CN113926464B - SCR catalyst using full-risk waste and solid waste as carriers and preparation method and application thereof - Google Patents
SCR catalyst using full-risk waste and solid waste as carriers and preparation method and application thereof Download PDFInfo
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- CN113926464B CN113926464B CN202111326567.4A CN202111326567A CN113926464B CN 113926464 B CN113926464 B CN 113926464B CN 202111326567 A CN202111326567 A CN 202111326567A CN 113926464 B CN113926464 B CN 113926464B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- 239000002699 waste material Substances 0.000 title claims abstract description 47
- 239000002910 solid waste Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000000969 carrier Substances 0.000 title claims abstract description 25
- 239000010802 sludge Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000003245 coal Substances 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 238000011065 in-situ storage Methods 0.000 claims abstract description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000003723 Smelting Methods 0.000 claims abstract description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 7
- 239000004927 clay Substances 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 239000000654 additive Substances 0.000 claims abstract description 4
- 230000000996 additive effect Effects 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 28
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 8
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- 239000005995 Aluminium silicate Substances 0.000 claims description 6
- 235000012211 aluminium silicate Nutrition 0.000 claims description 6
- 239000000440 bentonite Substances 0.000 claims description 6
- 229910000278 bentonite Inorganic materials 0.000 claims description 6
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 229920002907 Guar gum Polymers 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- 239000000665 guar gum Substances 0.000 claims description 4
- 229960002154 guar gum Drugs 0.000 claims description 4
- 235000010417 guar gum Nutrition 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005751 Copper oxide Substances 0.000 claims description 3
- 229910000431 copper oxide Inorganic materials 0.000 claims description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 238000007781 pre-processing Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 12
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 12
- 238000012360 testing method Methods 0.000 description 8
- 239000002920 hazardous waste Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 230000001788 irregular Effects 0.000 description 4
- 210000001161 mammalian embryo Anatomy 0.000 description 4
- 235000006408 oxalic acid Nutrition 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000010813 municipal solid waste Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011449 brick Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000010791 domestic waste Substances 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- B01J35/51—
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8877—Vanadium, tantalum, niobium or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- 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
Abstract
The invention relates to an SCR catalyst using full-risk waste and solid waste as carriers, and a preparation method and application thereof, wherein the method comprises the following steps: mixing and pre-treating the waste denitration catalyst, coal gangue and aluminum ash to obtain mixture powder; 7-10 parts of waste denitration catalyst, 1-2 parts of coal gangue, 0-1 part of aluminum ash and 1-3 parts of sludge by weight; adding sludge, deionized water and a forming additive into the mixture powder, uniformly mixing, adding ammonia water to adjust the pH to 6.5-7.5, mixing with the sludge, and smelting the sludge to obtain a sludge blank; preparing the clay blank into a raw material sphere with the diameter of 1-3 cm, drying, and calcining at the temperature of 350-1100 ℃ to obtain a calcined spherical carrier; impregnating the calcined spherical carrier with the precursor liquid of the active component, drying in situ, and repeating the process until the weight of the calcined spherical carrier is increased by 15% -20%; calcining the spherical carrier impregnated with the active component at 350-550 ℃ to obtain the catalyst. The preparation cost is low, and the method is suitable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of environmental protection catalysis, and particularly relates to an SCR catalyst using full-risk waste and solid waste as carriers, and a preparation method and application thereof.
Background
With the development and progress of society, the large-scale discharge of urban sewage and domestic wastewater causes the rapid increase of the production of sludge, the complex sludge components and difficult disposal and resource utilization, and the current sludge utilization method mainly comprises the steps of fertilizer preparation, activated carbon preparation, brick burning, land utilization and the like. However, the problems that the treatment scale is not kept up, the treatment technology is imperfect, the soil is negatively affected by improper treatment and the like still exist at present, and the treatment method needs to be continuously innovated.
