CN112588293A - Novel catalyst for degrading dioxin and preparation method thereof - Google Patents
Novel catalyst for degrading dioxin and preparation method thereof Download PDFInfo
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- CN112588293A CN112588293A CN202011465761.6A CN202011465761A CN112588293A CN 112588293 A CN112588293 A CN 112588293A CN 202011465761 A CN202011465761 A CN 202011465761A CN 112588293 A CN112588293 A CN 112588293A
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- dioxin
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- oxalic acid
- acid solution
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- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- 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 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 230000000593 degrading effect Effects 0.000 title claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 24
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 24
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 24
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 24
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 24
- 230000015556 catabolic process Effects 0.000 claims abstract description 18
- 238000006731 degradation reaction Methods 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 13
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 126
- 235000006408 oxalic acid Nutrition 0.000 claims description 42
- 239000002243 precursor Substances 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 31
- 238000001035 drying Methods 0.000 claims description 21
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 18
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 13
- 229910052720 vanadium Inorganic materials 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 10
- 239000012018 catalyst precursor Substances 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 9
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 9
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 9
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 9
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 8
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 8
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 8
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 5
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims 1
- 238000003379 elimination reaction Methods 0.000 abstract description 19
- 230000008030 elimination Effects 0.000 abstract description 18
- 239000003344 environmental pollutant Substances 0.000 abstract description 16
- 231100000719 pollutant Toxicity 0.000 abstract description 16
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 229910000510 noble metal Inorganic materials 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 238000004056 waste incineration Methods 0.000 abstract description 5
- 230000004913 activation Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 12
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 9
- 229910052721 tungsten Inorganic materials 0.000 description 9
- 239000010937 tungsten Substances 0.000 description 9
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 8
- 239000012692 Fe precursor Substances 0.000 description 8
- 238000007605 air drying Methods 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 208000005623 Carcinogenesis Diseases 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000036952 cancer formation Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 231100000504 carcinogenesis Toxicity 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- -1 comprises two parts Chemical compound 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—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
- 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
- B01D53/8659—Removing halogens or halogen compounds
- B01D53/8662—Organic halogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/394—Metal dispersion value, e.g. percentage or fraction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/20—Halogens or halogen compounds
- B01D2257/206—Organic halogen compounds
- B01D2257/2064—Chlorine
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
- B01D2258/0291—Flue gases from waste incineration plants
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The invention provides a novel catalyst with high activity and high stability and a preparation method thereof, which are used for catalytic oxidation degradation of waste incineration dioxin. The catalyst mainly comprises two parts of an active component and a carrier, wherein the active component is a transition metal oxide V2O5，WO3，Fe2O3In mass, V2O5Content of 0.5-10%, WO30.1-8% of Fe2O3The content is 0.1-6%; the catalyst carrier is made of TiO2And SiO2Composition by mass of TiO250-95% of SiO2The content is 5-20%. The catalyst does not contain noble metal, and the preparation cost is lowThe preparation method is simple, the activation temperature is low, the elimination efficiency of dioxin pollutants is high, the elimination rate of the catalyst at 180 ℃ is nearly 70%, and the elimination efficiency at 220 ℃ is over 90%.
Description
Technical Field
The invention belongs to the field of research on key technology for preparing catalysts, and relates to a catalyst for catalytic oxidative degradation of dioxin pollutants in waste incineration flue gas and a preparation method thereof.
Background
Dioxin is a chloro-oxygenated tricyclic aromatic compound, has the characteristics of stable chemical property, good thermal stability, difficult biodegradation and the like, can be accumulated in organisms and in the environment for a long time, and has the effects of carcinogenesis, teratogenesis and mutagenesis on the organisms.
