst, the speed of the fly ash particles which collide with the windward side of the catalyst is reduced after being blocked by the net structure, and the fly ash particles change the advancing path under the action of the 26-41 type fluororubber particles and enter the duct to be treated by the catalyst body, so that the abrasion degree of the windward side of the catalyst body is reduced, the active ingredients on the catalyst body are not easy to lose, and the denitration efficiency of the denitration catalyst is improved.
In a second aspect, the application provides a preparation method of a honeycomb type denitration catalyst, which adopts the following technical scheme:
a preparation method of a honeycomb type denitration catalyst comprises the following steps:
(1) preparing raw materials according to a mixture ratio for later use;
(2) preparing an ammonium metavanadate solution: ammonium metavanadate is fully dissolved in NH3Adding monoethanolamine into ammonia water with the mass content of 20% to adjust the pH of the solution to 7.8-9, so as to obtain an ammonium metavanadate solution;
(3) mixing: mixing ammonium metavanadate solution and other raw materials, and adding NH in the mixing process3Adjusting the pH value to be 7.8-9 by ammonia water with the mass content of 15%, adding deionized water in the mixing process to fully mix the raw materials to form a mixed material, wherein the water content of the finally obtained mixed material is 28-31%;
(4) filtration-pre-extrusion: filtering the mixed material, removing impurities to obtain a refined material, and pre-extruding the refined material to form a strip-shaped blank;
(5) and (3) staling: aging the blank for 24 hours;
(6) extruding: extruding and molding the aged blank to obtain a honeycomb blank;
(7) and (3) drying: drying the honeycomb blank;
(8) roasting: roasting the dried honeycomb blank at the final roasting temperature of 510-530 ℃;
(9) cutting: and cutting the roasted honeycomb blank to form a honeycomb catalyst body, wherein two end surfaces of the catalyst body are cut smoothly, and honeycomb openings on the end surfaces are communicated with the outside.
By adopting the technical scheme, the ammonium metavanadate solution is prepared firstly, so that the ammonium metavanadate is fully dissolved and can be better mixed with other raw materials, then mixing is carried out, so that the raw materials are uniformly mixed, and then the final denitration catalyst is obtained through filtering-pre-extrusion, ageing, extrusion, drying, roasting and cutting.
A preparation method of a honeycomb type denitration catalyst comprises the following steps:
s1, preparing a catalyst body:
(1) preparing raw materials according to a mixture ratio for later use;
(2) preparing an ammonium metavanadate solution: ammonium metavanadate is fully dissolved in NH3Adding monoethanolamine into ammonia water with the mass content of 20% to adjust the pH of the solution to 7.8-9, so as to obtain an ammonium metavanadate solution;
(3) mixing: mixing ammonium metavanadate solution and other raw materialsAdding NH during the mixing process3Adjusting the pH value to be 7.8-9 by ammonia water with the mass content of 15%, adding deionized water in the mixing process to fully mix the raw materials to form a mixed material, wherein the water content of the finally obtained mixed material is 28-31%;
(4) filtration-pre-extrusion: filtering the mixed material, removing impurities to obtain a refined material, and pre-extruding the refined material to form a strip-shaped blank;
(5) and (3) staling: aging the blank for 24 hours;
(6) extruding: extruding and molding the aged blank to obtain a honeycomb blank;
(7) and (3) drying: drying the honeycomb blank;
(8) roasting: roasting the dried honeycomb blank at the final roasting temperature of 510-530 ℃;
(9) cutting: cutting the roasted honeycomb blank to form a honeycomb catalyst body, wherein two windward sides of the catalyst body are cut smoothly, and honeycomb openings on the windward sides are communicated with the outside;
and S2, coating the mixed liquor of the wear-resistant coating on the windward side of the catalyst body prepared in the step S1, keeping the honeycomb-shaped opening on the windward side communicated with the outside, and forming the wear-resistant coating on the windward side of the catalyst body after the mixed liquor of the wear-resistant coating is cured to prepare the honeycomb-type denitration catalyst.
By adopting the technical scheme, the wear-resistant coating is formed by coating the wear-resistant coating mixed liquid on the windward side of the catalyst body, so that the wear degree of the windward side of the catalyst body can be effectively reduced, and the active ingredients on the catalyst body are not easy to run off, thereby obtaining the effect of improving the denitration efficiency of the denitration catalyst.