A Selective Catalytic Reduction (SCR) denitration technology is widely applied to industries such as thermal power, coking, steel and the like as a technology for removing nitrogen oxides by virtue of high denitration efficiency, but an SCR denitration catalyst is exposed to dust and SO for a long time in the use process 2 In the flue gas with higher content, the pore canal of the catalyst is blocked, the service life is greatly reduced, the service life of the imported catalyst is about 3 years, the domestic waste SCR denitration catalyst only has more than 5000 ten thousand cubic meters, and the waste denitration catalyst (vanadium-titanium series) is classified as a 'HW 50 waste catalyst' at present and is managed by hazardous waste.
If the hazardous waste such as sludge and waste denitration catalyst can be recycled, the industrial high-added-value chemical SCR denitration catalyst can be prepared and applied in engineering, and the exhaust nitrogen oxide can be removed while the solid waste and the hazardous waste are eliminated, so that waste is changed into valuable, and economic value and environmental protection value are created.
Liu Tao and the like, preparing a denitration catalyst [ J ] by using excess sludge of an urban sewage treatment plant; the chemical industry is environment-friendly; in the period of 2007 01, pyrolysis sludge is adopted as a carrier to prepare a denitration catalyst, but the catalyst has the problems that the activation temperature is too high, the active components are Zn and Fe transition metal elements, the stability is poor, and the activity is reduced within 10 hours; chinese patent publication No. CN111013636a discloses a preparation method of a low-temperature denitration catalyst based on municipal sludge, but the highest conversion efficiency of the catalyst still cannot reach 90%, the conversion efficiency is low in practical engineering use and the ammonia escapes, and the transition metal is adopted as the main active component and is subject to sulfur poisoning; chinese patent publication No. CN110961106a discloses a high-performance low-temperature denitration catalyst prepared by using waste solid resources and a preparation method thereof, which adopts sludge as a part to prepare the denitration catalyst, but the conversion rate is only about 55%, and the phenomenon of activity reduction occurs in a shorter operation time; chinese patent publication No. CN111744495a discloses a ceramic membrane denitration dioxin removal catalyst using sludge and steel slag as raw materials and a preparation method thereof, but the preparation method is relatively complicated, is not suitable for industrial mass production, and has a high applicable temperature of 500 ℃.
In summary, the problems of the prior art are:
(1) At present, hazardous waste denitration catalyst (vanadium-titanium system) and solid waste sludge are urgently needed to be treated or recycled;
(2) In the papers and reviews of the preparation of denitration catalysts by using sludge as part of raw materials reported at present, no method suitable for large-scale application exists;
(3) The high added value SCR denitration catalyst prepared by using hazardous waste and solid waste needs to find a proper preparation process and method to ensure high denitration efficiency and stability.
Disclosure of Invention
Aiming at the problems existing in the prior art, one of the purposes of the invention is to provide an SCR catalyst using full-risk waste and solid waste as carriers and a preparation method thereof, wherein the catalyst adopts the full-risk waste and solid waste to prepare the catalyst carriers, thereby greatly reducing the cost of the catalyst and providing a new path for large-scale, harmless and high-valued use of urban solid waste and hazardous waste; the preparation method is simple, easy to operate and suitable for large-scale production and industrialized popularization.
The invention also aims to provide an application of the SCR catalyst using the full-risk waste and the solid waste as carriers.
The invention is realized in such a way that the preparation method of the SCR catalyst by using the full-risk waste and the solid waste as carriers comprises carriers, forming aids and active components, wherein the carriers comprise 7-10 parts by weight of waste denitration catalyst, 1-2 parts by weight of coal gangue, 0-1 part by weight of aluminum ash and 1-3 parts by weight of sludge;
the preparation method of the catalyst comprises the following steps:
s1, pretreating a mixture of waste denitration catalyst, coal gangue and aluminum ash to obtain mixture powder;
s2, adding sludge, deionized water and a forming additive into the mixture powder, uniformly mixing, adding a certain amount of ammonia water to adjust the PH to 6.5-7.5, mixing with the sludge, and smelting the sludge to obtain a sludge blank;
s3, preparing the mud blank into a raw material sphere with the diameter of 1-3 cm, drying, and calcining at the temperature of 350-1100 ℃ for 2-5 hours to obtain a calcined spherical carrier;
s4, impregnating the calcined spherical carrier with the precursor liquid of the active component, drying in situ, and repeating the process until the weight of the calcined spherical carrier is increased by 15% -20%;
s5, calcining the spherical carrier impregnated with the active components at 350-550 ℃ for 1-5 h to obtain the catalyst.