At present, most of waste incineration dioxin treatment adopts an activated carbon adsorption technology, but the activated carbon adsorption technology has the defects of high operation cost and incomplete low-concentration dioxin treatment, and the concentration of dioxin in treated flue gas mostly exceeds the national standard. In addition, the activated carbon adsorption only seals dioxin in activated carbon pore channels, the dioxin is not really eliminated from the environment, and the activated carbon after adsorbing the dioxin has the risk of secondary pollution. Compared with the activated carbon adsorption technology, the method for eliminating dioxin through catalytic oxidation is used for directly decomposing and converting dioxin in flue gas into water, carbon dioxide and hydrogen chloride which are non-toxic or have small toxicity, and the method for eliminating dioxin through catalytic oxidation has the characteristics of high reaction efficiency, low later-stage operation cost, easiness in engineering and the like. But the biggest problem facing the elimination of dioxin by catalytic oxidation at present is the preparation and production of high-performance catalysts.
Disclosure of Invention
The invention aims to provide a novel catalyst with high activity and high stability and a preparation method thereof, aiming at the defect that a high-performance dioxin decomposition catalyst is lacked in the prior art, the novel catalyst is used for catalytic oxidation degradation of refuse-incinerated dioxin, and the catalyst can efficiently eliminate refuse-incinerated dioxin pollutants.
The novel catalyst for degrading dioxin mainly comprises two parts, namely an active component and a catalyst carrier; the active component is transition metal oxide V2O5，WO3，Fe2O3In mass, V2O5Content of 0.5-10%, WO30.1-8% of Fe2O3The content is 0.1-6%; the catalyst carrier is made of TiO2And SiO2Composition by mass of TiO250-95% of SiO2The content is 5-20%.
The novel catalyst for degrading dioxin is prepared by loading an active component precursor dissolved in an acid solution on the surface of a carrier, and then aging, drying and calcining the carrier.
The novel catalyst for degrading dioxin is characterized in that the acidic solution is an oxalic acid solution with the mass fraction of 10-20%.
The novel catalyst for the degradation of dioxin according to the invention, said V2O5The precursor comprises ammonium metavanadate, vanadyl oxalate and vanadyl sulfate; WO3The precursor comprises ammonium metatungstate, ammonium paratungstate and Fe2O3The precursor comprises ferric nitrate and ferric sulfate.
The preparation method of the novel catalyst for degrading dioxin comprises the following steps:
(1) firstly, V is firstly2O5Dissolving the precursor in a certain amount of oxalic acid solution, and keeping the molar ratio of oxalic acid to vanadium not less than 2;
(2) in the above-mentioned compound containing V2O5Adding WO into oxalic acid solution of precursor3Fully stirring the precursor at 40-70 ℃ to dissolve the precursor;
(3) adding Fe into the oxalic acid solution2O3Fully stirring the precursor at 40-70 ℃ to dissolve the precursor;
(4) adding catalyst carrier TiO into oxalic acid solution containing vanadium, tungsten and iron precursors2And SiO2Keeping the temperature and stirring for 5-10 hours to age the catalyst;
(5) after the aging is finished, TiO loaded with active component precursor2And SiO2Drying the mixture in a blast drying oven for 12-36 hours at 80-150 ℃;
(6) and calcining the dried catalyst precursor in a muffle furnace at the temperature of 400-600 ℃ for 5-20 hours to obtain the catalyst for degrading the dioxin after the calcination is finished.
The inventionCatalyst for degradation of dioxins, process for its preparation and use of TiO2And SiO2The concentration in the oxalic acid solution is 0.5-1.5 g/mL.
Compared with the prior dioxin catalyst technology, the catalyst of the invention has the following advantages:
(1) the catalyst does not contain noble metals, the preparation cost of the catalyst is lower, the price of 1 kg of noble metal precursor is hundreds of thousands, the price of 1 kg of active component vanadium precursor used in the invention is only 600 yuan, and the content of noble metals in the catalyst is about 1/10 of that of non-noble metals, so the cost of the non-noble metal catalyst is far lower than that of the noble metal catalyst;
(2) on one hand, the dioxin catalytic elimination reaction is a temperature sensitive reaction, the reaction activity of the catalyst is low at low temperature, and the catalytic performance is continuously increased along with the rise of the reaction temperature, so that the lower the reaction temperature of the dioxin at a certain elimination efficiency is, the better the reaction activity of the catalyst is; on the other hand, when the reaction temperature exceeds 300 ℃, the rate of synthesis of dioxin increases, resulting in a decrease in the efficiency of dioxin removal. The catalyst has strong oxidation-reduction performance and rich surface acidity, can efficiently eliminate dioxin pollutants generated by waste incineration, and can reduce the concentration of the dioxin pollutants to 0.1ng/m at low temperature3The following; )
(3) The preparation method of the catalyst is simple, and due to the complexation of the alkaline solvent, the active components vanadium, tungsten and iron can be uniformly dispersed on the surface of the carrier without agglomeration, so that the surface of the catalyst has higher reaction activity sites;
(4) the catalyst is a powder catalyst, has small particle size, and is convenient to form a cloverleaf, honeycomb or plate type monolithic catalyst by adding a forming auxiliary agent according to the actual application requirement.