In a third aspect, the present application provides an application of a honeycomb denitration catalyst, which adopts the following technical scheme:
the application of the honeycomb denitration catalyst is characterized in that the denitration efficiency of the denitration catalyst is more than or equal to 90% when denitration treatment is carried out on flue gas at the temperature of 120-280 ℃.
By adopting the technical scheme, the denitration catalyst has excellent treatment effect when denitration treatment is carried out on flue gas at the temperature of 120-280 ℃, and the denitration efficiency can reach more than 90%.
In summary, the present application has the following beneficial effects:
1. because the sulfur inhibitor containing one or two of silica sol and aluminum sol is adopted in the application, SO is reduced2To SO3Conversion rate of conversion, thereby reducing SO3And NH3The ammonium sulfate generated by the reaction blocks the pore channels of the catalyst body, so that the effect of improving the denitration efficiency of the denitration catalyst is obtained.
2. The wood pulp powder is preferably adopted in the application, and pores are formed in the catalyst body, SO that the pore volume and the specific surface area of the catalyst body are increased, and the SO is reduced by the sulfur inhibitor2After the conversion of (3), the successful SO is still converted3And NH3The ammonium sulfate generated after combination can enter the pores communicated with the pore channels through the pore channels on the catalyst body, so that the blocking condition of the pore channels is further reduced, and the effect of improving the denitration efficiency of the denitration catalyst is obtained.
3. Preferentially adopt wear-resisting coating in this application, reduced the degree of wear of catalyst body windward side, active ingredient on the catalyst body is difficult for running off, consequently, obtains the effect that improves the denitration efficiency of denitration catalyst, has prolonged the life of denitration catalyst simultaneously.
4. According to the method, the ammonium metavanadate solution is prepared firstly, so that the ammonium metavanadate is fully dissolved and can be better mixed with other raw materials, then mixing is carried out, so that the raw materials are uniformly mixed, and then the final denitration catalyst is obtained through filtering-pre-extrusion, ageing, extrusion, drying, roasting and cutting.
Detailed Description
The present application will be described in further detail with reference to examples. The special description is as follows: the following examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer, and the starting materials used in the following examples were obtained from ordinary commercial sources unless otherwise specified.
The titanium dioxide is pure anatase nano titanium dioxide with the model of SS-TA103 produced by Hangzhou Jikang new material limited company, and the granularity is 50 nanometers.
Ammonium metavanadate of CAS number 7803-55-6 produced by Hubei Hengheng Limited is used.
The ammonium molybdate is ammonium heptamolybdate with the CAS number of 13106-76-8, which is produced by Suzhou Junying chemical company Limited, and the granularity is 200 meshes.
The glass fiber is 20-23 μm in diameter and 36-38 mm in length.
The kaolin is kaolin with 325 mesh sieve residue (%) < 0.005.
Stearic acid adopts stearic acid with CAS number 57-11-4 produced by Jinan Shuangying chemical Limited company.
The polyethylene oxide is polyethylene oxide of type POLYOX WSR 308 produced by dow chemical in the united states, and has a molecular weight of over 800 ten thousand.
The silica sol is 15nm silica sol of JL-SiO2-J15, produced by Beijing Deke island gold science and technology Limited.
The aluminum sol is nanometer aluminum sol with model number DK-Al-SL produced by Beijing German island gold science and technology limited.
The carboxymethyl cellulose is made of HH-CMC manufactured by Shandong Yang Gu Huanghe chemical Co.
The wood pulp powder adopts 200-mesh wood pulp powder.
The liquid sodium silicate is water glass produced by Guangzhou emperor chemical company Limited.
The polypropylene reticular fiber is a 9870 polypropylene reticular fiber produced by gallery Tianya energy-saving science and technology Limited, and is crushed to a length of 36-38 mm.
The 26-41 type fluororubber particles are 26-41 type fluororubber particles with the particle size of 1-2 mm.
The monoethanolamine adopts monoethanolamine of HZ010 type produced by Shandong Huangcata new material Co.
Preparation example
Preparation example 1
70kg of liquid sodium silicate, 20kg of polypropylene reticular fiber and 10kg of 26-41 type fluororubber granules are mixed and stirred uniformly to prepare the wear-resistant coating mixed liquid.