In the above technical scheme, preferably, in the step S1, the waste denitration catalyst is crushed into small pieces before being used, and the method for preprocessing the mixture is to grind the mixture in a ball mill and then pass through a 200-mesh sieve.
In the above technical scheme, preferably, in the step S2, the forming auxiliary agent accounts for 0.5-2% of the total mass of the carrier.
In the above technical solution, preferably, in the step S2, the forming auxiliary agent includes one or a combination of several of deionized water, ethylene glycol, bentonite, kaolin, PEO, cellulose, and guar gum.
In the above technical scheme, preferably, in the step S3, the raw material spheres are dried at 100-120 ℃ for 2-5 hours.
In the above technical scheme, preferably, in the step S4, the active component accounts for 2% -18% of the total mass of the catalyst.
In the above technical solution, preferably, in the step S4, the active component includes one or a combination of several of vanadium pentoxide, zirconium oxide, cerium oxide, molybdenum trioxide, tungsten trioxide, manganese oxide, copper oxide, and iron oxide; the precursor liquid of the active component is a solution prepared by soluble salts of the active component.
In the above technical scheme, preferably, in the step S4, the calcined spherical carrier is placed into a vacuum impregnator, then the precursor solution of the active component is impregnated through the spherical carrier from bottom to top by vacuum suction, and is dried in situ at 90-120 ℃.
The SCR catalyst using the full-risk waste and the solid waste as the carriers is prepared by the preparation method of the SCR catalyst using the full-risk waste and the solid waste as the carriers.
The application of the SCR catalyst using the full-risk waste and the solid waste as carriers can be used for medium-low temperature denitration at 160-350 ℃, and the denitration efficiency is more than 92% in the temperature window range of 160-350 ℃. The denitration efficiency is higher along with the temperature rise.
The invention has the advantages and positive effects that:
(1) The invention adopts full-risk waste and solid waste to prepare the catalyst carrier, greatly reduces the catalyst cost, and provides a new path for large-scale harmless and high-valued use of urban solid waste and hazardous waste; the preparation method of the catalyst is simple, easy to operate, strong in repeatability and suitable for large-scale production and industrialized popularization; the prepared denitration catalyst has a wider denitration temperature window, can be used for medium-low temperature denitration at 160-350 ℃, has denitration efficiency of more than 92%, and has excellent sulfur resistance.
(2) According to the invention, the spherical denitration catalyst is adopted, and the spherical carrier is adopted as the catalyst carrier, so that the residence time of the catalyst in the pore canal can be prolonged in the use process, and the denitration efficiency is improved; and the loss of the catalyst can be reduced, and the service life of the catalyst can be prolonged.
(3) The elements such as Fe, K and the like in the domestic sludge and the red mud can be used as the auxiliary agent of the denitration catalyst to improve the denitration effect, and no additional addition is needed; the vanadium element in the waste denitration catalyst can be used as the supplement of the active component, so that the addition amount of the active component is reduced, and the production cost is reduced.
(4) In the calcination process of the raw material sphere, countless small gaps can be generated due to the loss of carbon elements, the surface area and the internal pore canal of the spherical carrier are increased, and the subsequent loading of active components in the pore canal is facilitated; and the spherical carrier is impregnated with the active components by a vacuum impregnation method, so that tiny bubbles in pore channels of the spherical carrier can be extracted, the pore channels are ensured to be completely filled and impregnated, and the impregnation effect is ensured.