Detailed Description
The catalyst of the present invention will be further described with reference to the following embodiments.
Example 1
(1) Firstly, 6.1g of ammonium metavanadate is dissolved in 150mL of oxalic acid solution with the concentration of 13 percent, and the solution is stirred to be completely dissolved;
(2) adding 4.0g of ammonium paratungstate into the oxalic acid solution, and then fully stirring at 40 ℃ to dissolve the ammonium paratungstate;
(3) continuously adding 1.2g of ferric sulfate into the oxalic acid solution, and fully stirring at 40 ℃ to dissolve the ferric sulfate;
(4) adding 79g of TiO into oxalic acid solution containing vanadium, tungsten and iron precursors2And 10g SiO2Keeping the temperature and continuing stirring for 5 hours to age the catalyst;
(5) after the aging is finished, TiO loaded with active component precursor2And SiO2Drying the mixture in a forced air drying oven for 12 hours at the drying temperature of 80 ℃;
(6) and calcining the dried catalyst precursor in a muffle furnace at 400 ℃ for 5 hours to obtain the dioxin degradation catalyst, wherein the test result of the dioxin pollutant elimination performance is shown in table 1.
Example 2
(1) Firstly, 8.5g of vanadyl oxalate is dissolved in 120mL of oxalic acid solution with the concentration of 18 percent, and the solution is stirred to be completely dissolved;
(2) adding 5.0g of ammonium metatungstate into the oxalic acid solution, and then fully stirring at 60 ℃ to dissolve the ammonium metatungstate;
(3) continuously adding 3.5g of ferric sulfate into the oxalic acid solution, and fully stirring at 60 ℃ to dissolve the ferric sulfate;
(4) adding 65g TiO into oxalic acid solution containing vanadium, tungsten and iron precursors2And 18.5g SiO2Keeping the temperature and continuing stirring for 7 hours to age the catalyst;
(5) after the aging is finished, TiO loaded with active component precursor2And SiO2Drying the mixture in a forced air drying oven for 20 hours at the drying temperature of 100 ℃;
(6) and calcining the dried catalyst precursor in a muffle furnace at 500 ℃ for 8 hours to obtain the dioxin degradation catalyst, wherein the test result of the dioxin pollutant elimination performance is shown in table 1.
Example 3
(1) Firstly, dissolving 4.3g of vanadyl sulfate in 140mL of oxalic acid solution with the concentration of 20%, and stirring to completely dissolve the vanadyl sulfate;
(2) adding 8.0g of ammonium metatungstate into the oxalic acid solution, and fully stirring at 70 ℃ to dissolve the ammonium metatungstate;
(3) 2.3g of ferric nitrate is continuously added into the oxalic acid solution, and the mixture is fully stirred at the temperature of 70 ℃ to be dissolved;
(4) 70g TiO is added into oxalic acid solution containing vanadium, tungsten and iron precursors2And 22g SiO2Keeping the temperature and continuing stirring for 10 hours to age the catalyst;
(5) after the aging is finished, TiO loaded with active component precursor2And SiO2Drying the mixture in a forced air drying oven for 15 hours at the drying temperature of 120 ℃;
(6) and calcining the dried catalyst precursor in a muffle furnace at 550 ℃ for 10 hours to obtain the dioxin degradation catalyst, wherein the test result of the dioxin pollutant elimination performance is shown in table 1.