Examples
Example 1
A preparation method of a honeycomb type denitration catalyst comprises the following steps:
(1) preparing the following raw materials for later use: 600kg of titanium dioxide, 12kg of ammonium metavanadate, 18kg of ammonium molybdate, 16kg of glass fiber, 12kg of kaolin, 1kg of stearic acid, 3.6kg of polyethylene oxide, 4.2kg of lactic acid and 10kg of sulfur inhibitor, wherein the sulfur inhibitor adopts silica sol;
(2) preparing an ammonium metavanadate solution: ammonium metavanadate is fully dissolved in NH3And adding monoethanolamine into ammonia water with the mass content of 20% to adjust the pH of the solution to 7.8, thereby obtaining an ammonium metavanadate solution.
(3) Mixing:
the first step is as follows: adding 54 percent of the total weight of the titanium dioxide, 65 percent of the total weight of the ammonium metavanadate solution, ammonium molybdate, stearic acid, lactic acid and kaolin into a mixing mill, mixing, and adding NH3Adjusting the pH value to be 7.8 by ammonia water with the mass content of 15%, adding deionized water in the mixing process to fully mix the raw materials, wherein the water content of the mixture is 42%. In the mixing process, firstly, the mixture rotates forwards for 30min at 350rpm, then rotates forwards for 7min at 750rpm, and the exhaust is closed.
The second step is that: and continuously adding 20 percent of the total weight of the titanium dioxide into the mixing roll for mixing, and adding deionized water to fully mix the raw materials, wherein the water content of the mixture is 37 percent. In the mixing process, firstly, the mixture rotates forwards at 350rpm for 15min, then rotates forwards at 750rpm for 20min, and the exhaust is closed.
The third step: continuously adding 13 percent of the total weight of the rest titanium dioxide and ammonium metavanadate solution into the mixing roll for mixing, adding NH3Adjusting the pH value to be 7.8 by ammonia water with the mass content of 15%, adding deionized water in the mixing process to fully mix the raw materials, wherein the water content of the mixture is 25%. In the mixing process, firstly, positively rotating at 350rpm for 15min, then positively rotating at 750rpm for 80min, and starting air exhaust when the material temperature is higher than 95 ℃.
The fourth step: and continuously adding glass fiber into the mixing roll for mixing, and adding deionized water in the mixing process to fully mix the raw materials, wherein the water content of the mixture is 28%. In the mixing process, firstly, the mixture rotates forwards at 350rpm for 15min, then rotates forwards at 750rpm for 10min, and the exhaust is opened.
The fifth step: the mixer was further charged with 13% by weight of the ammonium metavanadate solution and 50% by weight of the polyethylene oxide, and kneaded. In the mixing process, firstly, the mixture is reversed for 10min at 350rpm, then, the mixture is reversed for 5min at 750rpm, and the air exhaust is opened.
And a sixth step: continuously adding the rest of ammonium metavanadate solution, the rest of polyethylene oxide and the sulfur inhibitor into the mixing mill for mixing, adding NH3Adjusting the pH value to be 7.8 by ammonia water with the mass content of 15%, adding deionized water in the mixing process to fully mix the raw materials to obtain a final mixed material, wherein the water content of the mixed material is 28%. In the mixing process, firstly, the mixture is reversed for 15min at 350rpm, then, the mixture is reversed for 15min at 750rpm, and the air exhaust is opened.
(4) Filtration-pre-extrusion: and filtering the mixed material, wherein a rectangular filter screen with openings of 1.4mm x 0.8mm is adopted during filtering, and impurities are removed to obtain the fine material. Putting the fine material into a pre-extruder to pre-extrude to form a strip-shaped blank;
(5) and (3) staling: aging the blank for 24 hours;
(6) extruding: putting the aged blank into a vacuum extruder for extrusion molding, wherein the absolute vacuum degree is 93kPa, the pressure is 3MPa, and the extrusion speed is 1.4mm/min, so as to obtain a honeycomb blank with 25 holes;
(7) and (3) drying:
primary drying: drying the honeycomb blank by using water vapor as a heat source, wherein the drying time is 10 days, the temperature is (30 +/-5) DEG C and the humidity is (80 +/-5)%, the temperature is (35 +/-5) DEG C and the humidity is (75 +/-5)%, the temperature is (40 +/-5) DEG C and the humidity is (65 +/-5)%, the temperature is (40 +/-5) DEG C, the humidity is (55 +/-5)%, the temperature is (50 +/-5)% and the humidity is (45 +/-5)%, and the temperature is (50 +/-5) DEG C and the humidity is (30 +/-5)%, and the temperature is (60 +/-5) ° C and the humidity is (20 +/-5)%, wherein the drying time is 10 days, the temperature is (30 +/-5) ° C, the humidity is (40 +/-5)%, the temperature is (40 +/-5)%, and the humidity is (20 +/-5)%, and the humidity is in the 5) period of 7 days.