Drawings
FIG. 1 is an SEM photograph of a catalyst prepared according to example 2 of the present invention;
FIG. 2 is a sample of the catalyst prepared in example 2 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
The preparation method of the SCR catalyst using the full-risk waste and the solid waste as carriers comprises the following steps:
1) Firstly, crushing the waste denitration catalyst into irregular small blocks with the size of about 2-3 cm;
2) Uniformly mixing 1 part of coal gangue, 0.2 part of aluminum ash and 10 parts of waste denitration catalyst;
3) Grinding the mixture in the step 2) in a ball mill, sieving the ground mixture with a 200-mesh sieve to obtain mixture powder, and adding 1 part of sludge, a certain amount of ethylene glycol, bentonite and PEO (ethylene glycol: bentonite: PEO mass ratio = 1:2:1, uniformly mixing, adding a certain amount of deionized water and mud, adding a certain amount of ammonia water to adjust PH=7.5, and smelting mud to obtain mud blanks;
4) Preparing the clay embryo in the step 3) into a raw material sphere with the diameter of about 2cm by using a granulator, drying the raw material sphere at the temperature of 100 ℃ for 5h, and calcining the raw material sphere at the temperature of 550 ℃ for 2h to obtain a calcined spherical carrier;
5) A certain amount of ammonium metavanadate, oxalic acid, zirconium acetate, ammonium molybdate (vanadium pentoxide: zirconia: molybdenum trioxide mass ratio = 3:1:2) to prepare a precursor solution of an active component for later use, placing the calcined spherical carrier into a vacuum impregnator, leading the precursor solution of the active component to pass through the spherical carrier from bottom to top by vacuum suction, drying at the in-situ temperature of 120 ℃, and repeating the process for 2 times until the weight of the spherical carrier is increased by 20%;
6) Calcining the spherical carrier impregnated with the active component at 450 ℃ for 5 hours to obtain the catalyst.
Example 2
The preparation method of the SCR catalyst using the full-risk waste and the solid waste as carriers comprises the following steps:
1) Firstly, crushing the waste denitration catalyst into irregular small blocks with the size of about 3-5 cm;
2) Uniformly mixing 2 parts of coal gangue, 0.5 part of aluminum ash and 9 parts of waste denitration catalyst;
3) Grinding the mixture in the step 2) in a ball mill, sieving the ground mixture with a 200-mesh sieve to obtain mixture powder, and adding 2 parts of sludge, a certain amount of ethylene glycol, kaolin and PEO (ethylene glycol: kaolin: mass ratio of PEO = 3:2:1.5, adding a certain amount of deionized water and mud after uniformly mixing, adding a certain amount of ammonia water to adjust PH=6.5, and smelting mud to obtain mud blanks;
4) Preparing the clay embryo in the step 3) into a raw material sphere with the diameter of about 3cm by using a granulator, drying for 5h at 110 ℃, and calcining for 3h at 750 ℃ to obtain a calcined spherical carrier;
5) A certain amount of ammonium metavanadate, oxalic acid, cerium nitrate, ammonium tungstate (vanadium pentoxide: cerium oxide: tungsten trioxide mass ratio = 3:2:5) to prepare a precursor solution of an active component for later use, placing the calcined spherical carrier into a vacuum impregnator, enabling the precursor solution of the active component to pass through the spherical carrier from bottom to top by vacuum suction, drying at the in-situ 90 ℃, and repeating the process for 3 times until the weight of the spherical carrier is increased by 15%;
6) Calcining the spherical carrier impregnated with the active component at 400 ℃ for 5 hours to obtain the catalyst.
The prepared catalyst is subjected to scanning electron microscope test, as shown in figure 1, and the prepared catalyst is fully calcined, has uniform grain size distribution and higher strength. The prepared catalyst sample is shown in figure 2, the surface color of the catalyst sample particles is consistent, and the catalyst sample particles have a uniformly distributed micropore structure, so that the adsorption and desorption processes are facilitated.