Example 4
(1) Firstly, dissolving 3.8g of vanadyl oxalate in 100mL of oxalic acid solution with the concentration of 15%, and stirring to completely dissolve the vanadyl oxalate;
(2) adding 5.0g of ammonium metatungstate into the oxalic acid solution, and fully stirring at 50 ℃ to dissolve the ammonium metatungstate;
(3) continuously adding 5.5g of ferric nitrate into the oxalic acid solution, and fully stirring at 50 ℃ to dissolve the ferric nitrate;
(4) adding 80g TiO into oxalic acid solution containing vanadium, tungsten and iron precursors2And 15g SiO2Keeping the temperature and continuing stirring for 7 hours to age the catalyst;
(5) after the aging is finished, TiO loaded with active component precursor2And SiO2Drying the mixture in a forced air drying oven for 36 hours at the drying temperature of 80 ℃;
(6) and calcining the dried catalyst precursor in a muffle furnace at 450 ℃ for 20 hours to obtain the dioxin degradation catalyst, wherein the test result of the dioxin pollutant elimination performance is shown in table 1.
Example 5
(1) Firstly, dissolving 2.5g of ammonium metavanadate in 150mL of 10% oxalic acid solution, and stirring to completely dissolve the ammonium metavanadate solution;
(2) adding 10.0g of ammonium paratungstate into the oxalic acid solution, and then fully stirring at 40 ℃ to dissolve the ammonium paratungstate;
(3) continuously adding 8.5g of ferric nitrate into the oxalic acid solution, and fully stirring at 40 ℃ to dissolve the ferric nitrate;
(4) adding 90g TiO into oxalic acid solution containing vanadium, tungsten and iron precursors2And 5g SiO2Keeping the temperature and continuing stirring for 10 hours to age the catalyst;
(5) after the aging is finished, TiO loaded with active component precursor2And SiO2Drying the mixture in a forced air drying oven for 24 hours at the drying temperature of 120 ℃;
(6) and calcining the dried catalyst precursor in a muffle furnace at 400 ℃ for 15 hours to obtain the dioxin degradation catalyst, wherein the test result of the dioxin pollutant elimination performance is shown in table 1.
Example 6
(1) Firstly, dissolving 9.5g of vanadyl sulfate in 120mL of oxalic acid solution with the concentration of 20%, and stirring to completely dissolve the vanadyl sulfate;
(2) adding 3.0g of ammonium paratungstate into the oxalic acid solution, and then fully stirring at 45 ℃ to dissolve the ammonium paratungstate;
(3) continuously adding 5.5g of ferric sulfate into the oxalic acid solution, and fully stirring at 45 ℃ to dissolve the ferric sulfate;
(4) 60g of TiO is added into oxalic acid solution containing vanadium, tungsten and iron precursors2And 35g SiO2Keeping the temperature and continuing stirring for 8 hours to age the catalyst;
(5) after the aging is finished, TiO loaded with active component precursor2And SiO2Drying the mixture in a forced air drying oven for 12 hours at the drying temperature of 150 ℃;
(6) and calcining the dried catalyst precursor in a muffle furnace at 600 ℃ for 7 hours to obtain the dioxin degradation catalyst, wherein the test result of the dioxin pollutant elimination performance is shown in table 1.
Comparative example 1
Dissolving 10.5g of vanadyl sulfate and 6.0g of ammonium metatungstate in 120mL of 15% oxalic acid solution at 40 ℃, and stirring to completely dissolve the vanadyl sulfate and the ammonium metatungstate; adding 95g TiO into oxalic acid solution containing vanadium and tungsten precursor2Keeping the temperature and continuing stirring for 10 hours to age the catalyst; then TiO loaded with active component precursor2Drying the mixture in a forced air drying oven for 15 hours at the drying temperature of 100 ℃; and finally, calcining the dried catalyst precursor in a muffle furnace at 450 ℃ for 7 hours to obtain the dioxin degradation catalyst, wherein the test result of the dioxin pollutant elimination performance is shown in table 1.