And (3) secondary drying: and (3) sending the primary dried honeycomb blank into a tunnel kiln for secondary drying, and drying at 60 ℃ for 20 hours.
(8) Roasting: and roasting the dried honeycomb blank, wherein the roasting process comprises heating I, roasting I, heating II and roasting II in sequence, and cooling after roasting.
Heating I temperature from 100 deg.C to 200 deg.C at constant speed for 5.5 h.
The roasting I is carried out at the constant temperature of 200 ℃ for 4.5 h.
And (3) heating II, namely heating II to 510 ℃ at a constant speed from 200 ℃ for 8 h.
And roasting II at the constant temperature of 510 ℃ for 5.5 hours.
Cooled to room temperature for 9.5 h.
(9) Cutting: and cutting the roasted honeycomb blank according to the size requirement of the product to form a honeycomb catalyst body, wherein two windward sides of the catalyst body are cut smoothly, and a honeycomb opening on the windward side is communicated with the outside.
Example 2
This example differs from example 1 in that:
the weight of each raw material was varied and is detailed in table 1.
In the embodiment, the sulfur inhibitor adopts the combination of silica sol and aluminum sol, the silica sol adopts 12.5kg, and the aluminum sol adopts 2.5 kg.
In this example, 7kg of carboxymethyl cellulose and 3kg of wood pulp powder were added, 50% by weight of the total amount of carboxymethyl cellulose and 50% by weight of the total amount of wood pulp powder were added in the fifth step of the (3) mixing step, and the remaining carboxymethyl cellulose and wood pulp powder were added in the sixth step of the (3) mixing step.
In this example, the pH of the ammonium metavanadate solution was adjusted to 8 by monoethanolamine, the pH during kneading was also stabilized at 8, and the water content of the finally obtained kneaded product was 29%.
In this example (8), the final baking temperature was 515 ℃.
Example 3
This example differs from example 1 in that: the sulfur inhibitor in this example was a combination of silica sol and alumina sol, 20kg of silica sol and 5kg of alumina sol. The weight of other raw materials is different from that of example 1 and is detailed in table 1, and the differences of process parameters in the preparation method are detailed in table 2.
Example 4
This example differs from example 2 in that: the weight and the process parameters of the raw materials in the embodiment are different, the weight of each raw material is detailed in table 1, and the related process parameters in the preparation method are detailed in table 2.
Example 5
This example differs from example 1 in that: in the embodiment, the sulfur inhibitor adopts alumina sol, the weight and the process parameters of all the raw materials are different, the weight of all the raw materials is detailed in table 1, and the related process parameters in the preparation method are detailed in table 2.
Example 6
This example differs from example 3 in that: the sulfur inhibitor in this example was all silica sol.
Example 7
This example differs from example 3 in that: the sulfur inhibitor in this example was all alumina sol.
Example 8
This example differs from example 2 in that: the weight and the process parameters of the raw materials in the embodiment are different, the weight of each raw material is detailed in table 1, and the related process parameters in the preparation method are detailed in table 2.
Example 9
This example differs from example 8 in that: no carboxymethyl cellulose was present in this example.
Example 10
This example differs from example 8 in that: no wood pulp powder is used in this example.
Example 11
A preparation method of a honeycomb type denitration catalyst comprises the following steps:
s1, preparing a catalyst body: catalyst bodies were prepared according to the preparation method of example 3.
And S2, coating the wear-resistant coating mixed liquid prepared in the preparation example 1 on the windward side of the catalyst body prepared in the step S1, keeping the honeycomb-shaped opening on the windward side communicated with the outside, and curing the wear-resistant coating mixed liquid to form a wear-resistant coating on the windward side of the catalyst body to prepare the honeycomb-shaped denitration catalyst.