Example 3
The preparation method of the SCR catalyst using the full-risk waste and the solid waste as carriers comprises the following steps:
1) Firstly, crushing the waste denitration catalyst into irregular small blocks with the size of about 1-2 cm;
2) Uniformly mixing 1.5 parts of coal gangue and 8 parts of waste denitration catalyst;
3) Grinding the mixture in the step 2) in a ball mill, sieving the ground mixture with a 200-mesh sieve to obtain mixture powder, and adding 2.5 parts of sludge, a certain amount of glycol, guar gum and kaolin (glycol: guar gum: kaolin mass ratio = 1:3:2, adding a certain amount of deionized water and mud after uniformly mixing, adding a certain amount of ammonia water to adjust PH=7, and smelting mud to obtain mud blanks, wherein the forming auxiliary agent accounts for 1.5% of the total mass of the carrier;
4) Preparing the clay embryo in the step 3) into a raw material sphere with the diameter of about 2.5 cm by using a granulator, drying the raw material sphere at 100 ℃ for 5 hours, and calcining the raw material sphere at 850 ℃ for 2 hours to obtain a calcined spherical carrier;
5) A certain amount of ammonium metavanadate, oxalic acid, cerium nitrate, ammonium tungstate, copper nitrate (vanadium pentoxide: cerium oxide: tungsten trioxide: copper oxide mass ratio = 2:1:3:1) preparing a precursor solution of an active component for standby, placing the calcined spherical carrier into a vacuum impregnator, enabling the precursor solution of the active component to pass through the spherical carrier from bottom to top through vacuum suction, drying at the in-situ 100 ℃, and repeating the process for 5 times until the weight of the spherical carrier increases by 17%;
6) Calcining the spherical carrier impregnated with the active component at 500 ℃ for 5 hours to obtain the catalyst.
Comparative example 1
The same procedure as in example 3 was followed except that no sludge was added.
Comparative example 2
1) Firstly, crushing the waste denitration catalyst into irregular small blocks with the size of about 2-3 cm;
2) Uniformly mixing 1 part of coal gangue, 0.2 part of aluminum ash and 10 parts of waste denitration catalyst;
3) Grinding the mixture in the step 2) in a ball mill, sieving the ground mixture with a 200-mesh sieve to obtain mixture powder, and adding 1 part of sludge, a certain amount of ethylene glycol, bentonite and PEO (ethylene glycol: bentonite: PEO mass ratio = 1:2:1, forming auxiliary agent accounting for 2 percent of the total mass of the carrier), adding a certain amount of water and mud after uniformly mixing, adding a certain amount of ammonia water to adjust PH=7.5, and smelting mud to obtain mud blanks;
4) Preparing the clay embryo in 3) into raw material spheres with the diameter of about 2cm by a granulator, drying for 5h at 100 ℃, and calcining for 2h at 550 ℃; obtaining a calcined spherical carrier;
5) A certain amount of ammonium metavanadate, oxalic acid, zirconium acetate, ammonium molybdate (vanadium pentoxide: zirconia: molybdenum trioxide mass ratio = 3:1:2) to prepare a precursor solution of the active component for later use, and impregnating the precursor solution haploid of the active component onto the calcined spherical carrier;
6) Calcining the spherical carrier impregnated with the active component at 450 ℃ for 5 hours to obtain the catalyst.
Characterization of Performance
The catalysts prepared in examples 1-3 and comparative examples 1-2 were tested for nitrogen oxide removal under the conditions of sulfur dioxide and water.
Test conditions: the test temperature was 180℃and the NO inlet concentration was 500mg/Nm 3 ，NH 3 Introducing 500mg/Nm 3 、O 2 7% (v/v), N 2 To balance the gas, the gas volume space velocity is 4000h -1 . The concentration of NO at the inlet and outlet of the catalyst was measured by a nitrogen oxide detector, and the analysis results are shown in Table 1.
Table 1 test results
From the test results of table 1, it can be analyzed that the addition of the sludge can improve the sulfur resistance of the catalyst to some extent, possibly because of the synergistic effect of the active elements and the active components present in the sludge; meanwhile, compared with the common haploid product impregnation, the vacuum impregnation can improve the initial denitration efficiency, presumably because the active components can enter the pore channels of the carrier by adopting the vacuum impregnation, and the dispersion is more uniform.
The catalysts prepared in examples 1 to 3 were subjected to strength test using a particle strength tester, and the test results are shown in table 2.