Comparative example 2
Dissolving 4.5g of vanadyl sulfate and 3.5g of ferric nitrate in 150mL of 10% oxalic acid solution at 50 ℃, and stirring to dissolve; adding 90g of SiO into oxalic acid solution containing vanadium and iron precursors2Keeping the temperature and continuing stirring for 10 hours to age the catalyst; then loading the SiO loaded with the active component precursor2Drying the mixture in a forced air drying oven for 10 hours at the drying temperature of 150 ℃; and finally, calcining the dried catalyst precursor in a muffle furnace at 550 ℃ for 5 hours to obtain the dioxin degradation catalyst, wherein the test result of the dioxin pollutant elimination performance is shown in table 1.
The catalyst of the invention has dioxin pollutant elimination performance test:
because the o-dichlorobenzene and dioxin have similar structural properties, the simulated pollutant used in the reaction performance detection of the catalyst is the o-dichlorobenzene. In the reaction performance test process, the concentration of o-dichlorobenzene is 1500ppm, and the space velocity is as follows: 4000h-1Air is the balance gas.
The results of the tests on the reaction performance of the catalysts in table 1 show that the novel catalysts prepared by the invention have higher elimination efficiency on the dioxin simulant o-dichlorobenzene and low activation temperature of the catalysts, the elimination rate of dioxin pollutants of the catalysts prepared in examples 5 and 6 is nearly 70% at 180 ℃, and the elimination efficiency is over 90% at 220 ℃. The results show that the catalyst and the preparation method thereof have very large application potential in the elimination of the dioxin generated in the waste incineration.
In order to illustrate the superiority and advancement of the catalyst and the preparation method thereof, the catalyst prepared by two different methods is arranged and compared by an activity test, and the catalyst prepared by the method has higher reaction performance.
TABLE 1 results of tests for eliminating Dioxin contaminants
Claims (8)
1. A novel catalyst for degrading dioxin is characterized in that: the catalyst mainly comprises an active component and a catalyst carrier;
wherein the active component comprises a transition metal oxide V2O5、WO3And Fe2O3The catalyst carrier is TiO2And SiO2。
2. The novel catalyst for the degradation of dioxin according to claim 1, characterized in that: active ingredient by mass, V2O5Content of 0.5-10%, WO30.1-8% of Fe2O3The content is 0.1-6%.
3. The novel catalyst for the degradation of dioxin according to claim 1, characterized in that: catalyst support by mass, TiO250-95% of SiO2The content is 5-20%.
4. The method for preparing a novel catalyst for the degradation of dioxin according to claim 1, characterized in that: the method comprises the following steps:
(1) firstly, V is put in2O5Dissolving the precursor in a certain amount of oxalic acid solution;
(2) the above-mentioned compound containing V2O5Adding WO into oxalic acid solution of precursor3Fully stirring the precursor at 40-70 ℃ to dissolve the precursor;
(3) continuously adding Fe into the oxalic acid solution2O3Fully stirring the precursor at 40-70 ℃ to dissolve the precursor;
(4) adding catalyst carrier TiO2And SiO2Keeping the temperature and stirring for 5-10 hours to age the catalyst;
(5) after the aging is finished, TiO loaded with an active component precursor2And SiO2Drying the mixture in a blast drying oven for 12-36 hours at 80-150 ℃;
(6) and calcining the dried catalyst precursor in a muffle furnace at the temperature of 400-600 ℃ for 5-20 hours to obtain the catalyst for degrading the dioxin after the calcination is finished.
5. The method for preparing a novel catalyst for the degradation of dioxin according to claim 4, characterized in that: the mol ratio of oxalic acid to vanadium is more than or equal to 2.
6. The method for preparing a novel catalyst for the degradation of dioxin according to claim 4, characterized in that: the mass fraction of oxalic acid in the oxalic acid solution is 10-20%.
7. The method for preparing a novel catalyst for the degradation of dioxin according to claim 4, characterized in that: v in step (1)2O5The precursor comprises ammonium metavanadate, vanadyl oxalate or vanadyl sulfate; WO3The precursor comprises ammonium metatungstate or ammonium paratungstate, Fe2O3The precursor comprises ferric nitrate or ferric sulfate.
8. A process as claimed in claim 4The preparation method of the novel catalyst for degrading dioxin is characterized by comprising the following steps: TiO in the step (4)2And SiO2The concentration in the oxalic acid solution is 0.5-1.5 g/mL.
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