Example 12
This embodiment differs from embodiment 11 in that: catalyst bodies were prepared according to the preparation method of example 8.
Comparative example
Comparative example 1
This comparative example differs from example 3 in that: in the comparative example, the sulfur inhibitor is not used, the weight of each raw material is detailed in table 1, and the related process parameters in the preparation method are detailed in table 2.
Comparative example 2
This comparative example differs from example 8 in that: in the comparative example, the sulfur inhibitor is not used, the weight of each raw material is detailed in table 1, and the related process parameters in the preparation method are detailed in table 2.
TABLE 1
TABLE 2
Application example
Application example 1
According to the method of GB/T31587-.
Application example 2
According to the method of GB/T31587-.
Application example 3
According to the method of GB/T31587-.
Application example 4
The denitration catalyst prepared in each example and comparative example is adopted to carry out denitration treatment on flue gas at 380 ℃ according to the method of '6.5 reactivity determination' in GB/T31587-2015.
Application example 5
According to the method of GB/T31587-.
Performance test
Detection method
1. The pore volumes of the denitration catalysts prepared in the examples and the comparative examples were measured according to the method of GB/T21650.1-2008, and the results are shown in Table 3.
2. The specific surface areas of the denitration catalysts prepared in the examples and the comparative examples are detected according to the multipoint BET method in GB/T19587-2017, and the detection results are detailed in Table 3.
3. The denitration catalysts prepared in the examples and the comparative examples were tested for the wear rate of the part including the windward side according to the method of "determination of wear rate of 6.4.2" in GB/T31587-2015, and the test results are detailed in Table 3.
4. Denitration efficiency and SO of denitration catalyst in each application example2/SO3The conversion rate was measured and the results are shown in Table 4.
TABLE 3
| Examples/comparative examples | Pore volume (mL/g) | Specific surface area (m)2/g) | Wear rate (%/kg) |
| Example 1 | 0.26 | 49 | 0.143 |
| Example 2 | 0.52 | 122 | 0.072 |
| Example 3 | 0.28 | 52 | 0.136 |
| Example 4 | 0.53 | 125 | 0.07 |
| Example 5 | 0.24 | 44 | 0.147 |
| Example 6 | 0.27 | 50 | 0.141 |
| Example 7 | 0.25 | 46 | 0.145 |
| Example 8 | 0.62 | 142 | 0.062 |
| Example 9 | 0.48 | 109 | 0.084 |
| Example 10 | 0.46 | 104 | 0.088 |
| Example 11 | 0.28 | 54 | 0.022 |
| Example 12 | 0.62 | 146 | 0.013 |
| Comparative example 1 | 0.2 | 38 | 0.381 |
| Comparative example 2 | 0.45 | 101 | 0.124 |
TABLE 4
As can be seen by combining example 3 and comparative example 1 and the corresponding application examples, and by combining tables 3 and 4, the amount of the sulfur inhibitor in the raw material of the denitration catalyst obtained in example 3 is larger than that in the denitration catalyst obtained in comparative example 1. From the results of the examination, in the application example of the same temperature, the denitration catalyst prepared in example 3 had SO content in flue gas treatment2/SO3The conversion rate is lower than SO when the denitration catalyst prepared in the comparative example 1 is used for treating flue gas2/SO3The denitration efficiency of the denitration catalyst prepared in example 3 in treating flue gas is higher than that of the denitration catalyst prepared in comparative example 1 in treating flue gas. For example, in application example 2, SO in flue gas was treated with the denitration catalyst obtained in example 32/SO3The conversion rate is reduced by 13.26% compared with the conversion rate of the comparative example 1, and the denitration efficiency is improved by 31.2% compared with the denitration efficiency of the comparative example 1. Embodies that the addition of the sulfur inhibitor can reduce SO2To SO3Conversion rate of conversion, thereby reducing SO3And NH3The blockage condition of the ammonium sulfate generated by the reaction on the pore channel of the catalyst body reflects the effect of improving the denitration efficiency of the denitration catalyst after the sulfur inhibitor is added and used together with other raw materials.