TABLE 2 catalyst particle strength test results
| Name of the name | Example 1 | Example 2 | Example 3 |
| Particle strength | 523 N | 840N | 1058N |
As can be seen from Table 2, the catalyst particles of examples 1-3 have a strength between 523 and 1058N, and have good strength properties, which can reduce breakage of the catalyst during use.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments may be modified or some or all of the technical features may be replaced equivalently, and these modifications or replacements do not make the essence of the corresponding technical scheme deviate from the scope of the technical scheme of the embodiments of the present invention.
Claims (9)
1. A preparation method of an SCR catalyst using full-risk waste and solid waste as carriers is characterized by comprising the following steps: the catalyst comprises a carrier, a forming additive and an active component, wherein the carrier comprises 7-10 parts by weight of a waste denitration catalyst, 1-2 parts by weight of coal gangue, 0-1 part by weight of aluminum ash and 1-3 parts by weight of sludge;
the preparation method of the catalyst comprises the following steps:
s1, pretreating a mixture of waste denitration catalyst, coal gangue and aluminum ash to obtain mixture powder;
s2, adding sludge, deionized water and a forming additive into the mixture powder, uniformly mixing, adding a certain amount of ammonia water to adjust the PH to 6.5-7.5, mixing with the sludge, and smelting the sludge to obtain a sludge blank;
s3, preparing the clay blank into a raw material sphere with the diameter of 1-3 cm, drying, and calcining at the temperature of 350-1100 ℃ for 2-5 hours to obtain a calcined spherical carrier;
s4, impregnating the calcined spherical carrier with the precursor liquid of the active component, drying in situ, and repeating the process until the weight of the calcined spherical carrier is increased by 15% -20%;
and S5, calcining the spherical carrier impregnated with the active components at 350-550 ℃ for 1-5 hours to obtain the catalyst.
2. The method for preparing the SCR catalyst by using the full-risk waste and the solid waste as carriers according to claim 1, which is characterized in that: in the step S1, the waste denitration catalyst is crushed into small blocks before being used, and the method for preprocessing the mixture is to grind the mixture in a ball mill and then pass through a 200-mesh sieve.
3. The method for preparing the SCR catalyst by using the full-risk waste and the solid waste as carriers according to claim 1, which is characterized in that: in the step S2, the forming auxiliary agent accounts for 0.5-2% of the total mass of the carrier.
4. The method for preparing the SCR catalyst by using the full-risk waste and the solid waste as carriers according to claim 1, which is characterized in that: in the step S2, the forming auxiliary agent includes one or a combination of several of deionized water, ethylene glycol, bentonite, kaolin, PEO, cellulose and guar gum.
5. The method for preparing the SCR catalyst by using the full-risk waste and the solid waste as carriers according to claim 1, which is characterized in that: in the step S3, the raw material spheres are dried for 2-5 hours at the temperature of 100-120 ℃.
6. The method for preparing the SCR catalyst by using the full-risk waste and the solid waste as carriers according to claim 1, which is characterized in that: in the step S4, the active component comprises one or a combination of more of vanadium pentoxide, zirconium oxide, cerium oxide, molybdenum trioxide, tungsten trioxide, manganese oxide, copper oxide and ferric oxide; the precursor liquid of the active component is a solution prepared by soluble salts of the active component.
7. The method for preparing the SCR catalyst by using the full-risk waste and the solid waste as carriers according to claim 1, which is characterized in that: in the step S4, the calcined spherical carrier is firstly placed into a vacuum impregnator, then precursor liquid of the active component is impregnated through the spherical carrier from bottom to top by vacuum suction, and in-situ drying is carried out at the temperature of 90-120 ℃.
8. An SCR catalyst using all-risk waste and solid waste as carriers, wherein the catalyst is prepared by the preparation method of the SCR catalyst using all-risk waste and solid waste as carriers according to any one of claims 1 to 7.
9. The use of an SCR catalyst utilizing all-risk waste, solid waste as a carrier according to claim 8, characterized in that: the catalyst can be used for medium-low temperature denitration at 160-350 ℃, and the denitration efficiency is more than 92% within a temperature window range of 160-350 ℃.
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