It can be seen from the results of the examination that, although the denitration catalysts obtained in examples 3, 6 and 7 have different SO contents when used for treating flue gas, examples 3, 6 and 7 differ from comparative example 1 in the composition of the sulfur inhibitor in the denitration catalyst, the sulfur inhibitor in example 3 is prepared by compounding silica sol and alumina sol, the sulfur inhibitor in example 6 is prepared by using silica sol, the sulfur inhibitor in example 7 is prepared by using alumina sol, and the denitration catalysts obtained in examples 3, 6 and 7 have the same temperature in the application examples, when used for treating flue gas, in combination with tables 3 and 42/SO3The conversion rate is lower than SO when the denitration catalyst prepared in the comparative example 1 is used for treating flue gas2/SO3The conversion rate, the denitration efficiency of the denitration catalysts prepared in examples 3, 6 and 7 when treating flue gas is higher than that of the denitration catalyst prepared in comparative example 1, but the detection result of the denitration catalyst prepared in example 3 is the best. For example, in application example 2, SO in flue gas was treated with the denitration catalyst obtained in example 32/SO3The conversion rate is reduced by 13.26% compared with the conversion rate of the comparative example 1, and the denitration efficiency is improved by 31.2% compared with the denitration efficiency of the comparative example 1; SO in flue gas treatment with denitration catalyst prepared in example 62/SO3The conversion rate is reduced by 13.11% compared with the conversion rate of the comparative example 1, and the denitration efficiency is improved by 30.8% compared with the denitration efficiency of the comparative example 1; SO in flue gas treatment with denitration catalyst prepared in example 72/SO3The conversion rate is reduced by 13.09% compared with the comparative example 1, and the denitration efficiency is improved by 30.7% compared with the comparative example 1. Therefore, the method shows that when the silica sol and the aluminum sol are compounded and used and are matched with other raw materials, the excellent SO reduction effect is achieved2To SO3The conversion rate of the conversion, thereby improving the denitration efficiency of the denitration catalyst.
As can be seen from examples 8, 9, and 10 and example 3 and the corresponding application examples, and from tables 3 and 4, in comparison with example 3, carboxymethyl cellulose and wood pulp powder were added to the denitration catalyst obtained in example 8, wood pulp powder was added to the denitration catalyst obtained in example 9, and carboxymethyl cellulose was added to the denitration catalyst obtained in example 10. From the detection results, compared with the denitration catalyst prepared in example 3, the denitration catalyst prepared in example 8 has the advantages that the pore volume is increased by 121%, and the specific surface area is increased by 173%; the pore volume of the denitration catalyst prepared in the example 9 is increased by 71%, and the specific surface area is increased by 110%; the pore volume of the denitration catalyst prepared in example 10 is increased by 64%, and the specific surface area is increased by 100%. The denitration catalysts obtained in examples 8, 9 and 10 each had a larger pore volume and a larger specific surface area than those of the denitration catalyst obtained in example 3, but the denitration catalyst obtained in example 8 had the largest increase in pore volume and specific surface area.
In the application example of the same temperature, the denitration efficiency of the denitration catalyst prepared in example 8 in treating flue gas is improved by the most amount than that of the denitration catalyst prepared in example 3, and as in application example 2, compared with the denitration efficiency of the denitration catalyst prepared in example 3 in treating flue gas, the denitration efficiency of the denitration catalyst prepared in example 8 in treating flue gas is improved by 1.9%, while the denitration efficiency of the denitration catalyst prepared in example 9 in treating flue gas is improved by 1.4%, and the denitration efficiency of the denitration catalyst prepared in example 10 in treating flue gas is improved by 1.3%.
Therefore, it can be seen that the addition of carboxymethyl cellulose and wood pulp powder can increase the pore volume and specific surface area of the catalyst body, and reduce SO in the sulfur inhibitor2After the conversion of (3), the SO still converted3And NH3The ammonium sulfate generated after combination enters the pores communicated with the pore channels through the pore channels on the catalyst body, so that the blocking condition of the pore channels is further reduced, and the denitration efficiency of the denitration catalyst is improved. And when the carboxymethyl cellulose and the wood pulp powder are compounded, the catalyst has excellent effects of improving the pore volume and the specific surface area of the catalyst and improving the denitration efficiency of the denitration catalyst.
In combination with example 3, example 8, comparative example 1 and comparative example 2, and the corresponding application examples thereof, and in combination with tables 3 and 4, it can be seen that, compared with comparative example 1, the denitration catalyst prepared in example 3 contains a large amount of sulfur inhibitor, carboxymethyl cellulose and wood pulp powder, the denitration catalyst prepared in example 8 contains a large amount of sulfur inhibitor, carboxymethyl cellulose and wood pulp powder, and the denitration catalyst prepared in comparative example 2 contains a large amount of carboxymethyl cellulose and wood pulp powder.
In combination with examples 3, 8, 11 and 12 and their respective application examples, and in combination with tables 3 and 4, it can be seen that the denitration catalyst obtained in example 11 has a larger amount of the wear-resistant coating than in example 3, and the denitration catalyst obtained in example 12 has a larger amount of the wear-resistant coating than in example 8. The wear-resistant coating is formed by coating a wear-resistant coating mixed solution on the catalyst body and curing, wherein the wear-resistant coating mixed solution comprises liquid sodium silicate, polypropylene reticular fiber and 26-41 type fluororubber particles. From the results of the examination, the wear rate of the denitration catalyst obtained in example 11 was reduced by 0.114%/kg compared with the wear rate of the denitration catalyst obtained in example 3; the attrition rate of the denitration catalyst obtained in example 12 was reduced by 0.049%/kg compared to the attrition rate of the denitration catalyst obtained in example 8. The effect of improving the wear resistance of the denitration catalyst by adding the wear-resistant coating is reflected.
In the application examples of the same temperature, the denitration efficiency of the denitration catalyst prepared in example 11 was improved compared with the denitration efficiency of the denitration catalyst prepared in example 3, and the denitration efficiency of the denitration catalyst prepared in example 12 was improved compared with the denitration efficiency of the denitration catalyst prepared in example 8. For example, in application example 2, the denitration efficiency of the denitration catalyst prepared in example 11 was improved by 0.5% when the denitration catalyst prepared in example 3 was used to treat flue gas. Compared with the denitration efficiency of the denitration catalyst prepared in the embodiment 8 when treating flue gas, the denitration efficiency of the denitration catalyst prepared in the embodiment 12 when treating flue gas is improved by 0.2%.
The reason for the analysis is that: after the liquid sodium silicate is solidified, the polypropylene reticular fiber forms a reticular structure on the windward side of the catalyst body, and the 26-41 type fluororubber particles form a plurality of protruding points on the reticular structure. When flue gas carries large fly ash particles to pass through the denitration catalyst, the fly ash particles collide with the windward side of the catalyst, the speed is reduced after being blocked by the net structure, and meanwhile, the fly ash particles are converted into an advancing path under the action of 26-41 type fluororubber particles and enter the pore channel to be treated by the catalyst body, so that the abrasion degree of the windward side of the catalyst body is reduced, active ingredients on the catalyst body are not easy to lose, and the denitration efficiency of the denitration catalyst is improved.
As can be seen from the application examples and the combination of Table 4, the denitration catalyst prepared in each example has a good denitration treatment effect on flue gas within the temperature range of 120-280 ℃, and the denitration efficiency reaches more than 90%.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (8)
1. The honeycomb denitration catalyst is characterized by comprising a honeycomb catalyst body, wherein the catalyst body is made and molded by the following raw materials in parts by weight: 600-620 parts of titanium dioxide, 12-29 parts of ammonium metavanadate, 18-42 parts of ammonium molybdate, 16-45 parts of glass fiber, 12-34 parts of kaolin, 1-3 parts of stearic acid, 3.6-9.5 parts of polyethylene oxide, 4.2-8.4 parts of lactic acid and 10-50 parts of sulfur inhibitor, wherein the sulfur inhibitor comprises one or a combination of two of silica sol and alumina sol.
2. The honeycomb denitration catalyst of claim 1, wherein the catalyst body is made and molded from the following raw materials in parts by weight: 600-620 parts of titanium dioxide, 20.4-26.5 parts of ammonium metavanadate, 28.4-38.7 parts of ammonium molybdate, 26.4-41 parts of glass fiber, 17.5-28.3 parts of kaolin, 1.7-2.5 parts of stearic acid, 5.2-8 parts of polyethylene oxide, 5.8-7 parts of lactic acid and 15-45 parts of sulfur inhibitor, wherein the sulfur inhibitor comprises silica sol and alumina sol, and the weight ratio of the silica sol to the alumina sol is (2-5): 1.
3. the preparation method of the honeycomb type denitration catalyst, according to claim 1, is characterized in that the catalyst body further comprises 3-3.5 parts by weight of wood pulp powder.
4. The preparation method of the honeycomb denitration catalyst, according to claim 3, is characterized in that the catalyst body further comprises 1-7 parts by weight of carboxymethyl cellulose.
5. The honeycomb type denitration catalyst according to any one of claims 1 to 4, further comprising an abrasion-resistant coating, wherein the abrasion-resistant coating is formed by coating an abrasion-resistant coating mixed solution on the windward side of the catalyst body and then curing, and the abrasion-resistant coating mixed solution comprises liquid sodium silicate, polypropylene mesh fibers and 26-41 type fluororubber particles in a weight ratio of 7:2: 1.
6. The preparation method of the honeycomb type denitration catalyst according to any one of claims 1 to 4, wherein the preparation of the catalyst body comprises the following steps:
(1) preparing raw materials according to a mixture ratio for later use;
(2) preparing an ammonium metavanadate solution: ammonium metavanadate is fully dissolved in NH3Adding monoethanolamine into ammonia water with the mass content of 20% to adjust the pH of the solution to 7.8-9, so as to obtain an ammonium metavanadate solution;
(3) mixing: mixing ammonium metavanadate solution and other raw materials, and adding NH in the mixing process3Adjusting the pH value to be 7.8-9 by ammonia water with the mass content of 15%, adding deionized water in the mixing process to fully mix the raw materials to form a mixed material, wherein the water content of the finally obtained mixed material is 28-31%;
(4) filtration-pre-extrusion: filtering the mixed material, removing impurities to obtain a refined material, and pre-extruding the refined material to form a strip-shaped blank;
(5) and (3) staling: aging the blank for 24 hours;
(6) extruding: extruding and molding the aged blank to obtain a honeycomb blank;
(7) and (3) drying: drying the honeycomb blank;
(8) roasting: roasting the dried honeycomb blank at the final roasting temperature of 510-530 ℃;
(9) cutting: and cutting the roasted honeycomb blank to form a honeycomb catalyst body, wherein two end surfaces of the catalyst body are cut smoothly, and honeycomb openings on the end surfaces are communicated with the outside.
7. The method for preparing a honeycomb type denitration catalyst according to claim 5, characterized by comprising the steps of:
s1, preparing a catalyst body:
(1) preparing raw materials according to a mixture ratio for later use;
(2) preparing an ammonium metavanadate solution: ammonium metavanadate is fully dissolved in NH3Adding monoethanolamine into ammonia water with the mass content of 20% to adjust the pH of the solution to 7.8-9, so as to obtain an ammonium metavanadate solution;
(3) mixing: mixing ammonium metavanadate solution and other raw materials, and adding NH in the mixing process3Adjusting the pH value to be 7.8-9 by ammonia water with the mass content of 15%, adding deionized water in the mixing process to fully mix the raw materials to form a mixed material, wherein the water content of the finally obtained mixed material is 28-31%;
(4) filtration-pre-extrusion: filtering the mixed material, removing impurities to obtain a refined material, and pre-extruding the refined material to form a strip-shaped blank;
(5) and (3) staling: aging the blank for 24 hours;
(6) extruding: extruding and molding the aged blank to obtain a honeycomb blank;
(7) and (3) drying: drying the honeycomb blank;
(8) roasting: roasting the dried honeycomb blank at the final roasting temperature of 510-530 ℃;
(9) cutting: cutting the roasted honeycomb blank to form a honeycomb catalyst body, wherein two windward sides of the catalyst body are cut smoothly, and honeycomb openings on the windward sides are communicated with the outside;
and S2, coating the mixed liquor of the wear-resistant coating on the windward side of the catalyst body prepared in the step S1, keeping the honeycomb-shaped opening on the windward side communicated with the outside, and forming the wear-resistant coating on the windward side of the catalyst body after the mixed liquor of the wear-resistant coating is cured to prepare the honeycomb-type denitration catalyst.
8. The application of the honeycomb denitration catalyst of any one of claims 1 to 5, wherein the denitration efficiency of the denitration catalyst is more than or equal to 90% when denitration treatment is carried out on flue gas at the temperature of 120-280 ℃.
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| CN117181312A (en) * | 2023-05-25 | 2023-12-08 | 北京市中环博业环境工程技术有限公司 | Denitration catalyst in furnace and preparation method thereof |
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